Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3788—Graft polymers

Definitions

• the present invention relates to a liquid detergent composition, particularly a liquid detergent composition for textiles such as clothing.
• Such a surfactant-rich liquid detergent composition has a problem that a builder component is difficult to be stably blended in addition to the storage stability of the composition itself.
• a builder component is difficult to be stably blended in addition to the storage stability of the composition itself.
• polyacrylic acid-based polymers are known to have excellent mud dispersibility and re-contamination prevention properties.
• the substrate may be separated as a solid in the solution.
• JP-A-2008-7705, JP-A-2008-7706, and JP-A-2008-7707 describe concentrated liquid detergent compositions containing a specific nonionic surfactant. There is a problem in solubility in water, and there is no suggestion regarding stable blending of polymers.
• JP-A-10-60476 and JP-A-10-60496 disclose a monoethylenic monomer having a polyether compound such as polyethylene glycol as a main chain and acrylic acid or methacrylic acid as a main monomer. Describes a liquid detergent containing a graft polymerized polymer.
• the prior art discloses a high-concentration surfactant system, but does not take into account poor solubility during dilution.
• a nonionic surfactant is salted out by adding a large amount of a water-soluble inorganic salt, and in order to disperse the nonionic surfactant and a water-insoluble solid, A polymer having segments is disclosed.
• a concentrated solid dispersion type liquid detergent containing a polymer obtained by polymerizing polyethylene glycol acrylate and acrylic acid as the polymer is disclosed.
• the prior art stably disperses dropletized nonionic surfactants and the accompanying water-insoluble solid substances in a liquid detergent forming a multi-phase in an aqueous phase prepared with a high salt concentration.
• Technology not a uniform system.
• Japanese Patent Application Laid-Open No. 2005-187742 discloses a surfactant composition containing a nonionic surfactant to which EO and PO are added and a polymer, in which a water-soluble inorganic salt is dispersed.
• US-B 4814102 and US-B 4897215 disclose a detergent containing a copolymer of a monomer having a carboxyl group and a monomer having a polyglycol system.
• WO-A 98/023712 discloses a surfactant composition comprising a nonionic surfactant to which EO and PO are added and a polymer. Summary of invention
• the surfactant (A) [hereinafter referred to as component (A)] is 40 to 80% by mass, and the following polymer compound (B) [hereinafter referred to as component (B)] is 0.3 to 8% by mass.
• component (a1) a nonionic surfactant represented by the following general formula (1) (hereinafter referred to as component (a1)) in the composition
• component (a1) a nonionic surfactant
• component (a1)) in the composition Is a liquid detergent composition containing 30 to 70% by mass in:
• (A1) Nonionic surfactant whose component is represented by the following general formula (1): R 1 O— (C 2 H 4 O) m / (A′O) n H (1)
• R 1 is a hydrocarbon group having 8 to 22 carbon atoms
• A′O is an oxyalkylene group having 3 to 5 carbon atoms.
• m and n are the average added mole numbers, m is a number from 16 to 30, and n is a number from 1 to 5.
• the present invention also relates to a plastic container having a container for storing a liquid detergent composition, wherein the container is made of a plastic having a flexural modulus (JIS K7171) of 2000 MPa or more and has a wall thickness of 0.3 to 1.
• the present invention relates to a liquid detergent article obtained by filling a plastic container having a thickness of 5 mm with the liquid detergent composition of the present invention.
• this invention provides the liquid detergent use of the said composition.
• the present invention relates to a liquid detergent composition containing a polymer compound (hereinafter sometimes referred to as a polymer-based builder) and a high-concentration surfactant, and maintains the storage stability of the composition and is composed of water. Eliminates a decrease in solubility due to gelation when diluting the product. Moreover, this invention eliminates the deformation
• a polymer compound hereinafter sometimes referred to as a polymer-based builder
• the polymerization unit means a structural unit in a polymer compound corresponding to one monomer.
• a liquid detergent composition containing a polymer-based builder and a high-concentration surfactant, maintaining the storage stability of the composition, forming a gel when diluting the composition with water, etc.
• a liquid detergent composition capable of achieving no decrease in solubility due to.
• a liquid detergent article in which a container is filled with such a liquid detergent composition has excellent storage stability and does not cause deformation of the container due to storage.
• the liquid detergent composition of the present invention contains a surfactant and contains the component (a1) as an essential component as a surfactant.
• the component (a1) will be described.
• —C 2 H 4 O) m / (A′O) n H may be described as — (AO) x H.
• R 1 is a hydrocarbon group having 8 to 22 carbon atoms, preferably a hydrocarbon group having 10 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms.
• R 1 is preferably a linear hydrocarbon group.
• the hydrocarbon group for R 1 is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
• R 1 is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
• the average addition mole number x of alkylene oxide having 2 to 5 carbon atoms is 17 to 35.
• x is 17 or more, it is possible to sufficiently suppress the formation of liquid crystals and the decrease in solubility when diluted with water.
• x is 35 or less, the stability of the composition will be good.
• x is preferably 17 to 30, and more preferably 18 to 25.
• the compound of General formula (1) has an average of 11 mol or more of oxyethylene groups as AO, Preferably it has an average of 13 mol or more, More preferably, it has an average of 15 mol or more. All of AO may be an oxyethylene group.
• x may be a reaction ratio of an alkylene oxide having 2 to 5 carbon atoms to an alcohol represented by R 1 OH during the production of component (a1).
• the proportion of the compounds having an AO addition mole number of 0 to 5 among the individual compounds constituting the component (a1) is 0% in all the compounds constituting the component (a1).
• the proportion of the compound having ⁇ 6 mol% and AO addition mol number of 50 or more (70 or less from the measurement conditions etc.) is 0 to 5 mol% of the total compound constituting the component (a1). preferable.
• a polyoxyalkylene alkyl ether type nonionic surfactant having an average addition mole number outside the range of x is used in combination, if the mixture with the component (a1) satisfies the condition of the general formula (1), (A1) It shall be a component. In that case, it is preferable that the mixture satisfies the distribution condition of the AO addition mole number.
• the compound of the general formula (1) can be obtained by random or block addition reaction of an ethylene oxide and an alkylene oxide having 3 to 5 carbon atoms with an alcohol having 8 to 22 carbon atoms.
• m in the general formula (1) is the average number of moles of ethylene oxide added, and the lower limit is 16 or more from the viewpoint of storage stability, solubility, and washing performance, and the upper limit is preferably 27 or less. Preferably it is 24 or less.
• n is the average number of moles of alkylene oxide having 3 to 5 carbon atoms, and from the viewpoint of cleaning performance, the lower limit is 1 or more, preferably 2 or more, and the upper limit is 5 or less, preferably 4 or less.
• the oxyalkylene group which is A′O in the general formula (1) is obtained by addition reaction of a C 3-5 alkylene oxide, and the portion bonded by the addition reaction is a structure branched by methyl or propyl.
• A'O is preferably an oxypropylene group obtained by addition reaction of propylene oxide (hereinafter sometimes referred to as PO).
• a compound in which the average addition mole number n of propylene oxide is 1 to 4, more preferably 2 to 4, and the average addition mole number m of ethylene oxide is 15 to 27, more preferably 16 to 24 mole addition is most preferable because a liquid detergent composition having excellent storage stability, solubility, and cleaning performance can be obtained.
• “/” means that the relationship between the oxyethylene group (hereinafter sometimes referred to as EO) which is the C 2 H 4 O group of the component (a1) of the present invention and the AO group is a random bond.
• EO oxyethylene group
• a compound in which the carbon atom of R 1 bonded to the oxygen atom of R 1 —O— in the general formula (1) is the first carbon atom has better detergency than the compound having the second carbon atom.
• R 1 is preferably a linear alkyl group, and preferably has a first carbon atom.
• the compound of the general formula (1-1-2), (1-1-4) or (1-1-5) is Of these, general formula (1-1-5) is more preferable.
• the compound in which the oxyalkylene group bonded to R 1 —O— is an oxyethylene group, that is, the proportion of R 1 —O—EO— is 75 mol% or more in the compound constituting the component (a1), Furthermore, it is most preferable that it is 80 mol% or more (an upper limit is 100 mol% or less).
• Such a compound can be obtained by first adding ethylene oxide to an aliphatic alcohol and then removing unreacted alcohol, or initially adding ethylene oxide in an amount of 6 mol or more, particularly 8 mol or more.
• the average added mole number represented by m in the general formula (1-1-2) or m1 in the general formula (1-1-4) or the general formula (1-1-5) is 6 mol or more, In particular, the compound is 8 mol or more.
• the compound having the structure of -EO-H at the end in the general formula (1) is preferably 70 mol% or more, more preferably 80 mol% or more (the upper limit is 100 mol% or less). . If it is above this value, the stability at low temperatures will be excellent.
• such a compound is composed of an alkylene oxide having 3 to 5 carbon atoms, preferably propylene oxide, which is a base of A′O, and finally only ethylene oxide. Can be obtained by adding 6 mol or more, particularly 8 mol or more.
• it is a compound having an average addition mole number represented by m2 in the general formula (1-1-3) or the general formula (1-1-5) of 6 mol or more, particularly 8 mol or more.
• R 1 is a linear alkyl group having a first carbon atom bonded to an oxygen atom, and the moles of R 1 —O—EO— and —EO—H are the same. % Is most preferred.
• the ratio of R 1 —O—EO— or —EO—H can be determined by quantitative measurement using C 13 -NMR.
• the amount of component (a1) is 30 to 70% by mass, preferably 40 to 60% by mass in the composition.
• the amount of component (a1) is preferably 40 to 60% by mass.
• the linear ratio (%) for the component (a1) is [number of moles of the component (a1) having a linear alkyl group] / [total number of moles of the component (a1)] ⁇ 100.
• the component (A) in addition to the component (a1), it is preferable to use an anionic surfactant (a2) [hereinafter referred to as the component (a2)] from the viewpoint of solubility at low temperatures. This is particularly preferable because the component (B) can be stably blended without affecting the adhesion preventing property, and further, the detergency against sebum dirt is improved.
• an anionic surfactant (a2) hereinafter referred to as the component (a2)
• the content of the component (a2) satisfies a later-described ratio from the relationship with the component (a1).
• the anionic surfactant for example, the following (a2) -1 to (a2) -5 can be used, but the component (B) can be stably blended, and (a2) ) -1, (a2) -2, and (a2) -4 are preferable, and (a2) -1 is more preferable.
• (a2) -1 is contained, it accounts for 80% by mass or more, particularly 90% by mass in the component (a2), so that the component (B) can be blended stably and excellent cleaning performance and solubility can be obtained. And most preferred.
• (a2) -4 is contained as a foam regulator, it is preferably 1 to 30% by mass, more preferably 1 to 20% by mass in the component (a2) from the viewpoint of low temperature stability.
• (A2) -1 an alkylbenzenesulfonate having an alkyl group having an average carbon number of 10 to 20
• (a2) -2 an alkyl group derived from a linear primary alcohol or a linear secondary alcohol having an average carbon number of 10 to 20, or Polyoxyethylene alkyl ether sulfate ester salt (a2) -3 having an alkyl group derived from a branched alcohol, wherein one or two of the oxyethylene groups may be an oxypropylene group, and having an average addition mole number of 1 to 5 : Alkyl group having an average carbon number of 10 to 20 or alkyl or alkenyl sulfate ester salt having an alkenyl group (a2) -4: Fatty acid salt having an average carbon number of 8 to 20 (a2) -5: Directly having an average carbon number of 10 to 20 One or two oxyethylene groups having an alkyl group derived from a chain primary alcohol or a linear secondary alcohol or an alkyl group derived from a branched
• the salt constituting the component (a2) examples include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium.
• alkanolamine salts from the viewpoint of stability.
• the anionic surfactant may be added in an acid form in the liquid detergent and neutralized with alkali in the system.
• the component (a2) is preferably an alkanolamine salt or an acid form and neutralized with an alkanolamine [alkanolamine used as an alkali agent for the component (E) described later] in the system.
• Metal-type counter ions such as alkaline earth metals and the like may be contained through the production process of component (a1) or as a salt of a metal ion sequestering agent or other anionic compound, but storage stability From this point, the metal ion concentration is preferably low, and is substantially preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 0.5% by mass or less in the composition.
• the total content of the components (a1) and (a2) in the composition (B) can be stably blended, and excellent sebum cleaning performance is obtained ( a1) + (a2) is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less.
• the mass of the anionic surfactant as the component (a2) varies depending on the molecular weight of the salt, in the present invention, not the salt but the mass when the acid type, that is, the counter ion is assumed to be a hydrogen atom ion (a2) ) The mass of the component.
• (a1) / (a2) is 25/75 to 25% in terms of mass ratio in that component (B) can be stably blended and excellent sebum cleaning performance and solubility can be obtained. 90/10 is preferable, 50/50 to 85/15 is more preferable, and 55/45 to 80/20 is particularly preferable.
• the ratio of the components (a1) / (a2) is preferably not less than the lower limit, and the component (B) can be stably blended, and from the viewpoint of obtaining excellent sebum cleaning performance and solubility. It is preferable that it is below the value.
• the liquid detergent composition of the present invention can contain a surfactant other than the components (a1) and (a2) as long as the effects of the present invention are not impaired.
• Other surfactants include the following (a3) to (a5).
• Nonionic surfactant not corresponding to component (a1) [hereinafter referred to as component (a3)] Examples thereof include the following (a3) -1 to (a3) -3.
• (A3) -1 An alkyl polysaccharide surfactant represented by the following general formula. R 31- (OR 32 ) x ' G y' [Wherein R 31 is a chain hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl group, R 32 is an alkylene group having 2 to 4 carbon atoms, G is a reducing sugar having 5 or 6 carbon atoms, preferably glucose.
• X ′ is a number having an average value of 0 to 6, and y ′ is a number having an average value of 1 to 10, preferably 2 to 4.
• (A3) -2 a fatty acid alkanolamide having an alkyl group having 7 to 21 carbon atoms, an ethylene oxide compound thereof, or a polyhydroxy fatty acid amide.
• (A3) -3 polyglyceryl having an alkyl group having 8 to 22 carbon atoms (average degree of polymerization 2 to 5) monoalkyl ether
• component (a4) Cationic surfactant [hereinafter referred to as component (a4)]
• component (a4) For example, primary to tertiary amines having a long-chain alkyl group (except for alkanolamines described later), preferably having 8 to 8 carbon atoms which may have an ether bond, ester bond or amide bond in the middle Mention may be made, for example, of cationic surfactants having one or two 22 alkyl groups, the remainder being alkyl groups which may have a hydrogen atom or a hydroxy group having 4 or less carbon atoms.
• a quaternary ammonium type surfactant having one long-chain alkyl group having 8 to 22 carbon atoms and a tertiary amine having one long-chain alkyl group having 8 to 22 carbon atoms are preferable.
• Amphoteric surfactant [hereinafter referred to as component (a5)]
• component (a5) sulfobetaine or carbobetaine having an alkyl group having 10 to 18 carbon atoms can be used.
• the content of the components (a3) to (a5) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and most preferably 2% by mass or more in the liquid detergent composition of the present invention. It is preferably at most 10 mass%, more preferably at most 10 mass%, most preferably at most 8 mass%.
• the component (a3) is combined with the component (a1), and the mass ratio of ((a1) + (a3)] / (a2) is the above (a1) / (a2 ) Is preferably within the range of the mass ratio.
• the mass excluding the counter anion is the mass of the quaternary ammonium salt
• hydrogen atoms other than organic groups are substituted among the groups bonded to the nitrogen atom.
• the mass of the resulting structure is defined as the mass of the tertiary amine.
• the content of the component (A) is 40 to 80% by mass in the composition, and the lower limit is preferably 50% by mass. % Or more, more preferably 60% by mass or more, and the upper limit is preferably 75% by mass or less.
• the component (B) includes (i) a polyether chain part (hereinafter referred to as (i) a chain part) composed of polymer units derived from epoxides having 2 to 5 carbon atoms, and (ii) acrylic acid, methacrylic acid, and A polymer chain part comprising a polymer unit derived from one or more unsaturated carboxylic acid monomers selected from maleic acid (hereinafter referred to as (ii) chain part), and (i ) A polymer compound having a graft structure in which one of the chain portion and (ii) the chain portion is a trunk chain and the other is a branch chain.
• a polyether chain part hereinafter referred to as (i) a chain part
• a chain part composed of polymer units derived from epoxides having 2 to 5 carbon atoms, and (ii) acrylic acid, methacrylic acid
• a polymer chain part comprising a polymer unit derived from one or more unsaturated carboxylic acid monomers
• the component (B) is a polyether chain composed of a polymer unit derived from an epoxide having 2 to 5 carbon atoms except for the terminal, or the branch chain is made of acrylic acid, methacrylic acid and maleic acid. It is a polymer compound which is a polymer chain composed of polymerized units derived from one or more unsaturated carboxylic acid monomers selected.
• the main chain is a polyether chain composed of a polymer unit derived from an epoxide having 2 to 5 carbon atoms, excluding the polymer unit and terminal at the bond with the branch, or Or it is a high molecular compound which is a polymer chain in which a trunk chain consists of a polymer unit derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid.
• the chain portion is a polymer unit derived from one or more epoxides having an epoxy group such as an epoxide having 2 to 5 carbon atoms, preferably ethylene oxide, propylene oxide, glycidyl ether (eg, methyl glycidyl ether, ethyl glycidyl ether). It is a polyether chain comprising.
• the average degree of polymerization of the chain part is preferably 10 to 10 (i) after including the polymer unit of the binding part with the branch chain when the chain part becomes a trunk chain.
• the chain end may be a hydroxyl group or may be capped with a methyl group, a phenyl group or a benzyl group.
• the chain portion is most preferably a polyoxyalkylene chain from the viewpoint of stability, and is further based on a polyoxyalkylene chain composed of ethylene oxide and / or propylene oxide, particularly polymerized units derived from ethylene oxide.
• the average number of added moles of alkylene oxide is preferably 10 to 100, more preferably 15 inclusive of (i) when the chain portion becomes a trunk chain, including the polymer unit of the binding portion with the branch chain. 80 to 80, particularly preferably 19 to 30, and (i) when the chain portion is branched, it is preferably 10 to 100, more preferably 15 to 80, and particularly preferably 19 to 30 per branch. If the average added mole number is 10 moles or more, the stability at room temperature or higher is good, and if it is 100 moles or less, the low temperature stability is good.
• the chain portion includes a polymer unit derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid.
• the polymerized units derived from maleic acid monomers include those synthesized via maleic anhydride.
• the chain portion may contain a polymer unit derived from a monoethylenically unsaturated monomer other than the unsaturated carboxylic acid monomer.
• the other polymerized units are preferably polymerized units derived from nonionic or anionic monomers. For example, polymerization units derived from unsaturated carboxylic acids other than those described above may be included.
• Examples of the unsaturated carboxylic acid that can be used in combination with acrylic acid, methacrylic acid, and maleic acid include fumaric acid and itaconic acid.
• the polymerization unit derived from unsaturated alcohol monomers, such as allyl alcohol can be mentioned.
• the chain portion is a trunk chain
• ethylenically unsaturated monomers such as unsaturated alcohol monomers and unsaturated carboxylic acid monomers, or-unsaturated alcohol monomers or unsaturated
• a monomer in which a polyalkylene glycol having a polymer unit of oxyalkylene having 2 to 5 carbon atoms is bonded to an ethylenically unsaturated monomer such as a carboxylic acid monomer; (I) may be used as a monomer to which a chain moiety is bonded to produce component (B).
• a monomer to which a chain portion is bonded may be referred to as a macromonomer.
• the proportion of polymer units derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid in the chain portion is (ii) when the chain portion is branched, Of the total polymerized units occupying the chain, preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably substantially composed of polymerized units derived from the unsaturated carboxylic acid monomer. That is.
• the proportion of polymer units derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid is the binding portion with the branch chain Is preferably from 80 to 100 mol%, more preferably from 90 to 100 mol%, and most preferably from substantially all of the polymerized units derived from the unsaturated carboxylic acid monomer. It is configured.
• the component (B) of the present invention is a polymer compound having a graft structure in which one of the chain part (i) and the chain part (ii) is a trunk chain and the other is a branch chain.
• a method of obtaining (1) a method in which a polymer chain portion to be a trunk chain and a branch chain are separately polymerized and grafted separately, and (2) a monomer to be a branch chain is grafted from the polymer chain portion to be a backbone chain. Examples thereof include a polymerization method, and (3) a method of copolymerizing a monomer serving as a main chain and a monomer having a branched polymer chain portion.
• a monoethylenically unsaturated monomer containing one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid is grafted to the polyether backbone.
• Polymerized polymer compounds can be used, and the polyether compound used for the synthesis using the production method exemplified above is preferably a compound represented by the following general formula (B1).
• Y is a hydrogen atom, a methyl group, a phenyl group or a benzyl group, preferably a methyl group or a phenyl group, and n is an average added mole number, which is a number of 10 to 100.
• the chain part is a trunk chain and (ii) the chain part is a branched chain, it is derived from (i) the epoxide having 2 to 5 carbon atoms in the chain part per unit mass of the polymer compound (B).
• the proportion of the polymerized units is preferably 40 to 99% by mass, more preferably 50 to 90% by mass, and particularly preferably 60 to 85% by mass.
• the proportion of polymer units derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid in the chain part (ii) per unit mass of the polymer compound is 1 to 60% by mass. More preferably, it is 10 to 50% by mass, and particularly preferably 15 to 40% by mass.
• the component (B) of the present invention comprises (i) one or more unsaturated carboxylic acids selected from acrylic acid, methacrylic acid, and maleic acid as a monomer (macromonomer) having a chain portion bonded in advance. It may be copolymerized with a monoethylenically unsaturated monomer containing a monomer, and also contains one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid A polymer obtained by adding a polymerizable monomer such as alkylene oxide such as ethylene oxide or glycidyl ether to a polymer of monoethylenically unsaturated monomer may be used.
• a polymerizable monomer such as alkylene oxide such as ethylene oxide or glycidyl ether
• component (B) obtained by the former method is preferred, and in particular, (ii) the chain portion is a polymerization derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid.
• the chain part is a main chain and (i) the chain part is a branched chain, it is derived from (i) the epoxide having 2 to 5 carbon atoms in the chain part per unit mass of the polymer compound (B).
• the proportion of the polymerized units is preferably 30 to 98% by mass, more preferably 40 to 89% by mass.
• the proportion of polymer units derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid in the chain part (ii) per unit mass of the polymer compound is 1 to 60% by mass. More preferably, it is 10 to 50% by mass, and particularly preferably 15 to 40% by mass.
• the polymer unit at the bond part with the branch chain and the polymer unit at the terminal part are polymer units derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid. It shall not be counted.
• the component (B) of the present invention is preferably a polymer compound having (ii) a chain portion as a trunk chain and (i) a chain portion as a branch chain in view of storage stability.
• the component (B) includes a polymer compound composed of two polymerization units represented by the following general formula (B2) (any of random, alternating, block polymerization) May be preferred).
• the polymer compound is a polymer compound having (ii) a chain portion as a trunk chain and (i) a chain portion represented by the general formula (B3) in the structure as a branch chain.
• a 1 represents a hydrogen atom
• a 2 represents a hydrogen atom or —COOX 1 , preferably a hydrogen atom
• a 3 represents a hydrogen atom or a methyl group
• a 4 represents —COOX 2
• the total number of carbon atoms in A 1 , A 2 and A 3 is 0 or 1
• X 1 and X 2 are each independently or simultaneously a hydrogen atom, a monovalent or divalent metal. Represents an ammonium group or an organic amine group.
• a 5 represents a hydrogen atom
• a 6 represents a hydrogen atom or —COOX 1 , preferably a hydrogen atom
• a 7 represents a hydrogen atom or a methyl group
• a 8 represents —COO—Z or —CH 2 —.
• OZ is represented, and the total number of carbon atoms in A 5 , A 6 and A 7 is 0 or 1, and Z represents a group of the following general formula (B3).
• A represents one or more alkylene groups having 2 to 3 carbon atoms, preferably represents an alkylene group having 2 carbon atoms
• Y represents a hydrogen atom, a methyl group, a phenyl group or a benzyl group, preferably Represents a hydrogen atom, a methyl group, more preferably a hydrogen atom
• n represents an average addition mole number, preferably a number of 10 to 100, more preferably a number of 15 to 80.
• the proportion of polymer units constituting the polymer compound of the general formula (B2) is such that the proportion of polymer units of [—C (A 5 ) (A 6 ) -C (A 7 ) (A 8 )-] It is preferably set in the range of 40 to 99% by mass per unit mass of the polymer compound, more preferably 50 to 90% by mass, and particularly preferably 60 to 85% by mass. A lower limit value or more is preferable from the viewpoint of stability, and an upper limit value or less is preferable from the viewpoint of cleanability.
• the most preferred component (B) is represented by formula (B2), wherein A 1 is a hydrogen atom, A 2 is a hydrogen atom, A 3 is a hydrogen atom or a methyl group, A 4 is —COOX 2 , A 5 is a hydrogen atom, A 6 is a hydrogen atom, A 7 is a hydrogen atom or a methyl group, A 8 is —COO—Z or —CH 2 —OZ, Z is a general formula (B3), and A is an alkylene group having 2 carbon atoms, Y is a polymer compound represented by a hydrogen atom or a methyl group.
• (meth) acrylic acid means acrylic acid and / or methacrylic acid.
• GPC gel permeation chromatography
• the content of the component (B) in the liquid detergent composition of the present invention is 0.3 to 8% by mass in terms of storage stability and mud dirt cleaning power, and the lower limit is preferably 1% by mass or more. 1.5% by mass or more is more preferable.
• the upper limit is preferably 5% by mass or less, and more preferably 4% by mass or less.
• the content in the composition is 2.5% by mass or less from the viewpoint of storage stability. It is particularly preferred.
• the liquid detergent composition of the present invention preferably contains a water-miscible organic solvent [hereinafter referred to as component (C)] in that component (B) can be stably blended and excellent solubility is obtained.
• component (C) a water-miscible organic solvent having a hydroxyl group and / or an ether group is preferable in that the component (B) can be stably blended and excellent cleaning performance and solubility can be obtained.
• the water-miscible organic solvent referred to in the present invention refers to an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C., that is, an organic solvent having a degree of dissolution of 50 g / L or more.
• water-miscible organic solvent examples include (c1) alkanols such as ethanol, 1-propanol, 2-propanol, and 1-butanol, and (c2) carbon number 2 such as ethylene glycol, propylene glycol, butylene glycol, or hexylene glycol.
• glycols may be referred to as glycols
• diethylene glycol triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, or weight average molecular weight 400 to Polyalkylene glycols composed of alkylene glycol units having 2 to 4 carbon atoms such as 4000 polyethylene glycol or polypropylene glycol
• diethylene glycol monomethyl ether Ethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, Or a (poly) alkylene glycol (mono or di) alkyl ether (hereinafter (hereinafter (c2) may be referred to as glycols), (c3) diethylene glycol
• the component (C) is effective as a viscosity modifier and a gelation inhibitor of the composition, and it is preferable to use one or more selected from the above categories (c1) to (c6). It is preferable to use a solvent selected from the above (c1) alkanols, (c2) glycols, (c4) alkyl ethers, and (c6) aromatic ethers, and more specifically, ethanol, propylene glycol, diethylene glycol. By using one or more solvents selected from monobutyl ether, 2-phenoxyethanol, diethylene glycol monophenyl ether and triethylene glycol monophenyl ether, particularly two or more solvents in combination, it is possible to effectively adjust the viscosity of the composition and suppress gelation. It is more preferable because it can be achieved. In the present invention, particularly preferred examples include propylene glycol and / or diethylene glycol monobutyl ether.
• the component (C) is effective as a viscosity modifier and a gelation inhibitor of the composition, and it is preferable to use two or more selected from the above classifications (c1) to (c6), more preferably Two or more types selected from the classifications (c2), (c4) and (c6), and particularly preferably two or more types selected from the classifications (c2) and (c6) are used together to effectively improve the composition. Viscosity adjustment and gelation suppression can be achieved.
• the content of the component (C) is preferably 5 to 40% by mass, more preferably 10 to 35% by mass in the composition from the viewpoint that the component (B) can be stably blended and excellent solubility is obtained.
• it is preferably 15 to 30% by mass.
• the liquid detergent composition of the present invention contains water in that the component (B) can be stably blended and excellent solubility is obtained.
• the content of water in the composition is preferably 5% by mass or more, preferably 8 to 40% by mass, particularly preferably 10 to 30% by mass. It is preferable to use water that does not affect the composition, such as ion exchange water.
• the total of the components (A) to (C) and water is preferably 85% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
• the liquid detergent composition of the present invention preferably contains an alkali agent [hereinafter referred to as component (D)].
• the alkali agent include alkanolamines having 1 to 3 alkanol groups having 2 to 4 carbon atoms of alkanol, which are common in liquid detergents, in addition to alkali metal hydroxides, alkali metal carbonates, and the like.
• the alkanol is preferably a hydroxyethyl group.
• Other than the alkanol group is a hydrogen atom, but even a methyl group can be used as an alkali agent.
• Alkanolamines include 2-aminoethanol, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanol Alkanolamines such as amine and isopropanolamine mixtures (mono, di and tri mixtures) can be mentioned. In the present invention, monoethanolamine, triethanolamine, and particularly monoethanolamine are most preferred. (D) A component can be used as a pH adjuster mentioned later.
• the liquid detergent composition of the present invention contains the component (D) preferably 0.5 to 8% by mass, more preferably 1 to 7% by mass.
• alkanolamine can also be mix
• the liquid detergent composition of the present invention can contain a chelating agent [hereinafter referred to as component (E)].
• component (E) The chelating agent of a component can use the well-known thing used for a liquid detergent, for example, Aminopolyacetic acid or salts thereof such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid, Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid and the like, or salts thereof, Examples include amino
• the blending ratio of the component (E) in the composition is preferably 0.1 to 5% by mass, more preferably 0.1 to 4% by mass, and still more preferably 0.1 to 3% by mass when regarded as the acid type. %.
• the concentration as an index in the case where the above-mentioned optional components are blended is shown below, but the concentration is appropriately adjusted so as not to impair this effect, and is excluded when it is not suitable for blending.
• blend (I) as an anti-staining agent other than (B) component, and a dispersing agent in the grade which does not impair this effect.
• the concentration of the surfactant is increased, it is preferable that the component (a1) is not substantially contained particularly when a compound having an average addition mole number m of ethylene oxide of 16 or more is used.
• the content of the color transfer inhibitor (II) is preferably 0.01 to 10% by mass.
• the content of the bleaching agent (III) is preferably 0.01 to 10% by mass.
• the content of the bleach activator (VI) is preferably 0.01 to 10% by mass.
• the content of the enzyme (V) is preferably 0.001 to 2% by mass.
• the content of the enzyme stabilizer (VI) is preferably 0.001 to 2% by mass.
• the content of the fluorescent dye (VII) is preferably 0.001 to 1% by mass.
• the content of the antioxidant (VIII) is preferably 0.01 to 2% by mass.
• the solubilizer of (IX) is preferably 0.1 to 2% by mass.
• the water immiscible organic solvent (X) is preferably 0.001 to 2% by mass.
• the other component of (XI) can be mix
• the pH of the liquid detergent composition of the present invention is measured at 20 ° C. described in JIS K3362: 1998.
• the component (B) is preferably 6 to 11, and particularly preferably 8 to 10 (25 ° C.) in that the component (B) can be blended stably and excellent cleaning performance is obtained.
• the viscosity of the liquid detergent composition of the present invention at 20 ° C. is preferably 10 to 500 mPa ⁇ s, more preferably 50 to 400 mPa ⁇ s, and even more preferably 100 to 300 mPa ⁇ s from the viewpoint of ease of handling. It is preferable to adjust so that it may become such a range with (C) component and a solubilizer.
• the viscosity is measured with a B-type viscometer. Select a rotor that matches the viscosity.
• the liquid is rotated at a rotational speed of 60 r / min, and the viscosity 60 seconds after the start of the rotation is defined as the viscosity of the liquid detergent composition.
• the liquid detergent composition of the present invention is preferably a liquid composed of one isotropic phase from the viewpoint of use. Isotropicity can be confirmed, for example, by visual observation using crossed Nicols or by confirming that no structure exists by X-ray diffraction. The fact that it is one phase can be confirmed by, for example, being visually transparent, that phase separation is not observed when observed with a microscope, etc., and that it is not separated into two or more phases even after centrifugation.
• the liquid detergent composition of the present invention can be filled into a container, for example, a plastic container including a measuring cap and a bottle to obtain a liquid detergent article in a container.
• a container for example, a plastic container including a measuring cap and a bottle to obtain a liquid detergent article in a container.
• plastics such as polypropylene (PP), polyethylene terephthalate (PET), high density polyethylene (HDPE), medium density polyethylene (MDPE), and vinyl chloride (PVC) can be used.
• the container for filling the liquid detergent composition of the present invention is a plastic container having a container for containing a liquid detergent composition, from the viewpoint of suppressing deformation under reduced pressure due to a decrease in internal pressure of a plastic material molding container,
• the container is preferably a plastic container having a flexural modulus (JIS K7171) of 2000 MPa or more, preferably 5000 MPa or less, more preferably 3000 MPa or less, and a wall thickness of 0.3 to 1.5 mm.
• a bottle that satisfies such a flexural modulus and thickness is used.
• the liquid detergent composition of the present invention contains a nonionic surfactant at a high concentration, it is presumed that oxygen present in the space in the bottle dissolves.
• the light transmittance of the container of the liquid detergent composition is preferably 15% or less for light in the wavelength range of 600 nm to 700 nm.
• the bottle has such light transmittance.
• titanium oxide or carbon black can be added to the plastic constituting the container.
• the liquid detergent composition of the present invention is preferably enclosed in a bag formed by laminating a flexible laminated resin film from the viewpoint of storage stability. .
• a nozzle part with a dispensing channel is provided in a part of the upper edge of the bag body, laser processing, score processing, etc. are performed, and the nozzle upper part edge is opened by hand to form the nozzle part discharge port What can be made is preferable from the viewpoint of ease of use, and as a bag shape, a standing pouch type bag is easy to handle and is a preferable type.
• a flexible single layer resin film can be used, but a laminated resin film is generally used.
• stretched nylon film ONy
• PET polyethylene terephthalate
• OPP stretched polypropylene
• LLDPE linear low density polyethylene
• HDPE high density polyethylene
• LDPE low density polyethylene
• VM-PET aluminum vapor deposited polyethylene terephthalate
• ceramic vapor deposited polyethylene terephthalate aluminum foil, and the like as the barrier layer.
• the laminated resin film is composed of three or more layers, and is configured such that printing ink (ink layer) is not interposed between the intermediate layer and the innermost layer. Is preferred. Considering production aptitude, drop strength, openability and packaging material cost, the delamination is highly effective in suppressing delamination, and PET (preferably with a thickness greater than the outer layer (the layer farthest from the layer in contact with the liquid detergent composition)).
• a laminated film of 9 to 25 ⁇ m) / [ink layer + adhesive layer] / ONy (preferably having a thickness of 15 to 25 ⁇ m) / adhesive layer / LLDPE (preferably having a thickness of 60 to 200 ⁇ m) is most preferred.
• liquid detergent composition of the present invention is suitable for textile products such as clothing, bedding, and fabrics. Examples The following examples describe the practice of the present invention. The examples are illustrative of the invention and are not intended to limit the invention.
• the synthetic polymer (1) has (i) a chain part as a branch chain and (ii) a chain part as a trunk chain, and (i) a proportion of polymer units of epoxide having 2 to 5 carbon atoms in the chain part.
• the proportion of the monomer derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid in the chain portion is 63% by mass per unit mass of the polymer compound, The amount of the compound was 26% by mass per unit mass of the molecular compound.
• the synthetic polymer (2) has (i) a chain part as a branch chain and (ii) a chain part as a trunk chain, and (i) the proportion of the polymer part of the epoxide having 2 to 5 carbon atoms in the chain part is The proportion of the monomer derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid and maleic acid in the chain portion is 59% by mass per unit mass of the polymer compound. The amount of the compound was 35% by mass per unit mass of the compound.
• the synthetic polymer (3) has (i) a chain part as a branched chain and (ii) a chain part as a main chain, and (i) the proportion of the polymer part of the epoxide having 2 to 5 carbon atoms in the chain part is
• the proportion of the monomer derived from one or more unsaturated carboxylic acid monomers selected from acrylic acid, methacrylic acid, and maleic acid in the chain portion is 71% by mass per unit mass of the polymer compound.
• the amount of the compound was 25% by mass per unit mass of the compound.
• Reference Examples 1, 17, 18, Examples 2 to 16, 19 to 22, and Comparative Examples 1 to 6 The components shown in Tables 1 to 4 were mixed to obtain compositions of reference examples, examples and comparative examples. The following evaluations were performed using the obtained compositions. The results are shown in Tables 1 to 4.
• the composition of the Example was a liquid composition comprised from one phase which is isotropic.
• Mud reattachment prevention performance test method A white cotton cloth (gold width 2003 cloth) was cut into 10 cm ⁇ 10 cm to form a set of five sheets. To 1 liter of the detergent aqueous solution for evaluation, kanuma red clay for gardening was added, and the test was conducted with a tergotometer under the following conditions. ⁇ Experimental conditions> Washing time 10 minutes Detergent concentration 0.033% by mass Water hardness 4 ° DH Water temperature 20 °C Rinse running water for 20 minutes with tap water at 20 ° C.
• Recontamination prevention rate (%) (reflectance after test / reflectance of base fabric) ⁇ 100
• Component (a1) (Reference a1-1): An average of 20 moles of ethylene oxide added to a primary linear alcohol having 10 to 14 carbon atoms (a1-2): To a primary linear alcohol having 10 to 14 carbon atoms A block addition of an average of 18 mol of ethylene oxide and an average of 2 mol of propylene oxide. Among them, the compound containing the structure of R 1 —O—EO— was 90 mol% or more.
• A1-3 A linear straight chain alcohol having 10 to 14 carbon atoms, in which ethylene oxide is averagely 9 mol, propylene oxide is average 2 mol, and ethylene oxide is average 9 mol in block order.
• the compound containing the structure R 1 —O—EO— was 85 mol% or more, and the compound containing the structure —EO—H was 90 mol% or more.
• the compound containing the structure R 1 —O—EO— was 85 mol% or more, and the compound containing the structure —EO—H was 90 mol% or more.
• the compound containing the structure of R 1 —O—EO— was 80 mol% or more, and the compound containing the structure of —EO—H was 85 mol% or more.
• the compound containing the structure of R 1 —O—EO— was 90 mol% or more, and the compound containing the structure of —EO—H was 95 mol% or more.
• the compound containing the structure of R 1 —O—EO— was 90 mol% or more.
• (A3) Component (a3-1) A product obtained by adding an average of 3 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms [Softanol 30 (trade name), manufactured by Nippon Shokubai Co., Ltd.]
• (A3-2) An average of 12 moles of ethylene oxide added to a primary linear alcohol having 10 to 14 carbon atoms
• (a3-3) An average of 40 moles of ethylene oxide to a primary linear alcohol having 10 to 14 carbon atoms
• the compound containing the structure of R 1 —O—EO— was 90 mol% or more.
• Polymer (1) Polyacrylic acid (weight average molecular weight 10,000)
• Fluorescent dye Chino Pearl CBS-X (trade name) (manufactured by Ciba Specialty Chemicals)
• Enzyme Everase 16.0L-EX (trade name) (protease, manufactured by Novozyme)
• a case where a product for refilling was used that is, a case where a liquid detergent composition was filled in a bag-like container was also performed.
• a laminated film of PET 12 ⁇ m / [ink layer + adhesive layer] / ONy 15 ⁇ m / adhesive layer / LLDPE 150 ⁇ m is used from the outer layer (the layer farthest from the layer in contact with the liquid detergent composition).
• a self-supporting bag having a size of 120 mm ⁇ height 215 mm and a bottom folding width 34.5 mm was formed.
• the bag was filled with 320 g of the liquid detergent composition of Examples 1 to 21, which gave favorable results in the evaluation, and the upper part was sealed by heat sealing.
• the liquid detergent contained in the container packed in these plastic containers was stored at 20 ° C. for 20 days, no abnormality such as separation was observed in the internal composition, and the stability was good. Further, as an accelerated test for confirming delamination, the film was stored at 65 ° C. for 14 days, but no film delamination occurred.
• the storage stability was also evaluated in the case of using a container including a bottle, a main body cap attached to the mouth of the bottle, and a measuring cap that is detachably attached to the main body cap.
• a cylindrical bottle having a diameter of 61 mm, a barrel outer diameter of 59 mm, a height of 190 mm, and a bottle barrel average thickness of 0.5 mm was filled with 400 g of the liquid detergent composition of Examples 1 to 21, and a measuring cap (measuring capacity) (26 mL) was fitted into the bottle and sealed.
• the liquid detergent contained in the plastic container filled in the plastic container was stored at 20 ° C. for 20 days.
• the internal composition did not show any abnormalities such as separation or reduced pressure deformation on the side of the bottle, and the stability was good.
• neither decompression deformation on the side of the bottle was observed when stored for 14 days at 40 ° C. or when exposed to sunlight for about 1 month.

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