Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F216/04—Acyclic compounds
  • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/12—Hydrolysis
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate

Definitions

• the present invention relates to a composition (excluding a household cleaning product composition) containing a vinyl alcohol polymer, and a method for producing the composition.
• the present invention also relates to a vinyl alcohol polymer contained in the composition and a resin material containing the vinyl alcohol polymer.
• vinyl alcohol polymers have been used in a wide range of applications such as adhesives, processing agents for paper products and textile products, paints, and various binders.
• an appropriate surfactant may be added to dissolve the hydrophobic vinyl alcohol polymer in water. It is known to be used (Patent Document 1).
• An object of the present invention is to provide a composition (aqueous solution) containing a hydrophobic vinyl alcohol polymer that has high viscosity and excellent transparency, and a method for producing the composition.
• Another object of the present invention is to provide a vinyl alcohol polymer capable of providing the above composition (aqueous solution) and a resin material containing the vinyl alcohol polymer.
• the present inventors conducted extensive studies to solve the above problems, and as a result, they arrived at the present invention. That is, the present invention includes the following aspects.
• (A) Vinyl alcohol polymer containing a monomer unit having an alkyl group; (B) at least one surfactant; and (C) containing water;
• the vinyl alcohol polymer (A) has the following formula (1): 0.010 ⁇ X/(S ⁇ N) ⁇ 0.040 (1)
• S represents the content (parts by mass) of the monomer unit having an alkyl group based on 100 parts by mass of the total monomer units in the vinyl alcohol polymer (A), and represents the degree of saponification (mol%) of the polymer (A), and N represents the viscosity average degree of polymerization of the vinyl alcohol polymer (A)]
• Compositions (excluding household cleaning product compositions) that meet the following criteria: [2] The composition according to [1] above, wherein the vinyl alcohol polymer (A) contains a monomer unit having an alkyl group having
• the monomer unit having an alkyl group includes a monomer unit derived from an ⁇ -olefin, and the monomer unit having an alkyl group derived from an ⁇ -olefin relative to the total amount of monomer units having an alkyl group.
• [5] The content S of monomer units having an alkyl group based on 100 parts by mass of all monomer units in the vinyl alcohol polymer (A) is 1.2 to 9.0 parts by mass, [1] ] to [4].
• [6] The composition according to any one of [1] to [5] above, wherein the vinyl alcohol polymer (A) has a saponification degree X of 40 to 80 mol%.
• [7] The composition according to any one of [1] to [6] above, wherein the vinyl alcohol polymer (A) has a viscosity average degree of polymerization N of 400 to 2,000.
• Surfactant (B) is alkyl sulfate, alkyl sulfonate, alkylbenzene sulfonate, polyoxyalkylene alkyl ether sulfate (alkyl ether sulfate), polyoxyalkylene alkyl ether carboxylate (alkyl ether acetic acid)
• composition according to any one of [1] to [9] above comprising at least one selected from the following.
• [11] The composition according to any one of [1] to [10] above, wherein the content of the vinyl alcohol polymer (A) is 0.1 to 5.0% by mass based on the total mass of the composition. thing.
• [12] The composition according to any one of [1] to [11] above, wherein the content of the surfactant (B) is 1 to 50% by mass based on the total mass of the composition.
• Relative viscosity of the composition Viscosity of the composition at 20 °C / Viscosity at 20 °C of the viscosity standard composition consisting of the composition to be measured excluding the vinyl alcohol polymer (A) [14] At 20 °C The composition according to any one of [1] to [13] above, which has a viscosity of 1,300 to 3,000 mPa ⁇ s.
• the vinyl alcohol polymer (A) has the following formula (1): 0.010 ⁇ X/(S ⁇ N) ⁇ 0.040 (1)
• S represents the content (parts by mass) of the monomer unit having an alkyl group based on 100 parts by mass of the total monomer units in the vinyl alcohol polymer (A), and represents the degree of saponification (mol%) of the polymer (A)
• N represents the viscosity average degree of polymerization of the vinyl alcohol polymer (A)]
• the monomer unit having an alkyl group includes a monomer unit derived
• a vinyl alcohol polymer (A) containing a monomer unit having an alkyl group which has the following formula (1): 0.010 ⁇ X/(S ⁇ N) ⁇ 0.040 (1)
• S is the content (parts by mass) of monomer units having an alkyl group based on 100 parts by mass of all monomer units in the vinyl alcohol polymer (A)
• It is the degree of saponification (mol%) of the polymer (A)
• N is the viscosity average degree of polymerization of the vinyl alcohol polymer (A).
• the monomer unit having an alkyl group includes a monomer unit derived from an ⁇ -olefin, and the monomer unit having an alkyl group derived from an ⁇ -olefin relative to the total amount of monomer units having an alkyl group
• the ⁇ -olefin is an ⁇ -olefin having 6 to 18 carbon atoms.
• the ⁇ -olefin is at least one selected from the group consisting of 1-dodecene and 1-hexadecene.
• the present invention it is possible to provide a composition (aqueous solution) containing a hydrophobic vinyl alcohol polymer that has high viscosity and excellent transparency, and a method for producing the composition. Further, the present invention can provide a vinyl alcohol polymer capable of providing the above-mentioned composition (aqueous solution) and a resin material containing the vinyl alcohol polymer.
• the composition of the present invention includes (A) a vinyl alcohol polymer containing a monomer unit having an alkyl group, and the vinyl alcohol polymer (A) satisfies the following formula (1) (hereinafter referred to as "vinyl alcohol”). (also referred to as “alcohol-based polymer (A)").
• S is the content (parts by mass) of monomer units having an alkyl group based on 100 parts by mass of all monomer units in the vinyl alcohol polymer (A), and It is the saponification degree (mol %) of the coalescence (A), and N is the viscosity average degree of polymerization of the vinyl alcohol polymer (A).
• the above formula (1) can serve as a new index representing the balance between the solubility in water and the thickening effect of the vinyl alcohol polymer (A).
• the content (S) of monomer units having an alkyl group increases among all the monomer units constituting the vinyl alcohol polymer (A), and/or the vinyl alcohol polymer
• N the viscosity average degree of polymerization
• the solubility of the vinyl alcohol polymer decreases, and the viscosity of the composition containing it tends to increase.
• the degree of saponification (X) of the vinyl alcohol polymer (A) increases, the solubility of the vinyl alcohol polymer in the composition increases.
• thickening effect refers to the viscosity of a composition containing a target vinyl alcohol polymer that differs only in that the vinyl alcohol polymer is removed from the composition. It means the effect of increasing the viscosity compared to the viscosity.
• the lower limit of formula (1) is 0.010 or more.
• the value of formula (1) is 0.010 or more, a composition with excellent transparency can be obtained while ensuring high viscosity.
• the solubility of the vinyl alcohol polymer (A) in an aqueous solution usually increases (that is, a highly transparent composition can be obtained).
• the solubility may improve, but the viscosity tends to decrease.
• the upper limit of formula (1) is 0.040 or less.
• the value of formula (1) is 0.010 or more and 0.040 or less. When the value of formula (1) is within the above range, a composition with high viscosity and excellent transparency can be prepared.
• the value of formula (1) is preferably 0.010 to 0.038, more preferably 0.010 to 0.035, even more preferably 0.010 to 0.030, particularly preferably is from 0.010 to 0.025, particularly preferably from 0.010 to 0.024, and may also preferably be from 0.012 to 0.040, for example from 0.013 to 0.040.
• a composition with higher viscosity and better transparency can be obtained, and a decrease in the transparency of the composition over time can be suppressed.
• Cheap a composition with higher viscosity and better transparency can be obtained, and a decrease in the transparency of the composition over time can be suppressed.
• the saponification degree (X) (mol%) and viscosity average degree of polymerization (N) of the vinyl alcohol polymer (A) are determined according to JIS K 6726 "Polyvinyl alcohol test method", respectively. can be measured based on More specifically, it can be measured according to the method described in Examples below.
• the value of formula (1) is the content (parts by mass) of monomer units having an alkyl group in all monomer units constituting the vinyl alcohol polymer (A), It can be controlled by adjusting the degree of saponification of the vinyl alcohol polymer (A) and/or the viscosity average degree of polymerization of the vinyl alcohol polymer (A).
• the vinyl alcohol polymer (A) satisfying the above formula (1) can be obtained by copolymerizing, for example, a vinyl ester monomer and a monomer having an alkyl group (hereinafter also referred to as "alkyl group-containing monomer"). It can be prepared by saponifying the obtained vinyl ester copolymer.
• vinyl ester monomers used to form the vinyl alcohol polymer (A) include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, and vinyl stearate. , vinyl benzoate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, etc. It will be done. Among them, vinyl acetate is preferred from the viewpoint of being easily available and economical. As the vinyl ester monomer, only one type may be used, or two or more types may be used in combination.
• the content of structural units derived from vinyl ester monomers in the vinyl alcohol polymer (A) is preferably 82 to 82 parts by mass based on 100 parts by mass of all monomer units constituting the vinyl alcohol polymer (A). 97 parts by weight, more preferably 86 to 97 parts by weight.
• a structural unit derived from a vinyl ester monomer is a structural unit derived from a raw material vinyl ester monomer in the vinyl alcohol polymer (A)
• a "structural unit derived from a vinyl ester monomer""Units” include vinyl ester units and vinyl alcohol units obtained by converting vinyl ester units by saponification.
• the content of the structural units derived from the vinyl ester monomer in the vinyl alcohol polymer (A) is determined by 1 H NMR as follows: It can be determined by calculating the ratio (mol %) and converting it into parts by mass from the molecular weight of each structural unit.
• alkyl group-containing monomer any monomer that can be copolymerized with the vinyl ester monomer and contains an alkyl group in its structure can be used.
• ⁇ -olefins such as propylene, 1-butene, isobutene, pentene, 1-hexene, 1-octene, 1-dodecene, 1-hexadecene, 1-octadecene, methacrylic acid; methyl (meth)acrylate, ) Ethyl acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylate (meth)acrylic acid esters such as stearyl acid and octadecyl (meth)acrylate; acrylamide derivatives such as N-olef
• the "monomer unit having an alkyl group refers to a structural unit derived from an alkyl group-containing monomer in the vinyl alcohol polymer (A).
• the vinyl alcohol polymer (A) preferably contains an alkyl group-containing monomer unit having 4 to 16 carbon atoms.
• the number of carbon atoms in the alkyl group in the alkyl group-containing monomer unit is preferably 4 to 16, more preferably 6 to 16, even more preferably 8 to 16, particularly preferably 10 to 16, and preferably 4 to 16. ⁇ 14.
• the number of carbon atoms in the alkyl group in the alkyl group-containing monomer unit means the number of carbon atoms in the side chain of the vinyl alcohol polymer (A) in the unit.
• A vinyl alcohol polymer
• monomer units derived from 1-dodecene are The alkyl group has 10 carbon atoms.
• the alkyl group-containing monomer unit in the vinyl alcohol polymer (A) is preferably a monomer unit derived from an ⁇ -olefin.
• the content of the monomer units derived from ⁇ -olefin is preferably 60 to 60 to all the alkyl group-containing monomer units constituting the vinyl alcohol polymer (A).
• the amount is 100% by weight, more preferably 70 to 100% by weight, even more preferably 80 to 100% by weight, particularly preferably 90 to 100% by weight.
• the monomer unit derived from an ⁇ -olefin is included in the amount within the above range as the alkyl group-containing monomer unit, the thickening effect and solubility can be further improved.
• Examples of the ⁇ -olefin into which a monomer unit derived from an ⁇ -olefin can be introduced into the vinyl alcohol polymer (A) include the ⁇ -olefins exemplified above as alkyl group-containing monomers. Among them, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, It is preferably a monomer unit derived from an ⁇ -olefin having 6 to 18 carbon atoms, more preferably 8 to 18 carbon atoms, and still more preferably It is a monomer unit derived from 8 to 16 ⁇ -olefins.
• the content of alkyl group-containing monomer units in the vinyl alcohol polymer (A) is preferably from 1.2 to 100 parts by mass of all monomer units constituting the vinyl alcohol polymer (A). It is 9.0 parts by mass.
• the content of the alkyl group-containing monomer unit is at least the above-mentioned lower limit, the degree of polymerization tends to improve and high viscosity can be easily ensured. Moreover, when it is below the upper limit, it is easy to ensure solubility in water containing a surfactant.
• the content of the alkyl group-containing monomer unit can be appropriately determined depending on the desired viscosity and solubility, but in one embodiment of the present invention, it is preferably 1 part by mass based on 100 parts by mass of all monomer units. .5 to 9.0 parts by weight, more preferably 2.0 to 9.0 parts by weight, even more preferably 2.5 to 9.0 parts by weight, particularly preferably 2.8 to 9.0 parts by weight, Also, preferably 1.2 to 8.5 parts by mass, more preferably 1.2 to 8.0 parts by mass, even more preferably 1.2 to 7.5 parts by mass, particularly preferably 1.2 to 7.0 parts by mass. Part by mass.
• the content of the alkyl group-containing monomer units in the vinyl alcohol polymer (A) is determined by 1H NMR as the ratio (mol%) of the alkyl group-containing monomer units to the total constitutional units of the polyvinyl alcohol polymer (A). ) and convert it into parts by mass from the molecular weight of each structural unit.
• the content of the alkyl group-containing monomer unit in the vinyl alcohol polymer (A) is "parts by mass” based on 100 parts by mass of all monomer units constituting the vinyl alcohol polymer (A). ” controlled by.
• the proportion of monomers constituting a polymer is often controlled by "mol%".
• the length of the alkyl group of the monomer can also have a large effect on the solubility and thickening effect. Therefore, in the present invention, by controlling the amount of alkyl group-containing monomer units in "parts by mass” which easily reflects the length of the alkyl group, the value of formula (1) can be adjusted to improve solubility and thickening effect. It is used as an indicator.
• the vinyl alcohol polymer (A) has an alkyl group-containing monomer unit and usually exhibits hydrophobicity.
• the degree of saponification (X) of the vinyl alcohol polymer (A) is preferably 40 to 80 mol%.
• the degree of saponification (X) is within the above range, the solubility of the vinyl alcohol polymer (A) in water containing a surfactant is likely to improve, and a highly transparent composition is likely to be obtained.
• the degree of saponification (X) is preferably 40 to 75 mol%, more preferably 40 to 70 mol%, even more preferably 40 to 65 mol%, particularly preferably 40 to 60 mol% ( or less than 60 mol%), particularly preferably 40 to 50 mol% (or less than 50 mol%).
• the degree of saponification (X) is within the above lower and upper limits, not only the solubility and transparency are better, but also the effect of suppressing the deterioration of the transparency of the composition over time is excellent. Furthermore, when the vinyl alcohol polymer (A) has a relatively low saponification degree within the above range, a higher thickening effect is likely to be obtained.
• the viscosity average degree of polymerization (N) of the vinyl alcohol polymer (A) is preferably 400 to 2,000.
• the viscosity average degree of polymerization (N) is at least the above lower limit, a higher thickening effect can be expected, and when it is at most the upper limit, excessive thickening can be avoided and the necessary solubility can be easily ensured.
• the viscosity average degree of polymerization (N) is more preferably 450 to 2000, still more preferably 450 to 1800, particularly preferably 450 to 1700.
• the vinyl alcohol polymer (A) contains, in addition to structural units derived from vinyl ester monomers and structural units derived from the above-mentioned alkyl group-containing monomers, as long as it does not affect the effects of the present invention. It may have structural units other than these (hereinafter also referred to as "other structural units").
• Monomers into which such other structural units can be introduced include, for example, acrylic acid; hydroxy group-containing vinyl ethers such as ethylene glycol vinyl ether, 1,3-propanediol vinyl ether, and 1,4-butanediol vinyl ether; Buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 7-octen-1-ol, 9-decen-1-ol, 3-methyl-3-buten-1-ol, etc. Examples include hydroxy group-containing ⁇ -olefins; vinyltrimethoxysilane and the like. These monomers can introduce other structural units, and may be used alone or in combination of two or more.
• the content of the other structural units is based on 100 parts by mass of all monomer units constituting the vinyl alcohol polymer (A). , usually 9.0 parts by mass or less, preferably 8.0 parts by mass or less, more preferably 7.0 parts by mass or less.
• the vinyl alcohol polymer (A) can be produced according to a conventionally known method.
• methods for obtaining vinyl ester copolymers from vinyl ester monomers and alkyl group-containing monomers include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and dispersion polymerization. Can be adopted. Among these, solution polymerization is industrially preferred.
• a polymerization initiator may be used in the preparation of the vinyl ester copolymer.
• the polymerization initiator may be selected from known initiators depending on the polymerization method. Specifically, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4- azo initiators such as dimethylvaleronitrile); percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate; , ⁇ -cumylperoxyneodecanate, t-butylperoxydecanate, and other perester compounds; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxya
• the amount of the polymerization initiator may be appropriately determined depending on the monomer used, the type of initiator, the desired degree of polymerization, etc., but it is preferably 0.20% based on the total mass of the vinyl ester monomers. ⁇ 0.33% by mass.
• the polymerization conditions etc. may be appropriately determined depending on the type and amount of monomer used, desired physical properties, polymerization method employed, etc.
• the polymerization temperature is usually 0 to 150°C, preferably 20 to 120°C.
• the polymerization rate of the vinyl ester copolymer may be, for example, 20 to 95%. From the viewpoint of improving the yield and controlling the degree of polymerization, the polymerization rate is preferably 30% or more, more preferably 40% or more.
• the saponification reaction of the obtained vinyl ester copolymer is carried out using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methoxide, or an acidic catalyst such as p-toluenesulfonic acid. Alcoholysis or hydrolysis reactions may be applied.
• the solvent used in the saponification reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; and aromatic hydrocarbons such as benzene and toluene. These may be used alone or in combination of two or more. Among these, preferred is a method in which the saponification reaction is carried out using methanol or a mixed solution of methanol and methyl acetate as a solvent in the presence of sodium hydroxide, which is a basic catalyst.
• the amount of catalyst used in the saponification reaction may be appropriately determined depending on the type of catalyst used, the desired degree of saponification, etc.
• the ratio (molar ratio) of the catalyst to the vinyl ester monomer in the vinyl ester copolymer is preferably 0.0035. ⁇ 0.0095.
• the content of the vinyl alcohol polymer (A) in the composition of the present invention can be appropriately determined depending on the structure (type) of the vinyl alcohol polymer (A), the intended use of the composition, the desired viscosity, etc.
• the content of the vinyl alcohol polymer (A) is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the composition. 0.0% by weight, more preferably 0.5 to 4.0% by weight.
• the composition of the present invention contains two or more kinds of vinyl alcohol polymers (A), it is preferable that the total thereof is within the above range.
• the composition of the present invention may contain a vinyl alcohol polymer other than the vinyl alcohol polymer (A).
• the ratio of the vinyl alcohol polymer (A) to the total weight of the vinyl alcohol polymer contained in the composition is 80% by mass or more. It is preferably 90% by mass or more, and more preferably 90% by mass or more.
• the composition of the present invention includes (B) at least one surfactant.
• the surfactant may be any surfactant as long as it can contribute to dissolving the vinyl alcohol polymer (A) in water. Any of surfactants, nonionic surfactants, amphoteric ionic surfactants, etc. may be used. Among these, from the viewpoint of easily ensuring the solubility of the vinyl alcohol polymer (A) in water, the composition of the present invention preferably contains at least one type of anionic surfactant as a surfactant.
• Surfactants particularly anionic surfactants, used in the present invention include, for example, alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfates (alkyl ether sulfates), and polyoxyalkylene sulfates.
• Alkyl ether carboxylate alkyl ether acetate
• ⁇ -olefin sulfonate phosphate ester salt
• acylamino acid salt acyl taurate
• acyl lactate soap (higher fatty acid)
• alkyl sulfosuccinate alkyl hydrolysis
• At least one selected from the group consisting of collagen salts and acylisethionates is preferred.
• alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates, and polyoxyalkylene alkyl ether sulfates have excellent ability to solubilize the vinyl alcohol polymer (A) in water.
• polyoxyalkylene alkyl ether carboxylates (alkyl ether acetates), and ⁇ -olefin sulfonates At least one selected from the group consisting of sulfates) is more preferred.
• salts in the anionic surfactants exemplified herein include, for example, alkali metal salts (lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), ammonium salts, etc. salt or amine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.).
• alkyl sulfate for example, an alkyl sulfate having 6 to 18 carbon atoms is preferable, and specifically, sodium lauryl sulfate, ammonium lauryl sulfate, sodium hexyl sulfate, sodium heptyl sulfate, sodium octyl sulfate, sodium decyl sulfate, tridecyl sulfate, etc.
• Examples include sodium sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, and the like.
• alkyl sulfonate examples include alkyl sulfonate having 6 to 18 carbon atoms.
• alkylbenzene sulfonate for example, an alkylbenzene sulfonate having 6 to 18 carbon atoms is preferable, and specific examples include sodium laurylbenzene sulfonate.
• polyoxyalkylene alkyl ether sulfate examples include sodium laureth sulfate and ammonium laureth sulfate.
• polyoxyalkylene alkyl ether carboxylate examples include polyoxyethylene lauryl ether sodium acetate, polyoxyethylene stearyl ether sodium acetate, and the like.
• Examples of the ⁇ -olefin sulfonate include sodium ⁇ -olefin sulfonate having 6 to 18 carbon atoms.
• Examples of the phosphoric acid ester salt include sodium salt of monolauryl phosphoric acid.
• acylamino acid salt examples include N-acylglutamic acid salts such as sodium coconut oil fatty acid acylglutamate.
• acyl taurate examples include sodium cocoyl methyl taurate.
• acyl lactate examples include sodium stearoyl lactate, sodium isostearoyl lactate, and the like.
• soap higher fatty acid
• examples of the soap include sodium laurate, potassium laurate, sodium palmitate, potassium palmitate, potassium myristate, potassium stearate, and the like.
• alkyl sulfosuccinate examples include disodium lauryl sulfosuccinate.
• acylisethionate examples include lauroylisethionate and the like.
• the content of the surfactant (B) in the composition of the present invention can be appropriately determined depending on the type of surfactant, the intended use of the composition, the desired viscosity, and the like.
• the content of the surfactant (B) is preferably 1 to 50% by weight, more preferably 5 to 50% by weight, even more preferably 5 to 50% by weight, based on the total weight of the composition. It is 40% by mass.
• the amount of anionic surfactant if two or more types of anionic surfactants are included, the total amount may be within the above range. preferable.
• the amount of anionic surfactant is preferably 5 to 50% by weight, more preferably 10 to 50% by weight, and 15 to 50% by weight, based on the total weight of the composition. is even more preferable.
• the amount of the anionic surfactant is within the above range, and the amount of the other surfactant is the amount of the anionic surfactant.
• the content of surfactants other than the anionic surfactant is less than 30 parts by mass, and more preferably less than 10 parts by mass based on 100 parts by mass of the anionic surfactant. It is more preferable that it is the following.
• the mass ratio (A/B) of the vinyl alcohol polymer (A) to the surfactant (B) in the composition of the present invention is preferably 1/99 to 99/1 (0 .01 to 99.00), more preferably 1/99 to 80/20 (0.01 to 4.00), even more preferably 1/99 to 50/50 (0.01 to 1.00), Particularly preferred is 5/95 to 40/60 (0.05 to 0.67).
• the mass ratio of the vinyl alcohol polymer (A) to the surfactant (B) is within the above range, the solubility of the vinyl alcohol polymer (A) in water tends to improve. Thereby, a composition with excellent transparency can be obtained while ensuring the thickening effect of the vinyl alcohol polymer (A).
• the amount of anionic surfactant if two or more types of anionic surfactants are included, the total amount
• the vinyl alcohol polymer (A ) is preferably in the above relationship.
• the composition of the present invention is an aqueous solution of a vinyl alcohol polymer (A) containing (C) water.
• the content of water in the composition of the present invention is not particularly limited, and can be appropriately determined depending on the intended use of the composition, desired viscosity, and the like.
• the amount of water in the composition of the invention is preferably from 30 to 90% by weight, more preferably from 40 to 90% by weight, even more preferably from 40 to 90% by weight, based on the total weight of the composition. It is 80% by mass.
• the composition of the present invention may contain, in addition to the vinyl alcohol polymer (A), the surfactant (B), and water, additional additives depending on the use of the composition, etc., as long as they do not affect the effects of the present invention. It may contain ingredients. Such ingredients include, for example, pH adjusters, antioxidants, ultraviolet absorbers, water-soluble or hydrophilic organic solvents, preservatives, antibacterial agents, bactericidal agents, colorants, chelating agents, dispersants, and antistatic agents. agents, etc.
• the relative viscosity of the composition calculated according to the following is 1.60 to 3.10.
• (Relative viscosity of the composition) (Viscosity of the composition at 20°C) / (Viscosity at 20°C of a viscosity reference composition consisting of the composition to be measured excluding the vinyl alcohol polymer (A))
• “viscosity of the composition at 20°C” is the viscosity at 20°C of the composition whose relative viscosity is to be calculated.
• “Viscosity reference composition” means a composition that differs from the above-mentioned composition whose relative viscosity is to be calculated only in that it does not contain the vinyl alcohol polymer (A).
• the relative viscosity of the composition calculated according to the above is more preferably 1.65 to 3.10, and even more preferably 1.70 to 3.10.
• the viscosity of the composition and the viscosity reference composition are each measured at 20° C. using, for example, a B-type viscometer (spindles LV-03 and LV-04, rotation speed 60 rpm).
• the viscosity of the composition of the present invention at 20°C is preferably 1,300 to 3,000 mPa ⁇ s, more preferably 1,500 to 3,000 mPa ⁇ s, and even more preferably 1,700 to 3,000 mPa ⁇ s. be.
• the viscosity of the composition at 20° C. is within the above range, it can exhibit high thickening effects in various compositions while being excellent in handleability when used for various purposes.
• the composition of the present invention is used in the applications described below, if the viscosity of the composition is within the above range, the composition of the present invention can be easily mixed, dissolved, or dispersed in a composition composed of various components. .
• composition of the present invention due to the high viscosity increasing effect of the composition of the present invention, it is advantageous in that, for example, a composition that does not drip easily and is easy to handle, or has a good appearance due to its moderate viscosity. It can be.
• the composition of the present invention can be prepared, for example, by adding the solid vinyl alcohol polymer (A) to a solution containing the surfactant (B) and water, and mixing and stirring.
• the vinyl alcohol polymer (A) can be added in solid form to water containing the surfactant (B) without having to be prepared in advance as a water-soluble solution, making handling easier. It is easy and easy to control the desired concentration. Further, since the working process can be simplified, it is advantageous in that a desired composition can be efficiently prepared.
• the present invention also covers a method for producing a composition of the present invention, which includes adding a solid vinyl alcohol polymer (A) to a solution containing a surfactant (B) and water.
• a solid vinyl alcohol polymer (A) added to the water containing the surfactant (B) is not particularly limited, and may be powder, granules, paste, or the like.
• the conditions for mixing the solid vinyl alcohol polymer (A) into the water containing the surfactant (B) are not particularly limited.
• the mixing temperature may be 0-50°C, preferably 10-40°C.
• composition of the present invention contains components other than the vinyl alcohol polymer (A), the surfactant (B), and water, those other components are mixed in advance with the surfactant (B) in water. You can leave it there. Alternatively, it may be added to a solution containing a surfactant (B) and water together with the vinyl alcohol polymer (A), or it may be added to the solution after the vinyl alcohol polymer (A) has been dissolved. may be mixed.
• compositions of the present invention are various compositions other than those included in household cleaning products.
• a household cleaning product is a dish detergent, a dishwasher detergent, a laundry detergent, a hard surface detergent, a bleach, a fabric softener, a household detergent or a mixture thereof.
• composition of the present invention is an agricultural product composition, an automotive product composition, an aviation product composition, an industrial product composition, a livestock product composition, a marine product composition, a pharmaceutical composition, a personal care product composition.
• the composition is selected from the group consisting of commercial products, recreational product compositions, and water treatment compositions.
• Agricultural supplies refer to supplies and materials used in agriculture and gardening.
• Agricultural product compositions typically include agrochemical compositions, such as insecticides, fungicides, insecticides, herbicides, rodenticides, plant growth regulators, attractants, spreading agents, repellents, and defoliants. , fertilizers, trace elements/micronutrients, etc.
• the composition of the present invention is an agrochemical composition
• the composition contains a vinyl alcohol polymer (A), a surfactant (B), and water as well as desired functions such as insecticidal and herbicidal. It can contain an active ingredient for imparting.
• Automotive supplies means supplies and materials used in the automobile industry.
• automotive article compositions include car wash detergents, window washer fluids, and the like.
• Aviation supplies means supplies and materials used in the aviation industry.
• Examples of the aviation supplies composition include aircraft body cleaning agents.
• Industrial supplies refer to supplies and materials used in the manufacturing industry. Examples of industrial product compositions include machine cleaners and the like.
• Livestock products refer to supplies and materials used in dairy farming and livestock farming.
• livestock product compositions include livestock shed cleaners, agricultural equipment cleaners, and the like.
• Marine products refer to supplies and materials used in fishing, fisheries, shipbuilding, ocean exploration, etc.
• Examples of marine product compositions include ship cleaning agents, marine equipment cleaning agents, marine product processing equipment cleaning agents, and the like.
• compositions include pharmaceuticals, quasi-drugs, etc.
• Personal care product means a product that can be applied to the body of a human or non-human animal.
• body here includes skin, teeth, nails, and hair.
• Personal care products include, for example, cosmetics, shampoos, body washes, facial cleansers, toothpastes, and the like.
• Recreational supplies means supplies and materials used in recreation.
• Examples of recreational product compositions include foam sprays, bath salts, foaming agents for swimming pools, and the like.
• Water treatment agents are added to water or liquids whose main component is water (containing 50% or more of water based on the total mass) for the purpose of preventing the generation of microorganisms, corrosion, and scale. means the agent used.
• the water treatment composition include water treatment agents for municipal water supplies, industrial water treatment agents, sewage treatment agents, industrial wastewater treatment agents, pool water purification agents, and the like.
• the composition of the present invention is a water treatment agent composition
• the composition contains, for example, a water-soluble monomer as a constituent unit in addition to the vinyl alcohol polymer (A), the surfactant (B), and water.
• a polymer flocculant or an inorganic flocculant made of a water-soluble (co)polymer can be included.
• the present invention provides a vinyl alcohol polymer (A) containing a monomer unit having an alkyl group, which has the following formula (1): 0.010 ⁇ X/(S ⁇ N) ⁇ 0.040 (1)
• S is the content (parts by mass) of monomer units having an alkyl group based on 100 parts by mass of all monomer units in the vinyl alcohol polymer (A), and It is the degree of saponification (mol%) of the polymer (A), and N is the viscosity average degree of polymerization of the vinyl alcohol polymer (A).
• the present invention also provides a resin material containing an ⁇ -olefin, sodium acetate, and the above-mentioned vinyl alcohol polymer (A) of the present invention, wherein the ⁇ -olefin content is based on the total mass of the resin material. is 0.05% by mass or more, and the content of sodium acetate is 1.0% by mass or less.
• the vinyl alcohol polymer (A) is included in the composition of the present invention as a resin material containing an ⁇ -olefin and sodium acetate.
• the content of ⁇ -olefin in the resin material is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, even more preferably 0.11% by mass or more, based on the total mass of the resin material. Further, the content of ⁇ -olefin is preferably 1.0% by mass or less.
• the resin material may contain one type of ⁇ -olefin, or may contain two or more types.
• the above content of ⁇ -olefins means the total amount of the plurality of ⁇ -olefins contained in the resin material.
• the ⁇ -olefin contained in the resin material is preferably an ⁇ -olefin having 6 to 18 carbon atoms.
• the ⁇ -olefin include 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1- Preferred is octadecene, and more preferably contains at least one selected from the group consisting of 1-dodecene and 1-hexadecene.
• the ⁇ -olefin contained in the resin material may be the same as or different from the alkyl group-containing monomer described above. Further, the ⁇ -olefin contained in the resin material may be derived from an ⁇ -olefin used as an alkyl group-containing monomer in the production of the polyvinyl alcohol polymer (A), It may be added separately from (A).
• the content of sodium acetate in the resin material is preferably 2.0% by mass or less based on the total mass of the resin material, more preferably 1.0% by mass or less, even more preferably 0.9% by mass or less, even more preferably It is 0.85% by mass or less.
• the content of sodium acetate is within the above range, when the resin material is made into an aqueous solution, the molecular skeleton of the vinyl alcohol polymer (A) can be sufficiently spread in the solution, and a high thickening effect can be expected.
• the resin material may contain components other than the vinyl alcohol polymer (A), ⁇ -olefin, and sodium acetate, but in a preferred embodiment of the present invention, the resin material substantially comprises: Consists of vinyl alcohol polymer (A), ⁇ -olefin and sodium acetate.
• substantially means that, for example, components that may be unavoidably mixed in due to raw materials used in the manufacturing process of the polyvinyl alcohol polymer (A) and resin materials are not excluded.
• the content of components other than the vinyl alcohol polymer (A), ⁇ -olefin, and sodium acetate contained in the resin material is usually 5 mass based on the total mass of the resin material. % or less, preferably 3% by mass or less.
• a preferred embodiment of the composition of the present invention is a composition containing the above-mentioned resin material. That is, this composition contains a vinyl alcohol polymer (A), an ⁇ -olefin, sodium acetate, a surfactant (B), and water (C).
• the content of the resin material in the composition can be appropriately determined depending on the structure (type) of the vinyl alcohol polymer (A) contained in the resin material, the intended use of the composition, the desired viscosity, and the like.
• the content of the resin material is preferably from 0.1 to 5.0% by weight, more preferably from 0.5 to 5.0% by weight, based on the total weight of the composition. Preferably it is 0.5 to 4.0% by mass.
• Viscosity average degree of polymerization (N) of PVA (A) The viscosity average degree of polymerization (N) of PVA (A) was measured according to JIS K6726:1994. Specifically, when the saponification degree of PVA (A) is less than 99.5 mol%, saponification is performed until the saponification degree is 99.5 mol% or more, and the obtained PVA (A) is dissolved in water at 30% by weight.
• Amount (S) of alkyl group-containing monomer units in PVA (A) The amount (S) of the alkyl group-containing monomer units in PVA (A) is determined by calculating the ratio (mol%) of the alkyl group-containing monomer units to the total constitutional units of PVA (A) by 1 H NMR, and It was calculated by converting the molecular weight of the structural unit into parts by mass.
• Example 1 Production of resin material containing vinyl alcohol polymer (A) In a reactor equipped with a stirrer, a reflux condenser, a nitrogen introduction pipe, and an addition port for a polymerization initiator, 900 parts by mass of vinyl acetate, 900 parts by mass of methanol, and 1 - 40.0 parts by mass of dodecene was charged, and the inside of the system was purged with nitrogen for 30 minutes while bubbling nitrogen. The temperature of the reactor was started to rise, and when the internal temperature reached 60°C, 4.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) was added as a polymerization initiator to start polymerization. . After polymerizing at 60° C.
• AIBN 2,2'-azobisisobutyronitrile
• the saponification reaction was carried out using After adding the methanol solution of sodium hydroxide, a gel-like substance was formed in about 15 minutes, so this was pulverized using a pulverizer and left at 40° C. for 45 minutes to advance saponification. Thereafter, methyl acetate and methanol were added, and the mixture was left at 40° C. for 30 minutes for washing. After repeating this washing operation twice, the white solid obtained by removing liquid was vacuum dried at 40° C. for 16 hours to obtain a resin material containing PVA (PVA-1).
• PVA-1 is a resin material containing a vinyl alcohol polymer (A), an ⁇ -olefin, and sodium acetate.
• composition To 78 parts by mass of water, 2 parts by mass of PVA-1 as a resin material containing a vinyl alcohol polymer (A), and 20 parts by mass of sodium laureth sulfate (Na laureth sulfate) as a surfactant (B). A composition was obtained by adding 100% and stirring. Table 2 summarizes the ratio of each component contained in the composition and the type of surfactant (B). Note that since the contents of ⁇ -olefin and sodium acetate in the resin material were trace amounts, the ratio of the resin material and the ratio of the vinyl alcohol polymer (A) in each composition were substantially the same.
• composition The same procedure as in Example 1 was carried out, except that the type of resin material containing the vinyl alcohol polymer (A) and the type and amount of surfactant (B) added were changed as shown in Table 2. Each composition was obtained.
• composition The same procedure as in Example 1 was carried out, except that the type of resin material containing the vinyl alcohol polymer (A) and the type and amount of surfactant (B) added were changed as shown in Table 2. A composition was obtained.
• Example 13 A composition was obtained in the same manner as in Example 3, except that the amount of surfactant (B) added was changed as shown in Table 2.
• Viscosity of composition (actually measured value) The viscosity of the compositions obtained in Examples, Comparative Examples, and Reference Examples was measured at 60 rpm and 20° C. using a B-type viscometer (spindles LV-03 and LV-04). The measurement results are shown in Table 3.
• Relative Viscosity Viscosity of the composition of each example or comparative example (20°C) / Viscosity of the composition of Reference Example 1 (20°C)
• Relative viscosity Viscosity of the composition of each example or comparative example (20°C) / Viscosity of the composition of Reference Example 1 (20°C)
• the relative viscosities of Comparative Examples 1 to 9 are as follows: Calculated based on the composition excluding PVA-13 to 21 from the composition. The larger the relative viscosity value, the better the thickening effect.
• compositions according to the present invention (Examples 1 to 13) exhibited a high thickening effect and also had excellent transparency.

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• 2023
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