JP6730848B2 - Graft polymer - Google Patents

Description

The present invention relates to graft polymers. More specifically, it relates to a graft polymer useful as a raw material for detergent additives and the like.

Conventionally, a detergent builder (detergent aid) such as zeolite, carboxymethyl cellulose, or polyethylene glycol has been blended with a detergent used for clothing for the purpose of improving the cleaning effect of the detergent.
In addition to the above-mentioned various detergent builders, recently, polymers have been incorporated into detergent compositions as detergent builders.
For example, Patent Documents 1 to 4 disclose graft polymers having a specific structure in which a monomer component containing an unsaturated monocarboxylic acid is graft-polymerized to polyalkylene oxide.

International Publication No. 2008/020556 JP, 2010-0777427, A JP, 2007-254679, A JP, 2009-256656, A

Here, since the use of liquid detergents is increasing due to the spread of drum type washing machines in recent years, various detergent builders have sufficient compatibility with surfactants so that they can be incorporated into liquid detergents. Is required to have. Further, as a market trend in recent years, liquid detergents tend to be highly concentrated types (low composition ratio of water), and consumers' preference is that liquid detergents with no turbidity and high transparency are preferred. It is in. Therefore, the requirement for compatibility with other liquid detergent components typified by surfactants and the like, which is required for polymers, has become extremely strict as compared with conventional ones.
As described above, attempts have been made to develop various types of detergent builders, but their performance is not sufficient in terms of compatibility with liquid detergents.

The present invention has been made in view of the above circumstances, and provides a graft polymer in which the compatibility with a surfactant when used in a detergent application is further improved as compared with a conventional polymer. With the goal.

The present inventor conducted various studies on the graft polymer, and found that the average addition mole number of oxyalkylene groups in the graft polymer of the unsaturated carboxylic acid monomer and the polyether compound is 1 or more and less than 10, Alternatively, the average addition mole number of oxyalkylene groups in the graft polymer of the unsaturated carboxylic acid monomer and the polyether compound is 10 to 29, and the molar ratio of the unsaturated carboxylic acid monomer and the polyether compound is Is a polymer having a specific range or the end of the polyether compound is a linear alkyl group having 1 to 18 carbon atoms, and found to have excellent compatibility with a surfactant, and it is possible to solve the above problems brilliantly. The present invention has been made based on the idea that what can be done is achieved.

That is, the first aspect of the present invention is a polymer obtained by graft-polymerizing an ethylenically unsaturated monomer onto a polyether compound, wherein the polyether compound has the following formula (1);
_{^{R 1 - [X 1 - (}} A 1 O) p -H] q (1)
(In the formula (1), R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms. X ¹ represents a divalent linking group. A ¹ O is the same or different and has 2 to 2 carbon atoms. Represents an oxyalkylene group of 20. p represents the average number of moles of addition of A ¹ O, and is the same or different and is a number of 1 or more and less than 10. q is a number of 1 to 6, provided that: The total number of oxyalkylene groups present in the formula (1), that is, the total number of p present in q is 1 or more and less than 10) is a compound represented by the above-mentioned ethylenically unsaturated monomer. The body is a graft polymer containing an ethylenically unsaturated carboxylic acid monomer.
A second aspect of the present invention is a polymer obtained by graft-polymerizing an ethylenically unsaturated monomer onto a polyether compound, wherein the polyether compound has the following formula (2);
_{^{R 2 - [X 2 - (}} A 2 O) r -H] s (2)
(In the formula (2), R ² represents a hydrocarbon group having 1 to 18 carbon atoms. X ² represents a divalent linking group. A ² O is the same or different and has 2 to 2 carbon atoms. 20 represents an oxyalkylene group, r represents the average number of moles of A ² O added, and is the same or different and is a number of 1 to 29. s is a number of 1 to 6, provided that the formula ( The total number of oxyalkylene groups present in 2), that is, the total sum of s present in s is 10 to 29.), wherein the ethylenically unsaturated monomer is an ethylenically unsaturated monomer. Containing a saturated carboxylic acid-based monomer, the ratio of the ethylenically unsaturated carboxylic acid-based monomer is 51 mols based on 100 mol% of the total amount of the polyether compound and the ethylenically unsaturated carboxylic-acid-based monomer. % Of the graft polymer.
A third aspect of the present invention is a polymer obtained by graft-polymerizing an ethylenically unsaturated monomer onto a polyether compound, wherein the polyether compound has the following formula (3);
_{^{R 3 - [X 3 - (}} A 3 O) t -H] u (3)
(In the formula (3), R ³ represents a linear alkyl group having 1 to 18 carbon atoms. X ³ represents a divalent linking group. A ³ O is the same or different and has 2 carbon atoms. .t representing the 20 oxyalkylene group represents an average molar number of addition of ^{a 3} O, same or different, .u is the number of 1-29 is the number of 1-6. However, the formula The total number of oxyalkylene groups present in (3), that is, the sum of t present in u is 10 to 29.), wherein the ethylenically unsaturated monomer is an ethylenic unsaturated monomer. It is a graft polymer containing an unsaturated carboxylic acid monomer.
Hereinafter, in this specification, the term "present invention" simply means the items common to the first, second and third present inventions.
It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The graft polymer of the present invention is obtained by graft-polymerizing an ethylenically unsaturated monomer onto a polyether compound. Such a graft polymer is composed of a polyether chain (polyalkylene glycol chain) derived from a polyether compound and a graft chain in which an ethylenically unsaturated monomer is polymerized at the graft site of the polyether compound. ..
In the preparation of the above graft polymer, the ethylenically unsaturated monomer and the polyether compound may be used each alone or in combination of two or more.

<First invention>
The polyether compound used for preparing the graft polymer of the first present invention has the following formula (1);
_{^{R 1 - [X 1 - (}} A 1 O) p -H] q (1)
(In the formula (1), R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms. X ¹ represents a divalent linking group. A ¹ O is the same or different and has 2 to 2 carbon atoms. Represents an oxyalkylene group of 20. p represents the average number of moles of addition of A ¹ O, and is the same or different and is a number of 1 or more and less than 10. q is a number of 1 to 6, provided that: The total number of oxyalkylene groups present in the formula (1), that is, the total sum of q existing p is 1 or more and less than 10).

A ¹ O in the above formula (1) represents an oxyalkylene group having 2 to 20 carbon atoms. The carbon number of the alkylene group is preferably 2 to 15, more preferably 2 to 10, still more preferably 2 to 5, particularly preferably 2 to 3, and most preferably 2. These oxyalkylene groups are alkylene oxide adducts, and examples of such alkylene oxides include ethylene oxide (EO), propylene oxide (PO), isobutylene oxide, 1-butene oxide, 2-butene oxide, and trimethylethylene oxide. , Tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, octylene oxide, styrene oxide, 1,1-diphenylethylene oxide and the like. Among such alkylene oxides, ethylene oxide, propylene oxide and butylene oxide are preferable, and ethylene oxide and propylene oxide are more preferable.

The group ((poly)alkylene glycol chain) formed by an oxyalkylene group (that is, (A ¹ O) _p in the above formula (1)) is an oxyethylene group (—CH ₂ —CH ₂ —O—). It is preferable that the main component be the main component. As a result, the excellent effects that the polymerization during production proceeds smoothly and the water solubility is improved can be obtained.
The term “mainly” as used herein means that, when the (poly)alkylene glycol chain is composed of two or more kinds of alkylene oxides, the majority of the total number of alkylene oxides is present. When "comprising the majority" is expressed by mol% of ethylene oxide in 100 mol% of all alkylene oxides, 50 to 100 mol% is preferable. This further improves the water solubility of the (poly)alkylene glycol chain. It is more preferably 60 mol% or more, further preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more.

In the above formula (1), p is a number of 1 or more and less than 10, and q is a number of 1 to 6.
The length of the (poly)alkylene glycol chain possessed by the polyether compound in the first aspect of the present invention is represented by the total number of oxyalkylene groups present in the formula (1), that is, the sum of q existing p, and is 1 or more. It is a number less than 10.
The first aspect of the present invention is that the graft polymer in which the total number of p existing in q in the formula (1) is 1 or more and less than 10 is excellent in compatibility with a surfactant when used for detergent applications. Was found. The total sum of q p's in the formula (1) is preferably 3 to 8, and more preferably 5 to 7.
When q is 2 or more, in the polyether compound represented by the above formula (1), the different carbon atoms of the hydrocarbon group represented by the above R ¹ are bonded to -X ¹ -(of the above formula (1). A ¹ O) _{p —} H has a structure in which the groups represented by each are bonded, and a repeating structure having a group represented by —X ¹ -(A ¹ O) _{p —} H as a repeating unit is I don't have it. When q is 2 or more, the groups represented by -X ¹ -(A ¹ O) _p -H may be the same or different. The above q is preferably 1 to 4, more preferably 1 to 2, and most preferably 1.
The above p is preferably 2 to 9, more preferably 3 to 8, and further preferably 5 to 7.

R ¹ in the above formula (1) represents a hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms of R ¹ is preferably 2 to 17, more preferably 4 to 16, still more preferably 6 to 15, particularly preferably 8 to 14, and further preferably 10 to 14. , And most preferably 12 to 14.
As the hydrocarbon group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group , Octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, 2,3,5-trimethylhexyl group, decyl group, undecyl group, 4-ethyl-5-methyloctyl group, dodecyl group, tridecyl group, tetradecyl group, Linear or branched alkyl group such as pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 1-hexyl-heptyl group; cyclic alkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl Group: linear or branched alkenyl such as vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group, etc. Group: phenyl group, benzyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, benzhydryl group Groups and aryl groups such as pyrenyl groups.

The above R ¹ is preferably an alkyl group or an alkenyl group. An alkyl group is more preferable, and a linear alkyl group is still more preferable. When R ¹ does not have an aromatic ring, it is less harmful to the environment even when it is decomposed, and has a sufficient effect on the environment even when the graft polymer of the present invention is discharged into the environment. Can be suppressed. Further, if R ¹ is a linear alkyl group, the crystallinity of the graft polymer will be better, and the viscosity of the solution of the graft polymer will be favorable.
As the linear alkyl group, methyl group, ethyl group, propyl group, n-butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group , A hexadecyl group, a heptadecyl group, an octadecyl group, and the like, are preferably an alkyl group having 1 to 18 carbon atoms, more preferably 4 to 18 carbon atoms, still more preferably 8 to 15 carbon atoms, and particularly preferably 12 carbon atoms. ~13.

In the graft polymer of the first present invention, R ¹ in the above formula (1) is a straight chain alkyl group, and q is the sum of p in the above formula (1). By combining with the above, the viscosity of the solution of the graft polymer is further improved. In the graft polymer of the first invention, R ¹ in the above formula (1) is a straight-chain alkyl group, and the total number of p existing in q is 1 or more and less than 10 is preferable. It is one of the embodiments.

The divalent linking group for X ¹ in the above formula (1) includes the following formula (4);
-Y _k -Z- (4)
(In the formula, Y represents a p-phenylene group or a carbonyl group. Z represents any one of —O—, —S—, —SO ₂ —, and —NH—. k is 0 or 1. .) are preferred.
All of the divalent linking group of X ¹ to q number present in the compounds represented by the above formula (1) may be the same or may be different.
The above k is preferably 0. It is preferable that Z is —O—.
That is, it is preferable that X ¹ is —O—.

The polyether compound in the first aspect of the present invention has the formula (5):
_{^{R 1 -O- (A 1 O)}} p -H (5)
(In formula (5), R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms. A ¹ O is the same or different and represents an oxyalkylene group having 2 to 20 carbon atoms. p is A ^The compound represented by the average number of moles of ¹ O added is 1 or more and less than 10).
^{R 1, A} 1 O, p in the above formula (5) is the same as ^{R 1, A} 1 O, p in the formula (1).

The ethylenically unsaturated monomer in the graft polymer of the present invention contains an ethylenically unsaturated carboxylic acid monomer (hereinafter, also simply referred to as unsaturated carboxylic acid monomer).
The unsaturated carboxylic acid-based monomer is preferably an unsaturated monocarboxylic acid-based monomer, an unsaturated dicarboxylic acid-based monomer, or the like, and as the unsaturated monocarboxylic acid-based monomer, in the molecule Any monomer having one unsaturated group and one group capable of forming a carbanion may be used, and examples thereof include (meth)acrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, and 2-methyl-2. -Pentenoic acid, itaconic acid and the like; monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof are preferable. The unsaturated dicarboxylic acid-based monomer may be a monomer having one unsaturated group and two groups capable of forming a carbanion in the molecule, such as maleic acid, itaconic acid, mesaconic acid, Citraconic acid, fumaric acid, etc., their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, etc., their anhydrides or half esters are preferable.
As the unsaturated carboxylic acid type monomer, (meth)acrylic acid, maleic acid and salts thereof are preferable.

The ethylenically unsaturated monomer may contain another monomer other than the unsaturated carboxylic acid-based monomer.
Other monomers are not particularly limited as long as they can be copolymerized with the above-mentioned unsaturated carboxylic acid-based monomer, but for example, 2-acrylamido-2-methylpropanesulfonic acid, (meth)allylsulfonic acid, Monomers having sulfonic acid groups such as vinyl sulfonic acid, 2-hydroxy-3-allyloxy-1-propane sulfonic acid, 2-hydroxy-3-butene sulfonic acid; vinyl phosphonic acid, (meth)allyl phosphonic acid, etc. Phosphonic acid group-containing monomer; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl ( Hydroxyl group-containing alkyl (meth)acrylates such as (meth)acrylate and α-hydroxymethylethyl (meth)acrylate; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid Alkyl (meth)acrylates obtained by esterification of (meth)acrylic acid such as cyclohexyl with an alcohol having 1 to 18 carbon atoms; an amino group-containing acrylate such as dimethylaminoethyl (meth)acrylate or a quaternary compound thereof ( Amide group-containing monomers such as (meth)acrylamide, dimethylacrylamide, and isopropylacrylamide; vinyl esters such as vinyl acetate; alkenes such as ethylene and propylene; aromatic vinyl monomers such as styrene and styrenesulfonic acid Maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; vinyl monomers containing nitrile groups such as (meth)acrylonitrile; vinyl monomers containing aldehyde groups such as (meth)acrolein; methyl vinyl ether, ethyl vinyl ether , Alkyl vinyl ethers such as butyl vinyl ether; vinyl chloride, vinylidene chloride, allyl alcohol: other functional group-containing monomers such as vinylpyrrolidone.

The unsaturated carboxylic acid-based monomer is preferably more than 0% by mass and 20% by mass or less based on 100% by mass of the ethylenically unsaturated monomer. It is more preferably 1 to 15% by mass, and further preferably 3 to 11% by mass.

The other monomer is preferably 0 to 50 mass% with respect to 100 mass% of the ethylenically unsaturated monomer. It is more preferably 0 to 30% by mass, and further preferably 0 to 10% by mass.

The graft polymer of the first aspect of the present invention is such that the ratio of the ethylenically unsaturated carboxylic acid monomer is 51 mols based on 100 mol% of the total amount of the polyether compound and the ethylenically unsaturated carboxylic acid monomer. % Or less is preferable. When the proportion of the unsaturated carboxylic acid-based monomer is 51 mol% or less, the acid amount of the graft polymer is in a suitable range, and the precipitation of the polymer can be suppressed even under high hardness conditions. The proportion of the unsaturated carboxylic acid type monomer is more preferably 1 to 50 mol%, further preferably 3 to 45 mol%, and particularly preferably 5 to 30 mol%.

The effect of suppressing the precipitation of the polymer under the above-mentioned high hardness condition can be measured by a hardness resistance test by the following method.
Pure water and 48% sodium hydroxide are added to a 1 L beaker in which 67.6 g of glycine and 52.6 g of sodium chloride are weighed to prepare 600 g of a glycine buffer stock solution having a pH of 10. 54.0 g of this glycine buffer stock solution is weighed in another 1 L beaker, and pure water is added to dilute it to 1000 g to obtain a glycine buffer diluent. Separately, the polymer is dissolved in water to prepare a 1.0% aqueous polymer solution, and 80 g of the glycine buffer diluent is added to 2.5 g of this aqueous polymer solution to give a test solution. Separately, a 1 mol/L calcium chloride aqueous solution is prepared to make hard water. Using the automatic titrator COM-1700 manufactured by Hiranuma Sangyo Co., Ltd., 0.1 mL of hard water is dropped into the test solution every 3 seconds, and the transmittance (%) of 650 nm light at the time of dropping 6 mL is measured. The closer the value is to 100%, the better the hardness resistance.

The weight average molecular weight of the graft polymer of the present invention is not particularly limited because it can be appropriately set in consideration of the desired performance as a detergent builder, but the weight average molecular weight of the graft polymer of the present invention is preferably 100. Is 50,000, more preferably 500 to 10,000, and still more preferably 1,000 to 5,000. When the weight average molecular weight is 50,000 or less, the viscosity of the graft polymer falls within a suitable range and the handling becomes more excellent. When the weight average molecular weight is 100 or more, precipitation of anionic surfactant under high hardness conditions can be sufficiently suppressed, and the performance as a detergent builder can be more sufficiently exhibited.
The weight average molecular weight of the graft polymer of the present invention can be measured by the method described in Examples below.
The effect of suppressing the precipitation of the anionic surfactant under the high hardness condition can be measured by the sodium laurylbenzenesulfonate (hereinafter, also referred to as LAS) calcium salt precipitation suppressing ability evaluation by the following method.
Pure water and 48% sodium hydroxide are added to a 1 L beaker in which 67.6 g of glycine and 52.6 g of sodium chloride are weighed to prepare 600 g of a glycine buffer stock solution having a pH of 10. 11.25 g of this glycine buffer stock solution is weighed in another 1 L beaker, and further, 1.5 g of 15% LAS, 0.8 g of sodium sulfate, and pure water are added to make 500 g to prepare a glycine buffer diluent. Separately, the polymer is dissolved in water to prepare a 0.1% aqueous polymer solution, and then 8.2 g of pure water and 80 g of glycine buffer diluent are added to 1.8 g of this aqueous polymer solution to prepare a test solution. .. To this test solution, a 0.1 mol/L calcium chloride aqueous solution is dropped every 5 minutes by 0.045 mL, 0.27 mL in total. The 650 nm light transmittance (%) of the test liquid being dropped is measured. The closer the value is to 100%, the better the precipitation inhibiting ability.

The number average molecular weight of the graft polymer of the present invention is preferably 100 to 20,000, more preferably 200 to 5,000, and further preferably 500 to 2,000.
The number average molecular weight of the graft polymer of the present invention can be measured by the method described in Examples below.

<Second invention>
The polyether compound used for preparing the graft polymer of the second present invention has the following formula (2);
_{^{R 2 - [X 2 - (}} A 2 O) r -H] s (2)
(In the formula (2), R ² represents a hydrocarbon group having 1 to 18 carbon atoms. X ² represents a divalent linking group. A ² O is the same or different and has 2 to 2 carbon atoms. 20 represents an oxyalkylene group, r represents the average number of moles of A ² O added, and is the same or different and is a number of 1 to 29. s is a number of 1 to 6, provided that the formula ( The total number of oxyalkylene groups present in 2), that is, the total sum of s present in r is 10 to 29).
Specific examples and preferred examples of R ² , X ² , and A ² O in the above formula (2) are the same as R ¹ , X ¹ , and A ¹ O in the above formula (1).

In the above formula (2), r is a number from 1 to 29 and s is a number from 1 to 6. The preferable range of s in the above formula (2) is the same as q in the above formula (1).
The length of the (poly)alkylene glycol chain possessed by the polyether compound in the second aspect of the present invention is represented by the total number of oxyalkylene groups present in formula (2), that is, the sum of s present in r, There are 29 numbers.
The second aspect of the present invention is that the sum of r existing in s number in the formula (2) satisfies 10 to 29, and the total of the polyether compound and the ethylenically unsaturated carboxylic acid-based monomer described below is 100. It has been found that the graft polymer in which the ratio of the ethylenically unsaturated carboxylic acid-based monomer to the mol% is 51 mol% or less has excellent compatibility with the surfactant when used in detergent applications. is there. The total sum of s existing r in the formula (2) is preferably 10 to 21, and more preferably 10 to 15.
The above r is preferably 10 to 21, more preferably 10 to 15, and still more preferably 10 to 12.

The polyether compound in the second invention is represented by the following formula (6);
_{^{R 2 -O- (A 2 O)}} m -H (6)
(In formula (6), R ² represents a hydrocarbon group having 1 to 18 carbon atoms. A ² O is the same or different and represents an oxyalkylene group having 2 to 20 carbon atoms. m is A A compound represented by the average number of moles of ² O added and a number of 10 to 29 is preferable.
^R 2, ^{A 2} O in the formula (6) is the same as ^R 2, ^{A 2} O in the above formula (2). m is preferably 10 to 21, more preferably 10 to 15, and further preferably 10 to 12.

The graft polymer of the second aspect of the present invention has a ratio of the ethylenically unsaturated carboxylic acid monomer of 51 moles to the total 100 mole% of the polyether compound and the ethylenically unsaturated carboxylic acid monomer. % Or less. As long as the proportion of the unsaturated carboxylic acid-based monomer is 51 mol% or less and the sum of s existing r in the formula (2) satisfies 10 to 29, the graft polymer is prepared as described above. When used for detergents, the compatibility with the surfactant will be excellent. Further, in the second aspect of the present invention, when the proportion of the unsaturated carboxylic acid-based monomer is 51 mol% or less, the acid amount of the graft polymer is in a suitable range, and the polymer is obtained even under high hardness conditions. It was also found that the precipitation of can be suppressed. The proportion of the unsaturated carboxylic acid-based monomer is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and particularly preferably 5 to 30 mol%.
Specific examples and preferable examples of the unsaturated carboxylic acid-based monomer and preferable mass ratios in the ethylenically unsaturated monomer are as described in the first invention.

The ethylenically unsaturated monomer in the second aspect of the present invention may contain other monomer other than the unsaturated carboxylic acid monomer. Specific examples of other monomers and preferable mass ratios in the ethylenically unsaturated monomer are as described in the first invention.

<Third invention>
The polyether compound used for preparing the graft polymer of the third present invention has the following formula (3);
_{^{R 3 - [X 3 - (}} A 3 O) t -H] u (3)
(In the formula (3), R ³ represents a linear alkyl group having 1 to 18 carbon atoms. X ³ represents a divalent linking group. A ³ O is the same or different and has 2 carbon atoms. .t representing the 20 oxyalkylene group represents an average molar number of addition of ^{a 3} O, same or different, .u is the number of 1-29 is the number of 1-6. However, the formula The total number of oxyalkylene groups present in (3), that is, the sum of u present in t is 10 to 29.).
Specific examples and preferable examples of X ³ and A ³ O in the above formula (3) are the same as X ¹ and A ¹ O in the above formula (1).

In the above formula (3), t is a number from 1 to 29 and u is a number from 1 to 6. The preferred range of u in the above formula (3) is the same as q in the above formula (1).
The length of the (poly)alkylene glycol chain possessed by the polyether compound in the third aspect of the present invention is represented by the total number of oxyalkylene groups present in formula (2), that is, the sum of t present in u, There are 29 numbers.
A third aspect of the present invention is that the sum of t existing in u number in the formula (3) satisfies 10 to 29, and R ³ in the above formula (1) is a linear alkyl group having 1 to 18 carbon atoms. It was discovered that the above graft polymer has excellent compatibility with a surfactant when used for detergent applications. The preferable range of the total sum of t, u, and t existing u is the same as the total sum of r, s, and r existing s in the above formula (2).

R ³ is a straight-chain alkyl group having 1 to 18 carbon atoms, which makes the graft polymer of the third aspect of the present invention excellent in viscosity when made into a solution. Examples of the linear alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, n-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group. Examples thereof include linear alkyl groups such as group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group.
The number of carbon atoms of the linear alkyl group for R ³ is preferably 2 to 17, more preferably 4 to 16, still more preferably 6 to 15, particularly preferably 8 to 14, and further preferably Is 10 to 14, and most preferably 12 to 14.

The polyether compound in the third invention is represented by the following formula (7);
_{^{R 3 -O- (A 3 O)}} n -H (7)
(In the formula (7), ^{R 3} is .A ³ O that represents a linear alkyl group having 1 to 18 carbon atoms are the same or different, is .n representing an oxyalkylene group having 2 to 20 carbon atoms, The compound represented by the average number of moles of A ³ O added is 10 to 29).
^R 3, ^{A 3} O in formula (7) is the same as ^R 3, ^{A 3} O in formula (3). n is preferably 10 to 21, more preferably 10 to 15, and further preferably 10 to 12.

The graft polymer of the third aspect of the present invention is such that the ratio of the ethylenically unsaturated carboxylic acid monomer is 51 mols based on 100 mol% of the total amount of the polyether compound and the ethylenically unsaturated carboxylic acid monomer. % Or less is preferable. When the proportion of the unsaturated carboxylic acid-based monomer is 51 mol% or less, the acid amount of the graft polymer is in a suitable range, and the precipitation of the polymer can be suppressed even under high hardness conditions. The proportion of the unsaturated carboxylic acid-based monomer is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and further preferably 5 to 30 mol%.
Specific examples and preferable examples of the unsaturated carboxylic acid-based monomer and preferable mass ratios in the ethylenically unsaturated monomer are as described in the first invention.

The ethylenically unsaturated monomer in the third aspect of the present invention may contain other monomer other than the unsaturated carboxylic acid monomer. Specific examples of other monomers and preferable mass ratios in the ethylenically unsaturated monomer are as described in the first invention.

<Method for producing graft polymer of the present invention>
The production of the graft polymer of the present invention is not particularly limited, but it can be produced by polymerizing a monomer component (a polyether compound and an ethylenically unsaturated monomer), and specific examples of the monomer component and Preferred examples are as described above.
The above-mentioned polymerization is preferably carried out by bulk polymerization. Specifically, the amount of the solvent used in the polymerization reaction is preferably 10% by mass or less based on the total amount of the reaction system.

The graft polymer of the present invention is preferably produced by a method of polymerizing a monomer component in the presence of a polymerization initiator. The polymerization initiator is preferably an organic peroxide having a half-life at 135° C. of 6 to 300 minutes. By using such a polymerization initiator, the yield of the graft body is further improved.

In the present invention, the half-life of 135° C. is measured by the method described in NOF Corporation Organic Peroxide Catalog 10th Edition. Specifically, it means a value obtained by the following measuring method.
Using a relatively inert solvent (for example, benzene) as a polymerization initiator, prepare a 0.1 mol/L or 0.05 mol/L polymerization initiator solution and seal it in a nitrogen-substituted glass tube. .. It is immersed in a constant temperature bath set at 135° C. for thermal decomposition. By this thermal decomposition, the time at which the concentration of the polymerization initiator becomes half the initial concentration can be obtained as the half-life of 135°C.

Examples of the organic peroxide polymerization initiator having a half-life at 135° C. of 6 to 300 minutes include di-t-butyl peroxide (half-life 150 minutes) and t-butyl peroxyisopropyl monocarbonate (half-life 13 minutes). , T-hexylperoxyisopropyl monocarbonate (half-life 6.3 minutes), n-butyl 4,4-di(t-butylperoxy)valeate (half-life 30 minutes), t-butylperoxybenzoate (half-life) 22 minutes), t-hexylperoxybenzoate (half-life 15.6 minutes), 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (half-life 13.1 minutes). The organic peroxide polymerization initiator having a half-life at 135° C. of 6 to 300 minutes is preferably di-t-butyl peroxide.

The amount of the organic peroxide polymerization initiator having a half-life at 135° C. of 6 to 300 minutes used for the graft polymerization is not particularly limited, but it is based on 100% by mass of the ethylenically unsaturated monomer used for the graft polymerization. Therefore, it is preferably 1 to 15 mass %.
When the amount of the organic peroxide polymerization initiator used is 1% by mass or more, it is possible to sufficiently suppress the decrease in the yield of the graft product of the monomer component onto the polyoxyalkylene chain. When the amount of the organic peroxide polymerization initiator used is 15% by mass or less, it is possible to more sufficiently suppress the increase in the molecular weight due to the reaction between the polyether compounds. This makes it difficult to produce due to the increase in viscosity during the reaction due to the increase in the molecular weight, and it is possible to more sufficiently suppress the gelation of the composition due to the increase in the molecular weight, which leads to deterioration of quality and production cost. The rise can be suppressed more sufficiently.
The amount of the organic peroxide polymerization initiator used is more preferably 2 to 10% by mass, further preferably 3 to 7% by mass.

In addition to the organic peroxide polymerization initiator having a half-life at 135° C. of 6 to 300 minutes, other polymerization initiators may be used. The amount of the other polymerization initiator used is preferably 10% by mass or less based on the total amount of the polymerization initiator, from the viewpoint that the unreacted polyether compound is reduced and the effect of the present invention is remarkably obtained. The content is more preferably below, and further preferably 0% by mass (no other polymerization initiator is used). As the other polymerization initiator, an organic peroxide is preferably used, and as the organic peroxide, a commonly used organic peroxide can be used.

The addition form of the organic peroxide polymerization initiator having a half-life at 135° C. of 6 to 300 minutes and other polymerization initiators is not particularly limited. For example, the polymerization initiator may be previously added to a polyether compound or an ethylenic monomer. Examples thereof include a mode in which the graft polymerization is carried out in a state of being added to at least one of the saturated monomers, and a mode in which it is added at the same time as the ethylenically unsaturated monomer and not mixed with the polyether compound in advance. Preferably, it is added at the same time as the ethylenically unsaturated monomer and in a state where it is not mixed with the polyether compound in advance.

In the production of the graft polymer of the present invention, in addition to the above-mentioned polymerization initiator, a decomposition catalyst of the polymerization initiator or a reducing compound may be added to the reaction system. Examples of the decomposition catalyst of the polymerization initiator include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, nitric acid and the like. Inorganic acid metal salts; carboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, isolacic acid and benzoic acid, their esters and their metal salts; heterocyclic amines such as pyridine, indole, imidazole and carbazole, and their derivatives Can be mentioned. These decomposition catalysts may be used alone or in combination of two or more.

Examples of the reducing compound include organic metal compounds such as ferrocene; iron, copper, nickel, cobalt and manganese such as iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, manganese naphthenate and Mohr salt. Inorganic compounds capable of generating metal ions, such as boron trifluoride ether adduct, potassium permanganate, perchloric acid, etc.; Sulfur dioxide, sulfites, sulfates, bisulfites, thiosulfates, sulfoxy acids Sulfur-containing compounds such as salts, benzenesulfinic acid and its substitution products, and homologs of cyclic sulfinic acids such as paratoluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid, thiopropionic acid , Mercapto compounds such as α-thiopropionic acid sodium sulfopropyl ester and α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine and hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde, n- Aldehydes such as butyraldehyde, isobutyraldehyde, isovalerianaldehyde; and ascorbic acid. These reducing compounds may also be used alone or in combination of two or more. A reducing compound such as a mercapto compound may be added as a chain transfer agent.

The amount of the solvent used in the production of the graft polymer of the present invention is preferably 10% by mass or less based on the total amount of the reaction system. It is more preferably 7% by mass or less, further preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably substantially no solvent. The phrase "substantially free of solvent" means a mode in which no solvent is positively added during the graft polymerization, and means that the inclusion of a solvent such as impurities is acceptable.

When a solvent is used in the production of the graft polymer, the solvent to be used is not particularly limited, but one having a small chain transfer constant of the ethylenically unsaturated monomer to the solvent or a boiling point of 70° C. or higher which can be used under normal pressure And the like are preferable. Examples of such a solvent include isobutyl alcohol, n-butyl alcohol, tert-butyl alcohol, isopropyl alcohol, ethylene glycol, diethylene glycol, glycerin, triethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether. Alcohols such as: Diethers such as ethylene glycol dialkyl ether, propylene glycol dialkyl ether, etc.; Acetic acid such as acetic acid, ethyl acetate, propyl acetate, butyl acetate, acetic acid ester of ethylene glycol monoalkyl ether, acetic acid ester of propylene glycol monoalkyl ether, etc. System compounds; and the like. These solvents may be used alone or in combination of two or more. Examples of the alkyl group in the alcohols and diethers include a methyl group, an ethyl group, a propyl group and a butyl group.

The temperature during the polymerization reaction of the graft polymer of the present invention is preferably 100°C or higher, more preferably 100 to 160°C, and further preferably 110 to 150°C. When the temperature at the time of polymerization is 100° C. or higher, the viscosity of the reaction solution is prevented from becoming too high, the graft polymerization proceeds more sufficiently, and the graft ratio of the ethylenically unsaturated monomer decreases more sufficiently. Can be suppressed. When the temperature during polymerization is 160° C. or lower, thermal decomposition of the polyether compound and the resulting graft polymer and volatilization of the ethylenically unsaturated monomer and the initiator can be suppressed more sufficiently. The temperature during the graft polymerization does not need to be constantly kept constant during the progress of the polymerization reaction.For example, the polymerization is started from room temperature, and the temperature is raised to a set temperature at an appropriate heating time or heating rate. After that, the set temperature may be maintained, or the polymerization temperature may be changed over time during the progress of the polymerization reaction (increase or increase in temperature depending on the dropping method of the ethylenically unsaturated monomer, the initiator, etc.). The temperature may be lowered).

The polymerization time in the polymerization reaction is not particularly limited, but is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, further preferably 60 to 360 minutes, and most preferably 90 to 240 minutes. .. In addition, in this invention, "polymerization time" represents the time when a monomer is added.

The pressure in the reaction system may be under normal pressure (atmospheric pressure), under reduced pressure, or under pressure, but in terms of the molecular weight of the obtained polymer, it is under normal pressure or the reaction system is closed. However, it is preferable to carry out under pressure. Further, in terms of equipment such as a pressurizing device, a depressurizing device, a pressure-resistant reaction container and piping, it is preferable to carry out under normal pressure (atmospheric pressure). The atmosphere in the reaction system may be an air atmosphere, but an inert atmosphere is preferable, and for example, it is preferable to replace the inside of the system with an inert gas such as nitrogen before starting the polymerization.

In the graft polymerization, it is advisable to start the polymerization in a state where a part or the whole of the polyether compound serving as the backbone of the graft polymer is charged in the reaction system. For example, a mode in which the entire amount of the polyether compound is charged into the reaction system, the temperature of the reaction system is raised, and then the ethylenically unsaturated monomer and the polymerization initiator are separately added to proceed the graft polymerization reaction is exemplified. It According to such a form, the molecular weight of the obtained graft polymer can be easily adjusted, which is preferable. The graft polymerization may be carried out batchwise or continuously.

<Graft polymer composition>
The graft polymer of the present invention is essentially contained in the graft polymer composition of the present invention (hereinafter, also referred to as a polymer composition). In addition, unreacted polyether compounds, unreacted unsaturated carboxylic acid-based monomers, unreacted polymerization initiators, decomposition products of polymerization initiators, and the like may be included.
The content of the unreacted polyether compound present in the polymer composition is preferably less than 99% by mass based on 100% by mass of the solid content of the polymer composition. It is more preferably less than 90% by mass, and even more preferably less than 80% by mass.
The unreacted polyether compound can be quantified using liquid chromatography under the following conditions.

<Measurement conditions for unreacted polyether compound>
Measuring device: Tosoh Corporation 8020 series column: Shiseido Corporation CAPCELL PAK C1 UG120
Temperature: 40.0°C
Eluent: 10 mmol/L disodium hydrogen phosphate aqueous solution (pH adjusted to 7 with phosphoric acid)/acetonitrile=45/55 (volume ratio)
Flow rate: 1.0 ml/min
Detector: RI detector

The polymer composition referred to in the present application is not particularly limited, but from the viewpoint of production efficiency, it is preferably obtained without a purification step such as impurity removal. Further, a polymer obtained by diluting the obtained polymerization composition after the polymerization step with a small amount of water (about 1 to 400% by mass based on the obtained mixture) for convenience of handling is also referred to as a polymer in the present application. Included in the composition.

The graft polymer and polymer composition of the present invention can be used as a water treatment agent, a fiber treatment agent, a dispersant, a detergent builder (or a detergent composition), and the like. As a detergent builder, it can be used by being added to detergents for various uses such as clothes, tableware, housing, hair, body, toothpaste, and automobiles.
The present invention is also a detergent builder comprising the graft polymer of the present invention.

<Water treatment agent>
The polymer composition of the present invention can be used as a water treatment agent. If necessary, a polymeric phosphate, a phosphonate, an anticorrosive, a slime control agent, and a chelating agent may be used in the water treatment agent as other compounding agents.
The water treatment agent is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digester, a black liquor thickener, and the like. Further, any appropriate water-soluble polymer may be contained within a range that does not affect the performance and effect.

<Fiber treatment agent>
The polymer composition of the present invention can be used as a fiber treating agent. The fiber treating agent contains at least one selected from the group consisting of dyeing agents, peroxides and surfactants, and the polymer composition of the present invention.
The content of the polymer composition of the present invention in the fiber treatment agent is preferably 1 to 100% by weight, and more preferably 5 to 100% by weight, based on the whole fiber treatment agent. Further, any appropriate water-soluble polymer may be contained within a range that does not affect the performance and effect.
Below, the compounding example of the fiber treatment agent which is closer to the embodiment is shown. This fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. As the dyeing agent, the peroxide and the surfactant, those usually used for the fiber treating agent can be mentioned.

The blending ratio of the polymer composition of the present invention and at least one selected from the group consisting of a dyeing agent, a peroxide and a surfactant is, for example, whiteness of the fiber, uneven color, and improvement of dyeing waxiness. In order to achieve this, at least one selected from the group consisting of a dyeing agent, a peroxide and a surfactant is used in an amount of 0.1 to 0.1 part by weight of the polymer composition of the present invention in terms of the fiber treatment agent. It is preferable to use a composition blended at a ratio of 100 parts by weight as a fiber treating agent.
Any appropriate fiber can be adopted as the fiber for which the above fiber treatment agent can be used. Examples thereof include cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven fabrics and blended products thereof.
When the above fiber treatment agent is applied to the refining step, it is preferable to mix the polymer composition of the present invention with an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the polymer composition of the present invention, a peroxide, and a silicic acid agent such as sodium silicate as a decomposition inhibitor of an alkaline bleaching agent.

<Inorganic pigment dispersant>
The polymer composition of the present invention can be used as an inorganic pigment dispersant. If necessary, condensed phosphoric acid and salts thereof, phosphonic acid and salts thereof, and polyvinyl alcohol may be used in the inorganic pigment dispersant as other compounding agents.
The content of the polymer composition of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight based on the whole inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be contained within a range that does not affect the performance and effect.
The above inorganic pigment dispersant can exhibit good performance as a dispersant for heavy or light calcium carbonate or clay inorganic pigment used for paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, a high-concentration calcium carbonate having low viscosity, high fluidity, and good stability over time in its performance is obtained. High concentration inorganic pigment slurries such as slurries can be produced.
When the inorganic pigment dispersant is used as an inorganic pigment dispersant, the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant used is within the above range, a sufficient dispersion effect can be obtained, an effect corresponding to the added amount can be obtained, and it can be economically advantageous.

<Detergent composition>
The polymer composition of the present invention may also be added to detergent compositions.
The polymer composition of the present invention contains the above-mentioned graft polymer, but the content of the graft polymer in the detergent composition is not particularly limited. However, from the viewpoint of exhibiting excellent builder performance, the content of the graft polymer is preferably 0.1 to 15% by mass, and more preferably 0.3, with respect to the total amount of the detergent composition. 10 to 10% by mass, more preferably 0.5 to 5% by mass.

Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge in the detergent field can be appropriately referred to. The detergent composition may be a powder detergent composition or a liquid detergent composition.

The surfactant is one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass, based on the total amount of the surfactant. Or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate. , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester or The salt and the like are preferable. An alkyl group such as a methyl group may be branched in the alkyl group and the alkenyl group in these anionic surfactants.

As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkylglycoxide, fatty acid glycerin monoester Ester, alkylamine oxide and the like are preferable. An alkyl group such as a methyl group may be branched to the alkyl group and the alkenyl group in these nonionic surfactants.

As the cationic surfactant, a quaternary ammonium salt or the like is suitable. Further, as the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant and the like are preferable. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may have a branched alkyl group such as a methyl group.

The blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, and particularly preferably, the total amount of the detergent composition. Is 25 to 40% by mass. If the blending ratio of the surfactant is too low, sufficient detergency may not be exerted, and if the blending ratio of the surfactant is too high, the economical efficiency may be reduced.

As additives, alkali builders, chelate builders, anti-redeposition agents for preventing redeposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, color transfer Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaches, bleaching aids, enzymes, dyes , Solvents and the like are preferable. Further, in the case of a powder detergent composition, it is preferable to add zeolite.

The detergent composition may include other detergent builders in addition to the polymer composition of the present invention. Other detergent builders are not particularly limited, and examples thereof include alkali builders such as carbonates, hydrogen carbonates, and silicates, tripolyphosphates, pyrophosphates, Bow's salt, nitrilotriacetic acid salts, ethylenediaminetetraacetic acid salts, and quenching agents. Examples thereof include acid salts, copolymer salts of (meth)acrylic acid, acrylic acid-maleic acid copolymers, fumaric acid salts, chelate builders such as zeolite, and carboxyl derivatives of polysaccharides such as carboxymethyl cellulose. Examples of the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium, amine and the like.

Generally, the total compounding ratio of the additive and other detergent builders is preferably 0.1 to 50% by mass with respect to 100% by mass of the detergent composition. It is more preferably 0.2 to 40% by mass, still more preferably 0.3 to 35% by mass, particularly preferably 0.4 to 30% by mass, and most preferably 0.5 to 20% by mass. is there. If the mixing ratio of the additive/other detergent builder is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 50% by mass, the economical efficiency may be deteriorated.

In addition, the concept of the above-mentioned detergent composition includes synthetic detergents for household detergents, industrial detergents for the textile industry and others, hard surface detergents, and specific applications such as bleaching detergents having one function enhanced. Includes detergents used only.

When the above-mentioned detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by mass, more preferably the total amount of the liquid detergent composition. Is 0.2 to 70% by mass, more preferably 0.5 to 65% by mass, even more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, and most preferably It is preferably 1.5 to 50 mass %.

When the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg/L or less, more preferably 150 mg/L or less, and further preferably 120 mg/L or less. And particularly preferably 100 mg/L or less, and most preferably 50 mg/L or less.

Further, the change (difference) in kaolin turbidity between the case where the polymer composition of the present invention is added as a detergent builder to a liquid detergent composition and the case where it is not added is preferably 500 mg/L or less, more preferably It is 400 mg/L or less, more preferably 300 mg/L or less, particularly preferably 200 mg/L or less, and most preferably 100 mg/L or less. As the value of kaolin turbidity, the value measured by the following method shall be adopted.

<Method of measuring kaolin turbidity>
A 50 mm square cell with a thickness of 10 mm was charged with a uniformly stirred sample (liquid detergent), and after removing air bubbles, NDH2000 (trade name, turbidimeter) manufactured by Nippon Denshoku Industries Co., Ltd. (Kaolin turbidity: mg/L) is measured.

Protease, lipase, cellulase and the like are preferable as the enzyme that can be added to the detergent composition. Among them, protease, alkaline lipase and alkaline cellulase which have high activity in the alkaline washing solution are preferable.

The amount of the enzyme added is preferably 5% by mass or less based on 100% by mass of the detergent composition. If it exceeds 5% by mass, no improvement in detergency can be seen, and there is a risk that the economy will decrease.

Even when used in hard water (eg, 100 mg/L or more) areas where the concentration of calcium ions and magnesium ions is high, the detergent composition has little salt precipitation and has an excellent cleaning effect. This effect is particularly noticeable when the detergent composition contains an anionic surfactant such as LAS.

Since the graft polymer of the present invention has the above-mentioned constitution and has excellent compatibility with the surfactant, it can be suitably used as a raw material for detergent additives and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" means "part by weight" and "%" means "% by mass" unless otherwise specified.

<Viscosity measuring method>
The viscosity was measured under the following conditions.
Measuring device: Brookfield rotary viscometer LVDV3TCP
Spindle: Cone spindle CPA-51Z
Temperature: 25°C (Temperature controlled in a circulating thermostat)
A 75% aqueous polymer solution in terms of solid content was added to a sample cup in an amount of 1 to 2 mL, and the measured value 2 minutes after the start of spindle rotation was confirmed.

<Measuring method of weight average molecular weight of polymer>
The weight average molecular weight of the copolymer was measured under the following conditions.
Equipment: Tosoh high-speed GPC equipment (HLC-8320GPC)
Detector: RI Detector Column: Showdex Electric Co., Ltd. SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B
Column temperature: 40°C
Flow rate: 0.5 ml/min
Calibration curve: polyethylene glycol standard eluent manufactured by GL Science Co., Ltd.: 0.1N sodium acetate/acetonitrile=3/1 (mass ratio)

<Example 1>
A glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer was added to Newcol 2320 manufactured by Nippon Emulsifier Co., Ltd. (average 20 moles of ethylene oxide was added to linear primary alcohol having 12 to 13 carbon atoms). 274.3 g of the above compound, which is hereinafter also referred to as NC2320) was charged, and the temperature was raised to 128° C. with stirring. Then, under stirring, 780.0 μL of di-t-butyl peroxide (hereinafter, also referred to as PBD) and 14.4 g of 100% acrylic acid (hereinafter, also referred to as AA) were separately added to the polymerization reaction system in a constant state at 128° C. It dripped from the dropping nozzle. The reaction was started at the timing of starting the dropping of PBD. Regarding each dropping time and dropping sequence, PBD was kept constant at 195 minutes from the start of the reaction, and AA was kept constant at 225 minutes from 20 minutes after the start of the reaction. After the completion of all droppings, the reaction solution was kept at 128° C. for 70 minutes for aging to complete the polymerization. Then, 72.4 g of pure water was added. Thus, a polymer 1 having a solid content of 78% was obtained.

<Example 2>
A glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer was added to Newcol 2310 manufactured by Nippon Emulsifier Co., Ltd. (average 10 moles of ethylene oxide was added to linear primary alcohol having 12 to 13 carbon atoms). 243.7 g of the compound (hereinafter, also referred to as NC2310), which was heated to 128° C. under stirring. Then, with stirring, PBD 1462.5 μL and AA 27.1 g were dropped into the polymerization reaction system in a constant state at 128° C. from separate dropping nozzles. The reaction was started at the timing of starting the dropping of PBD. Regarding each dropping time and dropping sequence, PBD was kept constant at 195 minutes from the start of the reaction, and AA was kept constant at 225 minutes from 20 minutes after the start of the reaction. After the completion of all droppings, the reaction solution was kept at 128° C. for 70 minutes for aging to complete the polymerization. Then, 68.0 g of pure water was added. Thus, a polymer 2 having a solid content of 77% was obtained.

<Example 3>
A glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with Newcol 2305 manufactured by Nippon Emulsifier Co., Ltd. (5 mol of ethylene oxide was added to a straight-chain primary alcohol having 12 to 13 carbon atoms on average). 357.4 g of the compound (hereinafter, also referred to as NC2305) was charged, and the temperature was raised to 128° C. with stirring. Then, with stirring, PBD (195.0 μL) and AA (3.6 g) were dropped from separate dropping nozzles into the polymerization reaction system at 128° C. in a constant state. The reaction was started at the timing of starting the dropping of PBD. Regarding each dropping time and dropping sequence, PBD was kept constant at 195 minutes from the start of the reaction, and AA was kept constant at 225 minutes from 20 minutes after the start of the reaction. After the completion of all droppings, the reaction solution was kept at 128° C. for 70 minutes for aging to complete the polymerization. Then, 90.3 g of pure water was added. Thus, a polymer 3 having a solid content of 75% was obtained.

<Example 4>
In a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, Sophthanol 50 manufactured by Nippon Shokubai Co., Ltd. (5 mol of ethylene oxide was added on average to a linear secondary alcohol having 12 to 14 carbon atoms). 357.4 g was charged and the temperature was raised to 128° C. with stirring. Then, with stirring, PBD (195.0 μL) and AA (3.6 g) were dropped from separate dropping nozzles into the polymerization reaction system at 128° C. in a constant state. The reaction was started at the timing of starting the dropping of PBD. Regarding each dropping time and dropping sequence, PBD was kept constant at 195 minutes from the start of the reaction, and AA was kept constant at 225 minutes from 20 minutes after the start of the reaction. After the completion of all droppings, the reaction solution was kept at 128° C. for 70 minutes for aging to complete the polymerization. Then, 90.3 g of pure water was added. Thus, a polymer 4 having a solid content of 75% was obtained.

<Comparative Example 1>
In a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, Sophthanol 300 manufactured by Nippon Shokubai Co., Ltd. (average 30 mol of ethylene oxide was added to a linear secondary alcohol having 12 to 14 carbon atoms) was added. 181.3 g of a compound, which is hereinafter also referred to as SFT300) was charged, nitrogen was blown, and the temperature was raised to 126° C. with stirring to obtain a polymerization reaction system. Next, under stirring, 32.0 g of AA and 1.6 g of PBD were dropped from separate nozzles into the polymerization reaction system maintained at 126°C. The dropping time of each liquid was 200 minutes for PBD, and AA was 210 minutes from 20 minutes after the start of dropping PBD. Further, the dropping rate of each liquid was kept constant, and the dropping of each liquid was performed continuously. After the addition of AA was completed, the reaction solution was kept (aged) at 126° C. for another 60 minutes to complete the polymerization. After the completion of the polymerization, 53.7 g of pure water was added to the polymerization reaction liquid while stirring and cooling the polymerization reaction liquid to dilute the polymerization reaction liquid. Thus, Comparative Polymer 1 having a solid content of 80% was obtained.

<Comparative example 2>
A glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 243.7 g of SFT300, and the temperature was raised to 128° C. with stirring. Then, with stirring, PBD 1462.5 μL and AA 27.1 g were dropped into the polymerization reaction system in a constant state at 128° C. from separate dropping nozzles. The reaction was started at the timing of starting the dropping of PBD. Regarding each dropping time and dropping sequence, PBD was kept constant at 195 minutes from the start of the reaction, and AA was kept constant at 225 minutes from 20 minutes after the start of the reaction. After the completion of all droppings, the reaction solution was kept at 128° C. for 70 minutes for aging to complete the polymerization. Then, 68.0 g of pure water was added. Thus, Comparative Polymer 2 having a solid content of 79% was obtained.

<Compatibility test with surfactant>
4.23 g of 15% sodium laurylbenzenesulfonate (hereinafter, also referred to as LAS) was added to 0.77 g of an aqueous solution of 65% in terms of solid content of the polymers obtained in Examples and Comparative Examples, and well stirred, A mixed aqueous solution of a surfactant and a polymer was prepared. After standing for 1 hour, the degree of turbidity was visually evaluated. The results are shown in Table 1.
The evaluation results are based on the following three levels.
○: transparent △: slightly cloudy ×: cloudy

Claims (7)

A polymer obtained by graft-polymerizing an ethylenically unsaturated monomer onto a polyether compound,
The polyether compound has the following formula (1);
_{^{R 1 - [X 1 - (}} A 1 O) p -H] q (1)
(In the formula (1), R ¹ represents an alkyl group or an alkenyl group having 2 to 18 carbon atoms. X ¹ represents a divalent linking group. A ¹ O has the same or different carbon number. It represents an oxyalkylene group of 2 to 20. p represents the average number of moles of addition of A ¹ O, and is the same or different and is a number of 1 or more and less than 10. q is a number of 1 to 6. However, the total number of oxyalkylene groups present in the formula (1), that is, the total sum of q existing p is 1 or more and less than 10),
The ethylenically unsaturated monomer, see contains an ethylenically unsaturated carboxylic acid monomer,
Graft characterized in that the ratio of the ethylenically unsaturated carboxylic acid monomer is 51 mol% or less based on 100 mol% of the total of the polyether compound and the ethylenically unsaturated carboxylic acid monomer. Polymer. R ¹ Is an alkyl group or an alkenyl group having 4 to 18 carbon atoms, The graft polymer according to claim 1. A polymer obtained by graft-polymerizing an ethylenically unsaturated monomer onto a polyether compound,
The polyether compound has the following formula (2);
_{^{R 2 - [X 2 - (}} A 2 O) r -H] s (2)
(In the formula (2), R ² represents an alkyl group or an alkenyl group having 2 to 18 carbon atoms. X ² represents a divalent linking group. A ² O has the same or different carbon number. Represents an oxyalkylene group of 2 to 20. r represents the average number of moles of A ² O added, and is the same or different and is a number of 1 to 29. s is a number of 1 to 6. The total number of oxyalkylene groups present in formula (2), that is, the total sum of s present in r is 10 to 29.
The ethylenically unsaturated monomer includes an ethylenically unsaturated carboxylic acid monomer,
Graft characterized in that the ratio of the ethylenically unsaturated carboxylic acid monomer is 51 mol% or less based on 100 mol% of the total of the polyether compound and the ethylenically unsaturated carboxylic acid monomer. Polymer. R ^Two Is a C4-C18 alkyl group or alkenyl group, The graft polymer of Claim 3 characterized by the above-mentioned. A polymer obtained by graft-polymerizing an ethylenically unsaturated monomer onto a polyether compound,
The polyether compound has the following formula (3):
_{^{R 3 - [X 3 - (}} A 3 O) t -H] u (3)
(In the formula (3), R ³ represents a linear alkyl group having 2 to 18 carbon atoms. X ³ represents a divalent linking group. A ³ O is the same or different and has 2 carbon atoms. .t representing the 20 oxyalkylene group represents an average molar number of addition of ^{a 3} O, same or different, .u is the number of 1-29 is the number of 1-6. However, the formula The total number of oxyalkylene groups present in (3), that is, the sum of t present in u units is 10 to 29),
The ethylenically unsaturated monomer, see contains an ethylenically unsaturated carboxylic acid monomer,
Graft characterized in that the ratio of the ethylenically unsaturated carboxylic acid monomer is 51 mol% or less based on 100 mol% of the total of the polyether compound and the ethylenically unsaturated carboxylic acid monomer. Polymer. R ^Three Is a linear alkyl group having 4 to 18 carbon atoms, and the graft polymer according to claim 5. Detergent builder consisting of graft polymers according to any one of claims 1-6.