JP2007239156A - Liquid laundry starch composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a liquid laundry starch composition that provides an excellent starching with an extremely small amount added, actualizes an excellent starch removal in washing, has a high concentration and is easily handleable. <P>SOLUTION: The liquid laundry starch composition comprises a composition which is obtained by mixing a cationized starch containing a quaternary cationized starch in which at least one 7-18C hydrocarbon group is bonded to a quaternary cationic nitrogen with a nonionic water-soluble polymer and a nonionic surfactant and a monomer mixture which comprises a carboxylic acid vinyl ester-based monomer, an ethylenic unsaturated bond-containing carboxylic acid-based monomer and an ethylenic unsaturated bond-containing cationic monomer and may contain another monomer in the mass ratio of the cationized starch to the monomer mixture of 0.5/99.5-20/80 and subjecting the mixture to emulsion polymerization and has a nonvolatile content of ≥50 mass%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laundry paste composition for home use and business use, and in particular, imparts excellent paste standing property to various textile products such as clothing with an extremely small addition amount, and provides excellent paste removal property during washing. The present invention relates to a liquid laundry paste composition that is highly concentrated and easy to handle.

  Conventionally, in household and commercial laundry pastes, starch-based laundry pastes have been used, and vinyl acetate emulsions have been used as laundry pastes. The starch-based laundry paste is excellent in the property of adhering to the fibers and imparting hardness to the treated cloth, that is, the glue standing property, but there is a problem that the aqueous solution has a high viscosity. On the other hand, vinyl acetate emulsions have the advantage of low viscosity, but are not sufficient in terms of adhesiveness

  Thus, in vinyl acetate emulsions, vinyl acetate polymers obtained by copolymerizing cationic monomers have been proposed in order to improve pasting properties, but the pasting properties are still sufficient. However, the adhesive properties were insufficient. When the paste removal property is poor, the texture of the textile product such as clothing is impaired due to the adhesive residue even after washing, and furthermore, the stain removal is deteriorated, resulting in the problem of impairing the washing effect by washing. For this reason, it has been proposed for a long time to use a polymer obtained by copolymerizing an anionic monomer such as a carboxylic acid monomer for the purpose of improving the glue removal property, but the glueiness is lowered. There was a drawback of doing.

  Various improved techniques have been proposed for vinyl acetate emulsions as laundry pastes. For example, a laundry paste finishing agent comprising a copolymer of vinyl acetate and a carboxylic acid having an ethylenically unsaturated bond and cationic starch has been proposed (see, for example, Patent Document 1). However, it cannot be said that both the pasting property and the pasting property are sufficient.

  Further, a vinyl acetate / acrylic acid-based laundry paste emulsion using a water-soluble polymer as a protective colloid has been proposed (for example, see Patent Document 2), but it cannot be said that the adhesiveness is sufficient.

  Also disclosed is a paste composition for cellulose fibers mainly composed of a cationic emulsion obtained by polymerizing a vinyl ester and a cationic vinyl monomer in the presence of a specific cationic water-soluble polymer. (For example, refer to Patent Document 3) is not satisfactory in terms of adhesive removal.

  Furthermore, a vinyl acetate laundry paste composition having a reduced viscosity by using an inorganic electrolyte in combination with a specific cationic paste base material has been proposed (see, for example, Patent Document 4). None of sex is sufficient.

  As described above, in the emulsion as a laundry paste, it is required to simultaneously improve the pasting property and the pasting-off property, but in addition to this, in recent years, a higher concentration is required. The reason is not only high performance with high adhesiveness even in a small amount, but high concentration makes it easy for operators to handle, reduces costs during transportation and storage, and makes containers smaller This contributes to the reduction of waste, and such concentrated laundry paste is eagerly desired by the market.

  In this regard, the emulsion as a commercially available laundry paste usually has a non-volatile content of about 30 to 40% at most and a viscosity of about 300 to 2,000 mPa · s at room temperature. However, the viscosity is remarkably increased, so that it is not suitable for actual use, and the polymerization stability during production and the temporal stability during storage are lowered. Therefore, in any of the above-described conventional techniques, high concentration has not been achieved, and a high-performance and high-concentration laundry paste composition has not yet been put on the market.

JP-A-1-139871 (Claims) Japanese Patent Publication No. 8-9681 (Claims) JP-A-9-195174 (Claims and paragraph 0004) JP-A-9-209273 (Claims)

  The object of the present invention is to solve the problems of the prior art as described above, to give excellent glueing properties with an extremely small addition amount, to realize excellent glue removal properties during washing, to have a high concentration, and The object is to provide a liquid laundry paste composition that is easy to handle.

As a result of intensive studies, the present inventors have found a liquid laundry paste composition that can achieve the above-mentioned problems. That is, the present invention
[1] A cationized starch containing a quaternized cationized starch in which at least one hydrocarbon group having 7 to 18 carbon atoms is bonded to a quaternary cation nitrogen, a nonionic water-soluble polymer, a nonionic surfactant, and a carboxylic acid Monomers including a vinyl ester monomer, a carboxylic acid monomer having an ethylenically unsaturated bond, and a cationic monomer having an ethylenically unsaturated bond, which may contain other monomers From the composition obtained by mixing and emulsion polymerization so that the ratio of the mass of the cationized starch to the mass of the monomer mixture is in the range of 0.5 / 99.5 to 20/80. A liquid laundry paste composition having a nonvolatile content of 50% by mass or more;

[2] A cationized starch containing a quaternized cationized starch in which at least one hydrocarbon group having 7 to 18 carbon atoms is bonded to a quaternary cation nitrogen has a degree of cationization of 0.005 to 0.5, The liquid laundry paste composition according to [1] above, which is a cationized starch containing 0.01 to 5% by mass of a 2-hydroxypropoxyl group;

[3] The carboxylic acid vinyl ester monomer is a vinyl acetate monomer, and the carboxylic acid monomer having an ethylenically unsaturated bond is acrylic acid, methacrylic acid, crotonic acid, maleic acid (and its Alkyl ester) and fumaric acid (and its alkyl ester), which are monomers of one or more compounds selected from the group consisting of the above, and the cationic monomer having an ethylenically unsaturated bond is N, N -Dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, diallylamine, (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride, 3- (meth) acryloylaminopropyl-N , N, N-trimethylammonium chloride, 3- (meth) acryloyl A monomer of one or more compounds selected from the group consisting of xyl-2-hydroxypropyl-N, N, N-trimethylammonium chloride and diallyldimethylammonium chloride, and the other monomer is ( In the preceding item [1] or [2], which is a monomer of one or more compounds selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate The liquid laundry paste composition as described;

[4] The monomer mixture is 75 to 98% by mass of the carboxylic acid vinyl ester monomer, 1 to 15% by mass of the carboxylic acid monomer having an ethylenically unsaturated bond, and the ethylenic unsaturated. The liquid laundry paste composition according to any one of [1] to [3] above, comprising 0.1 to 10% by mass of a cationic monomer having a bond and 0 to 20% by mass of the other monomer; and

[5] The liquid laundry paste composition according to any one of [1] to [4], wherein the nonionic water-soluble polymer is a nonionic starch-based water-soluble polymer.

  The liquid laundry paste composition of the present invention imparts excellent glue standing to various textiles such as clothing with an extremely small addition amount, and realizes excellent paste removal properties during washing. Moreover, it is a high-performance liquid laundry paste composition that is highly concentrated and easy to handle, and is extremely useful for household and commercial laundry paste.

  The liquid laundry paste composition of the present invention comprises a cationized starch, a nonionic water-soluble polymer and a nonionic surfactant, a carboxylic acid vinyl ester monomer, and a carboxylic acid monomer having an ethylenically unsaturated bond. And a monomer mixture containing a cationic monomer having an ethylenically unsaturated bond, and a composition obtained by emulsion polymerization.

  In the present invention, the cationized starch needs to contain quaternized cationized starch in which at least one hydrocarbon group having 7 to 18 carbon atoms is bonded to quaternary cation nitrogen. When the quaternary cationized starch is not included, or even if it is a quaternary cationized starch, if the hydrocarbon group bonded to the quaternary cation nitrogen is outside the range of 7 to 18, the liquid of the present invention The stability of the laundry paste composition as a polymer emulsion is lowered, and a liquid laundry paste composition having a high concentration and easy to handle cannot be obtained.

  In the quaternized cationized starch in which at least one hydrocarbon group having 7 to 18 carbon atoms is bonded to quaternary cation nitrogen, the hydrocarbon group bonded to quaternary cation nitrogen has 7 to 7 carbon atoms. The ratio of the number of 18 hydrocarbon groups to the number of other hydrocarbon groups is preferably 1/20 to 2/1, and more preferably 1/15 to 1/1.

  In addition, about any of the quaternized cationized starch in which at least one hydrocarbon group having 7 to 18 carbon atoms is bonded to the quaternary cation nitrogen and other cationized starches, one or two or more of them are used in combination as appropriate. Can be used.

  Preferred examples of the quaternized cationized starch in which at least one hydrocarbon group having 7 to 18 carbon atoms is bonded to quaternary cation nitrogen in the present invention include starch having a chemical structure represented by the following formula [I]. .

[式中、（ＳＴＣ）は澱粉残基を表わし、Ａはヒドロキシル基を含有してもよい炭素数２〜４のアルキレン基を表わし、Ｘ⁻はアニオンを示し、Ｒ₁、Ｒ₂およびＲ₃のうちの少なくとも１つは炭素数７〜１８のアルキル基、アルケニル基もしくはアラルキル基を表わし、残りの０〜２個はメチル基もしくはエチル基を表わす。]

[In the formula, (STC) represents a starch residue, A represents an alkylene group having 2 to 4 carbon atoms which may contain a hydroxyl group, X ⁻ represents an anion, R ₁ , R ₂ and R ₃ At least one of them represents an alkyl group, alkenyl group or aralkyl group having 7 to 18 carbon atoms, and the remaining 0 to 2 represent a methyl group or an ethyl group. ]

In the compound represented by the formula [I], examples of the alkylene group having 2 to 4 carbon atoms which may contain the hydroxyl group represented by A include a hydroxyethyl group, a hydroxypropyl group and a hydroxybutyl group. Further, X ^- is a anion representing, for example chlorine, ions of an ion and the like methyl sulfate and ethyl sulfate halogens bromine and iodine. Examples of the alkyl group, alkenyl group or aralkyl group having 7 to 18 carbon atoms represented by at least one of R ₁ , R ₂ and R ₃ include a heptyl group, an octyl group, a 2-ethylhexyl group and a nonyl group. , Isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, hexadecyl group, stearyl group, oleyl group and benzyl group.

  Furthermore, the cationization degree (cation substitution degree) of the cationized starch in the present invention is preferably 0.005 to 0.5. If the degree of cationization is less than 0.005, the pasting property tends to decrease, whereas if it exceeds 0.5, the pasting property tends to decrease. The degree of cationization referred to here is an average of the degree of cationization of the entire cationized starch including the degree of cationization of the quaternized cationized starch in which at least one hydrocarbon group having 7 to 18 carbon atoms is bonded to nitrogen of the quaternary cation. It is a numerical value.

  Moreover, it is preferable that 2-hydroxypropoxyl group is contained in the cationized starch in this invention 0.01-5 mass% with respect to the whole quantity of cationized starch. When the content of 2-hydroxypropoxyl group in the cationized starch is less than 0.01% by mass, the stability during polymerization tends to decrease, whereas when it exceeds 5% by mass, the concentration is high and the handling is high. Therefore, neither is easy to obtain a liquid laundry paste composition.

  Moreover, as an average molecular weight of the cationized starch in this invention, it is preferable that a number average molecular weight is 5,000-1,000,000, and it is more preferable that it is 30,000-600,000.

  The nonionic water-soluble polymer in the present invention is not particularly limited, and one or two or more types of known nonionic water-soluble polymers can be appropriately selected and used. Nonionic water-soluble polymers that can be used in the present invention include, for example, nonionic starch-based water-soluble polymers, cellulose-based water-soluble polymers such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl methyl cellulose, and polyvinyl alcohol-based water-soluble polymers. And water-soluble polymers such as molecules, polyvinylpyrrolidone-based water-soluble polymers, and polyacrylamide-based water-soluble polymers. Of these, nonionic starch-based water-soluble polymers are particularly preferable.

  That is, in the present invention, it is desirable to use cationized starch and nonionic starch in combination. The cationized starch is not particularly limited except that it contains quaternized cationized starch in which at least one hydrocarbon group having 7 to 18 carbon atoms is bonded to quaternary cation nitrogen, Examples of preferred cationized starches include trialkylammonio-2-hydroxypropylated starch, dialkylamino-2-hydroxypropylated starch and dialkylaminoethylated starch. Further, the nonionic starch is not particularly limited, but preferred nonionic starch is exemplified by hydroxypropylated starch, alkyl etherified starch, acetylated starch, glycerol distarch, dialdehyde starch, Examples include dextrin, soluble starch and pregelatinized starch.

  The starch used as the base of the above-mentioned cationized starch or nonionic starch-based water-soluble polymer is not particularly limited. For example, corn starch, tapioca starch, potato starch, wheat starch, rice starch, sweet potato starch , Sago starch, waxy corn starch (waxy corn starch) and the like can be used, but corn starch and tapioca starch are preferred.

  In the present invention, the base starch as described above, starch modified from them, and starch obtained by cationizing those starch or modified starch are used as nonionic starch or cationized starch. Or can be used as anionic starch if desired. Examples of the modified starch include starch derivatives, starch degradation products, and pregelatinized starch. Examples of starch derivatives include etherified starch, esterified starch, cross-linked starch, and grafted starch. . More specifically, examples of the etherified starch among the starch derivatives include hydroxypropylated starch, hydroxyethylated starch, alkyl etherified starch and carboxymethylated starch. Examples of esterified starch include acetylated starch. Starch, octenyl succinylated starch, phosphorylated starch and the like can be mentioned, and examples of the crosslinked starch include phosphate distarch and glycerol distarch. Examples of the starch degradation product include dextrin, maltodextrin and soluble starch, and examples of the pregelatinized starch include unmodified pregelatinized starch and modified pregelatinized starch. In the present invention, these starches can be used in combination as appropriate.

  The nonionic surfactant in the present invention is not particularly limited as long as it is a nonionic surfactant, and one or two or more kinds of known nonionic surfactants may be appropriately selected and used. That's fine. Examples of nonionic surfactants that can be used in the present invention include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene aralkyl ether, polyoxyethylene aralkyl aryl ether, polyoxyethylene polyoxypropylene, and Examples thereof include polyoxyethylene sorbitan fatty acid esters and reactive surfactants in which a functional group such as a radical polymerizable vinyl group or allyl group is introduced. The amount of the nonionic surfactant used is not particularly limited, but is usually 100 parts by mass of the monomer mixture described below (the total of the parts by mass of each monomer is 100 parts by mass). It is about 0.1-10 mass parts.

  The liquid laundry paste composition of the present invention has the above-described cationized starch, nonionic water-soluble polymer and nonionic surfactant, a carboxylic acid vinyl ester monomer described below, and an ethylenically unsaturated bond. A monomer mixture containing a carboxylic acid-based monomer and a cationic monomer having an ethylenically unsaturated bond is obtained by emulsion polymerization, but within the range not impairing the object of the present invention, In addition to the cationized starch, a small amount of a cationic water-soluble polymer may be used in combination. Similarly, a small amount of an anionic water-soluble polymer, a small amount of an anionic surfactant, a small amount of a cationic surfactant, a small amount of an amphoteric surfactant may be used in combination.

  In the present invention, the monomer mixture used for emulsion polymerization includes, as its components, a) a carboxylic acid vinyl ester monomer, b) a carboxylic acid monomer having an ethylenically unsaturated bond, and c) an ethylenically unsaturated monomer. It is a monomer mixture that contains a cationic monomer having a saturated bond, and d) may contain other monomers. Hereinafter, each monomer will be described.

a) Carboxylic acid vinyl ester monomers a) Component carboxylic acid vinyl ester monomers include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pivalate, vinyl caproate, capric acid. Monomers such as vinyl, vinyl 2-ethylhexanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl versatate [eg Veova (registered trademark, made by Japan Epoxy Resin) and vinyl benzoate These can be used by appropriately selecting one or two or more of them, and among them, a particularly preferable monomer as the vinyl carboxylate monomer of component a) is a vinyl acetate monomer. It is.

b) Carboxylic acid monomer having an ethylenically unsaturated bond b) As the carboxylic acid monomer having an ethylenically unsaturated bond, for example, acrylic acid, methacrylic acid, crotonic acid, tiglic acid, angelic acid Senesic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, maleic acid methyl ester, maleic acid ethyl ester, maleic acid propyl ester, maleic acid butyl ester, maleic acid octyl ester, decyl maleic acid Ester, maleic acid dodecyl ester, maleic acid tetradecyl ester, maleic acid hexadecyl ester, maleic acid stearyl ester, maleic acid oleyl ester, maleic acid methoxyethyl ester, maleic acid ethoxyethyl ester, maleic acid butoxy Ciethyl ester, maleic acid methyl carbitol ester, maleic acid ethyl carbitol ester, maleic acid butyl carbitol ester, maleic acid benzyl ester, fumaric acid methyl ester, fumaric acid ethyl ester, fumaric acid propyl ester, fumaric acid butyl ester, Octyl fumarate, decyl fumarate, dodecyl fumarate, tetradecyl fumarate, hexadecyl fumarate, stearyl fumarate, oleyl fumarate, methoxyethyl fumarate, ethoxyethyl fumarate, fumarate ethoxyethyl ester Acid butoxyethyl ester, methyl fumarate carbitol ester, ethyl fumarate carbitol ester, butyl carbitol fumarate and Monomers include such succinimidyl ester, which may be used to select one or more appropriate. Among these, carboxylic acid monomers having an ethylenically unsaturated bond as component b) are preferably acrylic acid, methacrylic acid, crotonic acid, maleic acid (and its alkyl ester) and fumaric acid (and its alkyl ester). It is preferable to use one or more monomers selected from these. Particularly preferred are acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, maleic acid methyl ester, maleic acid ethyl ester, maleic acid propyl ester, maleic acid butyl ester, fumaric acid methyl ester, fumaric acid ethyl ester, fumaric acid. Examples thereof include monomers of acid propyl ester or fumaric acid butyl ester, and it is particularly preferable to use one or more monomers selected from these monomers.

c) Cationic monomer having an ethylenically unsaturated bond c) Examples of the cationic monomer having an ethylenically unsaturated bond include N, N-dialkylaminoalkyl (meth) acrylate, N, N -Dialkylaminoalkyl (meth) acrylamide, N, N-dialkylaminohydroxyalkyl (meth) acrylate, diallylamine, (meth) acryloyloxyalkyl-N, N, N-trimethylammonium salt, (meth) acryloylaminoalkyl-N, Monomers such as N, N-trimethylammonium salt, (meth) acryloyloxy-hydroxyalkyl-N, N, N-trimethylammonium salt and diallyldimethylammonium salt may be mentioned, and these may be used alone or in combination of two or more. You can select and use. Among them, the cationic monomer having an ethylenically unsaturated bond as the component c) is preferably N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, diallylamine, (meth). Acryloyloxyethyl-N, N, N-trimethylammonium chloride, 3- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride, 3- (meth) acryloyloxy-2-hydroxypropyl-N, N, Examples include N-trimethylammonium chloride and diallyldimethylammonium chloride monomers, and it is preferable to use one or more monomers selected from these monomers.

d) Other monomers As other monomers of component d), for example, (meth) acrylic acid ester, hydroxyalkyl (meth) acrylate, polyoxyalkylene (meth) acrylate, (meth) acrylamide, alkyl vinyl ether, Monomers such as acrylonitrile, styrene, and a sulfonic acid group-containing compound can be mentioned, and these can be used by appropriately selecting one or two or more. Among them, other preferable monomers for component d) are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-acrylamido-2-methylpropane. The monomer of a sulfonic acid is mentioned, It is preferable to use 1 type, or 2 or more types of monomers chosen from these.

  As a mixing ratio in the monomer mixture of the above-mentioned a) component, b) component and c) component, and d) component added as required, a) carboxylic acid vinyl ester monomer is 75 to 98% by mass. B) Carboxylic acid monomer having an ethylenically unsaturated bond is 1 to 15% by mass, c) Cationic monomer having an ethylenically unsaturated bond is 0.1 to 10% by mass, d) Others It is preferable that a monomer is 0-20 mass%.

  b) If the amount of the carboxylic acid monomer having an ethylenically unsaturated bond as the component is less than 1% by mass, the peeling property tends to be reduced, whereas if it exceeds 15% by mass, the adhesive property tends to be reduced. It is not preferable. c) When the amount of the cationic monomer having an ethylenically unsaturated bond is less than 0.1% by mass, the pasting property tends to be lowered, and when it exceeds 10% by mass, the pasting property tends to be lowered. Therefore, it is not preferable. On the other hand, when the amount of the other monomer of component d) exceeds 20% by mass, a liquid laundry paste composition that meets the object of the present invention may not be obtained.

  The liquid laundry paste composition of the present invention has a high concentration obtained by mixing the above-mentioned cationized starch, nonionic water-soluble polymer and nonionic surfactant with the above monomer mixture, and emulsion polymerization. In the emulsion polymerization, the ratio of the mass of the cationized starch to the mass of the monomer mixture is 0.5 / 99.5 to 20/80, preferably 0.5 / 99.5 to 10 in the emulsion polymerization. Emulsion polymerization is carried out by mixing to obtain / 90. When the mass ratio of the cationized starch is smaller than 0.5 / 99.5, the paste-forming property is lowered, and the emulsion polymerization stability is lowered, and the liquid laundry paste composition can be obtained as a high-concentration emulsion. Can not. On the other hand, when the mass ratio of the cationized starch is larger than 20/80, the paste removal property is lowered and the stability as an emulsion is also lowered.

  In the present invention, a generally known method can be adopted as a method for carrying out emulsion polymerization. As polymerization temperature, about 30-100 degreeC is preferable and about 60-80 degreeC is more preferable.

  The polymerization initiator is not particularly limited. For example, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] Azo compounds such as tert-butyl hydroperoxide, organic peroxide compounds such as cumene hydroperoxide, inorganic peroxide compounds such as potassium persulfate, sodium persulfate, ammonium persulfate, etc. Can be used. When a peroxide compound is used, redox polymerization can be performed by using a reducing agent such as tartaric acid, sodium tartrate, sodium bisulfite, sodium thiosulfate, sodium isoascorbate, and the like. The polymerization initiator is preferably used in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the monomer mixture described above.

  As the chain transfer agent, lower alcohols such as methanol, ethanol, isopropyl alcohol, mercaptans, halogenated carbons, halogenated hydrocarbons, hypophosphites, and the like may be used as appropriate.

  By performing emulsion polymerization as described above, the liquid laundry paste composition of the present invention is obtained as an emulsion. Although it does not specifically limit as an average particle diameter of an emulsion, Usually, it is about 0.1-10 micrometers.

  In the above emulsion polymerization, the cationized starch does not need to be used in its entirety before the start of the emulsion polymerization, and a part thereof may be added during the emulsion polymerization. In that case, the ratio of the mass of the cationized starch used before and after the start of emulsion polymerization to the mass of the monomer mixture should be 0.5 / 99.5 to 20/80. To conduct emulsion polymerization.

  Similarly, a part of the nonionic water-soluble polymer and the nonionic surfactant may be added during the emulsion polymerization.

  Further, one or more of cationized starch, nonionic water-soluble polymer, and nonionic surfactant may be added and added later to the emulsion obtained by emulsion polymerization.

  In addition, the liquid laundry paste composition of the present invention includes a pH adjuster, an antifoaming agent, a plasticizer, a viscosity adjuster, an antifreezing agent, an antiseptic, a softener, a lubricant such as silicone, and a disinfectant as necessary. Various additives such as an antibacterial agent, a deodorant, a fragrance, a colorant, a fluorescent brightener, an antioxidant, an ultraviolet absorber, and an inorganic filler may be added.

  The liquid laundry paste composition of the present invention is a high concentration emulsion and can be used as a highly concentrated laundry paste. The nonvolatile content in the liquid laundry paste composition of the present invention is 50% by mass or more and preferably 55% by mass or more with respect to the total mass of the liquid laundry paste composition. The upper limit of the non-volatile content can be 70% by mass or more, but it becomes more viscous as the non-volatile content increases. Therefore, it is preferable to limit the non-volatile content to about 68% by mass in consideration of handleability. It is more preferable to keep it at a minimum. The method for measuring the nonvolatile content is as follows.

[Measurement method of non-volatile content]
Based on JIS K 6828, measurement is performed using a forced convection dryer (DN43 model manufactured by Yamato Scientific Co., Ltd.). Specifically, first, a mass W _{0 of} about 1 g of a sample is accurately measured with a balance capable of measuring up to 4 decimal places in grams. Next, this sample is left to stand in a dryer set at a temperature of 105 ° C. for 60 minutes to remove volatile components, and the sample mass after being allowed to cool sufficiently at room temperature (about 23 ° C.) in a desiccator. W ₁ is also measured accurately. Then, the nonvolatile content is obtained by the following mathematical formula.
[Non-volatile content] = (W ₁ / W ₀ ) × 100 (%)

  The liquid laundry paste composition of the present invention has an appropriate viscosity and is easy to handle despite its high concentration. The viscosity of the liquid laundry paste composition of the present invention is about 500 to 2,000 mPa · s at room temperature (23 ° C.) and is excellent in handleability. In addition, the laundry paste of the present invention is excellent in storage stability, is stable for at least 6 months at room temperature (23 ° C.), and does not cause sedimentation or separation and increase in viscosity. In addition, the measuring method of a viscosity is as follows.

[Measurement method of viscosity]
Based on JIS K 6828, a Brookfield type rotational viscometer (BM type manufactured by Toki Sangyo Co., Ltd.) is used and the measurement is performed under conditions of a sample temperature of 23 ° C. and a rotational speed of 12 revolutions / minute.

  Usually, the laundry paste is diluted with water and prepared to an appropriate concentration (washing paste bath), and then used for the pasting step. In general emulsion-type laundry paste, it is usually diluted with water to be about 2 to 8% by mass to form a laundry paste bath (the weight of the laundry paste including volatile matter is 2 to 8 percent of that of the wash paste bath). It means that it is diluted so as to be about mass%), and the mass ratio of various textiles to be glued to the washing paste bath is about 3: 1 to 1:10. On the other hand, the laundry paste composition of the present invention is diluted with water so as to be about 0.6 to 1% by mass to form a laundry paste bath, and various textile products to be glued and the laundry paste It can be used at a bath ratio of about 3: 1 to 1:10. At this time, it exhibits excellent glueing properties and exhibits excellent performance in terms of glue removal. Therefore, compared to general emulsion-type laundry glue, the dilution ratio during use is high and the amount used in the form is very small, so it is excellent in workability especially when used for business use. . This has a great influence not only on the high concentration but also on the fact that the amount of use in terms of non-volatile content is small as can be seen from the above description. In order to achieve such advantageous effects, the laundry paste composition of the present invention can be commercialized as a concentrated laundry paste or a compact laundry paste that is excellent in workability and environmentally friendly.

  The liquid laundry paste composition of the present invention can be used for various fiber products and can be used without limiting the type of the target fiber product, but particularly for cotton, polyester / cotton blends, etc. Show excellent effects.

Hereinafter, the liquid laundry paste composition of the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereby. Various characteristics mentioned in Examples and Comparative Examples are measured or evaluated by the following methods.
[Non-volatile content]
Based on JIS K 6828, measurement was performed using a forced convection dryer (DN43 model manufactured by Yamato Kagaku Co.). Specifically, first, the mass W _{0 of} about 1 g of the sample was accurately measured with a balance capable of measuring up to four decimal places in grams. Next, this sample is left to stand in a dryer set at a temperature of 105 ° C. for 60 minutes to remove volatile components, and the sample mass after being allowed to cool sufficiently at room temperature (about 23 ° C.) in a desiccator. the W ₁ was also accurately measured. And the non volatile matter was calculated | required with the following numerical formula. In addition, the value rounded to the first decimal place by rounding off the second decimal place in% display was adopted.
[Non-volatile content] = (W ₁ / W ₀ ) × 100 (%)

[viscosity]
Based on JIS K 6828, it was measured using a Brookfield type rotational viscometer (BM type manufactured by Toki Sangyo Co., Ltd.) under the conditions of a sample temperature of 23 ° C. and a rotational speed of 12 revolutions / minute.

[pH]
In accordance with JIS K 6828, the finally obtained laundry paste composition was measured as it was using a pH meter (H-22 type F-22).

[Particle size]
It measured using the optical diffraction type particle size measuring apparatus (LA-700 type | mold by Horiba, Ltd.), and the value of the median diameter was employ | adopted.

[Adhesiveness and exfoliation]
Evaluation cloths were prepared by the following methods (1) and (2), and the bending resistance of the cloth was evaluated by the method (3). In addition, about the glue property, it shows that the glue property is so high that the value of bending resistance is large, and it shows that the glue property is so high that the value of glue property is small.
(1) 0.67% by mass in solid form (however, in Comparative Example 1 and Comparative Example 5 it is 2.00% by mass, in Example 6, Comparative Example 2 and Comparative Example 6 it is 1.00% by mass) %) Laundry paste bath, broad cloth (warp density 133 / 2.54 cm, weft density 72 / 2.54 cm) using cotton yarn (single yarn # 40) and polyester (Tetron: registered trademark) / Broad ratio of cotton blended yarn (single yarn # 45, polyester / cotton = 65/35) (warp density 136 / 2.54 cm, weft density 72 / 2.54 cm) to the washing paste bath The mass ratio of the cloth and the washing paste bath was dipped at 1:10 for 10 minutes for pasting. After pasting, the cloth taken out from the washing paste bath is dehydrated for 3 minutes with a household washing machine (COMACT 60 ASW-60S2 (HS) type, manufactured by Sanyo Electric Co., Ltd.) and subsequently dried with an iron. It was. The iron temperature was 200 ° C. for cotton and 160 ° C. for polyester / cotton blend.
(2) The evaluation cloth of (1) was washed with a household washing machine (manufactured by Sanyo Electric, COMPACT60 ASW-60S2 (HS) type). As washing conditions, a predetermined amount of synthetic detergent for household washing (“Attack (registered trademark)” manufactured by Kao) is used in 34 L of water at 45 ° C. After washing and dehydration in the standard course of the washing machine, As in (1), what was dried with an iron was used as an evaluation cloth for adhesive removal.
(3) After leaving the evaluation fabric prepared in the above (1) or (2) in a temperature-controlled room at 23 ° C. and 65% RH for 24 hours, JIS: L-1096-1990 “General Textile Testing Method” 6.19. 5 According to the bending resistance E method (handle ohmmeter method), the bending resistance was obtained by measuring with a hand tester (HOM-II type manufactured by Daiei Scientific Instruments).

Moreover, the content of the starch type compound as described in an Example and a comparative example is as follows, respectively. In the following chemical formula, (STC) represents a starch residue, and specifically (STC) -O- represents that any OH group in the starch was etherified.
1. Cationized starch CA
Cationized starch C-A is a starch compound in which three types of chemical structures represented by the following formulas [II] to [IV] are mixed in the structure, and the degree of cationization is 0.015. Yes, the 2-hydroxypropoxyl group content is 0.6% by weight and the number average molecular weight is about 400,000. In addition, the ratio of the number of hydrocarbon groups having 12 carbon atoms to the number of methyl groups among the hydrocarbon groups bonded to the quaternary cation nitrogen is 1/4.

2. Cationized starch CB
Cationized starch CB is a starch compound in which three types of chemical structures represented by the following formulas [V] to [VII] are mixed in the structure, and the degree of cationization is 0.030. Yes, the content of 2-hydroxypropoxyl group is 2.0% by mass, and the number average molecular weight is about 100,000. Further, among the hydrocarbon groups bonded to the quaternary cation nitrogen, the ratio of the number of hydrocarbon groups having 18 carbon atoms to the number of methyl groups is 1/15.

3. Cationized starch CC
Cationized starch CC is a starch compound in which three types of chemical structures represented by the following formulas [VIII] to [X] are mixed in the structure, and the degree of cationization is 0.150. Yes, the content of 2-hydroxypropoxyl group is 4.0% by mass, and the number average molecular weight is about 30,000. Further, among the hydrocarbon groups bonded to the quaternary cation nitrogen, the ratio of the number of hydrocarbon groups having 12 carbon atoms to the number of methyl groups is 1/10.

4). Cationized starch CD
Cationized starch CD is a starch compound in which three types of chemical structures represented by the following formulas [XI] to [XIII] are mixed in the structure, and the degree of cationization is 0.010. Yes, the 2-hydroxypropoxyl group content is 0.4% by mass, and the number average molecular weight is about 600,000. Of the hydrocarbon groups bonded to the quaternary cation nitrogen, the ratio of the number of hydrocarbon groups having 12 carbon atoms to the number of methyl groups is ½.

5). Acetylated starch A-A
Acetylated starch AA is a nonionic starch-based compound having a chemical structure represented by the following formula [XIV], and has a degree of acetylation of 0.080 and a number average molecular weight of about 600,000.

6). Acetylated starch AB
Acetylated starch AB is a nonionic starch-based compound having a chemical structure represented by the following formula [XV], the degree of acetylation is 0.040, and the number average molecular weight is about 400,000.

7). Hydroxypropylated starch HA
Hydroxypropylated starch HA is a nonionic starch-based compound having a chemical structure represented by the following formula [XVI], the degree of acetylation is 0.100, and the number average molecular weight is about 3,000,000. is there.

8). Cationized starch CE
Cationized starch CE is a starch compound in which two chemical structures represented by the following formulas [XVII] to [XVII] are mixed in the structure, and the degree of cationization is 0.200. Yes, the 2-hydroxypropoxyl group content is 2.0% by weight, and the number average molecular weight is about 400,000.

[Example 1]
In a separable flask equipped with a cooling tube, a nitrogen introducing tube, a thermometer, a stirrer, and a dropping funnel, 170 parts by mass of water, polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku "Neugen SD-300 (trade name)" 4 parts by weight, and while stirring, 20 parts by weight of cationized starch C-A and 20 parts by weight of nonionic water-soluble polymer acetylated starch A-A were added, and the temperature was raised to 70 ° C. And dissolved. Next, while stirring the contents, 26 parts by mass of vinyl acetate and 2,2′-azobis (2-amidinopropane) dihydrochloride (“V-50 (trade name)” manufactured by Wako Pure Chemical Industries, Ltd.) under a nitrogen atmosphere. 8 parts by mass of a 3% by weight aqueous solution of), and a mixture containing monomers separately prepared (430 parts by mass of vinyl acetate monomer, 12 parts by mass of acrylic acid monomer, crotonic acid monomer) A monomer mixture composed of 2.4 parts by mass and 9.6 parts by mass of dimethylaminopropylacrylamide monomer and 8 parts by mass of ethanol were added dropwise from a dropping funnel over 4 hours. Moreover, 72 mass parts of 3 mass% aqueous solution of 2,2'- azobis (2-amidino propane) dihydrochloride was dripped over 4.5 hours simultaneously with the dripping start of the said mixture. Further, after the dropping of the mixture was completed, the temperature was raised to 75 ° C., stirred at this temperature for 2 hours, cooled to 30 ° C., and finally a small amount of water was added for the purpose of adjusting the concentration and viscosity, and the liquid laundry paste was added. An emulsion as a composition was obtained. This emulsion had a nonvolatile content of 65.0% by mass, a viscosity of 1,810 mPa · s, a pH of 4.8, and a particle size of 1.9 μm.

[Example 2]
The starch and monomer composition to be used was the composition shown in Table 1 below, and instead of adding 8 parts by mass of a 3% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, tert-butyl hydro The addition of 5 parts by weight of a 1% by weight aqueous solution of peroxide and 5 parts by weight of a 2% by weight aqueous solution of sodium tartrate and 72 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride Implemented except that 45 parts by weight of a 1% by weight aqueous solution of tert-butyl hydroperoxide and 45 parts by weight of a 2% by weight aqueous solution of sodium tartrate were dropped over 4.5 hours instead of dropping over 4.5 hours. The same operation as in Example 1 was performed to obtain an emulsion as a liquid laundry paste composition. This emulsion had a nonvolatile content of 60.5% by mass, a viscosity of 620 mPa · s, a pH of 5.0, and a particle size of 1.8 μm.

[Example 3]
The starch and monomer composition to be used was the composition shown in Table 1 below, and instead of adding 8 parts by mass of a 3% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 1% by mass 5 parts by mass of an aqueous hydrogen peroxide solution and 5 parts by mass of a 2% by mass aqueous solution of sodium tartrate were added, and 72 parts by mass of a 3% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride was added to 4.5 parts. Instead of adding dropwise over time, 45 parts by mass of a 1% by mass aqueous hydrogen peroxide solution and 45 parts by mass of a 2% by mass aqueous sodium tartrate solution were added dropwise over 4.5 hours, and isopropyl alcohol 4 instead of 8 parts by mass of ethanol. Except having used a mass part, it carried out the same operation as Example 1 and obtained the emulsion as a liquid laundry paste composition. This emulsion had a nonvolatile content of 62.4% by mass, a viscosity of 1,040 mPa · s, a pH of 4.8, and a particle size of 2.0 μm.

[Example 4]
Instead of 4 parts by mass of polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku “Neugen SD-300 (trade name)”), polyoxyethylene tridecyl ether (Daiichi Kogyo Seiyaku “Neugen TDS-70 (trade name)” ]) An emulsion as a liquid laundry paste composition was obtained in the same manner as in Example 1 except that 3 parts by mass and the starch and monomer composition were as shown in Table 1 below. This emulsion had a non-volatile content of 59.7% by mass, a viscosity of 1,490 mPa · s, a pH of 4.6, and a particle size of 1.9 μm.

[Example 5]
1. Polyoxyethylene isodecyl ether (“Neugen SD-300 (trade name)” manufactured by Daiichi Kogyo Seiyaku) instead of 4 parts by mass polyoxyethylene alkyl ether (“Emulgen 1135S-70 (trade name)” manufactured by Kao) 8 parts by mass and 4 parts by mass of alkylbenzyldimethylammonium chloride (“Sanisol C (trade name)” manufactured by Kao) were used, and the starch and monomer composition were as shown in Table 1 below. Instead of adding 8 parts by mass of a 3% by mass aqueous solution of '-azobis (2-amidinopropane) dihydrochloride, 5 parts by mass of a 1% by mass aqueous solution of tert-butyl hydroperoxide and 5 parts by mass of a 2% by mass aqueous solution of sodium tartrate; A 2 mass% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride Instead of adding 4.5 parts by weight over 4.5 hours, 45 parts by weight of a 1% by weight aqueous solution of tert-butyl hydroperoxide and 45 parts by weight of a 2% by weight aqueous sodium tartrate solution were added dropwise over 4.5 hours and ethanol An emulsion as a liquid laundry paste composition was obtained in the same manner as in Example 1, except that 7 parts by mass of ethanol was used instead of 8 parts by mass. This emulsion had a nonvolatile content of 64.9% by mass, a viscosity of 1,860 mPa · s, a pH of 4.8, and a particle size of 1.9 μm.

[Example 6]
The starch and monomer composition were as shown in Table 1 below. Instead of adding 8 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, tert-butyl hydroperoxide 5 parts by mass of a 1% by mass aqueous hydrogen peroxide solution and 5 parts by mass of a 2% by mass aqueous sodium tartrate solution, and 72 parts by mass of a 3% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride Was added dropwise over 4.5 hours, and 45 parts by mass of a 1% by weight aqueous hydrogen peroxide solution and 45 parts by mass of a 2% by weight aqueous sodium tartrate solution were added dropwise over 4.5 hours, and instead of 8 parts by mass of ethanol. Except that 8 parts by mass of methanol was used, the same operation as in Example 1 was performed to obtain an emulsion as a liquid laundry paste composition. This emulsion had a nonvolatile content of 52.2% by mass, a viscosity of 2,040 mPa · s, a pH of 4.8, and a particle size of 0.7 μm.

[Example 7]
Instead of 4 parts by mass of polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku “Neugen SD-300 (trade name)”), polyoxyethylene tridecyl ether (Daiichi Kogyo Seiyaku “Neugen TDS-70 (trade name)” ") Same as Example 1 except that 3 parts by weight were used, the starch and monomer composition was as shown in Table 1 below, and 10 parts by weight of ethanol was used instead of 8 parts by weight of ethanol. Operation was performed to obtain an emulsion as a liquid laundry paste composition. This emulsion had a nonvolatile content of 64.0% by mass, a viscosity of 1,230 mPa · s, a pH of 5.2, and a particle size of 4.5 μm.

[Example 8]
Instead of 4 parts by mass of polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku “Neugen SD-300 (trade name)”), polyoxyethylene alkyl ether (Daiichi Kogyo Seiyaku “Neugen ET-135 (trade name)” ) An emulsion as a liquid laundry paste composition was obtained in the same manner as in Example 1 except that 4 parts by mass was used and that the starch and monomer compositions were as shown in Table 1 below. The emulsion had a non-volatile content of 64.3% by mass, a viscosity of 920 mPa · s, a pH of 4.6, and a particle size of 2.0 μm.

[Example 9]
The starch and monomer composition was as shown in Table 1 below; instead of adding 8 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 1% by weight hydrogen peroxide The addition of 5 parts by weight of an aqueous solution and 5 parts by weight of a 2% by weight aqueous solution of sodium tartrate, 72 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride over 4.5 hours Instead of dripping, 45 parts by mass of a 1% by mass aqueous hydrogen peroxide solution and 45 parts by mass of a 2% by mass aqueous sodium tartrate solution were dripped over 4.5 hours, and 8 parts by mass of methanol was used instead of 8 parts by mass of ethanol. Except for the above, the same operation as in Example 1 was performed to obtain an emulsion as a liquid laundry paste composition. This emulsion had a nonvolatile content of 58.4% by mass, a viscosity of 11,110 mPa · s, a pH of 4.6, and a particle size of 2.0 μm.

[Example 10]
The starch and monomer composition was as shown in Table 1 below; instead of adding 8 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 1% by weight hydrogen peroxide The addition of 5 parts by weight of an aqueous solution and 5 parts by weight of a 2% by weight aqueous solution of sodium tartrate, 72 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride over 4.5 hours Instead of dripping, 45 parts by mass of a 1% by mass hydrogen peroxide aqueous solution and 45 parts by mass of a 2% by mass aqueous sodium tartrate solution were dripped over 4.5 hours, and 9 parts by mass of ethanol was used instead of 8 parts by mass of ethanol. Except for the above, the same operation as in Example 1 was performed to obtain an emulsion as a liquid laundry paste composition. This emulsion had a nonvolatile content of 60.5% by mass, a viscosity of 1,280 mPa · s, a pH of 4.7, and a particle size of 1.5 μm.

[Example 11]
Instead of 4 parts by mass of polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku “Neugen SD-300 (trade name)”), polyoxyethylene tridecyl ether (Daiichi Kogyo Seiyaku “Neugen TDS-70 (trade name)” )) 4 parts by mass, starch and monomer composition as shown in Table 1 below, 8 parts by mass of 2,2′-azobis (2-amidinopropane) dihydrochloride 3% by mass aqueous solution Instead of adding 5 parts by weight of a 1% by weight aqueous solution of tert-butyl hydroperoxide and 5 parts by weight of a 2% by weight aqueous solution of sodium tartrate, and 2,2′-azobis (2-amidinopropane) dihydrochloride Instead of dropping 72 parts by weight of a 3% by weight aqueous solution over 4.5 hours, 1% by weight of tert-butyl hydroperoxide Except that a solution 45 parts by mass and 2% by weight aqueous solution of 45 parts by weight of sodium tartrate was added dropwise over 4.5 hours, and the same procedure as in Example 1 to obtain an emulsion of a liquid laundry starch composition. This emulsion had a nonvolatile content of 60.4% by mass, a viscosity of 1,770 mPa · s, a pH of 4.6, and a particle size of 1.8 μm.

[Example 12]
The starch and monomer composition were as shown in Table 1 below, and tert-butyl hydroperoxide was used instead of adding 8 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride. 5 parts by weight of a 1% by weight aqueous solution of 5 parts by weight and 5 parts by weight of a 2% by weight aqueous solution of sodium tartrate were added. Instead of adding dropwise over 5 hours, 45 parts by mass of a 1% by mass aqueous solution of tert-butyl hydroperoxide and 45 parts by mass of a 2% by mass aqueous solution of sodium tartrate were added dropwise over 4.5 hours, and 8 parts by mass of ethanol. Instead of using 4 parts by mass of isopropyl alcohol, the same operation as in Example 1 was carried out to obtain an emma as a liquid laundry paste composition. It was obtained John. This emulsion had a non-volatile content of 59.8% by mass, a viscosity of 1,510 mPa · s, a pH of 4.8, and a particle size of 3.0 μm.

[Example 13]
Instead of 4 parts by mass of polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku “Neugen SD-300 (trade name)”), polyoxyethylene alkyl ether (Daiichi Kogyo Seiyaku “Neugen ET-135 (trade name)” ) An emulsion as a liquid laundry paste composition was obtained in the same manner as in Example 1 except that 4 parts by mass was used and that the starch and monomer compositions were as shown in Table 1 below. This emulsion had a non-volatile content of 60.0% by mass, a viscosity of 1,550 mPa · s, a pH of 5.3, and a particle size of 2.0 μm.

[Example 14]
Instead of 4 parts by mass of polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku “Neugen SD-300 (trade name)”), polyoxyethylene alkyl ether (Daiichi Kogyo Seiyaku “Neugen ET-135 (trade name)” ) The same operation as in Example 1 except that 4 parts by mass, the starch and monomer composition were as shown in Table 1 below, and that 5 parts by mass of methanol was used instead of 8 parts by mass of ethanol. To obtain an emulsion as a liquid laundry paste composition. This emulsion had a nonvolatile content of 64.7% by mass, a viscosity of 1,800 mPa · s, a pH of 4.8, and a particle size of 2.0 μm.

[Example 15]
The starch and monomer composition were as shown in Table 1 below. Instead of adding 8 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, tert-butyl hydroperoxide 4 parts by weight of 5 parts by weight of a 1% by weight aqueous solution and 5 parts by weight of a 2% by weight aqueous sodium tartrate solution and 72 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride. Example 1 except that 45 parts by mass of a 1% by mass aqueous solution of tert-butyl hydroperoxide and 45 parts by mass of a 2% by mass aqueous solution of sodium tartrate were added dropwise over 4.5 hours instead of adding over 5 hours. The emulsion was obtained as a liquid laundry paste composition in the same manner as in Example 1. This emulsion had a non-volatile content of 55.4% by mass, a viscosity of 1,600 mPa · s, a pH of 4.5, and a particle size of 1.7 μm.

[Example 16]
Instead of 4 parts by mass of polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku “Neugen SD-300 (trade name)”), polyoxyethylene tridecyl ether (Daiichi Kogyo Seiyaku “Neugen TDS-70 (trade name)” )) 4 parts by weight, starch and monomer composition as shown in Table 1 below, and 72 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride. Instead of dripping over 4.5 hours, 45 parts by mass of a 1% by weight aqueous hydrogen peroxide solution and 45 parts by mass of a 2% by weight aqueous sodium tartrate solution were dripped over 4.5 hours, and instead of 8 parts by mass of ethanol. Except having used 10 mass parts of methanol, it carried out the same operation as Example 1 and obtained the emulsion as a liquid laundry paste composition. The emulsion had a non-volatile content of 64.9% by mass, a viscosity of 1,830 mPa · s, a pH of 4.2, and a particle size of 3.5 μm.

[Example 17]
Instead of 4 parts by mass of polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku “Neugen SD-300 (trade name)”), polyoxyethylene tridecyl ether (Daiichi Kogyo Seiyaku “Neugen TDS-70 (trade name)” )) 2 parts by weight and 2.5 parts by weight of nonionic reactive emulsifier (Adeka Soap ER-20 (trade name) manufactured by Asahi Denka Kogyo), starch and monomer composition are shown in Table 1 below. Except for using the composition shown and using 6 parts by mass of isopropyl alcohol instead of 8 parts by mass of ethanol, the same operation as in Example 1 was performed to obtain an emulsion as a liquid laundry paste composition. The content was 57.1% by mass, the viscosity was 840 mPa · s, the pH was 4.8, and the particle size was 2.8 μm.

[Example 18]
Instead of 4 parts by mass of polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku “Neugen SD-300 (trade name)”), polyoxyethylene tridecyl ether (Daiichi Kogyo Seiyaku “Neugen TDS-70 (trade name)” )) 2 parts by weight and 2.5 parts by weight of nonionic reactive emulsifier (Adeka Soap ER-20 (trade name) manufactured by Asahi Denka Kogyo), starch and monomer composition are shown in Table 1 below. The composition was as shown in the figure, instead of adding 8 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 5 parts by weight of a 1% by weight aqueous hydrogen peroxide solution and 2% by weight of sodium tartrate. 5 parts by weight of an aqueous solution was added and 72 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride was added dropwise over 4.5 hours. Instead of adding 45 parts by mass of a 1% by mass aqueous hydrogen peroxide solution and 45 parts by mass of a 2% by mass aqueous sodium tartrate solution over 4.5 hours, 14 parts by mass of ethanol was used instead of 8 parts by mass of ethanol. Except for this, an emulsion as a liquid laundry paste composition was obtained in the same manner as in Example 1. This emulsion had a nonvolatile content of 55.6% by mass, a viscosity of 1,540 mPa · s, and a pH of 4.6. The particle diameter was 1.5 μm.

[Example 19]
4. Polyoxyethylene isodecyl ether (Daiichi Kogyo Seiyaku "Neugen SD-300 (trade name)") Instead of 4 parts by mass, polyoxyethylene alkyl ether (Kao "Emulgen 1135S-70 (trade name)") The use of 7 parts by mass, the composition of starch and monomer as shown in Table 1 below, and the addition of 8 parts by mass of a 3% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride Instead, 5 parts by weight of a 1% by weight aqueous solution of tert-butyl hydroperoxide and 5 parts by weight of a 2% by weight aqueous solution of sodium tartrate were added, and 3 parts by weight of 2,2′-azobis (2-amidinopropane) dihydrochloride. 1% water by weight of tert-butyl hydroperoxide instead of dropwise addition of 72 parts by weight Except that added dropwise over a liquid 45 parts by mass of 2 wt% aqueous solution of 45 parts by weight of sodium tartrate 4.5 hours, it was by the same procedure as in Example 1 to obtain an emulsion of a liquid laundry starch composition. This emulsion had a non-volatile content of 54.4% by mass, a viscosity of 1,440 mPa · s, a pH of 4.6, and a particle size of 1.6 μm.

[Example 20]
The starch and monomer composition was as shown in Table 1 below; instead of adding 8 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 1% by weight hydrogen peroxide The addition of 5 parts by weight of an aqueous solution and 5 parts by weight of a 2% by weight aqueous solution of sodium tartrate and 72 parts by weight of a 3% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride over 4.5 hours Instead of dropping, 45 parts by mass of a 1% by mass aqueous hydrogen peroxide solution and 45 parts by mass of a 2% by mass aqueous sodium tartrate solution were added dropwise over 4.5 hours. An emulsion as a laundry paste composition was obtained. This emulsion had a nonvolatile content of 65.0% by mass, a viscosity of 1,480 mPa · s, a pH of 4.8, and a particle size of 2.7 μm.

[Comparative Example 1]
An emulsion as a comparative liquid laundry paste composition was obtained in the same manner as in Example 1 except that the starch and monomer compositions were as shown in Table 2 below. This emulsion had a nonvolatile content of 45.0% by mass, a viscosity of 800 mPa · s, a pH of 4.5, and a particle size of 5.0 μm.

[Comparative Example 2]
An emulsion as a comparative liquid laundry paste composition was obtained in the same manner as in Example 1 except that the starch and monomer compositions were as shown in Table 2 below. This emulsion had a nonvolatile content of 40.2% by mass, a viscosity of 8,800 mPa · s, a pH of 5.3, and a particle size of 1.5 μm.

[Comparative Example 3]
An emulsion as a comparative liquid laundry paste composition was obtained in the same manner as in Example 1 except that the starch and monomer compositions were as shown in Table 2 below. This emulsion had a nonvolatile content of 50.0% by mass, a viscosity of 600 mPa · s, a pH of 5.5, and a particle size of 1.8 μm.

[Comparative Example 4]
An emulsion as a comparative liquid laundry paste composition was obtained in the same manner as in Example 1 except that the starch and monomer compositions were as shown in Table 2 below. This emulsion had a nonvolatile content of 64.5% by mass, a viscosity of 2,100 mPa · s, a pH of 3.8, and a particle size of 2.2 μm.

[Comparative Example 5]
An emulsion as a comparative liquid laundry paste composition was obtained in the same manner as in Example 1 except that the starch and monomer compositions were as shown in Table 2 below. This emulsion had a nonvolatile content of 50.3% by mass, a viscosity of 400 mPa · s, a pH of 4.3, and a particle size of 4.0 μm.

[Comparative Example 6]
An emulsion as a comparative liquid laundry paste composition was obtained in the same manner as in Example 1 except that the starch and monomer compositions were as shown in Table 2 below. This emulsion had characteristics of 47.0% by mass, viscosity of 4,200 mPa · s, pH of 5.3, and particle size of 1.2 μm.

[Comparative Example 7]
A separable flask equipped with a cooling tube, a nitrogen introduction tube, a thermometer, a stirrer, and a dropping funnel was charged with 300 parts by weight of water, and 9.6 parts by weight of cationized starch CE was added while stirring this. The solution was heated to 80 ° C. and dissolved. After dissolution, the mixture was cooled to 70 ° C., and the contents were stirred, and a mixture of 48 parts by mass of 3-methacryloyloxy-2-hydroxypropyl-N, N, N-trimethylammonium chloride and 24 parts by mass of ethanol was added under a nitrogen atmosphere. Furthermore, 12 parts by mass of a 5% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride (“V-50 (trade name)” manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the reaction was performed for 1 hour. went. Thereafter, a mixture containing monomers prepared separately (336 parts by mass of vinyl acetate monomer, 38 parts by mass of ethyl acrylate monomer, 38 parts by mass of methyl methacrylate monomer, 3-methacryloyloxy-2 A mixture prepared by mixing 20 parts by mass of a hydroxypropyl-N, N, N-trimethylammonium chloride monomer and 3 parts by mass of ethanol was added dropwise from a dropping funnel over 5 hours. Simultaneously with the start of dropping of the mixture, 12 parts by mass of a 5% by weight aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride was dropped over 5 hours. Further, after the dropping of the mixture was completed, the temperature was raised to 80 ° C. and stirred at this temperature for 1 hour, and then cooled to 30 ° C. Finally, a small amount of water was added for the purpose of adjusting the concentration and viscosity, An emulsion as a liquid laundry paste composition was obtained. This emulsion had a nonvolatile content of 60.6% by mass, a viscosity of 20,000 mPa · s, a pH of 4.8, and a particle size of 20 μm.

The starch and monomer compositions used in the above examples and comparative examples are shown in Tables 1 and 2 below. The meanings of the symbols in Table 1 and Table 2 are as follows, and the numerical values below the symbols represent the starch and the parts by mass of each monomer converted to 100 parts by mass of the monomer mixture.
[symbol]
VAc: Vinyl acetate VeoVa10: Veova-10
EA: ethyl acrylate MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate AA: acrylic acid MAA: methacrylic acid CrA: crotonic acid MMa: maleic acid methyl ester DMAEA: N, N-dimethylaminoethyl acrylate DMAPAA: N, N -Dimethylaminopropylacrylamide DADMAC: Diallyldimethylammonium chloride HPTMAC: 3-Methacryloyloxy-2-hydroxypropyl-N, N, N-trimethylammonium chloride CA: Cationized starch CA
CB: Cationized starch CB
CC: Cationized starch CC
CD: Cationized starch CD
CE: Cationized starch CE
AA: Acetylated starch AA
AB: Acetylated starch AB
HA: Hydroxypropylated starch HA

  In addition, Table 3 and Table 4 below show the results of the evaluation of the pasting property and the pasting property. The numerical values in the following Table 2 and Table 3 are the bending resistance (unit: g). In Table 4 below, values when no laundry glue is used are also shown.

As is clear from the above results, the liquid laundry paste composition of the present invention gives excellent glue standing with an extremely small addition amount, gives excellent paste-off property during washing, has a high concentration, and It is useful as a new type of laundry paste that is easy to handle.

Claims (5)

  Cationized starch containing quaternized cationized starch in which at least one hydrocarbon group having 7 to 18 carbon atoms is bonded to quaternary cation nitrogen, nonionic water-soluble polymer and nonionic surfactant, and carboxylic acid vinyl ester system A monomer mixture containing a monomer, a carboxylic acid monomer having an ethylenically unsaturated bond, and a cationic monomer having an ethylenically unsaturated bond, which may contain other monomers And a composition obtained by mixing and emulsion polymerization so that the ratio of the mass of the cationized starch to the mass of the monomer mixture is in the range of 0.5 / 99.5 to 20/80, and is non-volatile. A liquid laundry paste composition having a content of 50% by mass or more.   The cationized starch containing a quaternized cationized starch in which at least one hydrocarbon group having 7 to 18 carbon atoms is bonded to a quaternary cation nitrogen has a degree of cationization of 0.005 to 0.5, and 2-hydroxy The liquid laundry paste composition according to claim 1, which is a cationized starch containing 0.01 to 5% by mass of a propoxyl group.   The carboxylic acid vinyl ester monomer is a vinyl acetate monomer, and the carboxylic acid monomer having an ethylenically unsaturated bond is acrylic acid, methacrylic acid, crotonic acid, maleic acid (and its alkyl ester). And a monomer of one or more compounds selected from the group consisting of fumaric acid (and alkyl esters thereof), wherein the cationic monomer having an ethylenically unsaturated bond is N, N-dimethylamino Ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, diallylamine, (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride, 3- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride, 3- (meth) acryloyloxy It is a monomer of one or more compounds selected from the group consisting of 2-hydroxypropyl-N, N, N-trimethylammonium chloride and diallyldimethylammonium chloride, and the other monomer is (meth) The liquid according to claim 1 or 2, which is a monomer of one or more compounds selected from the group consisting of methyl acrylate, ethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Laundry paste composition.   The monomer mixture has 75 to 98% by mass of the carboxylic acid vinyl ester monomer, 1 to 15% by mass of the carboxylic acid monomer having the ethylenically unsaturated bond, and the ethylenically unsaturated bond. The liquid laundry paste composition according to any one of claims 1 to 3, comprising 0.1 to 10% by mass of a cationic monomer and 0 to 20% by mass of the other monomer. The liquid laundry paste composition according to any one of claims 1 to 4, wherein the nonionic water-soluble polymer is a nonionic starch-based water-soluble polymer.