JP4859096B2 - High molecular compound - Google Patents

Description

  The present invention relates to a polymer compound excellent in solid adsorbability.

On the surface of building members, home appliances, furniture, etc., contamination by dust, pride, oil and exhaust gas, and contaminants such as graffiti, which are floating in the atmosphere, is often taken up as a problem.
Each surface once contaminated can be cleaned with normal water or a cleaning agent to remove contaminants and regain a beautiful surface.

For example, in the case of cleaning with water, cleaning may be performed using a brush or the like, but many contaminants are oil-soluble, and it is difficult to say that the cleaning effect is excellent.
In recent years, detergents using compounds such as special surfactants have been used (for example, Patent Documents 1 to 4).
For example, Patent Document 1 describes a cleaning agent using a fatty acid soap and a specific alkylamine oxide to improve the cleaning effect of contaminants.
Further, Patent Document 2 describes a cleaning agent using a specific sesquiterpene and a surfactant, and aims to improve the cleaning effect of the contaminant.
In the cleaning agents of these patent documents, the pollutants that are oil-soluble are each adsorbed by a specific compound, thereby exerting cleaning power.

However, in the above method, although a certain degree of cleaning effect can be expected, a satisfactory cleaning effect may not be obtained, and further improvement of the cleaning effect is desired.
In order to further enhance the cleaning effect, it is possible to increase the amount of a surfactant or the like, but in this case, the cost is higher than necessary, and it is not environmentally preferable.

JP 2003-238990 A JP 7-292390 A JP 2005-89610 A JP-A-10-251699

  In order to solve the above problems, the present invention has been made through extensive research. As a result, (A) an isocyanate compound having two or more isocyanate groups in one molecule is converted into (B) a functional group capable of reacting with the isocyanate group. A compound having a solubility in water of 50 g / g or more, (C) a polymer compound having a functional group capable of reacting with the isocyanate group and having a solubility in water of less than 50 g / g Has been found to be excellent in the adsorptivity of solid substances including contaminants and the like, and has an excellent decontamination ability even in a small amount, thereby completing the present invention.

That is, the present invention has the following characteristics.
1. (A) In an isocyanate compound having two or more isocyanate groups in one molecule,
(B) a compound having a functional group capable of reacting with the isocyanate group and having a solubility in water (temperature of 25 ° C.) of 50 g / 100 g or more, and
(C) a compound having a functional group capable of reacting with the isocyanate group and having a solubility in water (temperature: 25 ° C.) of less than 50 g / 100 g,
(B): (C) is in a weight ratio of 1:99 to 99: 1, and the total amount of (B) and (C) is 20% by weight to 90% by weight with respect to the total amount of the polymer compound. And
(B) is a polyethylene glycol methyl ether, dimethylol propionic acid and N, consists N- dimethylethanolamine,
(C) is polybutylene glycol,
A polymer compound characterized by the above.

  The polymer compound of the present invention exhibits excellent solid adsorptivity and can be suitably used as a cleaning agent or the like.

  Hereinafter, the present invention will be described in detail based on the best mode.

The polymer dispersant of the present invention comprises (A) an isocyanate compound in which the average number of functional groups of isocyanate groups in one molecule is 2 or more (hereinafter also referred to as “component (A)”), and (B) the isocyanate group and A compound having a functional group capable of reacting and having a solubility in water of 50 g / g or more (hereinafter also referred to as “component (B)”), and (C) having a functional group capable of reacting with the isocyanate group In addition, a compound having a solubility in water of less than 50 g / g (hereinafter also referred to as “component (C)”) is introduced.
The solubility in water is the solubility in 100 g of water (temperature 25 ° C.).

Component (A) is characterized in that the average number of functional groups of isocyanate groups in one molecule is 2 or more (preferably 2.2 or more and 20 or less, more preferably 2.5 or more and 10 or less). Such component (A) has a high solid adsorbing ability with various solids, and is characterized by, for example, excellent adsorbing ability with pollutants and various powders.
When the average number of functional groups of isocyanate groups contained in one molecule is 2 or more, it becomes easy to introduce the component (B) and the component (C) into the component (A), and the production of a compound having a balanced hydrophilic / hydrophobic property Is possible. When the average number of functional groups of the isocyanate group is less than 2, it is difficult to introduce the component (B) and the component (C), and it is difficult to apply to any solid. Moreover, when there are too many average functional groups of an isocyanate group, it becomes a structure where there are too many branches and may gelatinize.

Examples of the component (A) include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI). ), 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5- Pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, lysine diisocyanate Ne - DOO, dimer acid diisocyanate, aliphatic diisocyanates such as norbornene diisocyanate;
1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl- 2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate (IPDI), norbornane diisocyanate, dicyclohexylmethane diisocyanate (Hydrogenated MDI), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate and other alicyclic diisocyanates Over door;
m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4, 4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2, 2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'- Diiso Aneto, dianisidine diisocyanate, aromatic diisocyanates such as tetramethylene diisocyanate;
1,3-xylylene diisocyanate (XDI), 1,4-xylylene diisocyanate (XDI), ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis (1-isocyanate-1- Fragrances such as methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene, 1,5-naphthalene diisocyanate (NDI) Aliphatic diisocyanates;
And these isocyanate group-containing compounds derivatized by allohanation, biuretization, dimerization (uretidione), trimerization (isocyanurate), adduct formation, carbodiimide reaction, etc., and mixtures thereof, and these isocyanates Examples thereof include a copolymer of a group-containing compound and a copolymerizable monomer.

  In the present invention, in particular, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), 1,5-naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), and the like, and these isocyanate group-containing compounds are allohanated, biuretized, dimerized (uretidione), Uses those derivatized by trimerization (isocyanurate), adduct formation, carbodiimide reaction, mixtures thereof, and copolymers of these isocyanate group-containing compounds and copolymerizable monomers. Rukoto is Shi favored arbitrariness.

  The component (B) and the component (C) are compounds having a functional group capable of reacting with an isocyanate group. Examples of the functional group capable of reacting with an isocyanate group include a hydroxyl group and an amino group. Groups are preferred.

Examples of the compound containing a hydroxyl group include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, erythritol, sorbitol, pentaerythritol, dipentaerythritol and the like. A trifunctional or higher polyhydric alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3 -Butanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl -1,3-propanedioe 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, neopentyl Glycol, 1,3,5-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl- Aliphatic glycols such as 1,8-octanediol, alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, aromas such as xylylene glycol and bishydroxyethoxybenzene Monomer glycols such as aliphatic glycols, polyether polyols, polyester polyols, polyether ester polyols Polycarbonate polyol, acrylic polyol, polyolefin polyol, polycaprolactone polyol, polytetramethylene glycol polyol, polybutadiene polyol, polyoxypropylene polyol, polyoxypropylene ethylene polyol, epoxy polyol, alkyd polyol, fluorine-containing polyol, silicon-containing polyol, etc. High molecular weight polyols, etc.
Also, lactic acid, 12-hydroxystearic acid, ricinoleic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, ε-hydroxycaproic acid, P-hydroxyethyleneoxycarboxylic acid, 2-hydroxynaphthalene-3-carboxylic acid 2-hydroxynaphthalene-6-carboxylic acid, hydroxypivalic acid, 11-oxyhexadecanoic acid, 2-oxide decanoic acid, glycolic acid, malic acid, tartaric acid, gluconic acid, glyceric acid, mevalonic acid, dimethylolpropionic acid, di Hydroxyl group and carboxyl group-containing compounds such as methylol butanoic acid, dimethylol butanoic acid, dimethylol butyric acid, dimethylol valeric acid, dimethylol heptanoic acid, dimethylol octanoic acid, etc.,
Diethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine, N, N-dimethyl-1,3-propanediamine, N, N-dimethylaminoethanol, N, Hydroxyl group and amino group-containing compounds such as N-dimethylaminopropanol and N, N-dimethylaminohexanol;
Cellulose and / or derivatives thereof, polysaccharides such as amylose,
Etc.

  Among these, polyether polyols include glycols such as ethylene glycol, propylene glycol and diethylene glycol, polyols having 3 or more functional groups such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol, polyamines such as ethylenediamine and toluenediamines. Examples thereof include a hydroxyl group-containing polyether polyol obtained by addition polymerization of alkylene oxide such as ethylene oxide and propylene oxide, and polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

  Examples of the polyester polyol include dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, and phthalic acid, tri- and tetracarboxylic acids such as trimellitic acid and pyromellitic acid, ethylene glycol, propylene glycol, and 1,4 -Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2-diethylpropanediol, 2-ethyl-2-butylpropanediol, 1,6-hexanediol, neopentyl glycol By polycondensation reaction with diols such as diethylene glycol, 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, or triols such as trimethylolpropane and glycerin, or bisphenol A and bisphenol F What can be obtained

  Examples of polyether ester polyols include those obtained by reacting a mixture of an ether group-containing diol or other glycol with the dicarboxylic acid or an anhydride thereof, or by addition polymerization of an alkylene oxide to polyester glycol. (Polytetramethylene ether) adipate.

  Polycarbonate polyols include polyalcohol and dimethyl carbonate, dealcohol condensation reaction of dialkyl carbonates such as diethyl carbonate, polyphenol alcohol and diphenyl carbonate dephenol condensation reaction, polyhydric alcohol and ethylene carbonate deethylene glycol condensation reaction, etc. It is obtained by. Examples of the polyhydric alcohol include 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 2,2-diethyl. Aliphatic diols such as propanediol, 2-ethyl-2-butylpropanediol and neopentyl glycol, or alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol .

As a compound containing an amino group,
Aliphatic amino group-containing compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, dimethylethylenediamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, oleylamine;
Mensendiamine, isophoronediamine, norbornanediamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, 1,2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl) methane, bis (4- Aminocyclohexyl) alicyclic amino group-containing compounds such as methane, polycyclohexylpolyamine, DBU;
Aromatic amino group-containing compounds such as metaphenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone;
Aliphatic aromatic amino group-containing compounds such as xylenediamine, xylylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol;
3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylenediamine, polyoxypropylenetriamine, Amino group-containing compounds having an ether bond, such as polyoxyethylenediamine, polyoxyethylenealkylamine, polyoxypropylenealkylamine;
Acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride;
Polyamideamines such as polyamides obtained by reacting dimer acids with polyamines such as diethylenetriamine and triethylenetetramine, and polyamides using polycarboxylic acids other than dimer acids;
Imidazoles such as 2-ethyl-4-methylimidazole;
Polyoxypropylene amines such as polyoxypropylene diamine and polyoxypropylene triamine;
Epoxy-modified amine obtained by reacting an epoxy compound with the amines, modified amines such as Mannich-modified amine, Michael addition-modified amine, ketimine and aldimine obtained by reacting the amines with formalin and phenols; 2, 4 Amine salts such as 2-ethylhexanoate of, 6-tris (dimethylaminomethyl) phenol,
Also, primary amino group content such as aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, etc. Compound;
Secondary amino group-containing compounds such as N-methylaminoethyl (meth) acrylate and Nt-butylaminoethyl (meth) acrylate;
Etc.

  The compound which has a functional group which can react with these isocyanate groups can use 1 type (s) or 2 or more types.

As the component (B), a compound having a solubility in water of 50 g / g or more (preferably 60 g / g or more, more preferably 70 g / g or more) is used among the compounds described above.
As the component (C), among the compounds described above, compounds having a solubility in water of less than 50 g / g (preferably 30 g / g or less, more preferably 10 g / g or less) are used.
By introducing such a component (B) and component (C) into the component (A), it is possible to exhibit excellent solid adsorbing ability for a wide range of solids from hydrophilic to hydrophobic.

The polymer compound of the present invention can be obtained by introducing the component (B) and the component (C) into the component (A).
As a method of introducing, for example, (A) component and (B) component are mixed and reacted, then (C) component is mixed and reacted, (A) component and (C) component are mixed and reacted, Next, a method of mixing and reacting the component (B), a method of mixing and reacting the component (A), the component (B), and the component (C) all together are exemplified.
The reaction temperature may be about 50 ° C. to 110 ° C., and the reaction time may be about 1 hour to 24 hours.

Moreover, you may use the reaction catalyst which can be normally used for the above reactions.
For example, when a compound containing a hydroxyl group is used as the component (B) or (C), examples of the reaction catalyst include triethylamine, triethylenediamine, tetramethylbutanediamine, dimethylaminoethanol, dimer diamine, and dimer acid. Amines such as polyamidoamine; tin carboxylates such as butyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, tin octate, tin octylate; iron octylate, cobalt octylate, manganese octylate, zinc octylate, octylic acid Metal carboxylates such as iron, cobalt octylate, manganese octylate, zinc octylate; dibutyltin thiocarboxylate, dioctyltin thiocarboxylate, tributylmethylammonium acetate, trioctylme Carboxylates such as Le ammonium acetate; aluminum tris acetylacetonate aluminum compounds such like can be used.

The introduction ratio of the component (B) and the component (C) is (B) :( C) in the weight ratio of 1:99 to 99: 1 (preferably 10:90 to 95: 5, more preferably 20:80). ~ 90: 10).
In addition, the total amount of the component (B) and the component (C) is introduced at a ratio of 20% by weight to 90% by weight (preferably 25% by weight to 85% by weight) with respect to the total amount of the polymer compound. To do.
With such an introduction ratio and weight ratio, it is possible to exhibit excellent solid adsorbing ability for a wide range of solids from hydrophilic to hydrophobic.
(B): When (C) is outside the specified range, it may not be possible to exhibit an excellent solid adsorption ability for a wide range of solids.
The polymer compound of the present invention is also excellent in the reaggregation preventing effect, and in particular, the reaggregation preventing effect can be enhanced by introducing a carboxyl group, an amino group, or the like into the polymer compound.

The polymer compound thus obtained is excellent in solid adsorption ability. Therefore, it can be applied to various uses that require solid adsorption ability. Specifically, it is useful as a cleaning agent because of its excellent adsorptivity with dust, pride, oil, exhaust gas, and contaminants such as graffiti floating in the atmosphere.
The polymer compound of the present invention is 0.01 to 5 parts by weight (preferably 0.03 to 3 parts by weight, more preferably 0.05 to 1 part by weight) with respect to 100 parts by weight of water. It is sufficient to mix and use at a degree. With such a mixing amount, various solids (powder and the like) can be efficiently taken into the liquid. When used as a cleaning agent, such a small amount can exhibit a sufficient cleaning effect.
In addition to the above, the polymer compound of the present invention can exhibit excellent solid adsorption performance for a wide range of solids from hydrophilic to hydrophobic, and can be applied to various fields that require these performances. is there.

  Examples and Comparative Examples are shown below to clarify the features of the present invention, but the present invention is not limited to these Examples.

Example 1
Using the raw materials shown in Table 1, high molecular weight compounds were obtained by the following method.
400 parts by weight of ethyl acetate, 82.0 parts by weight of isocyanate compound 1 and 0.08 parts by weight of dibutyltin dilaurate as a catalyst were mixed and added to the polymerization kettle.
Next, a mixed solution in which 151.2 parts by weight of the compound 1 containing a hydroxyl group is mixed with 100 parts by weight of ethyl acetate is added dropwise to the polymerization kettle while stirring with a stirring blade (250 rpm) at 70 ° C. in a nitrogen atmosphere. did. After dropping, the mixture was further stirred for 1.5 hours.
Next, a mixed solution in which 160.0 parts by weight of compound 2 containing a hydroxyl group is mixed with 100 parts by weight of ethyl acetate is added dropwise to the polymerization kettle while stirring with a stirring blade (250 rpm) at 70 ° C. in a nitrogen atmosphere. did. After dropping, the mixture was further stirred for 1.5 hours.
Next, while stirring with a stirring blade (250 rpm) at 70 ° C. in a nitrogen atmosphere, a mixed solution in which 22.5 parts by weight of compound 3 containing a hydroxyl group is mixed with 200 parts by weight of ethyl acetate is dropped into the polymerization kettle. did. After dropping, the mixture was further stirred for 2 hours.
Next, a mixed solution in which 17.5 parts by weight of the compound 4 containing a hydroxyl group is mixed with 150 parts by weight of ethyl acetate is added dropwise to the polymerization kettle while stirring with a stirring blade (250 rpm) at 70 ° C. in a nitrogen atmosphere. did. After dropping, the mixture was further stirred for 5 hours to obtain a polymer compound.
The obtained polymer compound was subjected to the following detergency test.

(Detergency test)
A commercially available wallpaper was wiped with ink (black) and allowed to stand for 1 hour. Thereafter, the wall surface of the wallpaper surface was cleaned using a cleaning solution in which 100 parts by weight of water and 0.5 parts by weight of the polymer compound were mixed. The evaluation of the detergency test was performed in a five-step evaluation of 5 (stain (ink) could be cleaned)>4>3>2> 1 (stain (ink) remained). The results are shown in Table 2.

(Examples 2-4 , Comparative Examples 1-3 )
A polymer compound was obtained in the same manner as in Example 1 except for the composition ratio shown in Table 2. The obtained polymer compound was subjected to the same detergency test as in Example 1. The results are shown in Table 2.

Claims (1)

(A) In an isocyanate compound having two or more isocyanate groups in one molecule,
(B) a compound having a functional group capable of reacting with the isocyanate group and having a solubility in water (temperature of 25 ° C.) of 50 g / 100 g or more, and
(C) a compound having a functional group capable of reacting with the isocyanate group and having a solubility in water (temperature: 25 ° C.) of less than 50 g / 100 g,
(B): (C) is in a weight ratio of 1:99 to 99: 1, and the total amount of (B) and (C) is 20% by weight to 90% by weight with respect to the total amount of the polymer compound. And
(B) is a polyethylene glycol methyl ether, dimethylol propionic acid and N, consists N- dimethylethanolamine,
(C) is polybutylene glycol,
A polymer compound characterized by the above.