Vinyl alcohol polymer-containing composition, method for producing same, vinyl alcohol polymer, and resin material

Abstract

The present invention relates to a composition (excluding a household detergent article composition) containing: (A) a vinyl alcohol polymer containing a monomer unit having an alkyl group; (B) at least one surfactant; and (C) water. The vinyl alcohol polymer (A) satisfies the following formula (1): 0.010 < = X / (S * N) < = 0.040 (1). (In the formula, S represents the content (parts by mass) of monomer units having an alkyl group with respect to 100 parts by mass of all monomer units in the vinyl alcohol polymer (A), X represents the degree of saponification (mol%) of the vinyl alcohol polymer (A), and N represents the viscosity-average degree of polymerization of the vinyl alcohol polymer (A)).

Description

Technical Field

[0001] The present invention relates to a composition containing a vinyl alcohol polymer (excluding a household cleaning agent composition) and a method for producing the composition. In addition, the present invention also relates to a vinyl alcohol polymer contained in the composition and a resin material containing the vinyl alcohol polymer. Background Art

[0002] Conventionally, vinyl alcohol polymers have been used in a wide range of applications such as adhesives, paper products, processing agents for fiber products, coatings, and various binders. It is known that in a composition containing a vinyl alcohol polymer suitable for various applications, when the vinyl alcohol polymer is hydrophobic, an appropriate surfactant is used to dissolve the hydrophobic vinyl alcohol polymer in water (Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 53-133252 Summary of the invention

[0006] Problems to be solved by the invention

[0007] As described in the above-mentioned patent documents, an aqueous solution of a hydrophobic vinyl alcohol polymer can be obtained by adding a suitable surfactant to water. However, the composition (aqueous solution) in which a hydrophobic vinyl alcohol polymer is dissolved in water containing a surfactant has a tendency to be difficult to control the viscosity of the composition, especially to be difficult to obtain a thickening effect. Therefore, in order to obtain a composition with a higher viscosity, a large amount of vinyl alcohol polymer needs to be mixed, in which case, the transparency of the composition may decrease.

[0008] The object of the present invention is to provide a composition (aqueous solution) containing a hydrophobic vinyl alcohol polymer having excellent transparency despite high viscosity and a method for producing the composition. In addition, the object of the present invention is to provide a vinyl alcohol polymer capable of producing the above-mentioned composition (aqueous solution) and a resin material containing the vinyl alcohol polymer.

[0009] Means used to solve problems

[0010] The present inventors have conducted intensive studies to solve the above-mentioned problems and have completed the present invention. That is, the present invention includes the following aspects.

[0011] [1] A composition comprising:

[0012] (A) a vinyl alcohol polymer comprising a monomer unit having an alkyl group;

[0013] (B) at least one surfactant; and

[0014] (C) Water,

[0015] The vinyl alcohol polymer (A) satisfies the following formula (1):

[0016] 0.010≤X / (S×N)≤0.040 (1)

[0017] [wherein, S represents the content (parts by mass) of the monomer units having an alkyl group relative to 100 parts by mass of all the monomer units in the vinyl alcohol polymer (A), X represents the saponification degree (mol %) of the vinyl alcohol polymer (A), and N represents the viscosity average degree of polymerization of the vinyl alcohol polymer (A)]

[0018] (Wherein, the composition does not include a household cleaning agent composition).

[0019] [2] The composition according to [1] above, wherein the vinyl alcohol polymer (A) comprises a monomer unit having an alkyl group having 4 to 16 carbon atoms.

[0020] [3] The composition according to [1] or [2] above, wherein the monomer unit having an alkyl group is a monomer unit derived from an α-olefin.

[0021] [4] The composition according to any one of [1] to [3] above, wherein the monomer units having an alkyl group include monomer units derived from α-olefins, and the content of the monomer units having an alkyl group derived from α-olefins is 60% by mass or more relative to the total amount of the monomer units having an alkyl group.

[0022] [5] The composition according to any one of [1] to [4] above, wherein the content S of the monomer units having an alkyl group is 1.2 to 9.0 parts by mass based on 100 parts by mass of all the monomer units in the vinyl alcohol polymer (A).

[0023] [6] The composition according to any one of [1] to [5] above, wherein the saponification degree X of the vinyl alcohol polymer (A) is 40 to 80 mol%.

[0024] [7] The composition according to any one of [1] to [6] above, wherein the viscosity average degree of polymerization N of the vinyl alcohol polymer (A) is 400 to 2,000.

[0025] [8] The composition according to any one of [1] to [7] above, wherein the mass ratio (A / B) of the vinyl alcohol polymer (A) to the surfactant (B) is 1 / 99 to 99 / 1.

[0026] [9] The composition according to any one of [1] to [8] above, wherein the surfactant (B) is an anionic surfactant.

[0027]

[10] The composition according to any one of [1] to [9] above, wherein the surfactant (B) comprises at least one selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfates (alkyl ether sulfates), polyoxyalkylene alkyl ether carboxylates (alkyl ether acetates), α-olefin sulfonates, phosphate ester salts, acylamino acid salts, acyltaurates, acyl lactylates, soaps (higher fatty acids), alkyl sulfosuccinates, acyl hydrolyzed collagen salts, and acylhydroxyethanesulfonates.

[0028]

[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.

[0029]

[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.

[0030]

[13] The composition according to any one of [1] to

[12] above, wherein the relative viscosity of the composition calculated as follows is 1.60 to 3.10.

[0031] Relative viscosity of the composition = viscosity of the composition at 20°C / viscosity at 20°C of a viscosity-based composition consisting of a composition obtained by excluding the vinyl alcohol polymer (A) from the composition to be measured.

[0032]

[14] The composition according to any one of [1] to

[13] above, which has a viscosity at 20°C of 1,300 to 3,000 mPa·s.

[0033]

[15] A composition comprising:

[0034] (A) a vinyl alcohol polymer comprising a monomer unit having an alkyl group;

[0035] (B) a surfactant; and

[0036] (C) Water,

[0037] The vinyl alcohol polymer (A) satisfies the following formula (1):

[0038] 0.010≤X / (S×N)≤0.040 (1)

[0039] [wherein, S represents the content (parts by mass) of the monomer units having an alkyl group relative to 100 parts by mass of all the monomer units in the vinyl alcohol polymer (A), X represents the saponification degree (mol %) of the vinyl alcohol polymer (A), and N represents the viscosity average degree of polymerization of the vinyl alcohol polymer (A)]

[0040] The composition is selected from agricultural product compositions, automotive product compositions, aviation product compositions, industrial product compositions, livestock product compositions, marine product compositions, pharmaceutical compositions, personal care product compositions, recreational product compositions and water treatment agent compositions.

[0041]

[16] The composition according to

[15] above, wherein the monomer units having an alkyl group include monomer units derived from α-olefins, and the content of the monomer units having an alkyl group derived from α-olefins is 60% by mass or more relative to the total amount of the monomer units having an alkyl group.

[0042]

[17] The method for producing the composition according to any one of [1] to

[16] , comprising adding a solid vinyl alcohol polymer (A) to a solution containing a surfactant (B) and water.

[0043]

[18] A vinyl alcohol polymer (A), which is a vinyl alcohol polymer (A) comprising a monomer unit having an alkyl group and satisfies the following formula (1):

[0044] 0.010≤X / (S×N)≤0.040 (1)

[0045] [wherein, S is the content (parts by mass) of the monomer units having an alkyl group relative to 100 parts by mass of all the monomer units in the aforementioned vinyl alcohol polymer (A), X is the degree of saponification (mol %) of the aforementioned vinyl alcohol polymer (A), and N is the viscosity average degree of polymerization of the aforementioned vinyl alcohol polymer (A).]

[0046]

[19] The vinyl alcohol polymer (A) according to the above

[18] , wherein the monomer units having an alkyl group include monomer units derived from α-olefins, and the content of the monomer units having an alkyl group derived from α-olefins is 60% by mass or more relative to the total amount of the monomer units having an alkyl group.

[0047]

[20] A resin material comprising the vinyl alcohol polymer (A) described in

[18] or

[19] above, wherein the resin material comprises an α-olefin and sodium acetate, wherein the α-olefin content is greater than 0.05% by mass and the sodium acetate content is less than 2.0% by mass based on the total mass of the resin material.

[0048]

[21] The resin material according to

[20] above, wherein the α-olefin is an α-olefin having 6 to 18 carbon atoms.

[0049]

[22] The resin material according to

[20] or

[21] above, wherein the α-olefin is at least one selected from 1-dodecene and 1-hexadecene.

[0050] Effects of the Invention

[0051] According to the present invention, a composition (aqueous solution) containing a hydrophobic vinyl alcohol polymer having excellent transparency despite high viscosity and a method for producing the composition can be provided. In addition, the present invention can provide a vinyl alcohol polymer capable of achieving the above-mentioned composition (aqueous solution) and a resin material containing the vinyl alcohol polymer. DETAILED DESCRIPTION

[0052] Hereinafter, embodiments of the present invention will be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made within the scope that does not impair the gist of the present invention.

[0053] <Vinyl alcohol polymer (A)>

[0054] The composition of the present invention contains (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 also referred to as “vinyl alcohol polymer (A)”).

[0055] 0.010≤X / (S×N)≤0.040 (1)

[0056] In formula (1), S is the content (parts by mass) of the monomer units having an alkyl group relative to 100 parts by mass of all the monomer units in the vinyl alcohol polymer (A), X is the degree of saponification (mol %) of the vinyl alcohol polymer (A), and N is the viscosity average degree of polymerization of the vinyl alcohol polymer (A).

[0057] The above formula (1) can be a new index representing the balance between the solubility of the vinyl alcohol polymer (A) in water and the thickening effect. In formula (1), among all the monomer units constituting the vinyl alcohol polymer (A), if the content (S) of the monomer units having an alkyl group increases and / or the viscosity average degree of polymerization (N) of the vinyl alcohol polymer increases, the solubility of the vinyl alcohol polymer tends to decrease and the viscosity of the composition containing it tends to increase. On the other hand, if the saponification degree (X) of the vinyl alcohol polymer (A) increases, the solubility of the vinyl alcohol polymer in the composition tends to increase. Therefore, by adjusting the saponification degree (X) in the vinyl alcohol polymer (A), the content (S) of the monomer units having an alkyl group and / or the viscosity average degree of polymerization (N), the value of formula (1) is controlled, so that a composition having high viscosity, excellent solubility in water and high transparency can be obtained. The “thickening effect” referred to in the present specification refers to an effect in which the viscosity of a composition containing a target vinyl alcohol polymer becomes higher than the viscosity of a composition obtained by merely removing the vinyl alcohol polymer from the composition.

[0058] Generally, the smaller the value of the above formula (1), the higher the thickening effect (i.e., a high-viscosity composition can be obtained). On the other hand, if the value of formula (1) becomes too small, although a thickening effect can be expected, it is difficult to ensure high transparency. In the composition of the present invention, the lower limit of formula (1) is 0.010 or more. If the value of formula (1) is 0.010 or more, a composition that ensures high viscosity and excellent transparency can be obtained.

[0059] In addition, the larger the value of formula (1), the higher the solubility of the vinyl alcohol polymer (A) relative to the aqueous solution (i.e., a composition with high transparency can be obtained). On the other hand, if the value of formula (1) becomes too large, although the solubility can be improved, there is a tendency for the viscosity to decrease. In the composition of the present invention, the upper limit of formula (1) is less than 0.040. If the value of formula (1) is less than 0.040, a composition with both a thickening effect and high transparency can be obtained.

[0060] In the present invention, the value of formula (1) is greater than or equal to 0.010 and less than or equal to 0.040. If the value of formula (1) is within the above range, a composition having high viscosity and excellent transparency can be prepared. In one embodiment of the present invention, the value of formula (1) is preferably 0.010 to 0.038, more preferably 0.010 to 0.035, further preferably 0.010 to 0.030, particularly preferably 0.010 to 0.025, particularly preferably 0.010 to 0.024, and preferably 0.012 to 0.040, for example, 0.013 to 0.040. If the value of formula (1) is within the range of the above lower limit and upper limit, a composition having higher viscosity and better transparency can be obtained, and it is easy to suppress the decrease in the transparency of the composition over time.

[0061] When calculating the value of formula (1), the saponification degree (X) (mol %) and viscosity average polymerization degree (N) of the vinyl alcohol polymer (A) can be measured according to JIS K 6726 "Testing methods for polyvinyl alcohol". More specifically, they can be measured according to the methods described in the examples below.

[0062] The value of formula (1) can be controlled by adjusting the content (parts by mass) of the monomer units having an alkyl group in all monomer units constituting the vinyl alcohol polymer (A), the saponification degree of the vinyl alcohol polymer (A) and / or the viscosity average polymerization degree of the vinyl alcohol polymer (A).

[0063] The vinyl alcohol polymer (A) satisfying the above formula (1) can be prepared, for example, by copolymerizing a vinyl ester monomer and a monomer having an alkyl group (hereinafter also referred to as an "alkyl group-containing monomer") and saponifying the obtained vinyl ester copolymer.

[0064] As the vinyl ester monomer for forming the vinyl alcohol polymer (A), for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, 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. can be listed. Among them, vinyl acetate is preferred from the viewpoint of easy acquisition and economical saving. As the vinyl ester monomer, only one kind may be used, or two or more kinds may be used in combination.

[0065] The content of the structural unit derived from the vinyl ester monomer in the vinyl alcohol polymer (A) is preferably 82 to 97 parts by mass, more preferably 86 to 97 parts by mass, based on 100 parts by mass of all monomer units constituting the vinyl alcohol polymer (A).

[0066] It should be noted that the “structural unit derived from a vinyl ester monomer” refers to a structural unit derived from a raw material vinyl ester monomer in the vinyl alcohol polymer (A), and the “structural unit derived from a vinyl ester monomer” includes a vinyl ester unit and a vinyl alcohol unit obtained by converting a vinyl ester unit into a vinyl alcohol unit by saponification.

[0067] The content of the structural unit derived from the vinyl ester monomer in the vinyl alcohol polymer (A) can be determined by using 1 The ratio (mol %) of the structural unit derived from the vinyl ester monomer to all the structural units of the polyvinyl alcohol-based polymer (A) was calculated by H NMR and was determined from the molecular weight of each structural unit converted into parts by mass.

[0068] As the alkyl-containing monomer, any monomer that can be copolymerized with the vinyl ester monomer and that contains an alkyl group in its structure can be used. Examples thereof include α-olefins such as propylene, 1-butene, isobutylene, pentene, 1-hexene, 1-octene, 1-dodecene, 1-hexadecene, and 1-octadecene; methacrylic acid; (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, and octadecyl (meth)acrylate; acrylamide derivatives such as N-methylacrylamide and N-ethylacrylamide; and methacrylic acid esters such as N-methylmethacrylamide and N-ethylmethacrylamide. acrylamide derivatives; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, lauryl vinyl ether, and vinyl stearate ether; allyl acetate; allyl ethers such as propyl allyl ether, butyl allyl ether, and hexyl allyl ether; monomers having an oxyalkylene group; isopropenyl acetate; monomers having a silyl group such as vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, 3-(meth)acrylamidepropyltrimethoxysilane, and 3-(meth)acrylamidepropyltriethoxysilane. As the alkyl group-containing monomer, only one kind may be used, or two or more kinds may be used in combination.

[0069] The "monomer unit having an alkyl group (hereinafter also referred to as an alkyl-containing monomer unit)" in the present invention refers to a structural unit derived from an alkyl-containing monomer in the vinyl alcohol polymer (A). The vinyl alcohol polymer (A) preferably contains an alkyl-containing monomer unit having 4 to 16 carbon atoms. The number of carbon atoms of the alkyl group in the alkyl-containing monomer unit is preferably 4 to 16, more preferably 6 to 16, further preferably 8 to 16, particularly preferably 10 to 16, and preferably 4 to 14. If the number of carbon atoms of the alkyl group in the alkyl-containing monomer unit is within the range of the above lower limit and upper limit, the degree of polymerization is higher, and it is easy to ensure both the thickening effect and the solubility. It should be noted that in this specification, the number of carbon atoms of the alkyl group in the alkyl-containing monomer unit refers to the number of carbon atoms of the side chain of the vinyl alcohol polymer (A) in the unit. For example, the number of carbon atoms of the alkyl group of the monomer unit derived from 1-dodecene in the vinyl alcohol polymer obtained by copolymerizing vinyl acetate and 1-dodecene (carbon number 12) as an alkyl-containing monomer and saponifying is 10.

[0070] The alkyl-containing monomer units in the vinyl alcohol polymer (A) are preferably monomer units derived from α-olefins. In one embodiment of the present invention, the content of monomer units derived from α-olefins is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, further preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, relative to all alkyl-containing monomer units constituting the vinyl alcohol polymer (A). As alkyl-containing monomer units, if monomer units derived from α-olefins are included in an amount within the aforementioned range, the thickening effect and solubility can be further improved. As α-olefins capable of introducing monomer units derived from α-olefins into the vinyl alcohol polymer (A), α-olefins such as those exemplified above as alkyl-containing monomers can be cited. Among them, from the viewpoint of easily obtaining a predetermined thickening effect and easily controlling solubility, preferred are monomer units derived from α-olefins having 6 to 18 carbon atoms, such as 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, and 1-octadecene, more preferred are monomer units derived from α-olefins having 8 to 18 carbon atoms, and still more preferred are monomer units derived from α-olefins having 8 to 16 carbon atoms.

[0071] The content of the alkyl-containing monomer unit in the vinyl alcohol polymer (A) is preferably 1.2 to 9.0 parts by mass relative to 100 parts by mass of all monomer units constituting the vinyl alcohol polymer (A). If the content of the alkyl-containing monomer unit is above the above lower limit, the degree of polymerization is easily increased and high viscosity is easily ensured. In addition, if it is below the upper limit, it is easy to ensure its solubility in water containing a surfactant. The content of the alkyl-containing monomer unit can be appropriately determined according to the desired viscosity and solubility. In one embodiment of the present invention, relative to 100 parts by mass of all monomer units, it is preferably 1.5 to 9.0 parts by mass, more preferably 2.0 to 9.0 parts by mass, further preferably 2.5 to 9.0 parts by mass, particularly preferably 2.8 to 9.0 parts by mass, and preferably 1.2 to 8.5 parts by mass, more preferably 1.2 to 8.0 parts by mass, further preferably 1.2 to 7.5 parts by mass, particularly preferably 1.2 to 7.0 parts by mass.

[0072] The content of the alkyl-containing monomer unit in the vinyl alcohol polymer (A) can be adjusted by using 1 The ratio (mol %) of the alkyl group-containing monomer unit to all the structural units of the polyvinyl alcohol-based polymer (A) was calculated by HNMR and was determined by converting the molecular weight of each structural unit into parts by mass.

[0073] It should be noted that, in the present invention, the content of the alkyl-containing monomer units in the vinyl alcohol polymer (A) is controlled by "parts by mass" relative to 100 parts by mass of all monomer units constituting the vinyl alcohol polymer (A). In general, the proportion of monomers constituting a polymer is mostly controlled by "mol %". However, the length of the alkyl group possessed by the monomer may also have a significant effect on the solubility and thickening effect. Therefore, in the present invention, the "parts by mass" that can easily reflect the length of the alkyl group is controlled by controlling the amount of the alkyl-containing monomer units, thereby flexibly using the value of formula (1) as an indicator of the solubility and thickening effect.

[0074] In the present invention, the vinyl alcohol polymer (A) has an alkyl group-containing monomer unit and generally exhibits hydrophobicity.

[0075] The saponification degree (X) of the vinyl alcohol polymer (A) is preferably 40 to 80 mol%. If the saponification degree (X) is within the above range, the solubility of the vinyl alcohol polymer (A) in water containing a surfactant is easily improved, and a composition with high transparency is easily obtained. In one embodiment of the present invention, the saponification degree (X) is preferably 40 to 75 mol%, more preferably 40 to 70 mol%, further preferably 40 to 65 mol%, particularly preferably 40 to 60 mol% (or less than 60 mol%), and particularly preferably 40 to 50 mol% (or less than 50 mol%). If the saponification degree (X) is within the range of the above lower limit and upper limit, not only the solubility and transparency are more excellent, but also the effect of suppressing the decrease in the transparency of the composition over time is excellent. In addition, when a vinyl alcohol polymer (A) having a lower saponification degree such as the above range is included, a higher thickening effect is easily obtained.

[0076] The viscosity average degree of polymerization (N) of the vinyl alcohol polymer (A) is preferably 400 to 2000. If the viscosity average degree of polymerization (N) is above the lower limit, a higher thickening effect can be expected, and if it is below the upper limit, it is easy to avoid excessive thickening and ensure the necessary solubility. In one embodiment of the present invention, the viscosity average degree of polymerization (N) is more preferably 450 to 2000, further preferably 450 to 1800, and particularly preferably 450 to 1700.

[0077] The vinyl alcohol polymer (A) may have structural units other than the structural units derived from the vinyl ester monomer and the structural units derived from the above-mentioned alkyl-containing monomers, within the range not affecting the effects of the present invention (hereinafter also referred to as "other structural units"). Examples of monomers capable of introducing such other structural units include acrylic acid; hydroxyl-containing vinyl ethers such as ethylene glycol vinyl ether, 1,3-propylene glycol vinyl ether, and 1,4-butanediol vinyl ether; hydroxyl-containing α-olefins such as 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 7-octen-1-ol, 9-decene-1-ol, and 3-methyl-3-butene-1-ol; and vinyltrimethoxysilane. As monomers capable of introducing other structural units, only one type may be used, or two or more types may be used in combination.

[0078] When the vinyl alcohol polymer (A) has the above-mentioned other structural units, the content of the other structural units is usually 9.0 parts by mass or less, preferably 8.0 parts by mass or less, and more preferably 7.0 parts by mass or less, based on 100 parts by mass of all monomer units constituting the vinyl alcohol polymer (A).

[0079] The vinyl alcohol polymer (A) can be produced by a conventionally known method. For example, as a method for obtaining a vinyl ester copolymer from a vinyl ester monomer and an alkyl-containing monomer, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, etc. can be used. Among them, solution polymerization is industrially preferred.

[0080] In the preparation of vinyl ester copolymers, a polymerization initiator can be used. The polymerization initiator can be selected from known initiators according to the polymerization method. Specifically, azo initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) can be listed; percarbonate compounds such as diisopropyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, diethoxyethyl peroxydicarbonate; perester compounds such as tert-butyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, tert-butyl peroxydecanoate; acetylcyclohexylsulfonyl peroxide; peroxide initiators such as 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, etc.

[0081] The amount of the polymerization initiator may be appropriately determined depending on the monomers used, the type of initiator, the target degree of polymerization, etc., and is preferably 0.20 to 0.33% by mass based on the total mass of the vinyl ester monomers.

[0082] The polymerization conditions and the like may be appropriately determined according to the type and amount of the monomers used, desired physical properties, the polymerization method to be employed, etc. For example, the polymerization temperature is usually 0 to 150°C, preferably 20 to 120°C.

[0083] The polymerization rate in 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.

[0084] In the saponification reaction of the obtained vinyl ester copolymer, an alcohol decomposition or hydrolysis reaction using a known alkaline catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, or an acidic catalyst such as p-toluenesulfonic acid can be applied. As the solvent used in the saponification reaction, alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene, etc. can be listed. Only one of them can be used, or two or more of them can be used in combination. Among them, as a saponification reaction, a method in which methanol or a mixed solution of methanol and methyl acetate is used as a solvent, and the saponification reaction is carried out in the presence of sodium hydroxide as a basic catalyst is preferred.

[0085] The amount of the catalyst used in the saponification reaction can be appropriately determined according to the type of catalyst used, the target saponification degree, etc. For example, when sodium hydroxide is used as a catalyst for the saponification reaction, in one embodiment of the present invention, the ratio (molar ratio) of the catalyst to the vinyl ester monomer in the vinyl ester copolymer is preferably 0.0035 to 0.0095.

[0086] The content of the vinyl alcohol polymer (A) in the composition of the present invention can be appropriately determined according to the structure (type) of the vinyl alcohol polymer (A), the purpose of the composition, the desired viscosity, etc. In one embodiment of the present invention, the content of the vinyl alcohol polymer (A) is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 5.0% by mass, and further preferably 0.5 to 4.0% by mass based on the total mass of the composition. It should be noted that when the composition of the present invention includes two or more vinyl alcohol polymers (A), their total is preferably within the above range.

[0087] The composition of the present invention may contain a vinyl alcohol polymer other than the vinyl alcohol polymer (A). When containing a vinyl alcohol polymer other than the vinyl alcohol polymer (A), the proportion of the vinyl alcohol polymer (A) contained in the composition relative to the total mass of the vinyl alcohol polymer is preferably 80% by mass or more, more preferably 90% by mass or more.

[0088] <Surfactant (B)>

[0089] The composition of the present invention contains (B) at least one surfactant. In the composition of the present invention, the surfactant may be any one as long as it can help the vinyl alcohol polymer (A) dissolve in water, and may be any one of anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, etc. as long as it can play this role. Among them, 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 anionic surfactant as a surfactant.

[0090] As the surfactant used in the present invention, especially the anionic surfactant, it is preferred that at least one selected from the group consisting of, for example, alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfates (alkyl ether sulfates), polyoxyalkylene alkyl ether carboxylates (alkyl ether acetates), α-olefin sulfonates, phosphate ester salts, acylamino acid salts, acyl taurates, acyl lactylates, soaps (higher fatty acids), alkyl sulfosuccinates, acyl hydrolyzed collagen salts, and acyl isethionates. Among them, from the viewpoint of excellent effect of making the vinyl alcohol polymer (A) soluble in water, it is preferred that at least one selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfates (alkyl ether sulfates), polyoxyalkylene alkyl ether carboxylates (alkyl ether acetates), and α-olefin sulfonates, and it is more preferred that at least one selected from the group consisting of alkyl sulfates and polyoxyalkylene alkyl ether sulfates (alkyl ether sulfates).

[0091] The “salt” in the above-mentioned anionic surfactants exemplified in this specification is, for example, an alkali metal salt (lithium salt, sodium salt, potassium salt, etc.), an alkaline earth metal salt (magnesium salt, calcium salt, etc.), an ammonium salt or an amine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.).

[0092] As the above-mentioned alkyl sulfate, for example, alkyl sulfates having 6 to 18 carbon atoms are preferred, and specific examples include sodium lauryl sulfate, ammonium lauryl sulfate, sodium hexyl sulfate, sodium heptyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium tridecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, and the like.

[0093] Examples of the alkyl sulfonate include alkyl sulfonates having 6 to 18 carbon atoms.

[0094] As the alkylbenzene sulfonate, for example, an alkylbenzene sulfonate having 6 to 18 carbon atoms is preferred, and specific examples thereof include sodium laurylbenzene sulfonate.

[0095] Examples of the polyoxyalkylene alkyl ether sulfates (alkyl ether sulfates) include sodium laureth sulfate and ammonium laureth sulfate.

[0096] Examples of the polyoxyalkylene alkyl ether carboxylates (alkyl ether acetates) include polyoxyethylene lauryl ether sodium acetate and polyoxyethylene stearyl ether sodium acetate.

[0097] Examples of the α-olefin sulfonate include sodium α-olefin sulfonate having 6 to 18 carbon atoms.

[0098] Examples of the phosphoric acid ester salt include sodium salt of monolauryl phosphoric acid.

[0099] Examples of the acylamino acid salts include N-acylglutamic acid salts such as sodium coconut fatty acid acylglutamate.

[0100] As acyl taurine, sodium cocoyl methyl taurate etc. are mentioned, for example.

[0101] As acyl lactylate, sodium stearoyl lactylate, sodium isostearyl lactylate, etc. are mentioned, for example.

[0102] Examples of the soap (higher fatty acid) include sodium laurate, potassium laurate, sodium palmitate, potassium palmitate, potassium myristate, and potassium stearate.

[0103] Examples of the alkyl sulfosuccinate include disodium lauryl sulfosuccinate.

[0104] Examples of the acyl isethionate include lauroyl isethionate.

[0105] The content of the surfactant (B) in the composition of the present invention can be appropriately determined according to the type of surfactant, the purpose of the composition, the desired viscosity, etc. In one embodiment of the present invention, the content of the surfactant (B) is preferably 1 to 50% by mass, more preferably 5 to 50% by mass, and further preferably 5 to 40% by mass based on the total mass of the composition. When a plurality of surfactants are included in the composition of the present invention, the amount of the anionic surfactant (the total amount when two or more anionic surfactants are included) is preferably within the above range. In particular, the amount of the anionic surfactant is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 50% by mass based on the total mass of the composition. In addition, when anionic surfactants and other surfactants are included, it is preferred that the amount of the anionic surfactant is within the above range, and the amount of the other surfactants is less than the amount of the anionic surfactant, and the content of the surfactant other than the anionic surfactant is preferably 30 parts by mass or less relative to 100 parts by mass of the content of the anionic surfactant, and further preferably 10 parts by mass or less.

[0106] In one embodiment of the present invention, 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), further preferably 1 / 99 to 50 / 50 (0.01 to 1.00), and particularly preferably 5 / 95 to 40 / 60 (0.05 to 0.67). If 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 is easily improved. Thus, it is possible to ensure the thickening effect caused by the vinyl alcohol polymer (A) and obtain a composition with excellent transparency. When a plurality of surfactants are included in the composition of the present invention, the amount of the anionic surfactant (the total amount when two or more anionic surfactants are included) and the amount of the vinyl alcohol polymer (A) are preferably in the above relationship.

[0107] The composition of the present invention is an aqueous solution of a vinyl alcohol polymer (A) containing (C) water. The water content in the composition of the present invention is not particularly limited and can be appropriately determined according to the use of the composition, the desired viscosity, etc. In one embodiment of the present invention, the amount of water in the composition of the present invention is preferably 30 to 90% by mass, more preferably 40 to 90% by mass, and further preferably 40 to 80% by mass based on the total mass of the composition.

[0108] The composition of the present invention may contain additional components in addition to the vinyl alcohol polymer (A), the surfactant (B) and water, depending on the application of the composition, etc., within the range that does not affect the effect of the present invention. Examples of such components include pH adjusters, antioxidants, ultraviolet absorbers, water-soluble or hydrophilic organic solvents, preservatives, antibacterial agents, bactericides, colorants, chelating agents, dispersants, antistatic agents, etc.

[0109] In the composition of the present invention, the relative viscosity of the composition calculated as follows is preferably 1.60 to 3.10.

[0110] (Relative viscosity of composition) = (viscosity of composition at 20°C) / (viscosity at 20°C of a viscosity-based composition consisting of a composition excluding the vinyl alcohol polymer (A) from the composition to be measured)

[0111] Here, "viscosity of the composition at 20° C." refers to the viscosity of the composition to be calculated for relative viscosity at 20° C. "Viscosity reference composition" refers to a composition having a composition different from the above-mentioned composition to be calculated for relative viscosity only in that the vinyl alcohol polymer (A) is not blended.

[0112] If the relative viscosity of the composition calculated as above is within the above range, a sufficient thickening effect by the vinyl alcohol polymer (A) can be expected. From the viewpoint of obtaining a higher thickening effect, the relative viscosity of the composition calculated as above is more preferably 1.65 to 3.10, and even more preferably 1.70 to 3.10.

[0113] The viscosities of the above-mentioned composition and the viscosity reference composition are each measured at 20° C. using, for example, a B-type viscometer (rotor: LV-03 and LV-04, rotation speed: 60 rpm).

[0114] 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 further preferably 1,700 to 3,000 mPa·s. If the viscosity of the composition at 20°C is within the above range, the handling properties when used for various purposes are excellent, and a high thickening effect can be exerted in various compositions. In particular, when the composition of the present invention is used in the purposes described later, if the viscosity of the composition is within the above range, it is easy to mix, dissolve or disperse the composition of the present invention in a composition composed of various components. In addition, after mixing, the high thickening effect achieved by the composition of the present invention is advantageous in, for example, being able to obtain a composition that is difficult to drip, has excellent handling properties, or has a good appearance achieved by an appropriate viscosity.

[0115] The composition of the present invention can be prepared by, for example, adding a solid vinyl alcohol polymer (A) to a solution containing a surfactant (B) and water, and mixing and stirring. In the present invention, the vinyl alcohol polymer (A) can be put into water containing a surfactant (B) in a solid state without being prepared in advance as a water-soluble solution, so that it is easy to handle and easy to control to a desired concentration. In addition, the operation process can be simplified, and therefore, it is also advantageous in that the desired composition can be prepared efficiently.

[0116] Therefore, the present invention also provides a method for producing the composition of the present invention, which comprises adding a solid vinyl alcohol polymer (A) to a solution containing a surfactant (B) and water. The shape of the solid vinyl alcohol polymer (A) added to the water containing the surfactant (B) is not particularly limited, and may be a powder, granules, paste, etc.

[0117] In the production method of the present invention, the conditions for mixing the solid vinyl alcohol polymer (A) with water containing the surfactant (B) are not particularly limited. For example, the mixing temperature may be 0 to 50°C, preferably 10 to 40°C.

[0118] When the composition of the present invention contains components other than the vinyl alcohol polymer (A), the surfactant (B) and water, these other components may be mixed in water together with the surfactant (B) in advance. Alternatively, they may be added together with the vinyl alcohol polymer (A) into a solution containing the surfactant (B) and water, or the solution in which the vinyl alcohol polymer (A) is dissolved may be mixed.

[0119] One embodiment of the composition of the present invention is various compositions other than the composition contained in household cleaning agent products. In this specification, household cleaning agent products are tableware detergent, dishwasher detergent, clothing detergent, hard surface detergent, bleaching agent, softener, residential detergent or their mixture.

[0120] In addition, one embodiment of the composition of the present invention is a composition selected from agricultural product compositions, automotive product compositions, aviation product compositions, industrial product compositions, livestock product compositions, marine product compositions, pharmaceutical compositions, personal care product compositions, entertainment product compositions and water treatment agent compositions.

[0121] Agricultural products refer to products and materials used in agriculture and gardening. Typical examples of agricultural product compositions include pesticide compositions, such as insecticides, fungicides, insecticides and fungicides, herbicides, rodenticides, plant growth regulators, attractants, spreaders, insect repellents, defoliants, fertilizers, trace elements / trace nutrients, and the like.

[0122] When the composition of the present invention is an agricultural chemical composition, the composition may contain, in addition to the vinyl alcohol polymer (A), the surfactant (B) and water, an active ingredient for imparting a desired action or function such as insecticide or weed control.

[0123] Automobile products refer to products and materials used in the automobile industry. Examples of automobile product compositions include car wash detergents and window washer fluids.

[0124] Aviation products refer to products and materials used in the aviation industry. Examples of aviation product compositions include aircraft cleaning agents.

[0125] Industrial products refer to products and materials used in manufacturing. Examples of industrial product compositions include machine cleaning agents.

[0126] Livestock supplies refer to supplies and materials used in dairy farming and livestock production. Examples of livestock supply compositions include livestock house cleaning agents and farm equipment cleaning agents.

[0127] Marine products refer to articles and materials used in fisheries, aquaculture, shipbuilding, ocean exploration, etc. Examples of marine product compositions include ship cleaning agents, ship equipment cleaning agents, and marine product processing equipment cleaning agents.

[0128] Pharmaceutical compositions include medicines, therapeutic cosmetics, etc.

[0129] Personal care products refer to products that can be applied to the body of humans or animals other than humans. It should be noted that the "body" mentioned here includes skin, teeth, nails and hair. Personal care products include, for example, cosmetics, shampoo, shower gel, facial cleanser, toothpaste, etc.

[0130] Entertainment products refer to products and materials used in entertainment. Examples of entertainment product compositions include foam sprays, bath preparations, and foaming agents for swimming pools.

[0131] Water treatment agents refer to preparations added to water or liquids containing water as a main component (containing 50% or more of water relative to the total mass) for the purpose of preventing the generation of microorganisms, preventing corrosion, preventing oxidation, etc. Examples of water treatment agent compositions include water treatment agents for tap water pipes, industrial water treatment agents, sewage treatment agents, industrial wastewater treatment agents, and swimming pool water purifiers.

[0132] When the composition of the present invention is a water treatment agent composition, the composition may contain, on the basis of containing a vinyl alcohol polymer (A), a surfactant (B) and water, a polymer aggregating agent, an inorganic aggregating agent, etc., for example, composed of a water-soluble (co)polymer having a water-soluble monomer as a structural unit.

[0133] The vinyl alcohol polymer (A) has excellent solubility in water containing a surfactant, and therefore, the composition of the present invention containing the same can easily achieve high transparency while being controlled to a viscosity range that is consistent with the purpose of the composition. Therefore, the present invention also targets the vinyl alcohol polymer (A), which is a vinyl alcohol polymer (A) containing a monomer unit having an alkyl group and satisfies the following formula (1):

[0134] 0.010≤X / (S×N)≤0.040 (1)

[0135] [wherein, S is the content (parts by mass) of the monomer units having an alkyl group relative to 100 parts by mass of all the monomer units in the aforementioned vinyl alcohol polymer (A), X is the degree of saponification (mol %) of the aforementioned vinyl alcohol polymer (A), and N is the viscosity average degree of polymerization of the aforementioned vinyl alcohol polymer (A).]

[0136] In addition, the present invention also takes a resin material as an object, wherein the resin material comprises an α-olefin, sodium acetate and the vinyl alcohol polymer (A) of the present invention, wherein the α-olefin content is greater than 0.05 mass % and the sodium acetate content is less than 1.0 mass % based on the total mass of the resin material.

[0137] In a preferred embodiment of the present invention, the vinyl alcohol polymer (A) is included in the composition of the present invention in the form of a resin material containing α-olefins and sodium acetate. The content of α-olefin in the aforementioned resin material is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, and further preferably 0.11% by mass or more based on the total mass of the resin material. In addition, the content of α-olefin is preferably 1.0% by mass or less. If the content of α-olefin is within the above range, when the resin material is made into an aqueous solution, the alkyl groups in the monomer units having alkyl groups are easy to interact with each other between molecules, and the thickening effect of the aqueous solution is easy to increase. The α-olefin contained in the resin material may be one or more. When the resin material contains more than two α-olefins, the content of the above α-olefin refers to the total amount of the multiple α-olefins contained in the resin material.

[0138] The α-olefin contained in the resin material is preferably an α-olefin having 6 to 18 carbon atoms. As the α-olefin, for example, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene, etc. are preferred, and at least one selected from 1-dodecene and 1-hexadecene is more preferred. The α-olefin contained in the resin material may be the same as or different from the above-mentioned alkyl-containing monomer. In addition, the α-olefin contained in the resin material may be derived from the α-olefin used as the alkyl-containing monomer in the manufacture of the polyvinyl alcohol-based polymer (A), or may be added separately from the polyvinyl alcohol-based polymer (A).

[0139] The content of sodium acetate in the resin material is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, further preferably 0.9% by mass or less, and further preferably 0.85% by mass or less based on the total mass of the resin material. If 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) is easily fully expanded in the liquid, and a high thickening effect can be expected.

[0140] In the present invention, the resin material may contain components other than the vinyl alcohol polymer (A), α-olefin and sodium acetate. In a preferred embodiment of the present invention, the resin material is substantially composed of the vinyl alcohol polymer (A), α-olefin and sodium acetate. It should be noted that the aforementioned "substantially" does not exclude components that are inevitably mixed in, for example, from raw materials used in the production process of the polyvinyl alcohol polymer (A) and the resin material. In a preferred embodiment of the present invention, the content of components other than the vinyl alcohol polymer (A), α-olefin and sodium acetate contained in the resin material is generally 5% by mass or less, preferably 3% by mass or less, relative to the total mass of the resin material.

[0141] In addition, a preferred embodiment of the composition of the present invention is a composition comprising the above-mentioned resin material. That is, the composition comprises a vinyl alcohol polymer (A), an α-olefin, sodium acetate, a surfactant (B) and water (C). The content of the resin material in the composition can be appropriately determined according to the structure (type) of the vinyl alcohol polymer (A) contained in the resin material, the purpose of the composition, the desired viscosity, etc. In one embodiment of the present invention, the content of the resin material is preferably 0.1 to 5.0 mass %, more preferably 0.5 to 5.0 mass %, and further preferably 0.5 to 4.0 mass % based on the total mass of the composition.

[0142] Example

[0143] The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the following Examples. "%" and "parts" in Examples refer to mass % and mass parts, respectively, unless otherwise specified.

[0144] Hereinafter, for the resin materials containing the vinyl alcohol polymer (A) obtained in the Examples and Comparative Examples, the saponification degree (X), viscosity average degree of polymerization (N) and the amount of alkyl-containing monomer units (S) of the vinyl alcohol polymer (A) in the resin material are measured / calculated according to the following method. It should be noted that, hereinafter, "vinyl alcohol polymer" is sometimes abbreviated as "PVA".

[0145] (i) Saponification degree (X) of PVA (A)

[0146] The saponification degree (X) of PVA (A) is measured in accordance with JIS K6726:1994.

[0147] (ii) Viscosity average degree of polymerization (N) of PVA (A)

[0148] The viscosity average degree of polymerization (N) of PVA (A) is measured in accordance with JIS K6726: 1994. Specifically, when the saponification degree of PVA (A) is less than 99.5 mol %, the saponification is performed until the saponification degree reaches 99.5 mol % or more, and the viscosity average degree of polymerization is calculated by the following formula using the intrinsic viscosity [η] (liter / g) measured in water at 30°C for the obtained PVA (A).

[0149] Viscosity average degree of polymerization = ([η] × 10 4 / 8.29) (1 / 0.62)

[0150] (iii) Amount of alkyl-containing monomer units in PVA (A) (S)

[0151] The amount (S) of the alkyl-containing monomer units of PVA (A) is determined by using 1 The ratio (mol %) of the alkyl group-containing monomer unit to all the structural units of PVA (A) was calculated by H NMR and was determined by converting the molecular weight of each structural unit into parts by mass.

[0152] (iv) α-olefin content of resin material

[0153] The α-olefin content (mass %) of the resin material was measured using headspace gas chromatography.

[0154] (v) Sodium acetate content of resin material

[0155] The sodium acetate content (mass %) of the resin material was measured by a titration method in accordance with JIS-K6726.

[0156] [Example 1]

[0157] 1. Production of resin material containing vinyl alcohol polymer (A)

[0158] 900 parts by mass of vinyl acetate, 900 parts by mass of methanol and 40.0 parts by mass of 1-dodecene were added to a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe and a polymerization initiator addition port, and the nitrogen in the system was replaced for 30 minutes while nitrogen bubbling. The temperature of the reactor was started, 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 polymerization at 60°C for 4 hours, the polymerization was stopped by cooling. The solid content concentration at the time of polymerization termination was 31.3% by mass and the polymerization rate was 60%. Next, unreacted monomers were removed while adding methanol at any time under reduced pressure at 30°C to obtain a methanol solution of a vinyl ester polymer (concentration of 49.2% by mass). Next, in a methanol solution, under the conditions of a vinyl ester polymer concentration of 30%, a temperature of 40°C, and a water content of 1% in the saponification reaction liquid, a saponification reaction was carried out using sodium hydroxide as a saponification catalyst at a molar ratio of 0.0085 relative to the vinyl ester polymer. After adding the methanol solution of sodium hydroxide, a gel-like substance was generated in about 15 minutes, so it was crushed with a grinder and then placed at 40°C for 45 minutes for saponification. Thereafter, methyl acetate and methanol were added, and the mixture was placed at 40°C for 30 minutes and washed. After repeating this washing operation twice, the liquid was removed, and the obtained white solid was vacuum dried at 40°C for 16 hours to obtain a resin material (PVA-1) containing PVA. PVA-1 is a resin material containing a vinyl alcohol polymer (A), an α-olefin, and sodium acetate. The α-olefin content and sodium acetate content of the obtained PVA-1, and the saponification degree (X), viscosity average degree of polymerization (N), and amount of alkyl-containing monomer units (S) of the vinyl alcohol polymer (A) in PVA-1 were measured / calculated.

[0159] The content of the monomer units derived from α-olefin in the vinyl alcohol polymer (A) is 100% by mass based on the total amount of the monomer units having an alkyl group. The same applies to Examples 2 to 13 and Comparative Examples 1 to 5 described below.

[0160] 2. Preparation of the composition

[0161] A composition was obtained by adding 2 parts by mass of PVA-1 as a resin material containing a vinyl alcohol polymer (A) to 78 parts by mass of water, adding 20 parts by mass of sodium laureth sulfate as a surfactant (B) and stirring. The ratio of each component contained in the composition and the type of surfactant (B) are summarized in Table 2. It should be noted that since the content of α-olefin and sodium acetate in the resin material is trace, the ratio of the resin material in each composition is substantially the same as the ratio of the vinyl alcohol polymer (A).

[0162] [Examples 2 to 4, 6, 8], [Comparative Examples 2, 4 to 9]

[0163] 1. Production of resin material containing vinyl alcohol polymer (A)

[0164] The vinyl ester copolymers were prepared and saponified in the same manner as in Example 1 except that the feeding amounts of vinyl acetate and methanol, the type and amount of α-olefin used in the polymerization, and the saponification conditions such as the molar ratio of sodium hydroxide to vinyl acetate units in the saponification were changed according to Table 1. Since no gel was generated in these Examples and Comparative Examples, methyl acetate and water were added after the saponification reaction for 1 hour, and then vacuum drying was performed at 40° C. for 16 hours to obtain resin materials (PVA-2 to 4, 6, 8, 14, 16 to 21) containing the respective vinyl alcohol polymers (A).

[0165] 2. Preparation of the composition

[0166] Each composition was obtained in the same manner as in Example 1 except that the type of the resin material containing the vinyl alcohol polymer (A) and the type and addition amount of the surfactant (B) were changed as described in Table 2.

[0167] [Examples 5, 7, 9 to 12], [Comparative Examples 1, 3]

[0168] 1. Production of resin material containing vinyl alcohol polymer (A)

[0169] According to Table 1, except for changing the polymerization conditions such as the feeding amounts of vinyl acetate and methanol, the amount of α-olefin used in the polymerization, and the saponification conditions such as the molar ratio of sodium hydroxide to vinyl acetate units during saponification, the same procedures as in Example 1 were followed to produce resin materials (PVA-5, 7, 9 to 12, 13, 15) containing each vinyl alcohol polymer (A).

[0170] 2. Preparation of the composition

[0171] Except having changed the kind of the resin material containing a vinyl alcohol polymer (A) and the kind and addition amount of the surfactant (B) as described in Table 2, it carried out similarly to Example 1, and obtained the composition.

[0172] [Example 13]

[0173] Except having changed the addition amount of surfactant (B) as described in Table 2, it carried out similarly to Example 3, and obtained the composition.

[0174] [Reference Example 1]

[0175] A composition was obtained in the same manner as in Example 1 except that the resin material containing the vinyl alcohol polymer (A) was not used. This composition corresponds to the viscosity reference composition when calculating the relative viscosity of each composition.

[0176] [Measurement and evaluation of physical properties]

[0177] (1) Measurement of viscosity of composition

[0178] (i) Viscosity of the composition (measured value)

[0179] The viscosity of the compositions obtained in Examples, Comparative Examples, and Reference Examples was measured using a Brookfield viscometer (rotor: LV-03 and LV-04) at 60 rpm and 20° C. The measurement results are shown in Table 3.

[0180] (ii) Relative viscosity

[0181] The relative viscosity of the composition of each example and comparative example was calculated according to the following formula using the composition of Reference Example 1 as the viscosity reference composition.

[0182] Relative viscosity = viscosity of the composition of each example or comparative example (20°C) / viscosity of the composition of reference example 1 (20°C)

[0183] It should be noted that PVA-13 to 21 used in each comparative example is not equivalent to the polyvinyl alcohol polymer (A) described in the present invention, but for comparison, the relative viscosity of Comparative Examples 1 to 9 is calculated based on the composition after removing PVA-13 to 21 from the composition of each comparative example.

[0184] The larger the relative viscosity value, the better the thickening effect.

[0185] (2) Transparency

[0186] In the examples and comparative examples, the haze of each composition was measured using a haze meter (HZ-1 manufactured by Suga Test Instruments) using a cuvette with an optical path length of 1 cm immediately after the composition was prepared. Samples with a measured value of 5% or less were evaluated as transparent, and samples with a measured value of more than 5% were evaluated as opaque. The results are shown in Table 3.

[0187] (3) Solution stability

[0188] In the Examples and Comparative Examples, the haze of each composition was measured using a haze meter (HZ-1 manufactured by Suga Test Instruments) using a cuvette with an optical path length of 1 cm immediately after the composition was prepared and 44 days after the composition was prepared, and the solution stability was evaluated according to the following criteria. The results are shown in Table 3.

[0189] A: Haze was 5% or less immediately after the composition was prepared and 44 days after the preparation.

[0190] B: The haze immediately after the composition was prepared was 5% or less, but the haze exceeded 5% 44 days after the preparation.

[0191] C: Haze just after the composition is prepared exceeds 5%

[0192] [Table 1]

[0193]

[0194] [Table 2]

[0195]

[0196] [Table 3]

[0197]

[0198] The compositions of the present invention (Examples 1 to 13) showed a high thickening effect and were also excellent in transparency.

Claims

1. A composition comprising: (A) a vinyl alcohol polymer comprising a monomer unit having an alkyl group; (B) at least one surfactant; and (C) Water, The vinyl alcohol polymer (A) satisfies the following formula (1): 0.010≤X / (S×N)≤0.040 (1) In formula (1), S represents the content (parts by mass) of the monomer units having an alkyl group relative to 100 parts by mass of all the monomer units in the vinyl alcohol polymer (A), X represents the saponification degree (mol %) of the vinyl alcohol polymer (A), and N represents the viscosity average degree of polymerization of the vinyl alcohol polymer (A). in, The composition does not include household cleaning product compositions.

2. The composition according to claim 1, wherein The vinyl alcohol polymer (A) contains a monomer unit having an alkyl group having 4 to 16 carbon atoms.

3. The composition according to claim 1, wherein The monomer unit having an alkyl group is a monomer unit derived from an α-olefin.

4. The composition according to claim 1, wherein The monomer units having an alkyl group include monomer units derived from α-olefins, and the content of the monomer units having an alkyl group derived from α-olefins is 60% by mass or more based on the total amount of the monomer units having an alkyl group.

5. The composition according to claim 1, wherein The content S of the monomer units having an alkyl group is 1.2 to 9.0 parts by mass based on 100 parts by mass of all monomer units in the vinyl alcohol polymer (A).

6. The composition according to claim 1, wherein The saponification degree X of the vinyl alcohol polymer (A) is 40 to 80 mol%.

7. The composition according to claim 1, wherein The viscosity average polymerization degree N of the vinyl alcohol polymer (A) is 400 to 2,000.

8. The composition according to claim 1, wherein The mass ratio (A / B) of the vinyl alcohol polymer (A) to the surfactant (B) is 1 / 99 to 99 / 1.

9. The composition according to claim 1, wherein The surfactant (B) is an anionic surfactant.

10. The composition according to claim 1, wherein The surfactant (B) contains at least one selected from alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfates (alkyl ether sulfates), polyoxyalkylene alkyl ether carboxylates (alkyl ether acetates), α-olefin sulfonates, phosphate ester salts, acylamino acid salts, acyltaurates, acyl lactylates, soaps (higher fatty acids), alkyl sulfosuccinates, acyl hydrolyzed collagen salts and acylhydroxyethanesulfonates.

11. The composition according to claim 1, 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.

12. The composition according to claim 1, wherein The content of the surfactant (B) is 1 to 50% by mass based on the total mass of the composition.

13. The composition according to claim 1, wherein The relative viscosity of the composition calculated as follows 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-based composition consisting of a composition obtained by excluding the vinyl alcohol polymer (A) from the composition to be measured.

14. The composition according to claim 1, which has a viscosity at 20°C of 1,300 to 3,000 mPa·s.

15. A composition comprising: (A) a vinyl alcohol polymer comprising a monomer unit having an alkyl group; (B) a surfactant; and (C) Water, The vinyl alcohol polymer (A) satisfies the following formula (1): 0.010≤X / (S×N)≤0.040 (1) In formula (1), S represents the content (parts by mass) of the monomer units having an alkyl group relative to 100 parts by mass of all the monomer units in the vinyl alcohol polymer (A), X represents the saponification degree (mol %) of the vinyl alcohol polymer (A), and N represents the viscosity average degree of polymerization of the vinyl alcohol polymer (A). The composition is selected from agricultural product compositions, automotive product compositions, aviation product compositions, industrial product compositions, livestock product compositions, marine product compositions, pharmaceutical compositions, personal care product compositions, recreational product compositions and water treatment agent compositions.

16. The composition according to claim 15, wherein The monomer units having an alkyl group include monomer units derived from α-olefins, and the content of the monomer units having an alkyl group derived from α-olefins is 60% by mass or more based on the total amount of the monomer units having an alkyl group.

17. A method for producing the composition of claim 1 or 15, comprising: The solid vinyl alcohol polymer (A) is added to a solution containing a surfactant (B) and water.

18. A vinyl alcohol polymer (A), comprising a monomer unit having an alkyl group and satisfying the following formula (1): 0.010≤X / (S×N)≤0.040 (1) In formula (1), S is the content (parts by mass) of the monomer unit having an alkyl group relative to 100 parts by mass of all the monomer units in the vinyl alcohol polymer (A), X is the degree of saponification (mol %) of the vinyl alcohol polymer (A), and N is the viscosity average degree of polymerization of the vinyl alcohol polymer (A).

19. The vinyl alcohol polymer (A) according to claim 18, wherein The monomer units having an alkyl group include monomer units derived from α-olefins, and the content of the monomer units having an alkyl group derived from α-olefins is 60% by mass or more based on the total amount of the monomer units having an alkyl group.

20. A resin material comprising the vinyl alcohol polymer (A) according to claim 18 or 19, wherein the resin material comprises α-olefin and sodium acetate, wherein the content of α-olefin is greater than 0.05% by mass and the content of sodium acetate is less than 2.0% by mass based on the total mass of the resin material.

21. The resin material according to claim 20, wherein The α-olefin is an α-olefin having 6 to 18 carbon atoms.

22. The resin material according to claim 20, wherein The α-olefin is at least one selected from 1-dodecene and 1-hexadecene.

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