Vinyl alcohol polymer and use thereof

Abstract

The invention relates to a vinyl alcohol polymer and a use thereof. The present invention provides a vinyl alcohol polymer having properties equivalent to those of a vinyl alcohol polymer derived only from petroleum, which saves petroleum resources and suppresses carbon dioxide emissions during production when using a vinyl alcohol polymer (PVA). The present invention pertains to a vinyl alcohol polymer (X) obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), the molar ratio of (A) / (B) being 5 / 95 to 100 / 0.

Description

[0001] This application is a divisional application of a PCT application that entered the national phase, with the application number 202180056034.0 (international filing date: August 11, 2021) and the invention title "Vinyl Alcohol-Based Polymer and Its Uses". Technical Field

[0002] The present invention relates to a vinyl alcohol-based polymer obtained by polymerizing and saponifying vinyl acetate synthesized from plant-derived raw materials such as biomass, a slurry additive using the same, a drilling mud, a cement slurry, a filling agent for underground treatment, a multilayer structure having excellent oxygen barrier properties, a method for manufacturing the same, and a packaging material, a paper coating agent, a coated paper, a seed coating composition, an aqueous emulsion, an adhesive, a dispersion stabilizer for suspension polymerization of vinyl-based compounds, and a dispersion stabilization aid for suspension polymerization of vinyl-based compounds that include the same. Background Art

[0003] A vinyl alcohol-based polymer (hereinafter sometimes abbreviated as PVA) obtained by polymerizing and saponifying vinyl acetate has excellent interfacial properties and strength properties as one of the few crystalline water-soluble polymers. Therefore, in addition to being used as a stabilizer for paper processing, fiber processing, and emulsions, it also occupies an important position as PVA-based films and PVA-based fibers.

[0004] Ethylene and acetic acid, which are raw materials for vinyl acetate, are produced from fossil resources such as petroleum and natural gas. Specifically, ethylene is produced by mixing a hydrocarbon mainly composed of naphtha with steam, thermally decomposing it, and then subjecting the product to distillation separation. In addition, acetic acid is produced by a carbonylation reaction of methanol obtained by reacting carbon monoxide produced by partial oxidation of natural gas with hydrogen.

[0005] There is a risk of depletion of such fossil resources, and there are also concerns about the emission of carbon dioxide during the manufacturing process, which accelerates global warming.

[0006] In addition, in mines and the like for collecting buried substances such as petroleum and natural gas, civil engineering slurries represented by drilling cement slurries have been used.

[0007] Drilling mud serves functions such as transporting the drilled rock chips, drilling debris, etc., improving the lubricity of the drill bit or drill pipe, filling the holes in the porous foundation, offsetting the reservoir pressure (pressure from magmatic rock) generated by hydrostatic pressure, etc. This drilling mud usually has water and bentonite as the main components, and the target performance is achieved by further adding barite, salt, clay, etc. Such drilling mud is required to have temperature stability and appropriate flow characteristics such as not being significantly affected by changes in the concentration of electrolytes (such as carboxylates) in the foundation. To meet such requirements, it is necessary to adjust the viscosity of the drilling mud and inhibit the dissipation of water contained in the drilling mud (hereinafter sometimes also referred to as "dehydration"). To adjust the viscosity of the drilling mud and inhibit dehydration, a method of adding polymers such as starch, starch ether (such as carboxymethyl starch), carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, etc. is usually adopted.

[0008] However, the addition of these polymers sometimes causes the viscosity of the drilling mud to rise extremely, making it difficult to inject the drilling mud using a pump. There are also the following problems: starch and its derivatives do not sufficiently inhibit dehydration in the temperature range exceeding about 120°C, and carboxymethyl cellulose and carboxymethyl hydroxyethyl cellulose do not sufficiently inhibit dehydration in the temperature range of 140°C to 150°C.

[0009] On the other hand, drilling cement slurry is used for fixing the casing in the mine, protecting the inner wall of the mine, etc. by injecting it into the tubular void part between the formation and the casing installed in the mine and curing it. Generally, injecting the drilling cement slurry into the tubular void part is carried out using a pump. Therefore, in order to be able to easily inject it using a pump, the drilling cement slurry is required to have an extremely low viscosity and not separate.

[0010] However, in the cement grouting of the mine, material separation sometimes occurs, water escapes to the cracks in the mine, etc., resulting in defects in the cement grouting part. Therefore, an operation of adding dehydration reducers such as walnut shells, cotton seeds, clay minerals, polymer compounds, etc. to the drilling cement slurry is carried out. Among them, vinyl alcohol-based polymers are well-known dehydration reducers.

[0011] Regarding such dehydration reducers of vinyl alcohol-based polymers, for example, Patent Document 1 discloses a method of using PVA with a saponification degree of 95 mol% or more.

[0012] Patent Document 2 discloses a method of using PVA with a saponification degree of 92 mol% or less.

[0013] Patent Document 3 discloses a method of using PVA with a saponification degree of 99 mol% or more.

[0014] When recovering oil or other underground resources from natural resource layers underground, the low recovery rate of these resources becomes a problem, and various methods are used to improve it. As a representative method, there is a method of injecting a fluid into an underground oil field layer for displacement. As the fluid, brine, fresh water, a polymer aqueous solution, steam, etc. are used, and among them, the polymer aqueous solution is useful.

[0015] As an example, a method of injecting steam into an underground shale (slate) layer to cause cracks is widely adopted. In this method, first, a vertical hole (vertical mine) several kilometers deep is drilled vertically underground using a drill bit. When reaching the shale layer, a horizontal hole (horizontal mine) with a diameter of ten to several tens of centimeters is drilled horizontally. Then, a polymer aqueous solution is pressed into the vertical mine and the horizontal mine to generate cracks (fissures) from the mine, and natural gas, oil (shale gas / oil), etc. flowing out from these cracks are recovered.

[0016] At this time, in order to make the already generated cracks grow larger or generate more cracks, sometimes an underground treatment filler (additive) is used to temporarily block a part of the already generated cracks, and under this state, the fracturing fluid filled in the mine is pressurized, so that the fluid gradually infiltrates into other cracks, and the already existing cracks can be significantly grown or new cracks can be generated.

[0017] As described above, the underground treatment filler (also called a guiding agent) is used to temporarily block cracks, so sometimes a substance that can maintain its shape within a certain period of blocking the cracks and then hydrolyzes and disappears or is dissolved and removed when collecting natural gas, oil, etc. is used.

[0018] For example, there is an example of using PVA as an underground treatment filler, and Patent Document 2 discloses a guiding agent containing PVA.

[0019] In addition, Patent Document 3 discloses a guiding agent containing resin particles of PVA having a specific particle size.

[0020] In addition, Patent Document 4 discloses an underground treatment filler containing PVA with a swelling rate within a specific range after being immersed in water at 80 °C for 30 minutes.

[0021] A multilayer structure with excellent oxygen barrier properties is used as a packaging material, etc. Aluminum foil is used as an intermediate layer of such a multilayer structure because of its perfect oxygen barrier property. However, there are the following problems: if the multilayer structure containing aluminum foil is incinerated, residues will be generated, and when this multilayer structure is used as a packaging material, the contents cannot be seen, and it is also impossible to use a metal detector to check the contents.

[0022] Polyvinylidene chloride (hereinafter sometimes abbreviated as "PVDC") is not easily hygroscopic and has good oxygen barrier properties even at high humidity. Therefore, a multilayer structure formed by coating polyvinylidene chloride on various substrates is used as a packaging material or the like. As the aforementioned substrate, films such as biaxially oriented polypropylene (hereinafter sometimes abbreviated as "OPP"), biaxially oriented nylon (hereinafter sometimes abbreviated as "ON"), biaxially oriented polyethylene terephthalate (hereinafter sometimes abbreviated as "OPET"), and cellophane are used. However, there is a problem as follows: When the waste of the multilayer structure containing PVDC is incinerated, hydrogen chloride gas is generated.

[0023] For example, Patent Document 5 describes a film containing PVA, and the PVA contains 3 to 19 mol% of α-olefin units having 4 or less carbon atoms. And it is described that: The film has excellent water resistance and excellent oxygen barrier properties even at high humidity.

[0024] In addition, in particular, it is known that by coating PVA on paper, the paper strength can be enhanced, and water resistance, oil resistance, gas barrier properties, etc. can be imparted, and thus it is widely used. In addition, vinyl alcohol-based polymers are used as inorganic binders or dispersion stabilizers, and are also used as additives for imparting functions to paper. For example, as an example of using PVA as a paper coating agent, Patent Document 6 discloses an example of using PVA as a paper coating agent.

[0025] Seed treatment means: applying a material to seeds in order to improve processability, protect seeds before germination, and support the germination process. Furthermore, seed treatment imparts pest resistance characteristics to seeds or the plants generated as a result by combining the use of active "pesticide" components such as insecticides, fungicides, and nematicides. In addition, a plant growth regulator for improving seed treatment characteristics can be added to the seed coating mixture. Seed treatment eliminates or at least reduces the need for traditional broadcast spraying of foliar fungicides or insecticides.

[0026] Unfortunately, it is known that a variety of well-known seed treatments generate excessive dust during the storage and application of seed materials, which may cause large seeds to aggregate and may reduce the germination efficiency.

[0027] For example, Patent Documents 7 to 20 disclose various and multiple seed coating compositions and ingredients for improving the treatment, germination, storage, and growth characteristics of seeds.

[0028] Typically, an aqueous seed coating composition contains an aqueous medium, one or more functional additives, a binder that forms a matrix for various functional additives during drying after application, and a protective film for covering seeds.

[0029] Several seed treatments incorporate prophylactic treatments and enhancements, such as treatments with pesticides (such as fungicides and / or insecticides) combined with more than one plant-derived agent and / or inoculant.

[0030] As disclosed in the previously cited references, a variety of different materials have been used as binders in aqueous seed coating compositions.

[0031] For example, among the binder materials disclosed in Patent Documents 8 to 15, it generally includes polyvinyl alcohol homopolymers, copolymers, and their functionally modified and / or crosslinked types (versions).

[0032] Some of the commercially available polymeric binders containing several polyvinyl alcohols are plagued by low water solubility / dipole solubility, low mobility of covering seeds, high levels of dusting, and / or lack of plant properties.

[0033] For example, a seed coating additive optimized to reduce dusting may result in poor seed mobility. This can be illustrated by the fact that the components added to increase the adhesion of the coating are not easily affected by dust, and the adhesion that usually reduces dusting will cause problems with mobility, and thus may cause unacceptable mobility and flatness characteristics.

[0034] On the other hand, factors that increase the mobility of coated seeds have a negative impact on the dusting characteristics. For mechanical planting of seeds, it is essential that the seeds do not aggregate. Seeds coated with a polymer binder with insufficient hydrophobicity will stick to each other especially when exposed to warm and humid air in the storage room in summer.

[0035] It is necessary to improve long-term storage stability, maintain or improve seed germination and seed treatment characteristics, and provide a water-based matrix with low dusting characteristics, high biodegradability, and cost efficiency for seed coating.

[0036] Based on its use as a raw material for fibers and films, PVA also makes wide use of its water-soluble characteristics and is widely used as a paper processing agent, fiber processing agent, binder for inorganic substances, adhesive, stabilizer for emulsion polymerization and suspension polymerization, etc. In particular, PVA is known as a dispersion stabilizer for emulsion polymerization of vinyl ester monomers represented by vinyl acetate. When PVA is used as a dispersion stabilizer for emulsion polymerization and emulsion polymerization is carried out, the resulting vinyl ester-based aqueous emulsion is widely used in various fields such as various adhesives, coating matrices, coating agents, impregnated paper uses, non-woven products, etc., mainly in woodworking applications, as well as various binders, admixtures, concrete binding materials, paper processing, and fiber processing.

[0037] For example, Patent Document 21 discloses an aqueous emulsion with excellent high-speed coating properties and initial adhesiveness.

[0038] In addition, Patent Document 22 discloses a woodworking adhesive having excellent water-resistant adhesiveness by using PVA containing 1 to 10 mol% of ethylene units.

[0039] PVA is generally used as a dispersant for suspension polymerization of vinyl chloride. In suspension polymerization, a vinyl-based compound dispersed in an aqueous medium is polymerized using an oil-soluble catalyst to obtain a granular vinyl polymer. At this time, for the purpose of improving the quality of the obtained polymer, a dispersant is added to the aqueous medium. Dominant factors for the quality of the vinyl polymer obtained by suspension polymerization of a vinyl-based compound include: polymerization rate, ratio of water to vinyl-based compound (monomer), polymerization temperature, type and amount of oil-soluble catalyst, form of the polymerization vessel, stirring speed of the contents in the polymerization vessel, and type of dispersant. Among them, the type of dispersant has a significant impact on the quality such as the particle size distribution or plasticizer absorbability of the vinyl polymer. PVA is used alone as a dispersant, or in combination with PVA or cellulose derivatives such as methyl cellulose and carboxymethyl cellulose as a dispersant.

[0040] For example, there are examples of using PVA as a dispersion stabilizer for suspension polymerization. In Non-Patent Document 1, as a dispersant used in suspension polymerization of vinyl chloride, PVA having a polymerization degree of 2000 and a saponification degree of 80 mol% and PVA having a polymerization degree of 700 to 800 and a saponification degree of 70 mol% are disclosed.

[0041] In addition, Patent Document 23 discloses a dispersant containing PVA, wherein the PVA has an average polymerization degree of 500 or more, the ratio of weight-average polymerization degree Pw to number-average polymerization degree Pn (Pw / Pn) is 3.0 or less, and has a structure [-CO-(CH=CH) 2 , the absorbances at wavelengths of 280 nm and 320 nm in a 0.1% aqueous solution are 0.3 or more and 0.15 or more, respectively, and the ratio (b) / (a) of the absorbance (b) at wavelength 320 nm to the absorbance (a) at wavelength 280 nm is 0.30 or more.

[0042] It has been conventionally known that a partially saponified vinyl alcohol-based polymer is used as a dispersant for suspension polymerization of a vinyl-based compound (e.g., vinyl chloride). However, in the case of using a normal partially saponified PVA, regarding the properties required for the obtained vinyl-based resin, specifically (1) high plasticizer absorbability even when used in a small amount, (2) no foreign matters such as fish eyes, (3) easy removal of the remaining monomer components, and (4) less formation of coarse particles, it cannot be said that the required properties are necessarily satisfied.

[0043] In order to meet the above-mentioned required performance, methods have been proposed such as using PVA with a low degree of polymerization, a low degree of saponification, and an oxyalkylene group in the side chain as a dispersion aid for suspension polymerization of vinyl-based compounds (refer to Patent Documents 24 to 30); a method using PVA having an ionic group (refer to Patent Document 31); a method of previously preparing an aqueous solution using PVA having an alkyl group at the end and introducing it into a polymerization tank (refer to Patent Document 32), etc.

[0044] It is difficult to provide a vinyl alcohol-based polymer that has properties equivalent to or better than those of vinyl alcohol-based polymers derived solely from petroleum, can save petroleum resources, and suppress carbon dioxide emissions during the manufacturing process. Therefore, in order to reduce the amount of petroleum resources used, research has also been conducted on changing the composition of the resin composition according to the application, and for example, a packaging bag made of a biodegradable resin composition containing a biodegradable resin other than petroleum-derived raw materials in the resin composition has been developed (refer to Patent Document 33). However, in this case, compared with petroleum-based resin materials, it is difficult to improve productivity due to significantly poor processing adaptability such as tensile strength, tear strength, sealing strength, and hardness, and it is also difficult to improve durability (for example, refer to Paragraph 0004 of Japanese Unexamined Patent Application Publication No. 2021-14311).

[0045] Prior Art Documents

[0046] Patent Documents

[0047] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2000-119585

[0048] Patent Document 2: International Publication No. 2019 / 031613

[0049] Patent Document 3: International Publication No. 2019 / 131939

[0050] Patent Document 4: International Publication No. 2019 / 131952

[0051] Patent Document 5: Japanese Unexamined Patent Application Publication No. 2000-119585

[0052] Patent Document 6: Japanese Unexamined Patent Application Publication No. 2017-43872

[0053] Patent Document 7: Specification of US Patent Application Publication No. 3698133

[0054] Patent Document 8: Specification of US Patent Application Publication No. 3707807

[0055] Patent Document 9: Specification of US Patent Application Publication No. 3947996

[0056] Patent Document 10: Specification of US Patent Application Publication No. 4249343

[0057] Patent Document 11: US Patent Application Publication No. 4,272,417 Specification

[0058] Patent Document 12: US Patent Application Publication No. 5,849,320 Specification

[0059] Patent Document 13: US Patent Application Publication No. 5,876,739 Specification

[0060] Patent Document 14: US Patent No. 90,101,131 Specification

[0061] Patent Document 15: International Publication No. WO2017 / 187994

[0062] Patent Document 16: US Patent Application Publication No. 4,729,190 Specification

[0063] Patent Document 17: International Publication No. WO90 / 11011

[0064] Patent Document 18: International Publication No. WO2005 / 062899

[0065] Patent Document 19: International Publication No. WO2008 / 037489

[0066] Patent Document 20: International Publication No. WO2013 / 166020

[0067] Patent Document 21: Japanese Patent No. 6,647,217 Gazette

[0068] Patent Document 22: Japanese Patent No. 3,466,316 Gazette

[0069] Patent Document 23: Japanese Patent Publication No. 5-88251 Gazette

[0070] Patent Document 24: Japanese Patent Laid-Open No. 9-100301 Gazette

[0071] Patent Document 25: Japanese Patent Laid-Open No. 10-147604 Gazette

[0072] Patent Document 26: Japanese Patent Laid-Open No. 10-259213 Gazette

[0073] Patent Document 27: Japanese Patent Laid-Open No. 11-217413 Gazette

[0074] Patent Document 28: Japanese Patent Laid-Open No. 2001-040019 Gazette

[0075] Patent Document 29: Japanese Patent Laid-Open No. 2002-069105 Gazette

[0076] Patent Document 30: Japanese Patent Laid-Open No. 2007-063369

[0077] Patent Document 31: Japanese Patent Laid-Open No. 10-168128

[0078] Patent Document 32: International Publication No. 2015 / 019614

[0079] Patent Document 33: Japanese Patent Laid-Open No. 2009-155516

[0080] Non-Patent Document

[0081] Non-Patent Document 1: Published by the Polymer Society in 1984, "Poval", pp. 369 - 373 and p. 411 Summary of the Invention

[0082] Problems to be Solved by the Invention

[0083] There has not been obtained a vinyl alcohol-based polymer that has properties equivalent to or better than those of a vinyl alcohol-based polymer derived solely from petroleum, can save petroleum resources, and can suppress carbon dioxide emissions during the manufacturing process

[0084] An object of the present invention is to provide a vinyl alcohol-based polymer having properties equivalent to or better than those of a vinyl alcohol-based polymer derived solely from petroleum. Further, an object of the present invention is to provide a vinyl alcohol-based polymer having properties equivalent to or better than those of a vinyl alcohol-based polymer derived solely from petroleum, which can save petroleum resources and suppress carbon dioxide emissions during the manufacturing process when using the vinyl alcohol-based polymer (PVA).

[0085] Furthermore, another object of the present invention is to save petroleum resources and suppress carbon dioxide emissions during the manufacturing process when using the vinyl alcohol-based polymer (PVA) for each use as a sizing additive, drilling mud, cement slurry, underground treatment filler, multilayer structure with excellent oxygen barrier properties, its manufacturing method and packaging material having the same, paper coating agent, coated paper, seed coating composition, aqueous emulsion, adhesive, dispersion stabilizer for suspension polymerization of vinyl-based compounds, and dispersion stabilizing aid for suspension polymerization of vinyl-based compounds. Another object of the present invention is to provide an underground treatment filler containing a vinyl alcohol-based polymer (PVA) that does not have poor appearance

[0086] Means for Solving the Problems

[0087] As a result of intensive research, the present inventors have found that by using a vinyl ester monomer derived from plants in a part thereof and using a vinyl alcohol-based polymer obtained by polymerizing and saponifying the vinyl ester monomer, the above object can be achieved, and the present invention has been completed

[0088] That is, the invention includes the following.

[0089] [1] A vinyl alcohol-based polymer (X) which is obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), and the molar ratio of (A) / (B) is 5 / 95 to 100 / 0.

[0090] [2] The vinyl alcohol-based polymer (X) according to [1], which further contains an ethylene unit, and the content rate of the ethylene unit is 1 mol% or more and less than 20 mol%.

[0091] [3] An additive for slurry, which contains the vinyl alcohol-based polymer (X) according to [1] or [2].

[0092] [4] A drilling mud which contains the additive for slurry according to [3].

[0093] [5] The drilling mud according to [4], which further contains water and bentonite.

[0094] [6] A cement slurry which contains the additive for slurry according to [3].

[0095] [7] The cement slurry according to [6], which further contains a liquid agent and a curable powder.

[0096] [8] A filling agent for underground treatment, which contains the vinyl alcohol-based polymer (X) according to [1] or [2],

[0097] and the molar ratio of (A) / (B) is 5 / 95 to 90 / 10.

[0098] [9] The filling agent for underground treatment according to [8], wherein the vinyl alcohol-based polymer (X) contains another unsaturated monomer (C) capable of copolymerizing with the vinyl ester monomer.

[0099]

[10] The filling agent for underground treatment according to [8] or [9], which further contains a plasticizer.

[0100]

[11] A multilayer structure which has: a layer (C) containing the vinyl alcohol-based polymer (X) according to [1] or [2] and a layer (D) containing a resin,

[0101] wherein the resin is at least one resin selected from polyolefin resins, polyester resins, polyamide resins, polyvinyl chloride (PVC) resins, ABS resins, polylactic acid (PLA) resins, polybutylene succinate (PBS) resins, polyhydroxyalkanoate (PHA) resins, polyhydroxybutyrate / hydroxyhexanoate (PHBH) resins, starch, and cellulose.

[0102]

[12] The method for manufacturing a multilayer structure according to

[11] includes: a step of preparing a coating agent by preparing an aqueous solution containing the aforementioned vinyl alcohol-based polymer (X); and a step of coating the coating agent on the surface of a resin-containing substrate.

[0103] The aforementioned resin is at least one resin selected from polyolefin resins, polyester resins, polyamide resins, polyvinyl chloride (PVC) resins, ABS resins, polylactic acid (PLA) resins, polybutylene succinate (PBS) resins, polyhydroxyalkanoate (PHA) resins, polyhydroxybutyrate / hydroxyhexanoate (PHBH) resins, starch, and cellulose.

[0104]

[13] A packaging material comprising the multilayer structure according to

[11] .

[0105]

[14] A paper coating agent comprising the vinyl alcohol-based polymer (X) according to [1] or [2].

[0106]

[15] Coated paper obtained by coating the paper with the paper coating agent according to

[14] .

[0107]

[16] The coated paper according to

[15] , which is a base paper for release paper.

[0108]

[17] The coated paper according to

[15] , which is an oil-resistant paper.

[0109]

[18] A seed coating composition comprising the vinyl alcohol-based polymer (X) according to [1] or [2].

[0110]

[19] The seed coating composition according to

[18] , which further comprises one or more hydrophobic pesticides.

[0111]

[20] An aqueous emulsion which is an aqueous emulsion comprising a dispersant and a dispersed substance.

[0112] The aforementioned dispersed substance comprises a polymer (Y1) containing an ethylenically unsaturated monomer unit.

[0113] The aforementioned dispersant comprises the vinyl alcohol-based polymer (X) according to [1] or [2].

[0114]

[21] In the aqueous emulsion according to

[20] , the polymer (Y1) containing an ethylenically unsaturated monomer unit is a polymer having a specific unit derived from at least one selected from vinyl ester-based monomers, (meth)acrylate-based monomers, styrene-based monomers, and diene-based monomers, and the content of the aforementioned unit in the polymer relative to all monomer units is 70% by mass or more.

[0115]

[22] The aqueous emulsion according to

[20] or

[21] further contains a polyisocyanate compound.

[0116]

[23] An adhesive containing the aqueous emulsion described in any one of

[20] to

[22] .

[0117]

[24] A dispersion stabilizer for suspension polymerization of vinyl compounds, comprising the vinyl alcohol-based polymer (X) described in [1] or [2].

[0118]

[25] A method for producing a vinyl-based resin, comprising: a step of performing suspension polymerization of a vinyl compound in the presence of the dispersion stabilizer for suspension polymerization described in

[24] .

[0119]

[26] The method for producing a vinyl-based resin according to

[25] , comprising: a step of performing suspension polymerization of a vinyl compound in the presence of the aforementioned dispersion stabilizer for suspension polymerization and a further dispersion stabilizing aid,

[0120] The aforementioned dispersion stabilizing aid contains a vinyl alcohol-based polymer (Y2) having a saponification degree of less than 65 mol%.

[0121]

[27] A dispersion stabilizing aid for suspension polymerization of vinyl compounds, comprising the vinyl alcohol-based polymer (X) described in [1] or [2],

[0122] The saponification degree of the aforementioned vinyl alcohol-based polymer (X) is 20 mol% or more and less than 60 mol%.

[0123]

[28] A method for producing a vinyl-based resin, comprising: a step of performing suspension polymerization of a vinyl compound in the presence of the dispersion stabilizing aid for suspension polymerization described in

[27] and a dispersion stabilizer for suspension polymerization.

[0124] The aforementioned dispersion stabilizer for suspension polymerization contains a vinyl alcohol-based polymer (Y3) having a saponification degree of 65 mol% or more and a viscosity-average degree of polymerization of 600 or more.

[0125]

[29] The method for producing a vinyl-based resin according to

[28] , wherein the mass ratio of the aforementioned dispersion stabilizer to the aforementioned dispersion stabilizing aid (dispersion stabilizer / dispersion stabilizing aid) is 95 / 5 to 20 / 80.

[0126] Advantages of the Invention

[0127] According to the present invention, by using a part of PVA as a plant-derived substance, it is possible to provide a vinyl alcohol-based polymer having properties equal to or superior to those of a vinyl alcohol-based polymer derived only from petroleum. Therefore, according to the present invention, it is possible to save petroleum resources and reduce the emission of carbon dioxide during the manufacturing process to suppress global warming.

[0128] In addition, according to the present invention, by using a part of PVA used in various applications such as an additive for slurry, drilling mud, cement slurry, a filling agent for underground treatment, a multilayer structure having excellent oxygen barrier properties, a method for manufacturing the same, a packaging material including the same, a paper coating agent, an aqueous emulsion, an adhesive, a seed coating composition, a dispersion stabilizer for suspension polymerization of a vinyl-based compound, and an auxiliary agent for dispersion stabilization for suspension polymerization of a vinyl-based compound as a plant-derived substance, it is possible to save petroleum resources and reduce the amount of carbon dioxide emissions during the manufacturing process, thereby suppressing global warming.

[0129] In addition, according to the present invention, a filling agent for underground treatment containing a vinyl alcohol-based polymer (PVA) without appearance defects can be provided. Further, according to the present invention, a multilayer structure having excellent gas barrier properties under high humidity and a packaging material including the same can be provided. Detailed Embodiments

[0130] Hereinafter, embodiments for implementing the present invention will be described.

[0131] [Vinyl Alcohol-Based Polymer (X)]

[0132] The vinyl alcohol-based polymer (X) of the present invention is a vinyl alcohol-based polymer (X) (hereinafter sometimes abbreviated as PVA(X)) obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), and the molar ratio of (A) / (B) is 5 / 95 to 100 / 0.

[0133] The plant-derived vinyl ester monomer (A) (hereinafter also simply referred to as "vinyl ester monomer (A)") means that it is derived from biomass (non-fossil raw materials), specifically: a vinyl ester monomer (preferably vinyl acetate) obtained by reacting ethylene (hereinafter also referred to as bioethylene) obtained from plant raw materials such as sugarcane and corn with a lower carboxylic acid such as acetic acid. As the biomass, it can be a single non-fossil raw material or a mixture of non-fossil raw materials, and examples thereof include cellulose-based crops (pulp, hibiscus, wheat straw, rice straw, waste paper, papermaking residues, etc.), wood, charcoal, compost, natural rubber, cotton, sugarcane, okara, oils and fats (rapeseed oil, cottonseed oil, soybean oil, coconut oil, castor oil, etc.), carbohydrate-based crops (corn, tubers, wheat, rice, rice husk, rice bran, old rice, cassava, sago palm, etc.), bagasse, buckwheat, soybean, essential oils (pine oil, orange oil, eucalyptus oil, etc.), pulp black liquor, vegetable oil residues, etc. In addition, the biomass is not limited to biofuel harvests, and agricultural residues, municipal waste, industrial waste, sediments in the paper industry, waste in pastures, wood, forest waste, etc. can also be cited. More specifically, as an example, the sugar solution taken from sugarcane and corn is heated and concentrated and crystallized, and the crude sugar and waste syrup obtained therefrom are separated using a centrifuge, the waste syrup is diluted with water to an appropriate concentration, and ethanol (bioethanol) is generated by fermenting it with yeast. The bioethanol is heated and ethylene is obtained by an intramolecular dehydration reaction in the presence of a catalyst. In other examples, pulp black liquor is treated with an acid or an enzyme, etc. to generate ethanol (bioethanol), and ethylene is obtained in the same way. On the other hand, the petroleum-derived vinyl ester monomer (B) (hereinafter also simply referred to as "vinyl ester monomer (B)") means a vinyl ester monomer obtained using ethylene derived from naphtha obtained in the usual way as a raw material.

[0134] PVA(X) is synthesized by saponifying a vinyl ester polymer obtained by polymerizing the plant-derived vinyl ester monomer (A) and the petroleum-derived vinyl ester monomer (B).

[0135] As the polymerization method of the vinyl ester monomer, examples thereof include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, etc. From an industrial perspective, solution polymerization, emulsion polymerization or dispersion polymerization is preferred. The polymerization of the vinyl ester monomer can be any polymerization method among batch method, semi-batch method and continuous method.

[0136] Examples of the vinyl ester monomers (vinyl ester monomer (A) and vinyl ester monomer (B)) include, for example, vinyl acetate, vinyl formate, vinyl propionate, vinyl octanoate, vinyl tert-carboxylate, etc. Among these, from an industrial perspective, vinyl acetate is preferred. Vinyl ester monomer (A) and vinyl ester monomer (B) may be the same compound (e.g., vinyl acetate) or different compounds. That is, PVA(X) may be a homopolymer of one vinyl ester monomer or a copolymer of different vinyl ester monomers.

[0137] The polymerization initiator used in the polymerization is selected from known polymerization initiators, such as azo initiators, peroxide initiators, and redox initiators, according to the polymerization method. Examples of azo initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), etc. Examples of peroxide initiators include diisopropyl peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, diethoxyethyl peroxydicarbonate, etc., which are peroxydicarbonate compounds; tert-butyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, etc., which are perester compounds; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl 2-peroxybenzoate, etc. Potassium persulfate, ammonium persulfate, hydrogen peroxide, etc. can be combined with the above initiators to form a polymerization initiator. The redox initiator is, for example, a polymerization initiator obtained by combining the above peroxide initiator or oxidant (potassium persulfate, ammonium persulfate, hydrogen peroxide, etc.) with a reducing agent such as sodium bisulfite, sodium bicarbonate, tartaric acid, L-ascorbic acid, Rongalite, etc. The amount of the polymerization initiator varies depending on the polymerization catalyst, so it cannot be generalized and is selected according to the polymerization rate.

[0138] In addition, PVA(X) may be a substance obtained by saponifying a vinyl ester copolymer obtained by copolymerizing a vinyl ester monomer (vinyl ester monomer (A) and vinyl ester monomer (B)) and other copolymerizable unsaturated monomers within the scope not impairing the gist of the present invention. Examples of the other unsaturated monomers include α-olefins such as ethylene, propylene, n-butene, and isobutene; acrylic acid and its salts; acrylate esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and octadecyl acrylate; methacrylic acid and its salts; methacrylate esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and octadecyl methacrylate; acrylamide; acrylamide derivatives such as N-methylacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, diacetone acrylamide, acrylamidopropanesulfonic acid and its salts, acrylamidopropyldimethylamine and its salts or quaternary salts, and N-hydroxymethylacrylamide and its derivatives; methacrylamide; methacrylamide derivatives such as N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidopropanesulfonic acid and its salts, methacrylamidopropyldimethylamine and its salts or quaternary salts, and N-hydroxymethylmethacrylamide and its derivatives; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, dodecyl vinyl ether, and stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, and fumaric acid and their salts or monoalkyl esters or dialkyl esters; vinylsilyl compounds such as vinyltrimethoxysilane; and isopropyl acetate. Among them, one or more kinds may be copolymerized. Sometimes, PVA having such a copolymer component is referred to as "modified PVA".

[0139] As a component for copolymerization with vinyl ester monomers, that is, other unsaturated monomers, ethylene is sometimes particularly preferred. That is, PVA(X) sometimes preferably further contains ethylene units. When PVA(X) further contains ethylene units, the lower limit of the content of ethylene units only needs to exceed 0 mol%, and can be 0.1 mol% or more. The content of ethylene units is preferably 1 mol% or more and less than 20 mol%. The content of ethylene units is more suitably 1.5 mol% or more, and further suitably 2 mol% or more. On the other hand, the content of ethylene units is suitably 15 mol% or less, more suitably 10 mol% or less, and further suitably 8.5 mol% or less. When ethylene is used as the copolymerization component, the ethylene can be a substance usually produced from petroleum-derived raw materials, can use the above-mentioned bioethanol as a raw material, or can also be a mixture of the two.

[0140] In the uses of additives for slurries, drilling muds, and cement slurries, it is particularly preferred that PVA(X) is obtained by copolymerizing ethylene with vinyl ester monomer (A) and vinyl ester monomer (B). By copolymerizing ethylene with vinyl esters, the solubility of saponified PVA(X) can be reduced. Thereby, dehydration occurring from the slurry at high temperatures and an increase in the viscosity of the slurry can be further suppressed.

[0141] Regarding the content of ethylene units in PVA(X), from the viewpoint of having equivalent or better properties compared to petroleum-derived vinyl alcohol polymers in the uses of additives for slurries, drilling muds, and cement slurries, it is preferably less than 10 mol% of all the structural units of PVA(X), more preferably less than 9 mol%, and further preferably less than 8 mol%. When PVA(X) is a copolymer containing ethylene units in the structural units, the lower limit of the content of ethylene units only needs to exceed 0 mol%, and can be 0.1 mol% or more, or can also be 1 mol% or more.

[0142] The content of ethylene units in PVA(X) is a value obtained based on the (X) precursor of PVA, that is, the 1 1H-NMR of the vinyl ester polymer. That is, after subjecting the vinyl ester polymer as the precursor to reprecipitation purification three or more times with a mixed solution of n-hexane and acetone, it is dried under reduced pressure at 80 °C for 3 days to prepare a vinyl ester polymer for analysis. This vinyl ester polymer is dissolved in DMSO-d 6 , and using a 500 MHz 1 1H-NMR (JEOL GX-500), the measurement is carried out at 80 °C. Using the peak from the main-chain methylene of the vinyl ester (integral value P: 4.7 ppm to 5.2 ppm) and the peak from the main-chain methylene of ethylene, vinyl ester, and the third component (integral value Q: 0.8 ppm to 1.6 ppm), the content of ethylene units is calculated.

[0143] Content ratio of ethylene unit (mol%) = 100 × ((Q - 2P) / 4) / P

[0144] As described above, other unsaturated monomers copolymerizable with vinyl ester monomers may be copolymerized in PVA(X). PVA(X) obtained by copolymerization with unsaturated monomers such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids or their salts, their monoalkyl esters or dialkyl esters has a structural unit containing a carboxylic acid, and thus has more excellent water solubility. When used as a filling agent for underground treatment, a paper coating agent, a seed coating composition, or a dispersion stabilizer for suspension polymerization of vinyl-based compounds, it is preferable from the viewpoints of more appropriate dissolution and less environmental burden.

[0145] In the uses of a filling agent for underground treatment, a paper coating agent, a seed coating composition, or a dispersion stabilizer for suspension polymerization of vinyl-based compounds, when PVA(X) is a modified PVA, the modification rate of the modified PVA, that is, the content ratio of the structural unit derived from "other unsaturated monomers copolymerizable with vinyl ester monomers" relative to all the structural units constituting the modified PVA is preferably 0.5 mol% or more and 10 mol% or less, more preferably 0.7 mol% or more and 8 mol% or less, and further preferably 1.0 mol% or more and 5 mol% or less.

[0146] It should be noted that the modification rate in the modified PVA can be determined based on the 1 1H-NMR spectrum of a PVA-based resin with a saponification degree of 100 mol% (solvent: DMSO-d 6 , internal standard: tetramethylsilane). Specifically, the modification rate can be calculated based on the peak areas of protons, methylene protons and methylene protons in the modified group, methylene protons in the main chain, and protons of hydroxyl groups linked to the main chain.

[0147] As a component to be copolymerized with a vinyl ester monomer, i.e., other unsaturated monomers, in the uses of paper coating agents, multilayer structures, packaging materials using the same, aqueous emulsions, and adhesives using the same, ethylene is particularly preferred. The content of the ethylene unit in the PVA(X) containing an ethylene unit is preferably 1 mol% or more and less than 20 mol%. When the content of the ethylene unit is 1 mol% or more, the resulting PVA(X) has more excellent gas barrier properties. The content of the ethylene unit is more suitably 1.5 mol% or more, and further suitably 2 mol% or more. On the other hand, when the content of the ethylene unit is less than 20 mol%, the PVA(X) has appropriate water solubility and is easily prepared in the form of an aqueous solution. The content of the ethylene unit is suitably 15 mol% or less, more suitably 10 mol% or less, and further suitably 8.5 mol% or less. When ethylene is used as the copolymerization component, the ethylene can be a substance usually manufactured from petroleum-derived raw materials, can use the above-mentioned bioethanol as a raw material, and can also be a mixture of the two. When the PVA(X) is a copolymer containing an ethylene unit in the structural unit, the lower limit value of the content of the ethylene unit only needs to exceed 0 mol%, and can be 0.1 mol% or more, or 1 mol% or more.

[0148] When polymerizing the vinyl ester monomer (A) and the vinyl ester monomer (B), a chain transfer agent may coexist for the purpose of adjusting the degree of polymerization of the PVA(X), etc. Examples of the chain transfer agent include aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, and benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone, and cyclohexanone; thiols such as 2-hydroxyethanethiol; thioacids such as 3-mercaptopropionic acid and thioacetic acid; halogenated hydrocarbons such as trichloroethylene and perchloroethylene, etc., and aldehydes or ketones are preferred among them. The addition amount of the chain transfer agent only needs to be determined according to the chain transfer constant of the chain transfer agent, the degree of polymerization of the PVA to be achieved, etc.

[0149] As the saponification reaction of the vinyl ester polymer, a known alcoholysis and / or hydrolysis reaction using a basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methoxide or an acidic catalyst such as p-toluenesulfonic acid can be applied.

[0150] Examples of 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; aromatic hydrocarbons such as benzene and toluene, etc. They can be used alone in one kind, or two or more kinds can be used in combination. Among them, it is simple to use methanol or a mixed solution of methanol and methyl acetate as the solvent and carry out the saponification reaction in the presence of sodium hydroxide as the basic catalyst, so it is preferred.

[0151] (Degree of saponification)

[0152] In the uses as an additive for slurries, drilling mud, and cement slurry, the saponification degree of PVA(X) is preferably 99 mol% or more, more preferably 99.5 mol% or more. PVA is a crystalline polymer having a crystalline portion caused by hydrogen bonds of the contained hydroxyl groups. The crystallinity of PVA(X) increases with an increase in the saponification degree, and the increase in crystallinity reduces the water solubility of PVA(X). In particular, PVA(X) shows a significant change in solubility in hot water at a saponification degree of 99.5 mol%. Therefore, PVA(X) with a saponification degree of 99.5 mol% or more sometimes has high water resistance (low solubility) due to the strength of its hydrogen bonds and has water resistance comparable to that of chemically crosslinked PVA(X). Therefore, by setting the saponification degree of PVA(X) to 99.5 mol% or more, even non-chemically crosslinked PVA(X) can suppress dehydration and high viscosity increase of the slurry. As a result, corresponding to the ability to omit the chemical crosslinking process, it is advantageous in terms of cost. Especially when used as an additive for cement slurry, if the saponification degree is low, it may not be possible to sufficiently suppress dehydration at high temperatures.

[0153] It should be noted that the saponification degree of PVA(X) is a value measured in accordance with JIS K6726:1994.

[0154] In the uses as a filling agent for underground treatment and a paper coating agent, the saponification degree of PVA(X) is preferably 90 mol% or more, more preferably 98 mol% or more, further preferably 99 mol% or more, and particularly preferably 99.5 mol% or more. PVA is a crystalline polymer having a crystalline portion caused by hydrogen bonds of the contained hydroxyl groups. The crystallinity of PVA(X) increases with an increase in the saponification degree, and the increase in crystallinity reduces the water solubility of PVA(X).

[0155] In the uses as a multilayer structure and a packaging material using the same, the saponification degree of PVA(X) is not particularly limited and is preferably 80 to 99.99 mol%. When the saponification degree is 80 mol% or more, the oxygen barrier property of the obtained multilayer structure is more excellent. The saponification degree is more preferably 85 mol% or more, and further preferably 90 mol% or more. On the other hand, when the saponification degree is 99.99 mol% or less, PVA(X) can be stably produced. The saponification degree is more preferably 99.5 mol% or less, further preferably 99 mol% or less, and particularly preferably 98.5 mol% or less.

[0156] In the use as a seed coating composition, the saponification degree of PVA(X) is preferably 65 mol% or more, more preferably 67 mol% or more, further preferably 69 mol% or more, and particularly preferably 70 mol% or more. When the saponification degree of PVA(X) is 60 mol% or more, the water solubility of PVA(X) is more excellent, which is more advantageous in the production of the seed coating composition.

[0157] In the use of the aqueous emulsion and the adhesive using the same, the saponification degree of PVA(X) is not particularly limited, and is preferably 80 to 99.99 mol%. By making the saponification degree 80 mol% or more, it is sometimes possible to further suppress the aggregation of the particles of the aqueous emulsion during storage, and the stability can be made better. The saponification degree is more preferably 82 mol% or more, and still more preferably 85 mol% or more. On the other hand, by making the saponification degree 99.99 mol% or less, there is a tendency that the particles of the aqueous emulsion can be more stabilized and are easier to manufacture. The saponification degree is more preferably 99.5 mol% or less, still more preferably 99 mol% or less, and particularly preferably 98.5 mol% or less.

[0158] In the use of the dispersion stabilizer for suspension polymerization of vinyl-based compounds, the saponification degree of PVA(X) is preferably 60 mol% or more and 99.5 mol% or less, more preferably 65 mol% or more and 99.2 mol% or less, and still more preferably 68 mol% or more and 99.0 mol% or less. When the saponification degree is 60 mol% or more, the water solubility of PVA(X) is excellent, and it is easy to prepare an aqueous solution of the dispersion stabilizer. On the other hand, if the saponification degree is 99.5 mol% or less, when suspension polymerization is carried out using the obtained dispersant, the formation of a large amount of coarse particles can be further suppressed. In addition, sometimes the resulting vinyl-based polymer particles have high porosity and excellent plasticizer absorbability.

[0159] In the use of the dispersion stabilizing aid for suspension polymerization of vinyl-based compounds, the saponification degree of PVA(X) is 20 mol% or more and less than 60 mol%, preferably 25 mol% or more and 58 mol% or less, and more preferably 30 mol% or more and 56 mol% or less. When the saponification degree is 20 mol% or less, it is difficult to manufacture PVA(X). On the other hand, if the saponification degree is 60 mol% or more, it is sometimes difficult to remove the monomer component from the vinyl-based polymer particles obtained by suspension polymerization of vinyl-based compounds, or the plasticizer absorbability of the resulting vinyl-based polymer particles decreases.

[0160] (Degree of polymerization)

[0161] In the use of additives for slurries, drilling muds, and cement slurries, the degree of polymerization of PVA(X) is preferably 1,500 or more and 4,500 or less, and more preferably 2,000 or more and 3,800 or less. When the degree of polymerization of PVA(X) is 4,500 or less, when PVA(X) is used as an additive for this cement slurry, an appropriate viscosity can be obtained even at high temperatures. On the other hand, when the degree of polymerization of PVA(X) is 1,500 or more, dehydration can be sufficiently suppressed even at high temperatures.

[0162] In the uses of the filler for underground treatment, paper coating agent, seed coating composition, and dispersion stabilizer for suspension polymerization of vinyl compounds, the degree of polymerization of PVA(X) is preferably 150 or more and 5,000 or less, more preferably 300 or more and 4,000 or less, and further preferably 500 or more and 3,500 or less. When the degree of polymerization of PVA(X) is 5,000 or less, it is industrially advantageous from the viewpoint of the manufacturability of PVA(X). On the other hand, in the use of the filler for underground treatment, if the degree of polymerization of PVA(X) is 150 or more, a more appropriate filling effect can be obtained. In addition, in the use of the paper coating agent, if the degree of polymerization of PVA(X) is 150 or more, more appropriate water resistance can be imparted to the coated paper. In the use of the seed coating composition, if the degree of polymerization of PVA(X) is 150 or more, the effect based on coating is more excellent. If the degree of polymerization of PVA(X) is 150 or more, it is more advantageous in the manufacture of PVA(X), and the performance as a dispersion stabilizer for suspension polymerization is more excellent.

[0163] In the uses of the multilayer structure and the packaging material using the same, the degree of polymerization of PVA(X) is suitably 150 or more and 5,000 or less, and more suitably 200 or more and 5,000 or less. When the degree of polymerization of PVA(X) is 150 or more, it is more advantageous in the manufacture of the multilayer structure. The degree of polymerization is further suitably 250 or more, still further suitably 300 or more, and particularly suitably 400 or more. On the other hand, when the degree of polymerization of PVA(X) is 5,000 or less, the viscosity of the aqueous solution is not too high, and the processability can be made better. The degree of polymerization of PVA(X) is further suitably 4,500 or less, still further suitably 4,000 or less, and particularly suitably 3,500 or less.

[0164] In the use of the paper coating agent, the degree of polymerization of PVA(X) is preferably 150 or more and 5,000 or less, and more preferably 300 or more and 4,000 or less. When the degree of polymerization of PVA(X) is 5,000 or less, it is more advantageous in the manufacture of PVA(X). On the other hand, if the degree of polymerization of PVA(X) is 150 or more, more appropriate water resistance can be imparted to the coated paper.

[0165] In the use of the aqueous emulsion and the adhesive using the same, the degree of polymerization of PVA(X) is preferably 150 or more and 5,000 or less, more preferably 200 or more and 5,000 or less. When the degree of polymerization of PVA(X) is 150 or more, the storage stability of the obtained aqueous emulsion can be made better. The degree of polymerization is further preferably 250 or more, still more preferably 300 or more, and particularly preferably 400 or more. On the other hand, when the degree of polymerization of PVA(X) is 5,000 or less, the viscosity of the aqueous solution is not too high, and the processability can be made better. The degree of polymerization of PVA(X) is further preferably 4,500 or less, still more preferably 4,000 or less, and particularly preferably 3,500 or less.

[0166] In the use of the dispersion stabilizer for suspension polymerization of vinyl-based compounds, the degree of polymerization of PVA(X) is preferably 100 or more and 700 or less, more preferably 120 or more and 650 or less, and further preferably 150 or more and 600 or less. When the degree of polymerization of PVA(X) is 700 or less, it is easier to remove the monomer component from the vinyl-based polymer particles obtained by suspension polymerization of vinyl-based compounds, or the plasticizer absorbability of the obtained vinyl-based polymer particles is improved, or when provided in the form of a high-concentration aqueous solution of the dispersion stabilizer, the viscosity can be suppressed from becoming very high, and the operability is excellent. On the other hand, when the degree of polymerization of PVA(X) is 100 or more, it is more advantageous in the production of PVA(X).

[0167] The degree of polymerization (viscosity-average degree of polymerization) of PVA(X) is a value measured in accordance with JIS K 6726:1994. That is, the degree of polymerization of PVA can be obtained by the following formula based on the intrinsic viscosity [η] (dL / g) measured in water at 30°C.

[0168] Degree of polymerization = ([η] × 1000 / 8.29) (1 / 0.62)

[0169] In the present invention, from the viewpoint of obtaining desired effects and being industrially advantageous, the molar ratio (A) / (B) of the plant-derived vinyl ester monomer (A) to the petroleum-derived vinyl ester monomer (B) in the vinyl alcohol-based polymer (X) is 5 / 95 to 100 / 0. The molar ratio (A) / (B) can be arbitrarily set. By making the ratio of (A) 5 / 95 or more in terms of the (A) / (B) ratio, the properties are equal to or more than those of a vinyl alcohol-based polymer derived only from petroleum, the plant-derived raw materials can be fully utilized, and the effect of suppressing the environmental burden becomes greater. From the above viewpoints, as the lower limit value of the ratio of the plant-derived vinyl ester monomer (A), it is more suitable to be 10 / 90 in terms of the molar ratio (A) / (B), further suitable to be 20 / 80, still further suitable to be 25 / 75. In addition, as the upper limit value of the ratio of the plant-derived vinyl ester monomer (A), from the balance between the environmental burden and the raw material cost, it is suitable to be 90 / 10 in terms of the molar ratio (A) / (B), more suitable to be 80 / 20, further suitable to be 70 / 30, particularly suitable to be 60 / 40, and most suitable to be 50 / 50. If the upper limit value of the ratio of the plant-derived vinyl ester monomer (A) is the above value, problems such as appearance defects such as cracks in the obtained PVA (X) are less likely to occur, which is advantageous in terms of manufacturing.

[0170] (Degree of Biomass)

[0171] The biomass-derived carbon in the present invention means the carbon present in the organic matter synthesized by absorbing the carbon present in the atmosphere in the form of carbon dioxide into plants and using this as a raw material, and can be identified by measuring radioactive carbon (i.e., carbon-14). In addition, the content ratio of the biomass-derived component can be determined by measuring radioactive carbon (carbon-14). That is, since almost no carbon-14 atoms remain in fossil raw materials such as petroleum, the concentration of carbon-14 in the target sample is measured, and by using the carbon-14 content ratio in the atmosphere (107 pMC (percent Modern Carbon)) as an index and performing backward calculation, the ratio of the biomass-derived carbon in the carbon contained in the sample can be obtained.

[0172] The proportion of the biomass-derived carbon obtained by such measurement of radioactive carbon can be obtained as follows: For example, after the sample (vinyl ester) is made into carbon dioxide or graphite as needed, the content of carbon-14 relative to a standard substance (e.g., NIST oxalic acid in the United States) is measured by accelerator mass spectrometry (AMS method; Accelerator Mass Spectrometry) to obtain it. The content ratio (%) of the biomass-derived carbon can be calculated by [(the amount of biomass-derived carbon in the sample) / (the total amount of carbon in the sample) × 100].

[0173] The ratio of non-fossil raw materials to fossil raw materials of the vinyl ester monomer can be determined by measuring the above-mentioned 14 C / C, and it can be distinguished from the vinyl ester monomer obtained from ethylene derived from petroleum.

[0174] When using ethylene derived from biomass (non-fossil raw materials) as part of the raw materials of the vinyl ester monomer, the ratio of non-fossil raw materials of the vinyl ester monomer can be determined according to the 14 C (radiocarbon) / C (carbon) of the obtained vinyl ester monomer. In the vinyl ester monomer obtained from fossil raw materials, 14 C / C is less than 1.0×10 -14 , in contrast, the 14 C / C of the vinyl ester monomer (A) used in the present invention is preferably 1.0×10 -14 or more, more preferably 1.0×10 -13 or more, and further preferably 1.0×10 -12 . For example, it can be obtained by comparing and measuring the content of carbon-14 ( 14 C) in the reference material prepared by the National Institute of Standards and Technology in the United States, that is, oxalic acid. Through this 14 analysis of the C / C amount, the non-fossil raw material ratio in the vinyl ester monomer can be measured.

[0175] Artificially originated 14 C generated by nuclear experiments in the atmosphere exists naturally, so sometimes 14 the concentration of C is slightly higher than the standard level, and pMC occasionally becomes a little over one hundred percent, but as long as it is appropriately corrected to obtain the ratio of non-fossil raw materials to fossil raw materials. In addition, 14 the half-life of C is 5,730 years. Considering the period from manufacturing to entering the market of general chemical products, especially vinyl acetate and vinyl acetate-based resins and their saponified products polymerized therefrom, the reduction of the 14 C amount can be ignored. It should be noted that in the present invention, for the case where 14 C / C is 1.0×10 -14 , it can be appropriately replaced with pMC (percentage of modern carbon) for description.

[0176] The biogenicity of PVA(X) of the present invention is 5 to 90%. By measuring this biogenicity, it also contributes to the traceability of carbon raw materials in the product.

[0177] It should be noted that when PVA(X) contains copolymer components such as ethylene, it is expressed in the form of the biogenicity including the copolymer components, and by calculating according to the raw material characteristics and modification rate of the copolymer components, the non-fossil raw material ratio as the vinyl ester monomer can be calculated.

[0178] [Additive for slurry]

[0179] The additive for slurry of the present invention contains a vinyl alcohol-based polymer (X) obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), and the molar ratio of (A) / (B) is 5 / 95 to 100 / 0. In addition, the drilling mud of the present invention contains a vinyl alcohol-based polymer (X) obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), and the molar ratio of (A) / (B) is 5 / 95 to 100 / 0. Furthermore, the cement slurry of the present invention contains the aforementioned additive for slurry.

[0180] The additive for slurry of the present invention can be used as an additive for drilling mud slurry and an additive for cement slurry. This additive for slurry contains the above-mentioned PVA (X). This PVA (X) is contained in the additive for slurry in powder form (hereinafter, this powdered PVA (X) will also be referred to as "PVA powder"). This additive for slurry may contain only PVA powder, or may further contain optional components on the basis of containing PVA powder. The content rate of PVA powder in this additive for slurry is, for example, 50% by mass or more and 100% by mass or less, preferably 80% by mass or more and 100% by mass or less.

[0181] The particle size of the PVA powder is preferably the size that passes through a sieve with a nominal mesh of 1.00 mm (16 mesh). When this PVA powder is contained in a slurry such as drilling mud or cement slurry in the form of an additive, dehydration occurring from the slurry at high temperature is easily suppressed. On the other hand, the lower limit value of the particle size of the PVA powder is a range where the solubility does not increase extremely, preferably does not pass through a size with a nominal mesh of 45 μm (325 mesh), more preferably does not pass through a size with a nominal mesh of 53 μm (280 mesh).

[0182] [Drilling mud]

[0183] The drilling mud of the present invention exhibits functions such as transporting drilled rock chips, drilling debris, etc., improving the lubricity of drill bits and drill pipes, filling holes in porous foundations, and offsetting the reservoir pressure (pressure from igneous rock) generated by hydrostatic pressure. This drilling mud contains this additive for slurry and has water and mud as main components. This drilling mud may contain optional components within a range that does not impair the effects of the present invention.

[0184] The drilling mud of the present invention contains PVA(X). As a suitable embodiment, a drilling mud containing PVA(X), water, and argillaceous material can be cited. This kind of drilling mud is manufactured by mixing argillaceous material, water, and the aforementioned slurry with additives. Specifically, this drilling mud can be manufactured by using a water-clay suspension in which argillaceous material is dispersed and suspended in water as a matrix, and adding the slurry additives and optional components as needed.

[0185] <Additive for drilling mud slurry>

[0186] As a certain suitable embodiment, a drilling mud containing an additive for drilling mud slurry can be cited. This additive for drilling mud slurry contains the above-mentioned PVA powder. In addition, this additive for drilling mud slurry can contain only PVA powder. In a certain suitable embodiment, a drilling mud containing PVA(X), water, and bentonite can be cited. Since PVA(X) and PVA powder are as described above, the repeated description is omitted here.

[0187] Among them, in this drilling mud, as the particle size of the PVA powder, it is preferably the size that passes through a sieve with a nominal mesh size (JIS Z8801-1:2019) of 1.00 mm (16 mesh), and more preferably the size that passes through a sieve with a nominal mesh size of 500 μm (32 mesh). If the particle size of the PVA powder is the size that passes through a sieve with a nominal mesh size of 500 μm (32 mesh), the drilling mud containing PVA powder of this particle size can further inhibit dehydration occurring in the drilling mud at high temperatures. It should be noted that as the lower limit of the particle size of the PVA powder, as long as it is in a range where the solubility does not increase extremely, there is no particular limitation, and it is preferably a size that does not pass through a nominal mesh size of 45 μm (325 mesh), and more preferably a size that does not pass through a nominal mesh size of 53 μm (280 mesh).

[0188] As the content of the PVA powder in this drilling mud, it is preferably 0.5 kg / m 3 or more and 40 kg / m 3 or less, and more preferably 3 kg / m 3 or more and 30 kg / m 3 or less.

[0189] <Argillaceous material>

[0190] As the argillaceous material, for example, bentonite, attapulgite, selenite, hydrous magnesium silicate, etc. can be cited, and bentonite is preferably used among them.

[0191] As the mixing ratio of the argillaceous material in this drilling mud, relative to 1 kg of water used in this drilling mud, the argillaceous material is preferably 5 g to 300 g, and more preferably 10 g to 200 g.

[0192] <Optional component>

[0193] As an optional component, known additives can be used, such as an aqueous solution of a copolymer of an α-olefin having 2 to 12 carbon atoms and maleic anhydride or its derivative (such as maleamide, maleimide) or an alkali neutralized product, etc.; a dispersant, a pH regulator, an antifoaming agent, a thickener, etc. As the copolymer of an α-olefin having 2 to 12 carbon atoms and maleic anhydride or its derivative, copolymers of α-olefins such as ethylene, propylene, butene-1, isobutene, diisobutene, etc. and maleic anhydride or its derivatives (such as "Isobam" of Kuraray Co., Ltd.) can be cited. As the dispersant, for example, a humic acid-based dispersant, a lignin-based dispersant, etc. can be cited, and among them, a lignin-based dispersant containing sulfonate is preferred.

[0194] [Cement slurry]

[0195] The cement slurry of the present invention is used for fixing the casing in the mine and protecting the inner wall of the mine by, for example, injecting it into the tubular void portion between the formation and the casing provided in the mine and curing it. The cement slurry contains a slurry additive, a curable powder, and a liquid agent. The cement slurry may contain optional components within the range that does not impair the effects of the present invention.

[0196] This kind of cement slurry is manufactured by adding the slurry additive, the liquid agent, the curable powder, and optional components as needed and mixing them using a mixer or the like.

[0197] <Additive for cement slurry>

[0198] As a suitable embodiment, a cement slurry containing an additive for cement slurry can be cited. The additive for cement slurry contains the above-mentioned PVA powder. The additive for cement slurry may contain only PVA powder. In a suitable embodiment, a drilling mud containing PVA(X), a liquid agent, and a curable powder can be cited. Since PVA and PVA powder are as described above, the repeated description is omitted here.

[0199] Among them, in this cement slurry, the particle size of the PVA powder is preferably the size that passes through a sieve with a nominal mesh size of 1.00 mm (16 meshes), and more preferably the size that passes through a sieve with a nominal mesh size of 250 μm (60 meshes). If the particle size of the PVA powder is the size that passes through a sieve with a nominal mesh size of 250 μm (60 meshes), the cement slurry containing the PVA powder of this particle size can further suppress the dehydration of the cement slurry at high temperatures. It should be noted that as the lower limit of the particle size of the PVA powder, as long as it is within the range where the solubility does not increase extremely, there is no particular limitation, and it is preferably a size that does not pass through a nominal mesh size of 45 μm (325 meshes), and more preferably a size that does not pass through a nominal mesh size of 53 μm (280 meshes).

[0200] As the content of PVA powder in the cement slurry, it is preferably 0.1% (BWOC) or more and 2.0% (BWOC) or less, more preferably 0.2% (BWOC) or more and 1.0% (BWOC) or less. It should be noted that BWOC (By Weight Of Cement) refers to the cement mass basis.

[0201] <Curable powder>

[0202] As the curable powder, for example, portland cement, blended cement, environmentally friendly cement, special cement, etc. can be cited. Preferably, it is a hydraulic cement that solidifies by reacting with water. When this cement slurry is used for drilling purposes, preferably geothermal well cement and oil well cement. The curable powder can be used alone as 1 type, or 2 or more types can be used in combination.

[0203] As portland cement, the cement specified in JIS R5210:2019 can be cited. Specifically, as portland cement, ordinary portland cement, early strength portland cement, ultra-early strength portland cement, medium heat portland cement, low heat portland cement, sulfate-resistant portland cement, and low-alkali type portland cement can be cited.

[0204] As blended cement, the cement specified in JIS R5211:2019, JIS R5212:2019, and JIS R5213:2019 can be cited. Specifically, blast furnace cement, silica cement, and fly ash cement.

[0205] As special cement, it includes cement with portland cement as the matrix, cement obtained by changing the composition or particle size composition of portland cement, and cement with a composition different from that of portland cement.

[0206] As special cement with portland cement as the matrix, expansive cement, low heat release cement in a two-component system, and low heat release cement in a three-component system can be cited.

[0207] As special cement obtained by changing the composition and particle size composition of portland cement, white portland cement, cement-based solidifying materials (geopolymer cement), ultra-fine cement, and high dicalcium silicate-based cement can be cited.

[0208] As special cement with a composition different from that of portland cement, ultra-rapid hardening cement, alumina cement, phosphoric acid cement, and air-hardening cement can be cited.

[0209] <Liquid agent>

[0210] As the liquid agent, it is selected according to the type of curable powder, etc., and examples thereof include water, solvents, and mixtures thereof, and water is usually used. One type of solvent can be used alone, or two or more types can be used in combination.

[0211] The ratio of the curable powder to the liquid agent in the slurry can be appropriately determined according to the specific gravity of the target slurry or the strength of the solidified body, etc. For example, in the case where the slurry is constituted in the form of a drilling slurry using hydraulic cement, as the ratio of water to cement (W / C), from the viewpoints of the specific gravity of the slurry and the strength of the solidified body, it is preferably 25% by mass or more and 100% by mass or less, more preferably 30% by mass or more and 80% by mass or less.

[0212] <Optional component>

[0213] As optional components, a dispersant, a retarder, an antifoaming agent can be contained, and additives other than them can be optionally included. One type of optional component can be used alone, or two or more types can be used in combination.

[0214] (Dispersant)

[0215] As the dispersant, examples thereof include anionic polymers such as naphthalene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate, polycarboxylic acid-based polymers, etc., and among them, naphthalene sulfonic acid formaldehyde condensate is preferred. The content of the dispersant is usually 0.05% (BWOC) or more and 2% (BWOC) or less, preferably 0.2% (BWOC) or more and 1% (BWOC) or less.

[0216] (Retarder)

[0217] As the retarder, examples thereof include hydroxycarboxylic acids or their salts, sugars such as monosaccharides and polysaccharides, and among them, sugars are preferred. The content of the retarder is usually 0.005% (BWOC) or more and 1% (BWOC) or less, preferably 0.02% (BWOC) or more and 0.3% (BWOC) or less.

[0218] (Antifoaming agent)

[0219] As the antifoaming agent, examples thereof include alcohol alkylene oxide adducts, fatty acid alkylene oxide adducts, polypropylene glycol, fatty acid soaps, silicon-based compounds, etc., and among them, silicon-based compounds are preferred. The content of the antifoaming agent is usually 0.0001% (BWOC) or more and 0.1% (BWOC) or less, preferably 0.001% (BWOC) or more and 0.05% (BWOC) or less.

[0220] (Additive)

[0221] The cement slurry may contain, for example, a cement hardening accelerator, a low specific gravity additive, a high specific gravity additive, a foaming agent, a crack reducing agent, a foaming agent, an AE agent, a cement expansion material, a cement strength stabilizing material, silica powder, silicon-containing fume, soot, limestone powder, fine aggregates such as crushed sand, coarse aggregates such as gravel, and additives such as hollow spheres, depending on the intended use, composition, etc. In addition, these additives can be used alone or in combination of two or more kinds.

[0222] [Underground treatment filling agent]

[0223] The underground treatment filling agent of the present invention contains a vinyl alcohol-based polymer (X) obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), and the molar ratio of (A) / (B) is 5 / 95 to 90 / 10.

[0224] The underground treatment filling agent of the present invention contains the above-mentioned PVA (X). The content of PVA (X) is not particularly limited, and is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and further preferably 90 to 100% by mass, relative to the entire underground treatment filling agent. By making the content of PVA (X) within the above range, there is a tendency for the filling effect to be more excellent.

[0225] The underground treatment filling agent of the present invention enters into the cracks formed during the drilling of oil or shale gas, etc., and temporarily seals the cracks, thereby enabling the formation of new cracks. As a method of using the underground treatment filling agent of the present invention to seal cracks, the underground treatment filling agent can be made to flow into the cracks to be sealed by riding on the flow of the fluid in the mine.

[0226] In addition, the underground treatment filling agent of the present invention temporarily seals the cracks in the ground, but slowly dissolves in water and is removed during or after the recovery of underground resources such as oil and natural gas, so it will not remain in the ground for a long time. Therefore, the burden on the environment caused by the underground treatment filling agent of the present invention is also extremely small.

[0227] The shape of the PVA (X) used in the underground treatment filling agent is not particularly limited, and can be in the form of pellets, granules, powder, etc. Pelletization can be carried out by a usual method such as an extrusion molding method, and a plasticizer such as polyethylene glycol described later can be appropriately added at this time.

[0228] When using a powdery substance as the PVA (X) used in the underground treatment filling agent, its average particle diameter is preferably 10 to 5000 μm, more preferably 50 to 4000 μm, further preferably 100 to 3500 μm, and particularly preferably 500 to 3000 μm.

[0229] By making the average particle diameter of PVA(X) within the above range, the PVA-based resin is less likely to fly off, etc., and is easier to handle. In addition, even when the PVA(X) is subsequently modified, for example, the reaction tends to become more uniform and better. It should be noted that the average particle diameter refers to the diameter at which the cumulative value (cumulative distribution) reaches 50% when measuring the volume distribution of each particle diameter by laser diffraction. Specifically, for the laser diffraction scattering method, a laser diffraction type particle size distribution measuring device (SALD-2300: manufactured by Shimadzu Corporation) can be used, and a 0.2% aqueous solution of sodium hexametaphosphate is used as the dispersion medium and measured on a volume basis.

[0230] The filling agent for underground treatment of the present invention may further contain additives. Examples of additives include fillers, plasticizers, starches, etc. The additives can be used alone or in combination of two or more.

[0231] The filler sometimes further improves the mechanical properties by mixing with PVA(X), or can adjust the water-soluble rate. The addition amount of the filler is appropriately selected according to the purpose. For example, it is preferably 50% by mass or less of the whole filling agent, more preferably 30% by mass or less, and still more preferably 5% by mass or less.

[0232] The specific gravity of the filling agent for underground treatment is preferably close to the specific gravity of the fluid used in underground treatment, so that it can be more evenly distributed throughout the system by, for example, pump power. From the viewpoint of adjusting the specific gravity of the filling agent for underground treatment, a bulking agent can be added to PVA(X). By adding the bulking agent, the specific gravity of PVA(X) can be increased. Examples of the bulking agent include natural minerals, salts of inorganic substances and organic substances, and can be, for example, compounds formed by one or more metal ions selected from calcium, magnesium, silicon, barium, copper, zinc, manganese and one or more counter ions selected from fluoride, chloride, bromide, carbonate, hydroxide, formate, acetate, nitrate, sulfate, phosphate. Among them, calcium carbonate, calcium chloride, zinc oxide, etc. are preferred.

[0233] In order to improve the fluid properties of the filling agent for underground treatment, the filling agent for underground treatment may further contain a plasticizer on the basis of containing PVA(X). In other words, PVA(X) may be added and mixed with a plasticizer. At this time, in order to uniformly add the plasticizer to PVA(X), a method of spray-coating the plasticizer on the surface of PVA(X) may be used. By adding the plasticizer, the generation of fine powder can sometimes be further suppressed. As the plasticizer, known substances can be used, and as suitable plasticizers, water, glycerin, polyglycerin, ethylene glycol, polyethylene glycol, ethanol acetamide, ethanol formamide, triethanolamine acetate, glycerin, trimethylolpropane, neopentyl glycol, etc. can be cited. They can be used alone or in combination of two or more. Substances such as trimethylolpropane that are solid or crystalline at normal temperature can be used for spraying after being dissolved in water or other liquids. The content of the plasticizer is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less based on the mass of PVA(X) (100% by mass).

[0234] As a certain preferred embodiment, a filling agent for underground treatment containing a composition of PVA(X) and an additive, and the additive contains a filler and a plasticizer can be cited. As the compounding ratio of each component in the filling agent for underground treatment, preferably: PVA(X) is 60 to 94% by mass, the filler is 5 to 40% by mass, and the plasticizer is 1 to 15% by mass.

[0235] In addition, in the filling agent for underground treatment of the present invention, starch can be mixed into PVA(X). When PVA(X) is set to 100% by mass, the addition amount of starch is preferably 10 to 90% by mass relative thereto, and more preferably 30% by mass or more. As the starch, for example, natural products, synthetic products, physically modified or chemically modified starches, etc. can be cited.

[0236] In the filling agent for underground treatment of the present invention, according to needs, additives such as a chelating agent, a pH regulator, an oxidizing agent, a mud loss material, an anti-scale agent, a rust inhibitor, clay, an iron agent, a reducing agent, an oxygen remover, etc. can also be contained.

[0237] [Multi-layer structure]

[0238] The multi-layer structure of the present invention has a layer (C) containing a vinyl alcohol-based polymer (X) and a layer (D) containing a resin, and the vinyl alcohol-based polymer (X) is obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B).

[0239] The aforementioned resin is at least one resin selected from polyolefin resins, polyester resins, polyamide resins, polyvinyl chloride (PVC) resins, ABS resins, polylactic acid (PLA) resins, polybutylene succinate (PBS) resins, polyhydroxyalkanoate (PHA) resins, polyhydroxybutyrate / hydroxyhexanoate (PHBH) resins, starch, and cellulose.

[0240] [Layer (C)]

[0241] The above-mentioned PVA(X) is contained in layer (C) constituting the multilayer structure of the present invention.

[0242] The content of the aforementioned PVA(X) in layer (C) is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 95% by mass or more. In addition, in layer (C), the mass ratio of the aforementioned vinyl alcohol-based polymer to all polymer components (vinyl alcohol-based polymer / all polymer components) is preferably 0.9 or more, and more preferably the polymer components contained in layer (C) substantially consist only of the aforementioned PVA(X). In the case of substantially consisting only of the aforementioned PVA(X), the content rate of components other than PVA(X) is preferably less than 0.5% by mass, more preferably less than 0.1% by mass, and further preferably less than 0.01% by mass.

[0243] [Layer (D)]

[0244] Layer (D) is a substrate containing a resin. Examples of the resin include polyolefin resins, polyester resins, polyamide resins, polyvinyl chloride (PVC) resins, ABS resins, polylactic acid (PLA) resins, polybutylene succinate (PBS) resins, polyhydroxyalkanoate (PHA) resins, polyhydroxybutyrate / hydroxyhexanoate (PHBH) resins, starch, and cellulose. The resin may be used alone or in combination of two or more. The thickness of layer (D) (the final thickness when stretched) is preferably 5 to 100 μm.

[0245] Examples of the polyolefin resin include polyethylene, polypropylene, copolymerized polypropylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylate copolymer, etc. Examples of polyethylene include high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), etc. Among them, polyethylene and polypropylene are preferred. It should be noted that in this specification, “(meth)acrylic acid” is a general term for acrylic acid and methacrylic acid. The same applies to expressions such as “(meth)acrylate”.

[0246] As the polyester resin, examples include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalic acid ethylene glycol ester, etc. Among them, polyethylene terephthalate (PET) is preferred.

[0247] As the polyamide resin, examples include homopolymers such as polycaprolactam (nylon-6), polyundecanamide (nylon-11), polylaurolactam (nylon-12), polyhexamethylene adipamide (nylon-6,6), polyhexamethylene sebacamide (nylon-6,12), etc.; copolymers such as aromatic polyamides, and the aromatic polyamides are caprolactam / laurolactam copolymer (nylon-6 / 12), caprolactam / aminoundecanoic acid polymer (nylon-6 / 11), caprolactam / ω-aminononanoic acid polymer (nylon-6,9), caprolactam / hexamethylene adipamide salt copolymer (nylon-6 / 6,6), caprolactam / hexamethylene adipamide salt / hexamethylene sebacamide salt copolymer (nylon-6 / 6,6 / 6,12), polymer of adipic acid and metaxylenediamine, and polymer of hexamethylenediamine and isophthalic acid, terephthalic acid. Among them, polycaprolactam (nylon-6) and polyhexamethylene adipamide (nylon-6,6) are preferred.

[0248] As the polyvinyl chloride resin, a homopolymer of vinyl chloride or a copolymer of vinyl chloride and other monomers can be used. As other monomers, examples include α-olefins such as ethylene, propylene, butene, etc.; dienes such as butadiene, isoprene, etc.; vinyl esters such as vinyl acetate, vinyl propionate, etc.; vinyl ethers such as butyl vinyl ether, cetyl vinyl ether, etc.; (meth)acrylate esters such as (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, butyl acrylate, phenyl methacrylate, (meth)acrylic acid hydroxyethyl ester, etc.; aromatic vinyls such as styrene, α-methylstyrene, etc.; vinyl halides such as vinylidene chloride, vinylidene fluoride, etc.; N-substituted maleimides such as N-phenyl maleimide, N-cyclohexyl maleimide, etc.; (meth)acrylic acid, maleic anhydride, acrylonitrile, polyorganosiloxane, etc. They can be used alone or in combination of two or more. The monomer capable of copolymerizing with vinyl chloride monomer is preferably in the range of 0 to 50 parts by mass based on the total 100 parts by mass of vinyl chloride and the monomer capable of copolymerizing with vinyl chloride monomer.

[0249] As an ABS (Acrylonitrile Butadiene Styrene) resin, resins containing acrylonitrile, butadiene, and styrene as structural units can be cited. For example, flame-retardant ABS resins, reinforced ABS resins reinforced with glass fibers, etc., and phenyl maleimide-based ABS resins can be cited. Further, as an ABS resin, α-methylstyrene-based ABS resins obtained by changing styrene to α-methylstyrene, ASA (Acrylonitrile-Styrene-Acrylate resin) resins obtained by changing butadiene to acrylic rubber, ACS (Chlorinated-polyethylene-Acrylonitrile-Styrene resin) resins obtained by changing butadiene to chlorinated polyethylene, AES (Acrylonitrile-Ethylene-Styrene resin) resins obtained by changing butadiene to EPDM (ethylene propylene diene terpolymer), etc. can be cited.

[0250] As a polylactic acid (PLA) resin, resins obtained by polymerizing lactic acid monomers as a main component can be cited, which contain structural units derived from lactic acid in an amount exceeding 50 mol%. As a polylactic acid resin, for example, poly(L-lactic acid) having an L-lactic acid structural unit, poly(D-lactic acid) having a D-lactic acid structural unit, poly(DL-lactic acid) having L-lactic acid and D-lactic acid structural units, and polymers having a mixture thereof as a main component can be cited.

[0251] Polybutylene succinate (PBS) resins contain 1,4-butanediol and succinic acid in the structural units, and copolymers further copolymerized with 3-alkoxy-1,2-propanediol on the basis of 1,4-butanediol and succinic acid can also be used. In the 3-alkoxy-1,2-propanediol used in the copolymer, the number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 8. PBS resins can use PBS resins derived from plants.

[0252] As a polyhydroxyalkanoate (PHA) resin, poly(3-hydroxyvalerate), poly(3-hydroxybutyrate), poly(3-hydroxypropionate), poly(4-hydroxybutyrate), poly(3-hydroxyoctanoate), poly(3-hydroxydecanoate), etc. can be cited.

[0253] Polyhydroxybutyrate / hydroxyhexanoate (PHBH) resin is a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate (3-hydroxybutyrate-co-3-hydroxyhexanoate polymer). In the copolymer, the amount of 3-hydroxyhexanoate can be 1 to 20 mol% in all the structural units.

[0254] As starches, raw starches (self-modified starches) such as corn starch, potato starch, sweet potato starch, wheat starch, cassava starch, sago starch, tapioca starch, sorghum starch, rice starch, bean starch, kudzu starch, bracken starch, lotus root starch, water chestnut starch, etc. can be cited: α-starch, fractionated amylose, heat-moisture treated starch, thermochemically modified starch, etc. as physically modified starches: hydrolyzed dextrin, enzyme-decomposed dextrin, amylose, etc. as enzyme-modified starches; acid-treated starch, hypochlorous acid-oxidized starch, etc. as oxidized starches; dialdehyde starch, etc. as chemically decomposed modified starches; esterified starch, etherified starch, cationized starch, crosslinked starch, etc. as chemically modified starch derivatives; alkyl starch, hydroxyalkyl starch, hydroxyalkylalkyl starch, etc. As alkyl starch, methyl starch, ethyl starch, propyl starch, etc. can be cited. As hydroxyalkyl starch, hydroxymethyl starch, hydroxyethyl starch, hydroxypropyl starch, etc. can be cited. As hydroxyalkylalkyl starch, hydroxymethylmethyl starch, hydroxyethylmethyl starch, hydroxypropylmethyl starch, etc. can be cited. As the esterified starch among the chemically modified starch derivatives, for example, acetic acid-esterified starch, succinic acid-esterified starch, nitric acid-esterified starch, phosphoric acid-esterified starch, urea phosphoric acid-esterified starch, xanthic acid-esterified starch, acetoacetylated starch, carbamate-esterified starch, etc. can be cited. As the etherified starch, for example, allyl-etherified starch, methyl-etherified starch, carboxy-etherified starch, carboxymethyl-etherified starch, hydroxyethyl-etherified starch, hydroxypropyl-etherified starch, etc. can be cited. As the cationized starch, for example, the reaction product of starch and 2-diethylaminoethyl chloride, the reaction product of starch and 2,3-epoxypropyltrimethylammonium chloride, etc. can be cited. As the crosslinked starch, for example, formaldehyde-crosslinked starch, epichlorohydrin-crosslinked starch, phosphoric acid-crosslinked starch, acrolein-crosslinked starch, etc. can be cited.

[0255] As celluloses, alkyl cellulose, hydroxyalkyl cellulose, cellulose acetate, etc. can be cited. As alkyl cellulose, methyl cellulose, etc. can be cited. The content of methoxy groups in methyl cellulose is preferably 26.0 to 33.0% by mass, more preferably 27.5 to 31.5% by mass. The content of methoxy groups in methyl cellulose can be measured according to the analysis method related to methyl cellulose in the 17th revised Japanese Pharmacopoeia. As hydroxyalkyl cellulose, hydroxypropyl cellulose, etc. can be cited. The content of hydroxypropoxy groups in hydroxypropyl cellulose is preferably 53.4 to 80.5% by mass, more preferably 60.0 to 70.0% by mass. The content of hydroxypropoxy groups in hydroxypropyl cellulose can be measured according to the analysis method related to hydroxypropyl cellulose in the 17th revised Japanese Pharmacopoeia.

[0256] The oxygen permeability of the multilayer structure of the present invention is preferably 150 cc / m2 ·per day·atm or less, more preferably 100 cc / m 2 ·per day·atm or less. In the present invention, the oxygen permeability of the multilayer structure is determined by the method described in the examples.

[0257] In each layer of the multilayer structure of the present invention, for the purpose of improving gas barrier properties, enhancing strength, or improving processability, an inorganic layered compound may be contained. Examples of the inorganic layered compound include mica, talc, montmorillonite, kaolinite, vermiculite, etc., which may be naturally occurring substances or synthetic compounds.

[0258] In each layer of the multilayer structure of the present invention, for the purpose of improving water resistance, a crosslinking agent may be contained. Examples of the crosslinking agent include epoxy compounds, isocyanate compounds, aldehyde compounds, titanium compounds, silica compounds, aluminum compounds, zirconium compounds, boron compounds, etc. Among them, silica compounds such as colloidal silica and alkyl silicate are preferred.

[0259] The method for producing the multilayer structure of the present invention is not particularly limited, and a method having the following steps is preferred: a step of preparing an aqueous solution containing the aforementioned vinyl alcohol-based polymer (X) (hereinafter sometimes abbreviated as PVA(X) aqueous solution) to obtain a coating agent; and a step of coating the coating agent on the surface of a substrate containing at least one resin selected from polyolefin resins, polyester resins, and polyamide resins. It should be noted that, as described later, as a preferred embodiment of the present invention, when there is a layer such as an adhesive component layer between layer (C) and layer (D), the multilayer structure can be produced by coating the coating agent on the layer such as the adhesive component layer formed on the substrate. In the present application, even in such a case, it is sometimes expressed as "coating the coating agent on the surface of the substrate".

[0260] As the aforementioned base material, a film containing the aforementioned resin can be cited. In a suitable embodiment, as the aforementioned base material, a film containing a polyolefin resin (hereinafter also referred to as a polyolefin film), a film containing a polyester resin (hereinafter also referred to as a polyester film), and a film containing a polyamide resin (hereinafter also referred to as a polyamide film) can be cited. In other suitable embodiments, as the aforementioned base material, a film containing a polyvinyl chloride (PVC) resin (hereinafter also referred to as a PVC film), a film containing an ABS resin (hereinafter also referred to as an ABS film), a film containing a polylactic acid (PLA) resin (hereinafter also referred to as a PLA film), a film containing a polybutylene succinate (PBS) resin (hereinafter also referred to as a polybutylene succinate film), a film containing a polyhydroxyalkanoate (PHA) resin (hereinafter also referred to as a polyhydroxyalkanoate film), a film containing a polyhydroxybutyrate / hydroxyhexanoate (PHBH) resin (hereinafter also referred to as a polyhydroxybutyrate / hydroxyhexanoate film), a film containing starch (hereinafter also referred to as a starch film), and a film containing cellulose (hereinafter also referred to as a cellulose film) can be cited. This base material forms layer (D).

[0261] The content of the aforementioned PVA(X) in the aforementioned aqueous PVA(X) solution is not particularly limited, and is preferably 5 to 50% by mass. If it is within the above range, the drying burden is reduced or the viscosity of the aqueous solution is appropriate, and thus the coatability becomes better. By drying after coating the coating agent containing the aforementioned aqueous PVA(X) solution on the surface of the aforementioned base material, layer (C) is formed. The evaporation rate during the drying treatment is preferably 2 to 2000 g / m 2 ·min, more preferably 50 to 500 g / m 2 ·min.

[0262] The aforementioned PVA(X) aqueous solution and coating agent may contain surfactants, leveling agents, etc. Additionally, from the perspective of coatability, the aforementioned PVA(X) aqueous solution and coating agent may contain lower aliphatic alcohols such as methanol, ethanol, and isopropanol. In this case, the content of the lower aliphatic alcohol contained in the aforementioned PVA(X) aqueous solution is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 20 parts by mass or less relative to 100 parts by mass of water. From the perspective of the working environment, the liquid medium contained in the aforementioned PVA(X) aqueous solution is preferably only water. Additionally, the aforementioned PVA(X) aqueous solution may contain mildew-proof agents, preservatives, etc. The temperature during the coating of the aforementioned PVA(X) aqueous solution is preferably 20 to 80°C. The coating method preferably uses a gravure roll coating method, an inverse gravure coating method, a reverse roll coating method, or a wire bar coating method. Tensile treatment or heat treatment can be performed on the substrate before coating the coating agent or on the obtained multilayer structure. In this case, considering workability, the following method is preferred: after performing one-stage stretching on the aforementioned substrate, coating the coating agent on the substrate, and then further performing two-stage stretching, and performing heat treatment during or after the two-stage stretching.

[0263] The aforementioned heat treatment is carried out in air. The heat treatment temperature can be adjusted according to the type of the aforementioned substrate. Generally, in the case of a polyolefin film, it is 140°C to 170°C. In the case of a polyester film and a polyamide film, the heat treatment temperature is 140°C to 240°C. In the case of a polyvinyl chloride film, the heat treatment temperature is 140°C to 200°C. In the case of an ABS film, the heat treatment temperature is 140°C to 170°C. In the case of a polylactic acid film, the heat treatment temperature is 140°C to 240°C. In the case of a polybutylene succinate film, the heat treatment temperature is 140°C to 240°C. In the case of a polyhydroxyalkanoate film, the heat treatment temperature is 140°C to 240°C. In the case of a polyhydroxybutyrate / hydroxyhexanoate film, the heat treatment temperature is 140°C to 240°C. In the case of a starch film, the heat treatment temperature is 140°C to 240°C. In the case of a cellulose film, the heat treatment temperature is 140°C to 240°C. In the case of performing heat treatment on layer (C), it is usually carried out simultaneously with the heat treatment of layer (D) as the substrate.

[0264] The thickness of layer (C) (when stretching is performed, it is the final thickness after stretching) is preferably 0.1 to 20 μm, more preferably 0.1 to 9 μm. Additionally, the multilayer structure may include two or more layers of layer (C). The PVA(X) contained in two or more layers of layer (C) may be the same or different. In the case where the multilayer structure includes two or more layers of layer (C), the thickness of the aforementioned layer (C) represents the thickness of one layer (C).

[0265] The thickness ratio ((C) / (D)) of layer (C) to layer (D) in the aforementioned multilayer structure is preferably 0.9 or less, more preferably 0.5 or less. When the multilayer structure includes two or more layers of layer (C), it represents the thickness ratio of layer (D) to each layer of layer (C).

[0266] For the purpose of improving adhesion, an adhesive component layer can be formed between layer (C) and layer (D). Examples of the adhesive component include an anchor coating agent. The aforementioned adhesive component layer can be formed by a method such as coating the adhesive component on the surface of the aforementioned substrate before coating the aforementioned coating agent.

[0267] In the multilayer structure of the present invention, a heat-sealing resin layer can be further formed on the surface of layer (C) that does not contact layer (D). The heat-sealing resin layer is usually formed by an extrusion lamination method or a dry lamination method. As the heat-sealing resin, polyethylene resins such as HDPE, LDPE, and LLDPE, polypropylene resin, ethylene-vinyl acetate copolymer, ethylene-α-olefin random copolymer, ionomer resin, etc. can be used.

[0268] [Packaging material]

[0269] The packaging material having the multilayer structure of the present invention is also a preferred embodiment of the present invention. The packaging material has excellent oxygen barrier properties due to the multilayer structure of the present invention.

[0270] The packaging material is used for packaging, for example, foods; beverages; chemical products such as pesticides and pharmaceuticals; medical devices; industrial materials such as mechanical parts and precision materials; clothing, etc. In particular, the packaging material is suitable for applications that require oxygen barrier properties and applications where the inside of the packaging material is replaced with various functional gases.

[0271] Examples of the form of the packaging material include, for example, a stand-up pouch filling and sealing bag, a vacuum packaging bag, a soft pouch with a bag mouth, a laminated tube container, a lid material for a container, etc.

[0272] [Paper coating agent]

[0273] The paper coating agent of the present invention contains a vinyl alcohol-based polymer (X) obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), and the molar ratio of (A) / (B) is 5 / 95 to 100 / 0.

[0274] The substrate coated with the paper coating agent of the present invention is not particularly limited, and examples include paper, a resin-containing substrate, etc. As the paper coating agent, the paper coating agent of the present invention can be used directly, or other components can be further added for use.

[0275] As the above other components, components as described above can be cited as other components in addition to the vinyl alcohol polymer (X) and water. Further, as the above other components, water resistance agents such as glyoxal, urea resin, melamine resin, polyvalent metal salts, and water-soluble polyamide resins can be cited; pH adjusters such as ammonia, sodium hydroxide, sodium carbonate, and phosphoric acid; release agents; coloring agents such as pigments; various modified PVAs such as unmodified PVA, carboxyl-modified PVA, sulfonic acid group-modified PVA, acrylamide-modified PVA, cationic group-modified PVA, and long-chain alkyl-modified PVA that do not belong to the vinyl alcohol polymer (X); water-soluble polymers such as casein, raw starch (wheat, corn, rice, potato, sweet potato, cassava, sago palm), raw starch decomposition products (such as dextrin), starch derivatives (oxidized starch, etherified starch, esterified starch, cationized starch, etc.), seaweed polysaccharides (sodium alginate, carrageenan, agar (agarose, agar gum), funori gum, etc.), and water-soluble cellulose derivatives (carboxyalkyl cellulose, alkyl cellulose, hydroxyalkyl cellulose, etc.); synthetic resin emulsions such as styrene-butadiene copolymer latex, polyacrylate emulsion, vinyl acetate-ethylene copolymer emulsion, and vinyl acetate-acrylate copolymer emulsion. The concentration of the vinyl alcohol polymer (X) in the paper coating agent is arbitrarily selected according to the coating amount (increase in the dry mass of the paper formed by coating), the apparatus used in coating, the operating conditions, etc., and is preferably 1.0 to 30% by mass, more preferably 2.0 to 25.0% by mass.

[0276] As a method for coating the paper coating agent of the present invention on paper, known methods can be cited, for example, a method of coating on one or both sides of the paper using an apparatus such as a sizing machine, coating roller, SYM-SIZER, bar coater, or curtain coater; or a method of impregnating the paper with a paper coating liquid (paper coating agent). Drying of the coated paper can be carried out by a known method, for example, a method obtained by hot air, infrared rays, a heating cylinder, or a combination thereof. The dried coated paper can be further improved in barrier properties by humidity conditioning and calendering treatment. As the calendering treatment conditions, the roller temperature is preferably room temperature to 100°C, and the roller line pressure is preferably 20 to 300 kg / cm.

[0277] As another embodiment, a coated paper obtained by coating the paper coating agent of the present invention on paper can be cited. The coated paper obtained by using the paper coating agent of the present invention can be used as a base paper for release paper, oil-resistant paper, gas-barrier paper, thermal paper, inkjet paper, pressure-sensitive paper, etc. Among them, a base paper for release paper or oil-resistant paper is preferred. That is, as an embodiment, the above coated paper as a base paper for release paper or oil-resistant paper can be cited.

[0278] The release paper base paper has a filling layer (barrier layer) formed from a paper coating solution on a base material (paper). Examples of the base material (paper) include cardboard such as abaca board, white cardboard, and liner; printing paper such as general high-quality paper, medium-quality paper, and intaglio paper. The release paper has a release layer laminated on the filling layer of the above-mentioned release paper base paper. The release layer is preferably composed of a silicone resin. Examples of the silicone resin include known silicone resins, such as solvent-based silicone, solventless silicone, and emulsion-based silicone. The coating amount in the release paper base paper (the increase in the dry mass of the paper generated by coating) is not particularly limited, for example, it is 0.1 to 5.0 g / m 2 , preferably 0.1 to 2.5 g / m 2 .

[0279] The oil-resistant paper has an oil-resistant layer formed from a paper coating solution on a base material (paper). Examples of the base material (paper) include cardboard such as abaca board, white cardboard, and liner; printing paper such as general high-quality paper, medium-quality paper, and intaglio paper; kraft paper, cellophane, and parchment paper. The coating amount in the oil-resistant paper (the increase in the dry mass of the paper generated by coating) is not particularly limited, for example, it is 0.1 to 20 g / m 2 .

[0280] If it is within the range that does not hinder the effects of the present invention, the paper coating agent (paper coating solution) of the present invention may contain other components in addition to PVA(X) and water. Examples of the above other components include resins other than PVA(X), organic solvents, plasticizers, crosslinking agents, surfactants, anti-settling agents, thickeners, fluidity improvers, preservatives, adhesion improvers, antioxidants, penetrants, defoamers, fillers, wetting agents, colorants, binders, water retention agents, fillers, saccharides such as starch and its derivatives, and additives such as latex. They can be used alone or in combination of two or more. The content of the above other components in the paper coating agent of the present invention is preferably 10% by mass or less, and sometimes preferably 5% by mass or less, 2% by mass or less, 1% by mass or less, or 0.5% by mass or less.

[0281] [Seed coating composition]

[0282] The seed coating composition of the present invention contains a vinyl alcohol-based polymer (X) (hereinafter sometimes abbreviated as PVA(X)) obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), and the molar ratio of (A) / (B) is 5 / 95 to 100 / 0.

[0283] (Pesticide)

[0284] The seed coating composition may further comprise one or more hydrophobic pesticides. In the present invention, "pesticide" is widely used to refer to pesticides, fungicides, nematicides, and the same materials such as those that prevent or reduce damage to seeds caused by living organisms, etc.

[0285] In the description of the present invention, a "hydrophobic" pesticide additive (for example, when no surfactant is used) is insoluble in water or can be stably dispersed in water.

[0286] Such hydrophobic pesticides are generally known to those skilled in the art and are usually commercially available. As commercially available products of hydrophobic pesticides, Acceleron, which is a mixture of a fungicide and an insecticide, can be cited. TM Kit (containing pyraclostrobin, fluxapyroxad, metalaxyl, and imidacloprid), etc.

[0287] Examples of suitable fungicides include pyraclostrobin, fluxapyroxad, ipconazole, trifloxystrobin, metalaxyl (metalaxyl 265ST), fludioxonil (fludioxonil 4L ST), thiabendazole (thiabendazole 4L ST), tebuconazole, tefluthrin, and combinations thereof.

[0288] Examples of suitable insecticides include clothianidin, imidacloprid, SENATOR (registered trademark) 600ST (Nufarm US), tefluthrin, terbufos, cypermethrin, thiodicarb, lindane, furathiocarb, methamidophos, and combinations thereof.

[0289] Typically, the hydrophobic pesticide is used in a small amount (used to achieve the desired pesticide effect in an "effective amount") according to the dosage recommended by the manufacturer of such pesticide.

[0290] (aqueous coating composition)

[0291] In a suitable embodiment, the seed coating composition is an aqueous coating composition. The aqueous coating composition contains water as the main carrier medium.

[0292] The lower limit of the content of PVA(X) in the coating composition is preferably 0.5% by mass, more preferably 1.0% by mass, and still more preferably 2.0% by mass based on the total mass of the coating composition. In addition, the upper limit of the content of PVA(X) in the coating composition is preferably 10% by mass, more preferably 8% by mass, and still more preferably 6% by mass based on the total mass of the coating composition.

[0293] Based on the optional components as described below, the lower limit value of the solid components of the aqueous coating composition according to the present invention is preferably 1% by mass, more preferably 2% by mass, and further preferably 5% by mass based on the total mass of the aqueous coating composition. In addition, the upper limit value of the solid components of the aqueous coating composition according to the present invention is preferably 25% by mass, more preferably 20% by mass based on the total mass of the aqueous coating composition.

[0294] In addition, the aqueous coating composition can be provided in the form of a concentrate that can be diluted with water for application to seeds.

[0295] Based on PVA(X) and other optional components, the aqueous coating composition can be in the form of a solution, dispersion, emulsion or suspension as understood by those skilled in the art. For example, several components can be present in solution, while other components can be dispersed, emulsified and / or suspended. In this case, the components of the aqueous coating composition are preferably substantially uniformly dispersed in the aqueous coating composition before application. Therefore, the aqueous coating composition is preferably a stable solution, emulsion and / or dispersion; or a solution, emulsion, dispersion and / or suspension in which the components can be easily and uniformly dispersed by existing means such as stirring with gentle heating or without gentle heating.

[0296] (Optional components)

[0297] In the seed coating composition according to the present invention, other optional components can be included in addition to PVA(X). Examples of other optional components include other polymers, plasticizers, talc, wax, pigments and debinders other than PVA(X). They can be used alone or in combination of two or more. For example, other polymers other than PVA(X) can be blended with PVA(X) to improve coating properties. Examples of other polymers other than PVA(X) include polyvinylpyrrolidone, starch and high molecular weight polyethylene glycol. In addition, plasticizers, talc, wax, pigments and debinders can be added to the seed coating solution, emulsion or suspension as needed.

[0298] (Application of the aqueous coating composition)

[0299] Methods for applying the aqueous coating composition to seeds are well known to those skilled in the art. Existing methods include, for example, mixing, spraying or a combination thereof. Various coating machines applying various coating techniques such as spin coaters, drum coaters, fluidized beds are commercially available. Seeds can be coated by means of batch or continuous coating processes.

[0300] The seeds are preferably coated substantially uniformly with a film of the coating composition.

[0301] (Covering the seeds)

[0302] Examples of seeds treated with the seed coating composition of the present invention include, for example, wheat, barley, rye, sorghum, apple, peach, cherry, strawberry, blackberry, sugar beet, beet, lentil, pea, soybean, pepper, olive, sunflower, coconut oil plant, cacao bean, tuna, sea cucumber, melon, flax, hemp, orange, lemon, grapefruit, satsuma, lettuce, asparagus, cabbage, carrot, onion, tomato, red pepper, avocado, flower, broad-leaved tree, corn, potato, bulb, rice, tobacco, nut, coffee, and sugar cane.

[0303] [Aqueous emulsion]

[0304] The aqueous emulsion of the present invention contains a dispersant and a dispersed substance. The dispersed substance contains a polymer (Y1) containing an ethylenically unsaturated monomer unit, and the dispersant contains a vinyl alcohol-based polymer (X) obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), and the molar ratio of (A) / (B) is 5 / 95 to 100 / 0.

[0305] The aqueous emulsion of the present invention is an aqueous emulsion containing the above-mentioned PVA (X) as a dispersant and a polymer (Y1) containing an ethylenically unsaturated monomer unit as a dispersed substance. The ratio of PVA (X) to the polymer (Y1) containing an ethylenically unsaturated monomer unit is not particularly limited, and the mass ratio ((X) / (Y1)) based on the solid content is preferably 2 / 98 to 20 / 80, more preferably 5 / 95 to 15 / 85. By setting the mass ratio within the above range, the viscosity stability of the resulting aqueous emulsion tends to be better and the water resistance of the resulting coating film tends to be better.

[0306] The solid content in the aqueous emulsion of the present invention is not particularly limited, and is preferably 30% by mass or more and 60% by mass or less, more preferably 35% by mass or more and 55% by mass or less.

[0307] [Ethylenically unsaturated monomer unit]

[0308] Examples of the ethylenically unsaturated monomer that is a material for forming the polymer (Y1) containing ethylenically unsaturated monomer units include olefin monomers such as ethylene, propylene, and isobutylene; vinyl halide monomers such as vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride; vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl versatate; (meth)acrylate monomers such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate; (meth)acrylic acid dimethylaminoethyl ester and its quaternized products; (meth)acrylamide monomers such as (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, (meth)acrylamide-2-methylpropanesulfonic acid and its sodium salt; styrene monomers such as styrene, α-methylstyrene, styrenesulfonic acid and its sodium salt and potassium salt; diene monomers such as butadiene, isoprene, and chloroprene; N-vinylpyrrolidone, etc. They may be used alone or in combination of two or more.

[0309] As the polymer (Y1) containing ethylenically unsaturated monomer units, a polymer having specific units derived from at least one selected from vinyl ester monomers, (meth)acrylate monomers, styrene monomers, and diene monomers is preferred. As the content rate of the above specific units, it is preferably 70% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to all monomer units of the polymer. If the content rate of the specific units is less than 70% by mass, there is a tendency that the emulsion polymerization stability of the aqueous emulsion is insufficient.

[0310] Furthermore, among the above specific units, vinyl ester monomers are particularly preferred, and vinyl acetate is most preferred. That is, the content rate of vinyl ester monomer units is preferably 70% by mass or more, more preferably the content rate of monomer units derived from vinyl acetate is 70% by mass or more, and still more preferably the content rate of monomer units derived from vinyl acetate is 90% by mass or more, relative to all monomer units of the polymer.

[0311] [Method for producing aqueous emulsion]

[0312] As an example of the method for producing the aqueous emulsion of the present invention, a method of emulsion polymerizing the aforementioned ethylenically unsaturated monomer in the presence of PVA (X) using a polymerization initiator can be cited. The aqueous emulsion obtained by such an operation particularly does not generate aggregates and has excellent water resistance.

[0313] In the above emulsion polymerization, the dispersion medium is preferably an aqueous medium with water as the main component. In the aqueous medium with water as the main component, water-soluble organic solvents (such as alcohols and ketones) that can be miscible with water in any proportion may be included. Here, the "aqueous medium with water as the main component" refers to a dispersion medium containing 50% by mass or more of water. From the viewpoints of cost and environmental burden, the dispersion medium is preferably an aqueous medium containing 90% by mass or more of water, and more preferably water.

[0314] In the above method, when PVA(X) is introduced into the polymerization system as a dispersion stabilizer for emulsion polymerization, its feeding method and addition method are not particularly limited. Examples include: a method of adding the dispersion stabilizer for emulsion polymerization to the polymerization system all at once in the initial stage; a method of continuously adding it during emulsion polymerization. Among them, from the viewpoint of increasing the grafting rate of PVA(X) onto the ethylenically unsaturated monomer, a method of adding the dispersion stabilizer for emulsion polymerization to the polymerization system all at once in the initial stage is preferred. At this time, it is preferably added to cold water or preheated warm water, and heated to 80 - 90 °C and stirred to uniformly disperse PVA(X).

[0315] The content of PVA(X) as a dispersion stabilizer for emulsion polymerization during emulsion polymerization is not particularly limited. Relative to 100 parts by mass of the ethylenically unsaturated monomer, it is preferably 0.2 parts by mass or more and 40 parts by mass or less, more preferably 0.3 parts by mass or more and 20 parts by mass or less, and still more preferably 0.5 parts by mass or more and 15 parts by mass or less. When the blending amount of PVA(X) is less than 0.2 parts by mass, there is a tendency for the dispersed particles of the aqueous emulsion to aggregate or the polymerization stability to decrease. On the other hand, when the blending amount of PVA(X) exceeds 40 parts by mass, there is a tendency for the viscosity of the polymerization system to become too high, the emulsion polymerization not to proceed uniformly, or the removal of the polymerization heat to be insufficient.

[0316] In the above emulsion polymerization, as the polymerization initiator, a water-soluble single initiator or a water-soluble redox initiator commonly used in emulsion polymerization can be used. These initiators can be used alone, or two or more of them can be used in combination. Among them, a redox initiator is preferred.

[0317] Examples of the water-soluble single initiator include azo initiators, hydrogen peroxide, peroxides such as persulfates (potassium, sodium, or ammonium salts), etc. Examples of azo initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), etc.

[0318] As a redox initiator, a substance obtained by combining an oxidizing agent and a reducing agent can be used. As the oxidizing agent, a peroxide is preferably used. Examples of the reducing agent include metal ions and reducing compounds. Examples of the combination of the oxidizing agent and the reducing agent include the combination of a peroxide and a metal ion, the combination of a peroxide and a reducing compound, and the combination of a peroxide and a metal ion and a reducing compound. Examples of the peroxide include hydroxy peroxides such as hydrogen peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide; persulfates (potassium, sodium, or ammonium salts), tert-butyl peracetate, peracid esters (tert-butyl perbenzoate), etc. Examples of the metal ion include metal ions such as Fe 2+ 、Cr 2+ 、V 2+ 、Co 2+ 、Ti 3+ 、Cu + that can accept single-electron transfer. Examples of the reducing compound include sodium bisulfite, sodium bicarbonate, tartaric acid, fructose, glucose, sorbose, inositol, Rongalite, and ascorbic acid. Among these, a combination of one or more oxidizing agents selected from hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate and one or more reducing agents selected from sodium bisulfite, sodium bicarbonate, tartaric acid, Rongalite, and ascorbic acid is preferred, and a combination of hydrogen peroxide and one or more reducing agents selected from sodium bisulfite, sodium bicarbonate, tartaric acid, Rongalite, and ascorbic acid is more preferred.

[0319] In addition, when performing emulsion polymerization, alkali metal compounds, surfactants, buffers, polymerization degree regulators, plasticizers, or film-forming aids can be appropriately used within the range that does not impair the effects of the present invention.

[0320] The alkali metal compound is not particularly limited as long as it contains an alkali metal (sodium, potassium, rubidium, cesium), and it can be the alkali metal ion itself or a compound containing an alkali metal.

[0321] The content of the alkali metal compound (in terms of alkali metal) can be appropriately selected according to the type of the alkali metal compound used. The content of the alkali metal compound (in terms of alkali metal) is preferably 100 to 15000 ppm, more preferably 120 to 12000 ppm, and further preferably 150 to 8000 ppm relative to the total mass of the aqueous emulsion (in terms of solid content). When the content of the alkali metal compound is less than 100 ppm, the emulsion polymerization stability tends to decrease. On the other hand, when it exceeds 15000 ppm, the obtained coating film tends to be colored. It should be noted that the content of the alkali metal compound can be measured by an ICP emission analyzer. In this specification, "ppm" means "mass ppm".

[0322] As compounds containing an alkali metal, specifically, weakly basic alkali metal salts (e.g., alkali metal carbonates, alkali metal acetates, alkali metal hydrogencarbonates, alkali metal phosphates, alkali metal sulfates, alkali metal halide salts, alkali metal nitrates), strongly basic alkali metal compounds (e.g., hydroxides of alkali metals, alkoxides of alkali metals), etc. can be cited. These alkali metal compounds can be used alone or in combination of two or more.

[0323] As weakly basic alkali metal salts, for example, alkali metal carbonates (e.g., sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate), alkali metal hydrogencarbonates (e.g., sodium hydrogencarbonate, potassium hydrogencarbonate, etc.), alkali metal phosphates (sodium phosphate, potassium phosphate, etc.), alkali metal carboxylates (sodium acetate, potassium acetate, cesium acetate, etc.), alkali metal sulfates (sodium sulfate, potassium sulfate, cesium sulfate, etc.), alkali metal halide salts (cesium chloride, cesium iodide, potassium chloride, sodium chloride, etc.), alkali metal nitrates (sodium nitrate, potassium nitrate, cesium nitrate, etc.) can be cited. Among these, from the viewpoint of presenting alkalinity in the emulsion, alkali metal carboxylates, alkali metal carbonates, and alkali metal hydrogencarbonates that act in the form of salts of weak acids and strong bases upon dissociation are preferably used, and alkali metal carboxylates are more preferred.

[0324] By using these weakly basic alkali metal salts, the weakly basic alkali metal salts act as pH buffers in emulsion polymerization, and thus emulsion polymerization can be stably carried out.

[0325] As the surfactant, any of nonionic surfactants, anionic surfactants, and cationic surfactants can be used. As nonionic surfactants, there is no particular limitation, and for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, etc. can be cited. As anionic surfactants, there is no particular limitation, and for example, alkyl sulfates, alkyl aryl sulfates, alkyl sulfonates, sulfates of hydroxyalkanols, sulfosuccinates, sulfates and phosphates of alkyl or alkyl aryl polyethoxyalkanols, etc. can be cited. As cationic surfactants, there is no particular limitation, and for example, alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamines, etc. can be cited. From the viewpoints of water resistance, warm water resistance, and boiling resistance, the amount of the surfactant is preferably 2% by mass or less relative to the total amount of the ethylenically unsaturated monomer (e.g., vinyl acetate).

[0326] As buffers, acids such as acetic acid, hydrochloric acid, sulfuric acid, etc.; bases such as ammonia, amines, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.; or basic carbonates, phosphates, acetates, etc. can be cited. As polymerization degree regulators, mercaptans, alcohols, etc. can be cited.

[0327] In the aqueous emulsion of the present invention, known plasticizers or film-forming aids shown below can be added. Examples of the plasticizer or film-forming aid include dimethyl phthalate, diethyl phthalate, dipentyl phthalate, dibutyl phthalate, tributyl acetylcitrate, diisobutyl adipate, dibutyl sebacate, dimethyl glycol adipate, dimethyl glycol sebacate, diethyl glycol sebacate, dimethyl glycol phthalate, diethyl glycol phthalate, dibutyl glycol phthalate, tricresyl phosphate, dioctyl phthalate, TEXANOL, polyethylene glycol monophenyl ether, polypropylene glycol monophenyl ether, benzyl alcohol, butyl carbitol acetate, butyl carbitol, 3-methyl-3-methoxybutanol, ethylene glycol, acetylenic glycol butyl cellosolve, ethylene cellosolve, butyl cellosolve, chlorinated biphenyl, propylene glycol-mono-2-ethylhexanoate, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, etc. As the addition amount when adding the plasticizer or film-forming aid, it is preferably 1 to 200 parts by mass, more preferably 2 to 50 parts by mass, relative to 100 parts by mass of the polymer containing the ethylenically unsaturated monomer.

[0328] In the aqueous emulsion of the present invention, known fillers, extenders or pigments shown below can be added after emulsion polymerization. Examples of the filler, extender or pigment include calcium carbonate, kaolin clay, steatite clay, talc, titanium oxide, iron oxide, pulp, various resin powders, mica, sericite, bentonite, asbestos, calcium silicate, aluminum silicate, diatomaceous earth, silica, anhydrous silicic acid, hydrous silicic acid, magnesium carbonate, aluminum hydroxide, barium sulfate, calcium sulfate, carbon black, etc. As the addition amount when adding the filler, extender or pigment, it can be preferably 1 to 200 parts by mass, more preferably 20 to 150 parts by mass, relative to 100 parts by mass of the polymer (Y1) containing the ethylenically unsaturated monomer.

[0329] The aqueous emulsion of the present invention obtained by the above method can be used for coating, fiber processing, etc., in addition to bonding applications such as woodworking and paper processing, and is particularly suitable for bonding applications. This aqueous emulsion can be used in its original state, and if necessary, various conventionally known emulsions and commonly used additives can be combined within the scope that does not impair the effects of the present invention to form an emulsion composition. Examples of additives include organic solvents (aromatic compounds such as toluene and xylene; alcohols, ketones, esters, halogen-containing solvents, etc.), crosslinking agents, surfactants, plasticizers, anti-settling agents, thickeners, fluidity improvers, preservatives, defoamers, fillers, wetting agents, colorants, binders, water retention agents, etc. They can be used alone or in combination of two or more. Examples of crosslinking agents include polyisocyanate compounds; hydrazine compounds; polyamide polyamine epichlorohydrin resins (PAE); water-soluble aluminum salts such as aluminum chloride and aluminum nitrate; glyoxal resins such as urea-glyoxal resins. A polyisocyanate compound is a compound having two or more isocyanate groups in the molecule. Examples of polyisocyanate compounds include toluene diisocyanate (TDI), hydrogenated TDI, trimethylolpropane-TDI adduct (e.g., "Desmodur L" of Bayer), triphenylmethane triisocyanate, methylene diphenyl diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (PMDI), hydrogenated MDI, polymeric MDI, hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), etc. As the polyisocyanate compound, a prepolymer having an isocyanate group at the terminal group obtained by polymerizing a polyol in advance with an excess of polyisocyanate can be used. The crosslinking agent can be used alone or in combination of two or more. The content of the crosslinking agent is preferably 1 to 50 parts by mass relative to 100 parts by mass of the polymer (Y1). If the content of the crosslinking agent is 1 part by mass or more, the water resistance and heat resistance of the emulsion composition are more excellent. On the other hand, if the content of the crosslinking agent is 50 parts by mass or less, it is easy to form a good coating film, and the water resistance and heat resistance are more excellent.

[0330] As the adherends of the adhesive obtained by the above method, paper, wood, plastics, etc. can be applied. This adhesive is particularly suitable for wood among these materials and can be applied to uses such as laminates, plywood, decorative plywood, fiberboards, etc.

[0331] In addition, the aqueous emulsion of the present invention can be used for a wide range of applications such as inorganic binders, cement admixtures, and mortar primers. Furthermore, it can also be effectively utilized in the form of a so-called powder emulsion obtained by powderizing the obtained aqueous emulsion by spray drying or the like.

[0332] [Dispersion stabilizer for suspension polymerization]

[0333] The dispersion stabilizer for suspension polymerization of the vinyl-based compound of the present invention comprises a vinyl alcohol-based polymer (X) obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), and the molar ratio of (A) / (B) is 5 / 95 to 100 / 0.

[0334] A suitable use of the PVA (X) of the present invention is as a dispersion stabilizer for polymerization of a vinyl-based compound (hereinafter also referred to as "vinyl-based monomer") used as a monomer, and it can be suitably used for suspension polymerization of a vinyl-based monomer. As a certain suitable embodiment of the present invention, there can be mentioned a method for producing a vinyl-based resin, which includes: a step of performing suspension polymerization of a vinyl-based compound in the presence of the above-mentioned dispersion stabilizer for suspension polymerization.

[0335] Examples of the vinyl-based monomer include vinyl halides such as vinyl chloride; vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth)acrylic acid, their esters and salts; maleic acid, fumaric acid, their esters and anhydrides; styrene, acrylonitrile, vinylidene chloride, vinyl ether, and the like. Among these, it is suitable to perform suspension polymerization of vinyl chloride alone or together with a monomer copolymerizable with vinyl chloride. Examples of the monomer copolymerizable with vinyl chloride include vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth)acrylate esters such as methyl (meth)acrylate and ethyl (meth)acrylate; α-olefins such as ethylene and propylene; unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid; acrylonitrile, styrene, vinylidene chloride, vinyl ether, and the like.

[0336] As the medium used in the above-mentioned suspension polymerization, an aqueous medium is preferably used. Examples of the aqueous medium include water or a medium containing water and an organic solvent. The amount of water in the above-mentioned aqueous medium is preferably 90% by mass or more.

[0337] The amount of the above-mentioned dispersant used in the above-mentioned suspension polymerization is not particularly limited. Generally, it is 1 part by mass or less, preferably 0.01 to 0.5 part by mass, relative to 100 parts by mass of the vinyl-based compound.

[0338] Regarding the mass ratio of the aqueous medium to the vinyl-based compound when performing suspension polymerization of the vinyl-based compound, the aqueous medium / vinyl-based compound (mass ratio) is generally preferably 0.9 to 1.2.

[0339] In the suspension polymerization of vinyl-based monomers, oil-soluble or water-soluble polymerization initiators that have been conventionally used in the polymerization of vinyl chloride monomers and the like can be used. Examples of the oil-soluble polymerization initiators include peroxydicarbonate compounds such as diisopropyl peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, and diethoxyethyl peroxydicarbonate; perester compounds such as tert-butyl peroxyneodecanoate, tert-butyl peroxypentanoate, tert-hexyl peroxypentanoate, and α-cumyl peroxyneodecanoate; peroxides such as acetylcyclohexanesulfonyl peroxide, 2,4,4-trimethylpentyl 2-peroxybenzoate, 3,5,5-trimethylhexanoyl peroxide, and lauroyl peroxide; azo compounds such as azobis-2,4-dimethylvaleronitrile and azobis(4-2,4-dimethylvaleronitrile). Examples of the water-soluble polymerization initiators include potassium persulfate, ammonium persulfate, hydrogen peroxide, and cumene hydroperoxide. These oil-soluble or water-soluble polymerization initiators can be used alone or in combination of two or more.

[0340] In the suspension polymerization of vinyl-based monomers, various other additives can be added to the polymerization reaction system as needed. Examples of the additives include polymerization degree regulators such as aldehydes, halogenated hydrocarbons, and thiols; polymerization inhibitors such as phenolic compounds, sulfur compounds, and N-oxide compounds. In addition, a pH regulator, a crosslinking agent, etc. can be optionally added.

[0341] In the suspension polymerization of vinyl-based monomers, the polymerization temperature is not particularly limited. Needless to say, it can be adjusted to a low temperature of about 20°C, or can be adjusted to a high temperature exceeding 90°C. In addition, in order to improve the heat removal efficiency of the polymerization reaction system, using a polymerizer equipped with a reflux condenser is also one of the preferred embodiments.

[0342] Additives such as preservatives, mildew inhibitors, anti-blocking agents, and defoaming agents that are commonly used in suspension polymerization can be blended into the dispersion stabilizer as needed. The content of such additives is usually 1.0% by mass or less. The additives can be used alone or in combination of two or more.

[0343] When using the PVA(X) of the present invention as a dispersion stabilizer for suspension polymerization, the dispersion stabilizer can be used alone or together with water-soluble cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropylmethyl cellulose; water-soluble polymers such as polyvinyl alcohol and gelatin; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan trioleate, glyceryl tristearate, and ethylene oxide-propylene oxide block copolymer; water-soluble emulsifiers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glyceryl oleate, and sodium laurate. They can be used alone or in combination of two or more.

[0344] When using the PVA(X) of the present invention as a dispersion stabilizer for suspension polymerization, a water-soluble or water-dispersible dispersion stabilizing aid can be used in combination. As the dispersion stabilizing aid, a vinyl alcohol-based polymer (Y2) (hereinafter sometimes abbreviated as PVA(Y2)) can be used. As the PVA(Y2) used as the dispersion stabilizing aid, for example, a partially saponified PVA having a saponification degree of less than 65 mol% can be cited. The saponification degree of the partially saponified PVA is preferably 20 mol% or more and less than 60 mol%, more preferably 25 mol% or more and 58 mol% or less, and still more preferably 30 mol% or more and 56 mol% or less. In addition, as the degree of polymerization of other PVA(Y2), it is preferably 50 or more and 750 or less, more preferably 100 or more and 700 or less, still more preferably 120 or more and 650 or less, and particularly preferably 150 or more and 600 or less. The method for measuring the saponification degree and the degree of polymerization of PVA(Y2) is the same as that of PVA(X). In a suitable embodiment, a dispersion stabilizing aid in which PVA(Y2) is a partially saponified PVA having a saponification degree of less than 65 mol% and a degree of polymerization of 50 or more and 750 or less can be cited. In other suitable embodiments, a dispersion stabilizing aid in which PVA(Y2) is a partially saponified PVA having a saponification degree of 30 mol% or more and less than 60 mol% and a degree of polymerization of 180 or more and 650 or less can be cited. The PVA(Y2) used in the dispersion stabilizing aid can be a vinyl alcohol-based polymer obtained by polymerizing and saponifying a petroleum-derived vinyl ester monomer in the usual manner, or a vinyl alcohol-based polymer obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B). In addition, the dispersion stabilizing aid can be imparted with self-emulsifying properties by introducing ionic groups such as carboxylic acid or sulfonic acid.

[0345] When using the dispersion stabilizing aid in combination, the mass ratio of the dispersion stabilizer to the dispersion stabilizing aid (dispersion stabilizer / dispersion stabilizing aid) varies depending on the type of the dispersion stabilizer used, etc., and thus cannot be generalized. The range of 95 / 5 to 20 / 80 is preferred, and 90 / 10 to 30 / 70 is more preferred. The dispersion stabilizer and the dispersion stabilizing aid can be added together at the initial stage of polymerization, or can be added in batches during the polymerization process.

[0346] [Dispersion Stabilizing Aid for Suspension Polymerization]

[0347] The vinyl alcohol-based polymer (PVA) used in the present invention includes a vinyl alcohol-based polymer (X) obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), and the molar ratio of (A) / (B) is 5 / 95 to 100 / 0.

[0348] A suitable use of the PVA(X) of the present invention is as a dispersion stabilizing aid for the polymerization of vinyl-based compounds used as monomers, and it can be suitably used for the suspension polymerization of vinyl-based monomers. As the vinyl-based monomers, the same monomers as those described for the dispersion stabilizer for suspension polymerization can be cited.

[0349] As the medium used in the above-mentioned suspension polymerization, an aqueous medium is preferred. As such an aqueous medium, water or a medium containing water and an organic solvent can be cited. The amount of water in the above-mentioned aqueous medium is preferably 90% by mass or more.

[0350] In the suspension polymerization of vinyl-based monomers, an oil-soluble or water-soluble polymerization initiator that has been conventionally used in the polymerization of vinyl chloride monomers and the like can be used. As the oil-soluble or water-soluble polymerization initiator, the same substances as those described for the dispersion stabilizer for suspension polymerization can be cited.

[0351] In the suspension polymerization of vinyl-based monomers, various other additives can be added to the polymerization reaction system as needed. As the additives, for example, polymerization degree regulators such as aldehydes, halogenated hydrocarbons, and thiols; polymerization inhibitors such as phenolic compounds, sulfur compounds, and N-oxide compounds, etc. can be cited. In addition, a pH regulator, a crosslinking agent, etc. can also be optionally added.

[0352] In the suspension polymerization of vinyl-based monomers, the polymerization temperature is not particularly limited. Needless to say, it can be adjusted to a low temperature of about 20°C, or it can also be adjusted to a high temperature exceeding 90°C. In addition, in order to improve the heat removal efficiency of the polymerization reaction system, using a polymerizer equipped with a reflux condenser is also one of the preferred embodiments.

[0353] Additives such as preservatives, mildew inhibitors, anti-blocking agents, and defoaming agents that are usually used in suspension polymerization can be blended into the dispersion stabilizing aid as needed. The content of such additives is usually 1.0% by mass or less. The additives can be used alone as 1 type, or 2 or more types can be used in combination.

[0354] The dispersion stabilizing aid of the present invention can be used in combination with a dispersion stabilizer for suspension polymerization. As other suitable embodiments of the present invention, a method for manufacturing a vinyl-based resin can be cited, which includes: a step of performing suspension polymerization of a vinyl-based compound in the presence of the above-mentioned dispersion stabilizing aid and a dispersion stabilizer for suspension polymerization, and the dispersion stabilizer for suspension polymerization contains a vinyl alcohol-based polymer (Y3) (hereinafter sometimes abbreviated as PVA(Y3)) having a saponification degree of 65 mol% or more and a viscosity-average polymerization degree of 600 or more.

[0355] When using the PVA(X) of the present invention as a dispersion stabilizing aid for suspension polymerization, a dispersion stabilizer containing PVA(Y3) can be used in combination. PVA(Y3) can be a conventional vinyl alcohol-based polymer obtained by polymerizing and saponifying a vinyl ester monomer derived from petroleum, or a vinyl alcohol-based polymer (Y3-1) obtained by polymerizing and saponifying a vinyl ester monomer (A) derived from plants and a vinyl ester monomer (B) derived from petroleum.

[0356] The viscosity-average degree of polymerization of PVA(Y3) is preferably 150 or more and 5,000 or less, more preferably 300 or more and 4,000 or less, and further preferably 600 or more and 3,500. The saponification degree of PVA(Y3) is preferably 60 mol% or more and 99.5 mol%, more preferably 65 mol% or more and 99.2 mol% or less, and further preferably 68 mol% or more and 99.0 mol% or less. The methods for measuring the saponification degree and the degree of polymerization of PVA(Y3) are the same as those of PVA(X). PVA(Y3) can be manufactured by using existing well-known methods. The manufacturing method of the vinyl alcohol-based polymer (Y3-1) is the same as that of PVA(X). The polymerization conditions and saponification conditions can be appropriately set to the aforementioned desired ranges. In a suitable embodiment, the saponification degree of PVA(Y3) is 65 mol% or more and the viscosity-average degree of polymerization is 600 or more. In addition, in another suitable embodiment, the viscosity-average degree of polymerization is 500 or more and 5,000 or less, and the saponification degree is 65 mol% or more and 99 mol% or less.

[0357] When using a dispersion stabilizer in combination, the mass ratio (dispersion stabilizer / dispersion stabilizing aid) of the addition amounts of the dispersion stabilizer and the dispersion stabilizing aid varies depending on the type of the dispersion stabilizer used, etc., and thus cannot be generalized. It is preferably in the range of 95 / 5 to 20 / 80, and more preferably 90 / 10 to 30 / 70. The dispersion stabilizer and the dispersion stabilizing aid can be added together at the initial stage of polymerization, or can be added in batches during the polymerization process.

[0358] The aforementioned dispersion stabilizing aid for suspension polymerization can be used in combination with water-soluble cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropylmethyl cellulose, which are commonly used when suspending and polymerizing vinyl compounds in an aqueous medium; water-soluble polymers such as gelatin; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan trioleate, glyceryl tristearate, and ethylene oxide-propylene oxide block copolymers; and water-soluble emulsifiers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glyceryl oleate, and sodium laurate. Regarding its addition amount, there is no particular limitation, and it is preferably 0.01 part by mass or more and 1.0 part by mass or less relative to 100 parts by mass of the vinyl compound.

[0359] In the suspension polymerization of vinyl-based compounds, the method of introducing the above-mentioned dispersion stabilizing aid for suspension polymerization into the polymerization tank is not particularly limited. An aqueous solution of the dispersion stabilizing aid for suspension polymerization can be prepared and introduced. Alternatively, a mixed solution of water and methanol or ethanol of the dispersion stabilizing aid for suspension polymerization can be prepared and introduced. Further, the above-mentioned dispersion stabilizing aid for suspension polymerization can be mixed with an aqueous solution containing a dispersion stabilizer for suspension polymerization and introduced. Additionally, the aqueous solution of the dispersion stabilizing aid for suspension polymerization and the aqueous solution of the dispersion stabilizer for suspension polymerization can be introduced separately.

[0360] In the suspension polymerization of vinyl-based compounds, the feeding amount of the above-mentioned dispersion stabilizing aid for suspension polymerization in the polymerization tank is not particularly limited. It is preferred to introduce the aqueous solution of the dispersion stabilizing aid for suspension polymerization such that PVA(X) is 30 ppm or more and 1000 ppm or less relative to the vinyl-based compound (e.g., vinyl chloride monomer), more preferably 50 ppm or more and 800 ppm or less, and still more preferably 100 ppm or more and 500 ppm or less.

[0361] By carrying out the suspension polymerization of vinyl-based compounds by the above-mentioned method in the presence of the above-mentioned dispersion stabilizing aid for suspension polymerization, vinyl-based polymer particles with high absorbability of plasticizers, no foreign matters such as fish eyes, few formed coarse particles, and easy removal of the remaining monomer components can be obtained. The obtained vinyl-based polymer particles can be appropriately blended with plasticizers, etc. and used for various molded product applications.

[0362] Examples

[0363] Hereinafter, examples are shown to more specifically illustrate the present invention, but the present invention is not limited by these examples. It should be noted that in the examples, "parts" and "%" refer to mass basis unless otherwise specified.

[0364] (Content of ethylene unit in ethylene-modified PVA)

[0365] The content of the ethylene unit in the ethylene-modified PVA is determined based on the precursor or re-saponified product of the ethylene-modified PVA, that is, the 1 1H-NMR of the ethylene-modified vinyl ester polymer. Specifically, after subjecting the ethylene-modified vinyl ester polymers of the samples of Synthesis Examples 7-3 and 7-5 to reprecipitation purification three or more times using a mixed solution of n-hexane and acetone, they are dried under reduced pressure at 80 °C for 3 days to prepare ethylene-modified vinyl ester polymers for analysis. The ethylene-modified vinyl ester polymers for analysis are dissolved in DMSO-d 6 , and measured at 80 °C 1H-NMR (500 MHz): The ethylene unit content was calculated by the following formula using the peak derived from the main chain methine protons of vinyl acetate (integrated value P: 4.7 to 5.2 ppm) and the peak derived from the main chain methylene protons of ethylene and vinyl acetate (integrated value Q: 1.0 to 1.6 ppm).

[0366] Ethylene unit content (mol%) = 100 × ((Q-2P) / 4) / P

[0367] (Viscosity average degree of polymerization of PVA)

[0368] The viscosity average polymerization degree of PVA is measured in accordance with JIS K6726: 1994. Specifically, when the degree of saponification is less than 99.5 mol%, the viscosity average polymerization degree is determined by the following formula using the intrinsic viscosity [η] (dL / g) measured in water at 30°C for PVA or ethylene-modified PVA saponified to a degree of saponification of 99.5 mol% or more.

[0369] Viscosity average degree of polymerization = ([η] × 1000 / 8.29) (1 / 0.62)

[0370] (Saponification degree of PVA)

[0371] The saponification degree of PVA is measured in accordance with JIS K 6726:1994.

[0372] (Synthesis Example 1-1)

[0373] The silica spherical carrier is impregnated with an aqueous solution containing an aqueous solution of sodium tetrachloropalladate and an aqueous solution of tetrachloroauric acid tetrahydrate and equivalent to the water absorption of the carrier, and is immersed in an aqueous solution containing sodium metasilicate nonahydrate and allowed to stand. Next, an aqueous solution of hydrazine hydrate is added, and after standing at room temperature, it is washed with water until the chloride ions in the water disappear, and then dried. The palladium / gold / carrier composition is immersed in an acetic acid aqueous solution and allowed to stand. Next, it is washed with water and dried. Thereafter, it is impregnated in an aqueous solution of potassium acetate equivalent to the water absorption of the carrier, and dried, thereby obtaining a vinyl acetate synthesis catalyst.

[0374] The catalyst obtained above was diluted with glass beads and filled into a SUS reaction tube, and a mixed gas of ethylene, oxygen, water, acetic acid and nitrogen was circulated to react. Bioethylene derived from sugar cane (manufactured by Braskem SA) was used as ethylene. In addition, acetic acid was gasified and then introduced into the reaction system by steam. The yield and selectivity of vinyl acetate were obtained by analyzing the reaction outlet gas. The obtained vinyl acetate was analyzed by the above method, and the 14 The result of C / C is 5.0×10 -13 .

[0375] (Synthesis Example 1-2)

[0376] 50 parts of plant-derived vinyl acetate and 50 parts of ordinary petroleum-derived vinyl acetate obtained in the above Synthesis Example 1-1 were uniformly mixed and used as raw materials to synthesize PVA by the following method.

[0377] 127.5 kg of the above vinyl acetate and 22.5 kg of methanol were charged into a 250 L reaction tank equipped with a stirrer, a nitrogen inlet, an ethylene inlet, an initiator addition port, and a retarder solution addition port. After heating to 60 °C, nitrogen replacement was carried out by nitrogen bubbling for 30 minutes. Then, ethylene was introduced so that the pressure in the reaction tank became 3.4 Kg / cm 2 . 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile) (AMV) as an initiator was dissolved in methanol to prepare a reaction initiation solution with a concentration of 2.8 g / L, and nitrogen replacement was carried out by bubbling this reaction initiation solution with nitrogen. 45 mL of this initiator solution was injected into the reaction tank adjusted to 60 °C to start polymerization. During polymerization, ethylene was introduced to maintain the pressure in the reaction tank at 3.4 kg / cm 2 , and the polymerization temperature was maintained at 60 °C. The initiator solution was continuously added to the reaction tank at 143 mL / hr to carry out polymerization. When the polymerization rate reached 50% after 5 hours, the reaction tank was cooled to stop polymerization. Furthermore, after opening the reaction tank to remove ethylene, nitrogen was bubbled to completely remove ethylene. Then, unreacted vinyl acetate monomer was removed under reduced pressure to prepare a methanol solution of polyvinyl acetate. Methanol was added to this polyvinyl acetate solution to adjust the concentration of polyvinyl acetate to 25% by mass. Furthermore, 23.3 g (0.1 in molar ratio relative to the vinyl acetate units in polyvinyl acetate) of an alkali solution (10% by mass methanol solution of NaOH) was added to 400 g of this methanol solution of polyvinyl acetate (100 g of polyvinyl acetate in the solution) for saponification. About 1 minute after adding the alkali, the gelled substance was crushed with a crusher, and after standing at 40 °C for 1 hour for saponification, 1000 g of methyl acetate was added and left at room temperature for 30 minutes. 1000 g of methanol was added to the white solid (PVA) obtained by filtration, and after standing and washing at room temperature for 3 hours, centrifugal dewatering was carried out, and the PVA thus obtained was placed in a dryer at 100 °C for 3 hours to obtain PVA (PVA1-1).

[0378] <Characteristics Analysis of PVA>

[0379] For PVA (PVA1-1), the degree of saponification, average degree of polymerization, and proportion of ethylene units were analyzed according to the following method.

[0380] (Degree of Saponification)

[0381] The saponification degree of PVA (PVA1-1), as determined in accordance with JIS K 6726:1994, was 99.5 mol%.

[0382] (Average degree of polymerization)

[0383] The methanol solution of polyvinyl acetate obtained by removing the unreacted vinyl acetate monomer after polymerization in Synthesis Example 1-2 was saponified at a base molar ratio of 0.5, followed by pulverization. The resulting substance was allowed to stand at 60 °C for 5 hours for saponification. Subsequently, methanol Soxhlet extraction was carried out for 3 days, and then vacuum drying was carried out at 80 °C for 3 days to obtain purified PVA. The average degree of polymerization of this purified PVA, as determined in accordance with JIS K6726:1994, was 2,450.

[0384] (Ratio of ethylene units)

[0385] The methanol solution of polyvinyl acetate obtained by removing the unreacted vinyl acetate monomer after polymerization in Synthesis Example 1-2 was subjected to reprecipitation purification by precipitation in n-hexane three times and dissolution in acetone, and then vacuum drying was carried out at 80 °C for 3 days to obtain purified polyvinyl acetate. This purified polyvinyl acetate was dissolved in DMSO-d 6 , and the ethylene unit content was measured at 80 °C using a 500 MHz proton NMR (JEOL GX-500). The result was 3.0 mol%.

[0386] (Synthesis Example 1-3)

[0387] 30 parts of plant-derived vinyl acetate and 70 parts of ordinary petroleum-derived vinyl acetate obtained in Synthesis Example 1-1 above were uniformly mixed and used as raw materials. Without introducing ethylene, PVA (PVA1-2) was synthesized using the method based on Synthesis Example 1-2. The saponification degree of PVA1-2 was 99.5 mol%, the average degree of polymerization was 2,640, and the ethylene unit was 0 mol%.

[0388] (Synthesis Example 1-4)

[0389] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and PVA (PVA1-3) was synthesized using the same method as in Synthesis Example 1-2. The saponification degree of PVA1-3 was 99.6 mol%, the average degree of polymerization was 2,480, and the ethylene unit was 3.0 mol%.

[0390] (Synthesis Example 1-5)

[0391] The usual petroleum-derived vinyl acetate was used as a 100% raw material, and PVA (PVA1-4) was synthesized in the same manner as in Synthesis Examples 1-3. The degree of saponification of PVA1-4 was 99.6 mol%, the average degree of polymerization was 2,580, and the ethylene unit was 0 mol%.

[0392] [Example 1-1]

[0393] <Preparation of Cement Slurry>

[0394] PVA (PVA1-1) was placed on a sieve with a nominal mesh size of 250 μm (60 mesh). 4 g of the PVA powder that passed through this sieve, 320 g of ion-exchanged water, 800 g of mine-use H-class cement, 4 g of sodium naphthalene sulfonate formaldehyde condensate ("Daxad-19" from Dippersity Technologies), and 0.16 g of sodium lignosulfonate ("Keling 32L" from Lignotech USA) were put into a juice blender and stirred and mixed to prepare a cement slurry (S-1). It should be noted that the addition amount of the PVA powder was set to 0.5% based on the mass of the cement (BWOC). As described above, the PVA powder had a particle size of less than 250 μm in terms of particle size distribution (volume basis) by the sieving method.

[0395] [Example 1-2]

[0396] Using PVA (PVA1-2), except for this, the same operation as in Example 1-1 was carried out to prepare a cement slurry (S-2).

[0397] [Reference Example 1-1]

[0398] Using PVA (PVA1-3), except for this, the same operation as in Example 1-1 was carried out to prepare a cement slurry (s-1).

[0399] [Reference Example 1-2]

[0400] Using PVA (PVA1-4), except for this, the same operation as in Example 1-2 was carried out to prepare a cement slurry (s-2).

[0401] [Evaluation]

[0402] For the cement slurries (S-1), (S-2) and (s-1), (s-2) of Example 1-1, 1-2 and Reference Example 1-1, 1-2, the viscosity and water separation amount were evaluated according to the following method. The evaluation results are shown in Table 1. And the solubility of the PVA used in the preparation of these cement slurries in water is shown in Table 1.

[0403] <Solubility in Water>

[0404] Add 4 g of PVA powder to a 300 mL beaker pre-filled with 100 g of water at 60 °C. While preventing the evaporation of water, use a magnetic stirrer equipped with a 3 cm long rod and stir at 280 rpm for 3 hours at 60 °C. Then, use a metal mesh with a nominal mesh size of 75 μm (200 mesh) to separate the undissolved powder. Dry the undissolved PVA powder using a heating dryer at 105 °C for 3 hours and then measure its mass. Calculate the solubility of the PVA powder based on the mass of the undissolved PVA powder and the mass of the PVA powder (4 g) added to the beaker.

[0405] <Viscosity>

[0406] Viscosity is evaluated in the form of plastic viscosity (PV) and yield value (YV). Plastic viscosity (PV) is the value of the flow resistance generated by the mechanical friction of the solid components contained in the cement slurry. Yield value (YV) is the shear force required for continuous flow when the fluid is in a flowing state and is the flow resistance generated by the traction force between the solid particles contained in the cement slurry.

[0407] Plastic viscosity (PV) and yield value (YV) are measured by adjusting the temperature of the cement slurry to 25 °C or 90 °C and following the method described in "Appendix H" of "API 10" (American Institute Specification 10). It should be noted that plastic viscosity (PV) and yield value (YV) are calculated using the following formulas.

[0408] Plastic viscosity (PV) = (Reading at 300 rpm - Reading at 100 rpm) × 1.5

[0409] Yield value (YV) = (Reading at 300 rpm - Plastic viscosity)

[0410] <Water separation amount>

[0411] The water separation amount is measured in the form of the water separation amount of the cement slurry adjusted to 90 °C under a pressure difference of 1000 psi for 30 minutes following the method described in "Appendix H" of "API 10" (American Institute Specification 10).

[0412] [Table 1]

[0413]

[0414] From the results in Table 1, it is clear that the slurries (S-1) and (S-2) of Examples 1-1 and 1-2 have excellent viscosity, with water loss amounts at 150 °C of 25 mL and 32 mL respectively, and water loss at high temperatures is suppressed. Moreover, their values are not inferior to those of the slurries (s-1) and (s-2) of Reference Examples 1-1 and 1-2 which are made of only petroleum-derived vinyl acetate, and they have equivalent performance as slurries. Additionally, it was visually confirmed that the slurries (S-1) and (S-2) of Examples 1-1 and 1-2 did not separate. Such a slurry can contribute to the conservation of petroleum resources and the suppression of global warming.

[0415] <Drilling mud>

[0416] (Synthesis Example 1-6) Preparation of PVA (PVA1-5)

[0417] 50 parts of plant-derived vinyl acetate obtained in the above Synthesis Example 1-1 and 50 parts of ordinary petroleum-derived vinyl acetate were uniformly mixed and used as raw materials to synthesize PVA by the following method.

[0418] 127.5 kg of vinyl acetate and 22.5 kg of methanol were charged into a 250 L reaction tank equipped with a stirrer, a nitrogen inlet, an ethylene inlet, an initiator addition port, and a retarder solution addition port. After heating to 60 °C, nitrogen replacement was carried out by nitrogen bubbling for 30 minutes. Then, ethylene was introduced so that the pressure in the reaction tank became 4.9 Kg / cm 2 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (AMV) as an initiator was dissolved in methanol to prepare a reaction initiation solution with a concentration of 2.8 g / L, and nitrogen replacement was carried out by bubbling this reaction initiation solution with nitrogen. 45 mL of this initiator solution was injected into the reaction tank adjusted to 60 °C to start polymerization. During polymerization, ethylene was introduced to maintain the pressure in the reaction tank at 4.9 Kg / cm 2, and the polymerization temperature was maintained at 60°C. The initiator solution was continuously added to the reaction tank at a rate of 143 mL / hr to conduct the polymerization. When the polymerization rate reached 40% after 4 hours, the reaction tank was cooled to stop the polymerization. Further, the reaction tank was opened to remove ethylene, and then nitrogen was introduced to completely remove ethylene. Subsequently, the unreacted vinyl acetate monomer was removed under reduced pressure to prepare a methanol solution of polyvinyl acetate. Methanol was added to this polyvinyl acetate solution to adjust the concentration of polyvinyl acetate to 25% by mass. Further, 23.3 g (molar ratio of 0.1 based on the vinyl acetate units in polyvinyl acetate) of an alkali solution (10% by mass methanol solution of NaOH) was added to 400 g of this methanol solution of polyvinyl acetate (100 g of polyvinyl acetate in the solution) for saponification. Approximately 1 minute after adding the alkali, the gelled substance was crushed with a crusher, and after saponification by standing at 40°C for 1 hour, 1000 g of methyl acetate was added and left standing at room temperature for 30 minutes. 1000 g of methanol was added to the white solid (PVA) obtained by filtration, and after standing and washing at room temperature for 3 hours, centrifugal dewatering was performed. The PVA thus obtained was placed in a dryer at 100°C for 3 hours to obtain PVA (PVA1-5).

[0419] <Characteristic Analysis of PVA>

[0420] For PVA (PVA1-5), the degree of saponification, average degree of polymerization, and proportion of vinyl units were analyzed according to the following method.

[0421] (Degree of Saponification)

[0422] The degree of saponification of PVA (PVA1-5) was 99.9 mol% as determined according to JIS K6726:1994.

[0423] (Average Degree of Polymerization)

[0424] The methanol solution of polyvinyl acetate obtained by removing the unreacted vinyl acetate monomer after polymerization in Synthesis Examples 1-6 was saponified at an alkali molar ratio of 0.5, crushed, and then saponified by standing at 60°C for 5 hours. Subsequently, methanol Soxhlet extraction was performed for 3 days, and then vacuum drying was performed at 80°C for 3 days to obtain purified PVA. The average degree of polymerization of this purified PVA was 1,720 as determined according to JIS K6726:1994.

[0425] (Content of Vinyl Units)

[0426] For the methanol solution of polyvinyl acetate obtained by removing the unreacted vinyl acetate monomer after polymerization in Synthesis Examples 1-6, after performing reprecipitation purification by precipitating three times in n-hexane and dissolving in acetone, vacuum drying was carried out at 80 °C for 3 days to obtain purified polyvinyl acetate. The purified polyvinyl acetate was dissolved in DMSO-d 6 , and using a 500 MHz 1 1H-NMR (JEOL GX-500), the result of measuring the proportion of ethylene units at 80 °C was 5.0 mol%.

[0427] (Synthesis Example 1-7) Preparation of PVA (PVA1-6)

[0428] 30 parts of plant-derived vinyl acetate obtained in Synthesis Example 1-1 above and 70 parts of ordinary petroleum-derived vinyl acetate were uniformly mixed and used as raw materials. Without introducing ethylene, otherwise, PVA (PVA1-6) was synthesized using the method based on Synthesis Example 1-6. The saponification degree of PVA1-6 was 99.9 mol%, the average degree of polymerization was 2,520, and the ethylene unit was 0 mol%.

[0429] (Synthesis Example 1-8)

[0430] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and PVA (PVA1-7) was synthesized using the same method as in Synthesis Example 1-6. The saponification degree of PVA1-7 was 99.9 mol%, the average degree of polymerization was 1,740, and the ethylene unit was 5.0 mol%.

[0431] (Synthesis Example 1-9)

[0432] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and PVA (PVA1-8) was synthesized using the same method as in Synthesis Example 1-7. The saponification degree of PVA1-8 was 99.9 mol%, the average degree of polymerization was 2,480, and the ethylene unit was 0 mol%.

[0433] [Example 1-3]

[0434] <Preparation of Drilling Mud>

[0435] 300 g of ion exchange water was placed in the cup of Hamilton-Beach (Hamichi) blender, 6 g of bentonite (TELNITE "Telgel E") was added and stirred thoroughly, and then left for 24 hours to allow the bentonite to swell fully. On the other hand, PVA (PVA1-5) was placed on a sieve with a nominal mesh of 1.00 mm (16 mesh), 1.5 g of the powder of PVA (PVA1-5) that passed through the sieve was taken, and the powder was added to the bentonite dispersion to obtain drilling mud (D-1). As described above, the powder of PVA has a particle size of less than 1.00 mm in terms of particle size distribution (volume basis) by sieving.

[0436] [Examples 1-4]

[0437] A drilling mud (D-2) was prepared in the same manner as in Example 1-3 except that the powder of PVA (PVA1-6) was used.

[0438] [Reference Example 1-3]

[0439] A drilling mud (d-1) was prepared in the same manner as in Example 1-3 except that the powder of PVA (PVA1-7) was used.

[0440] [Reference Example 1-4]

[0441] A drilling mud (d-2) was prepared in the same manner as in Example 1-3 except that the powder of PVA (PVA1-8) was used.

[0442] [evaluate]

[0443] The viscosity and water removal amount of the drilling muds (D-1), (D-2) and (d-1), (d-2) were evaluated by the following method. In addition, the solubility in water of PVA (PVA1-5) to (PVA1-8) used in the preparation of these drilling muds was evaluated by the following method. The evaluation results are shown in Table 2.

[0444] <Solubility in water>

[0445] 4 g of PVA powder was added to a 300 mL beaker pre-filled with 100 g of 60°C water, and stirred at 280 rpm for 3 hours at 60°C using a magnetic stirrer with a 3 cm long rod without evaporating the water. Next, a metal mesh with a nominal mesh size of 75 μm (200 mesh) was used to separate the undissolved powder. The undissolved PVA powder was dried for 3 hours in a heating dryer at 105°C, and its mass was measured. The solubility of the PVA powder was calculated based on the mass of the undissolved PVA powder and the mass of the PVA powder put into the beaker (4 g).

[0446] <Viscosity>

[0447] The viscosity of the drilling mud was measured using a B-type viscometer at 25 °C and 30 rpm, and the value after 10 seconds was adopted.

[0448] <Water loss>

[0449] The water loss of the drilling mud was measured using the "HPHT Filter Press Series 387" of Fann Instrument Company. After putting the drilling mud into the unit adjusted to 150 °C and leaving it for 3 hours, it was pressurized from the upper and lower parts of the unit until the pressure difference reached 500 psi.

[0450] [Table 2]

[0451]

[0452] It can be clarified from the results in Table 2 that the viscosities of the drilling muds (D-1) and (D-2) of Examples 1-3 and 1-4 are low and the water loss at 150 °C is 25 mL or less, and the dehydration at high temperature is very little inhibited. Moreover, their values are not inferior to those of the PVA synthesized only from petroleum-derived vinyl acetate, namely the drilling muds (d-1) and (d-2) of Reference Examples 1-3 and 1-4, and they have equivalent performance as drilling muds. Such drilling mud can contribute to saving petroleum resources and suppressing global warming.

[0453] (Synthesis Example 2-2)

[0454] 50 parts of plant-derived vinyl acetate obtained in the above Synthesis Example 1-1 and 50 parts of ordinary petroleum-derived vinyl acetate were uniformly mixed as raw materials, and further 5 mol% of methyl acrylate was copolymerized, and polyvinyl acetate was synthesized according to a conventional method. It was made into a methanol solution, and saponification reaction was carried out using an alkali catalyst, and then dried to obtain PVA. The average degree of polymerization of this PVA was 1,450, and the saponification degree was 99.5 mol%. 1.5 mass% of polyethylene glycol was added to the obtained PVA and kneaded. Then, using a twin-screw extrusion molding machine, it was extruded and molded into a sheet at a molding pressure of 1259 psi. It was put into a granulator and granulated into 6 / 8 mesh (ASTM E11 standard) to obtain PVA resin pellets (PVA2-1). It should be noted that "granulated into 6 / 8 mesh" means granulated into a particle size that passed through 6 mesh but did not pass through 8 mesh, and the particle diameter of the granulated particles of 6 / 8 mesh is 2380 μm or more and 3350 μm or less.

[0455] (Synthesis Example 2-3)

[0456] 30 parts of plant-derived vinyl acetate obtained in Synthesis Example 1-1 and 70 parts of ordinary petroleum-derived vinyl acetate were uniformly mixed and used as raw materials. Without copolymerizing methyl acrylate, PVA was obtained in the same manner as in Synthesis Example 2-2. The average degree of polymerization of this PVA was 1,620 and the saponification degree was 99.5 mol%. 1.5% by mass of polyethylene glycol was added to the obtained PVA and kneaded. Then, using a twin-screw extrusion molding machine, it was extruded into a sheet at a molding pressure of 1250 psi, and then put into a granulator and granulated into 6 / 8 mesh to obtain PVA resin pellets (PVA2-2).

[0457] (Synthesis Example 2-4)

[0458] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and PVA resin pellets (PVA2-3) were synthesized in the same manner as in Synthesis Example 2-2. The saponification degree of this PVA was 99.5 mol%, the average degree of polymerization was 1,480, and the content of methyl acrylate was 5 mol%.

[0459] (Synthesis Example 2-5)

[0460] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and PVA resin pellets (PVA2-4) were synthesized in the same manner as in Synthesis Example 2-3. The saponification degree of this PVA was 99.6 mol% and the average degree of polymerization was 1,580.

[0461] [Examples 2-1 and 2-2, Comparative Examples 2-1 and 2-2]

[0462] <Underground treatment filler>

[0463] For the obtained PVA2-1 to PVA2-4, the swelling degree (%) based on water and the solubility (%) in water were measured by the following method to evaluate the filling effect. The results are shown in Table 3.

[0464] <Swelling degree based on water>

[0465] 0.5 g of PVA resin pellets were put into a test tube with an inner diameter of 18 mm, and the height (height A) occupied by the PVA resin pellets in the test tube was measured. Then, 7 mL of distilled water was put into the test tube and shaken well to disperse the PVA resin pellets. Thereafter, the test tube was immersed in a water bath set at 40 °C. After the water temperature in the test tube reached 40 °C, it was left standing for 30 minutes, and then the height (height B) occupied by the PVA resin pellets in the test tube was measured. According to the following formula, the swelling degree (%) based on water was calculated from the obtained values of height A and height B.

[0466] Swelling degree based on water (%) = (height B / height A) × 100

[0467] <Solubility in water>

[0468] Put 100 g of distilled water into a 200 mL glass container with a lid, and add 6 g of PVA resin pellets. Let it stand in a constant temperature bath at 65 °C for 5 hours. Then, pass the contents of the glass container through a nylon sieve with 120 meshes (mesh size is 125 μm), and dry the PVA resin pellets remaining on the sieve at 140 °C for 3 hours, and measure the mass after drying (mass A). On the other hand, for the same measurement object, dry the PVA resin pellets separately taken for measuring the solid content rate at 105 °C for 3 hours, measure the mass before drying (mass B) and the mass after drying (mass C), and calculate the solid content rate. Using this solid content rate and mass A, calculate the solubility (%) of the PVA resin pellets in water according to the following formula.

[0469] Solid content rate (%) = (mass C / mass B) × 100

[0470] Solubility in water (%) = {6 - (mass A × 100 / solid content rate)} / 6 × 100

[0471] <Filling effect confirmation test>

[0472] Set a 120 - mesh stainless - steel sieve in a stainless - steel column with an inner diameter of 10 mm, and put 5 g of PVA resin pellets into the upstream side. Then, put warm water adjusted to 50 °C into the column and apply a pressure of 100 psi. Observe the column visually, record the situation where the outflow of warm water stops within 15 seconds as "〇", and the situation where it does not stop within 15 seconds as "×", and evaluate the filling effect.

[0473] [Table 3]

[0474]

[0475] The solubility and swelling degree values of the PVA resin pellets in Example 2 - 1 and 2 - 2 are not inferior to those in Reference Example 2 - 1 and 2 - 2 respectively, and it can be confirmed that they have the same degree of (thermal) water - solubility and swelling property. In addition, while fully exerting the filling effect, it can contribute to saving petroleum resources and suppressing global warming. The filling agent for underground treatment containing such PVA temporarily plugs the cracks in the ground and slowly dissolves in water, and is removed when recovering underground resources such as petroleum and natural gas or after recovery. Therefore, it will not remain in the ground for a long time and can reduce the burden on the environment.

[0476] (Synthesis Example 2 - 6)

[0477] Using 100 parts of the plant-derived vinyl acetate obtained in Synthesis Example 1-1 above, a raw material was prepared without adding any conventional petroleum-derived vinyl acetate at all. Using the same method as in Synthesis Example 2-3, PVA was obtained. The average degree of polymerization of this PVA was 1,580 and the degree of saponification was 99.6 mol%. 1.5% by mass of polyethylene glycol was added to the obtained PVA and kneaded. Then, using a twin-screw extrusion molding machine, it was extruded into a sheet at a molding pressure of 1250 psi, and then put into a granulator and granulated into 6 / 8 mesh to obtain PVA resin pellets (PVA2-5).

[0478] [Comparative Example 2-1]

[0479] Cracks were observed in the appearance of the obtained PVA2-5. In contrast, the appearance of PVA2-3 obtained by the same method was smooth. The reason is not clear yet, but it was confirmed that by setting the plant-derived vinyl acetate in the raw material to 10 mol% or more, the cracks in the PVA can be improved.

[0480] In the present invention, by using the plant-derived vinyl ester monomer (A) as a monomer, a vinyl alcohol-based polymer having the same properties as a vinyl alcohol-based polymer derived only from petroleum was obtained. It was confirmed that the occurrence of manufacturing problems generated during the production of PVA can be suppressed. Furthermore, when using PVA, petroleum resources can be saved and carbon dioxide emissions during the manufacturing process can be suppressed.

[0481] (Synthesis Example 3-2)

[0482] 50 parts of the plant-derived vinyl acetate obtained in Synthesis Example 1-1 above and 50 parts of a conventional petroleum-derived vinyl acetate were uniformly mixed and used as a raw material. The polymerization conditions such as the polymerization temperature and polymerization time were adjusted to the desired range, and polyvinyl acetate was synthesized by a conventional method. It was made into a methanol solution, and the saponification conditions such as the amount of the alkali catalyst used and the saponification time were adjusted to the desired range, and a saponification reaction was carried out using an alkali catalyst by a conventional method, and dried to obtain PVA (PVA3-1). The average degree of polymerization of this PVA was 1,750 and the degree of saponification was 88.5 mol%.

[0483] (Synthesis Example 3-3)

[0484] 30 parts of the plant-derived vinyl acetate obtained in Synthesis Example 1-1 above and 70 parts of a conventional petroleum-derived vinyl acetate were uniformly mixed and used as a raw material, and copolymerization of a conventional petroleum-derived ethylene was carried out. Except for this, using the same method as in Synthesis Example 3-2, PVA (PVA3-2) was obtained. The average degree of polymerization of this PVA was 1,720, the degree of saponification was 97.5 mol%, and the ethylene content was 4.2 mol%.

[0485] (Synthesis Example 3-4)

[0486] Using ordinary petroleum-derived vinyl acetate as 100% raw material, a PVA resin (PVA3-3) was synthesized in the same manner as in Synthesis Example 3-2. The saponification degree of this PVA was 88.7 mol% and the average degree of polymerization was 1,780.

[0487] (Synthesis Example 3-5)

[0488] Using ordinary petroleum-derived vinyl acetate as 100% raw material, a PVA resin (PVA3-4) was synthesized in the same manner as in Synthesis Example 3-3. The saponification degree of this PVA was 98.1 mol%, the average degree of polymerization was 1,680, and the ethylene content was 4.1 mol%.

[0489] [Example 3-1]

[0490] For the obtained PVA3-1, an aqueous emulsion was prepared by the following method, and whether aggregates were formed, the normal adhesion performance, and the coatability were evaluated.

[0491] <Preparation of Aqueous Emulsion>

[0492] 275 g of ion-exchanged water was put into a 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet, and heated to 85°C. 120.9 g of PVA-1 was dispersed and stirred for 45 minutes to dissolve it. Further, 0.3 g of sodium acetate was added and mixed to dissolve it. Then, after cooling the aqueous solution in which this PVA-1 was dissolved and performing nitrogen replacement, while stirring at 200 rpm, the temperature was raised to 60°C, and then 2.4 g of a 20% by mass aqueous solution of tartaric acid and 3.2 g of a 5% by mass aqueous hydrogen peroxide solution were added dropwise, and then 27 g of vinyl acetate was added to start polymerization. After 30 minutes from the start of polymerization, it was confirmed that the initial polymerization was completed (the residual amount of vinyl acetate was less than 1%). After adding dropwise 1 g of a 10% by mass aqueous solution of tartaric acid and 3.2 g of a 5% by mass aqueous hydrogen peroxide solution, 251 g of vinyl acetate was continuously added over 2 hours, and the polymerization temperature was maintained at 80°C to complete the polymerization, obtaining a polyvinyl acetate-based emulsion (Em-1) with a solid content concentration of 49.8% by mass.

[0493] <Amount of Aggregates Formed>

[0494] 500 g of the aqueous emulsion obtained in the examples and reference examples was filtered through a 60-mesh metal screen, the filtration residue was weighed, and the evaluation was carried out as follows.

[0495] A: The filtration residue was less than 1.0% by mass

[0496] B: The filtration residue was 1.0% by mass or more and less than 2.5% by mass

[0497] C: The filtration residue is 2.5% by mass or more and less than 5.0% by mass

[0498] D: The filtration residue is 5.0% by mass or more, and it is difficult to filter

[0499] <Normal adhesiveness>

[0500] The normal adhesiveness is evaluated in accordance with JIS K 6852 (1994).

[0501] (Adhesion conditions)

[0502] Adherend: Hemlock / hemlock

[0503] Coating amount: 150 g / m 2 (Coated on both sides)

[0504] Pressing conditions: 20 °C, 24 hours, pressure of 10 kg / cm 2

[0505] (Measurement conditions)

[0506] The test piece cured for 7 days in an environment of 20 °C and 65% RH is subjected to a compression shear test to measure the adhesive strength (unit: kgf / cm 2 ).

[0507] <Coatability>

[0508] Drop 0.8 g of the aqueous emulsion onto a covering material with a width of 25 mm and a length of 20 cm, and rub it 4 times with a rubber roller, and observe the situation. Evaluation is carried out in 4 stages of A to D according to the following criteria.

[0509] A: Uniformly coated on the entire surface of the covering material, and no aggregates are generated

[0510] B: Uniformly coated on an area of more than 1 / 2 of the covering material, no aggregates are generated and the coated surface is not peeled off

[0511] C: Coated on an area of more than 1 / 2 of the covering material, aggregates are generated and the coated surface is peeled off

[0512] D: Coated on an area of less than 1 / 2 of the covering material, aggregates are generated and the coated surface is peeled off

[0513] [Example 3-2, Reference Examples 3-1 and 3-2]

[0514] PVA-2, PVA-3, and PVA-4 were used to replace copolymer 1 of Example 3-1. Otherwise, the operation was the same as that of Example 3-1 to prepare an aqueous emulsion. According to the above method, the amount of aggregates formed, the normal adhesiveness, and the coatability of the obtained aqueous emulsions (Em-2 to Em-4) were evaluated, and the results obtained were summarized in Table 4.

[0515] [Table 4]

[0516]

[0517] It was confirmed that no aggregates were formed in the aqueous emulsions obtained by using the PVAs of Examples 3-1 and 3-2 as dispersion stabilizers for emulsion polymerization, and the normal adhesiveness was not inferior to that of Reference Examples 3-1 and 3-2, respectively, and the adhesiveness was at the same level. In addition, the coatability, which is an important index when used as an adhesive, was also sufficient, which can contribute to saving petroleum resources and suppressing global warming.

[0518] (Synthesis Example 4-2)

[0519] <Polyvinyl alcohol-based polymer>

[0520] 50 parts of plant-derived vinyl acetate and 50 parts of conventional petroleum-derived vinyl acetate obtained in the above Synthesis Example 1-1 were uniformly mixed and used as raw materials, and polyvinyl acetate was synthesized according to a conventional method. It was made into a methanol solution, and a saponification reaction was carried out using an alkali catalyst, and dried to obtain PVA (PVA4-1). The average degree of polymerization of this PVA obtained by changing the manufacturing conditions (polymerization conditions, saponification conditions) within the desired range from Example 3-2 was 1700, and the saponification degree was 98.5 mol%.

[0521] (Synthesis Example 4-3)

[0522] 30 parts of plant-derived vinyl acetate and 70 parts of conventional petroleum-derived vinyl acetate obtained in the above Synthesis Example 1-1 were uniformly mixed and used as raw materials, and PVA (PVA4-2) was obtained by the same method as in Synthesis Example 4-2. The average degree of polymerization of this PVA was 2400, and the saponification degree was 88.0 mol%.

[0523] (Synthesis Example 4-4)

[0524] Conventional petroleum-derived vinyl acetate was used as 100% raw material, and PVA resin particles (PVA4-3) were synthesized by the same method as in Synthesis Example 4-2. The saponification degree of this PVA was 98.5 mol%, and the average degree of polymerization was 1700.

[0525] (Synthesis Example 4-5)

[0526] Using the usual petroleum-derived vinyl acetate as 100% raw material, PVA resin pellets (PVA4-4) were synthesized in the same manner as in Synthesis Example 4-3. The saponification degree of this PVA was 88.0 mol% and the average degree of polymerization was 2400.

[0527] [Examples 4-1 and 4-2, Comparative Examples 4-1 and 4-2]

[0528] For the obtained PVA4-1 to PVA4-4, the dust removal step, warm germination, germination test, accelerated aging test were carried out by the following methods, and the fluidity was measured to evaluate as a coating agent. The results are shown in the table.

[0529] (Treatment of soybean seeds)

[0530] The seed coating composition was prepared according to Table 5. The soybean seeds were treated with the Acceleron TM package (Monsanto Company; containing metalaxyl, pyraclostrobin, imidacloprid and fluxapyroxad), Color Coat Red and a water matrix to achieve a rate of 5.8 fl.oz / cwt of the Acceleron TM package. 15.64 mL of the slurry was applied to 2400 g of seeds.

[0531] [Table 5]

[0532]

[0533] (Dust removal step)

[0534] The dried and treated soybean seeds were put into a closed system container equipped with a filter, and stirred and vibrated under vacuum. Air was introduced into the container and discharged through the filter to filter the dust. The measurement results of the dust amount on the filter are shown in Table 6 below. It was confirmed that the amount of dust generated in the seed coating compositions of Examples 4-1 and 4-2 was low and was not inferior to those of Comparative Examples 4-1 and 4-2, respectively.

[0535] [Table 6]

[0536] PVA Coating composition Average gram weight of dust per 100,000 seeds Example 4-1 PVA 4-1 #1 0.0071 Example 4-2 PVA4-1 #2 0.0062 Example 4-3 PVA 4-2 #1 0.0079 Reference Example 4-1 PVA4-3 #1 0.0072 Reference Example 4-2 PVA 4-3 #2 0.0062 Reference Example 4-3 PVA 4-4 #1 0.0080

[0537] (Warm germination)

[0538] This test was used to determine the maximum germination ability of treated seeds and untreated seeds. Four sets of 100 seeds were prepared, planted on moist crêpe cellulose paper, and placed at 25 °C for 7 days. Then, according to the AOSA rules (Association of Official Seed Analysts rules), the seedlings were evaluated as "normal", "abnormal", or "dead". The "normal" germination percentage was determined as follows: subtract the number of "abnormal" or "dead" seeds from the average number of germinated seeds during the test, divide by the total number of original seeds, and multiply by 100. The results are shown in Table 7 below. It was confirmed that the seed coating compositions of Examples 4-1 and 4-2 did not have a harmful effect on the germination rate under ideal conditions and were not inferior to those of Reference Examples 4-1 and 4-2, respectively.

[0539] [Table 7]

[0540] PVA Coating Normal Abnormal Dead Example 4-1 PVA 4-1 Coating #1 96 4 0 Example 4-2 PVA 4-1 Coating #2 95 4 1 Reference Example 4-1 PVA 4-3 Coating #1 96 4 0 Reference Example 4-2 PVA 4-3 Coating #2 95 4 1

[0541] (Low-temperature germination test)

[0542] This test was designed to determine the ability of seeds to germinate under conditions of high soil moisture, low soil temperature, and adverse conditions related to microbial activity. Four sets of 100 seeds were prepared, planted on moist crêpe cellulose paper, and covered with sand. The covered film was placed at 10 °C for 7 days and then transferred to 25 °C for 4 days. Thereafter, considering viability, the seedlings were evaluated as "normal", "abnormal", or "dead" according to the AOSA rules. The proportion of "normal" germination was determined as follows: subtract the number of "abnormal" or "dead" seeds from the average number of germinated seeds during the test, divide by the total number of original seeds, and multiply by 100. The results are shown in Table 8 below. From the results of the low-temperature germination test, it was confirmed that the normal germination rates of the seeds of the seed coating compositions of Examples 4-1 and 4-2 were not inferior to those of Reference Examples 4-1 and 4-2, respectively.

[0543] [Table 8]

[0544] PVA Coating Normal Example 4-1 PVA 4-1 Coating #1 83 Example 4-2 PVA 4-1 Coating #2 86 Reference Example 4-1 PVA4-3 Coating #1 83 Reference Example 4-2 PVA 4-3 Coating #2 86

[0545] (Accelerated aging test)

[0546] Weigh the seeds, place them in a chamber with a water jacket, and maintain at 43 °C and high humidity for 72 hours. Prepare 4 sets of 100 seeds, plant them on moist creped cellulose paper, and cover with sand. Place the planted and covered film at 25 °C for 7 days. Thereafter, evaluate the normal seedlings according to the AOSA rules. The "normal" germination percentage is determined as follows: Subtract any "abnormal" or "dead" seeds from the average number of seeds germinated during the test period, divide by the total number of original seeds, and multiply by 100 times. The results are shown in Table 9 below. It can be confirmed that the seed coating compositions of Examples 4-1 and 4-2 do not reduce germination and are not inferior to those of Reference Examples 4-1 and 4-2, respectively.

[0547] [Table 9]

[0548] PVA Coating Normal Example 4-1 PVA 4-1 Coating #1 71 Example 4-2 PVA 4-1 Coating #2 78 Reference Example 4-1 PVA 4-3 Coating #1 71 Reference Example 4-2 PVA 4-3 Coating #2 78

[0549] (Fluid flowability)

[0550] For the drying fluid of soybeans, it is measured in the form of the time required for 1200 g of seeds (4 groups of 300 g) to flow through a funnel at a relative humidity of 56% and 25 °C. Adding a coating to soybeans has a tendency to extremely slow down the seed flow, which is not a desirable property. As shown in Table 9, it can be confirmed that when using the seed coating composition of the present invention, it flows as effectively and quickly as the seeds of Reference Examples 4-1 and 4-2, respectively, and is not inferior.

[0551] Seeds bridging occurs when the seeds coming out of the coating machine are collected in the storage hopper and compressed by the opposing seeds. It reveals problems in seed treatment facilities from the viewpoints of machine short-circuit, labor, and time. As shown in Table 10, it can be confirmed that when using the seed coating composition of the present invention, there is no tendency to show bridging and is not inferior to those of Reference Examples 4-1 and 4-2, respectively.

[0552] [Table 10]

[0553]

[0554] (Synthesis Example 5-2)

[0555] (Dispersion stabilizer for suspension polymerization)

[0556] Mix 50 parts of the plant-derived vinyl acetate obtained in Synthesis Example 1-1 above and 50 parts of the usual petroleum-derived vinyl acetate uniformly as raw materials, use acetaldehyde as a chain transfer agent, and synthesize polyvinyl acetate according to a conventional method. Make it into a methanol solution, carry out a saponification reaction using an alkali catalyst, and dry to obtain PVA (PVA5-1). The average degree of polymerization of this PVA is 750, and the saponification degree is 72.0 mol%.

[0557] (Synthesis Example 5-3)

[0558] 50 parts of plant-derived vinyl acetate and 50 parts of ordinary petroleum-derived vinyl acetate obtained in Synthesis Example 1-1 above were uniformly mixed and used as raw materials, and polyvinyl acetate was synthesized by a conventional method. It was made into a methanol solution, and saponification reaction was carried out using an alkali catalyst, followed by drying to obtain PVA (PVA5-2). The average degree of polymerization of this PVA obtained by changing the manufacturing conditions (polymerization conditions, saponification conditions) within the desired range from Synthesis Example 3-2 was 2400, and the degree of saponification was 80.0 mol%.

[0559] (Synthesis Example 5-4)

[0560] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and PVA (PVA5-3) was synthesized by the same method as in Synthesis Example 5-2. The average degree of polymerization of this PVA was 750, and the degree of saponification was 72.0 mol%.

[0561] (Synthesis Example 5-5)

[0562] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and PVA (PVA5-4) was synthesized by the same method as in Synthesis Example 5-3. The average degree of polymerization of this PVA was 2400, and the degree of saponification was 80.0 mol%.

[0563] [Table 11]

[0564]

[0565] [Examples 5-1 and 5-2, Comparative Examples 5-1 and 5-2]

[0566] For the obtained PVA5-1 to PVA5-4, suspension polymerization of vinyl chloride was carried out by the following method. Then, for the obtained vinyl chloride polymer particles, evaluation of average particle size, amount of coarse particles, and plasticizer absorbability was carried out. The evaluation results are shown in Table 12.

[0567] (Suspension Polymerization of Vinyl Chloride)

[0568] The ethylene-vinyl alcohol copolymer obtained above was dissolved in deionized water in an amount equivalent to 800 ppm with respect to vinyl chloride to prepare an aqueous dispersion stabilizer solution. 1150 g of the aqueous dispersion stabilizer solution thus obtained was charged into a 5-L autoclave. Subsequently, 1.5 g of a 70% toluene solution of diisopropyl peroxydicarbonate was charged into the autoclave. The autoclave was degassed until the pressure inside reached 0.0067 MPa to remove oxygen. Thereafter, 1000 g of vinyl chloride was charged, the contents inside the autoclave were heated to 57 °C, and polymerization was started under stirring. The pressure inside the autoclave at the start of polymerization was 0.83 MPa. Polymerization was stopped at the moment when the pressure inside the autoclave became 0.44 MPa 7 hours after the start of polymerization, and unreacted vinyl chloride was removed. Thereafter, the polymerization slurry was taken out and dried at 65 °C overnight to obtain vinyl chloride polymer particles.

[0569] (Evaluation of vinyl chloride polymer particles)

[0570] (1) Average particle diameter of vinyl chloride polymer particles

[0571] Using a wire mesh based on Tyler standard sieve numbers, the particle size distribution was measured by dry sieving analysis, and the results were plotted in a Rosin-Rammler distribution, and the average particle diameter (d p50 ; median particle diameter) was calculated.

[0572] (2) Amount of coarse particles of vinyl chloride polymer particles

[0573] The content of the residue on a JIS standard sieve No. 42 is expressed in mass%. The smaller the number, the fewer the coarse particles and the more excellent the polymerization stability.

[0574] (3) Plasticizer absorbency (CPA)

[0575] The mass of a 5-mL syringe filled with 0.02 g of absorbent cotton was measured (denoted as A (g)), 0.5 g of vinyl chloride polymer particles was added thereto and the mass was measured (denoted as B (g)), 1 g of dioctyl phthalate (DOP) was added thereto, after standing for 15 minutes, it was centrifuged at 3000 rpm for 40 minutes, and the mass was measured (denoted as C (g)). And the plasticizer absorbency (%) was calculated according to the following calculation formula.

[0576] Plasticizer absorbency (%) = 100 × [{(C - A) / (B - A)} - 1]

[0577] [Table 12]

[0578] PVA Average particle size (μm) Amount of coarse particles (%) Plasticizer absorbency (%) Example 5-1 PVA 5-1 155 0.5 26.0 Example 5-2 PVA 5-2 140 0.2 15.0 Reference Example 5-1 PVA 5-3 156 0.6 25.9 Reference Example 5-2 PVA 5-4 141 0.2 14.8

[0579] It was confirmed that the average particle diameter, amount of coarse particles, and plasticizer absorbency values of the vinyl chloride polymer particles of the PVA resins in Examples 5-1 and 5-2 were not inferior to those in Reference Examples 5-1 and 5-2, respectively, and had the performance as a dispersion stabilizer for suspension polymerization of the same level. In addition, it can contribute to saving petroleum resources and suppressing global warming.

[0580] (Synthesis Example 6-2)

[0581] <Dispersion Stabilizing Aid for Suspension Polymerization>

[0582] Fifty parts of plant-derived vinyl acetate obtained in Synthesis Example 1-1 above and fifty parts of ordinary petroleum-derived vinyl acetate were uniformly mixed and used as raw materials, and polyvinyl acetate was synthesized by a conventional method. It was made into a methanol solution, and a saponification reaction was carried out using an alkali catalyst, followed by drying to obtain PVA (PVA6-1). The average degree of polymerization of this PVA obtained by changing the manufacturing conditions (polymerization conditions, saponification conditions) within the desired range from Synthesis Example 3-2 was 300, and the saponification degree was 55.0 mol%.

[0583] (Synthesis Example 6-3)

[0584] Fifty parts of plant-derived vinyl acetate obtained in Synthesis Example 1-1 above and fifty parts of ordinary petroleum-derived vinyl acetate were uniformly mixed and used as raw materials, and 3-mercaptopropionic acid (3-MPA) was used as a chain transfer agent, and polyvinyl acetate was synthesized by a conventional method. It was made into a methanol solution, and a saponification reaction was carried out using an alkali catalyst, followed by drying to obtain PVA (PVA6-2). The average degree of polymerization of this PVA was 500, and the saponification degree was 40.0 mol%.

[0585] (Synthesis Example 6-4)

[0586] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and a PVA resin (PVA6-3) was synthesized by the same method as in Synthesis Example 6-2. The average degree of polymerization of this PVA was 300, and the saponification degree was 55.0 mol%.

[0587] (Synthesis Example 6-5)

[0588] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and PVA resin pellets (PVA6-4) were synthesized by the same method as in Synthesis Example 6-3. The average degree of polymerization of this PVA was 500, and the saponification degree was 40.0 mol%.

[0589] (Synthesis Example 6-6)

[0590] <Dispersion Stabilizer for Suspension Polymerization>

[0591] Using the usual petroleum-derived vinyl acetate as a 100% raw material, polyvinyl acetate was synthesized by a conventional method. It was made into a methanol solution, and saponification reaction was carried out using an alkali catalyst, followed by drying to obtain PVA (PVA6-5). The average degree of polymerization of this PVA was 2000, and the saponification degree was 80 mol%.

[0592] [Table 13]

[0593]

[0594] [Examples 6-1 and 6-2, Comparative Examples 6-1 and 6-2]

[0595] For the obtained PVA6-1 to PVA6-4, suspension polymerization of vinyl chloride was carried out by the following method. Then, for the obtained vinyl chloride polymer particles, evaluations were made on (1) average particle size, (2) plasticizer absorbability, (3) monomer removal property, and (4) fish eyes. The evaluation results are shown in Table 14.

[0596] [Preparation Example 1 of Aqueous Solution of Dispersion Stabilizing Aid for Suspension Polymerization]

[0597] PVA, methanol, and distilled water were mixed so that the concentration of PVA6-1 or PVA6-3 described in Table 13 became 40% by mass and the concentration of methanol became 5% by mass, and they were stirred at room temperature for 2 hours using a magnetic stirrer to obtain an aqueous solution of a dispersion stabilizing aid for suspension polymerization.

[0598] [Preparation Example 2 of Aqueous Solution of Dispersion Stabilizing Aid for Suspension Polymerization]

[0599] PVA6-2 and PVA6-4 described in Table 13 with a concentration of 5% by mass of PVA and distilled water were mixed, and they were stirred at room temperature for 2 hours using a magnetic stirrer to obtain an aqueous solution of a dispersion stabilizing aid for suspension polymerization.

[0600] (Suspension Polymerization of Vinyl Chloride)

[0601] The suspension polymerization dispersant stabilizer (PVA6-5) with a viscosity-average degree of polymerization of 2000 and a saponification degree of 80 mol% was added to a 5 L autoclave in the form of 100 parts of deionized aqueous solution at a concentration of 1000 ppm relative to vinyl chloride monomer. The aqueous solution of the suspension polymerization dispersant stabilizer obtained in Preparation Example 1 was added at a concentration of 200 ppm of PVA6-1 in the aqueous solution of the dispersant stabilizer relative to vinyl chloride monomer. Deionized water was additionally added to make the total amount of the charged deionized water 1640 parts. Then, 1.07 parts of a 70% toluene solution of di(2-ethylhexyl) peroxydicarbonate was added to the autoclave. A total of 5 times of nitrogen was introduced into the autoclave until the pressure inside the autoclave reached 0.2 MPa, and then the introduced nitrogen was purged. After the autoclave was thoroughly purged with nitrogen to remove oxygen, 940 parts of vinyl chloride was added. The contents inside the autoclave were heated to 65 °C, and the polymerization of vinyl chloride monomer was started under stirring. The pressure inside the autoclave at the start of polymerization was 1.05 MPa. After about 3 hours from the start of polymerization, the polymerization was stopped when the pressure inside the autoclave reached 0.70 MPa. After removing the unreacted vinyl chloride monomer, the polymerization product was taken out and dried at 65 °C for 16 hours to obtain vinyl chloride polymer particles.

[0602] (Evaluation of vinyl chloride polymer particles)

[0603] (1) Average particle size of vinyl chloride polymer particles

[0604] Using a metal mesh based on Tyler standard sieve number, the particle size distribution was measured by dry sieve analysis, and the results were plotted in the Rosin-Rammler distribution, and the average particle size (d p50 ; median particle size) was calculated.

[0605] (2) Plasticizer absorbency

[0606] The mass of a 5 mL syringe filled with 0.02 g of absorbent cotton was measured (denoted as A (g)), 0.5 g of vinyl chloride polymer particles was added to it and the mass was measured (denoted as B (g)), 1 g of dioctyl phthalate (DOP) was added to it, and after standing for 15 minutes, it was centrifuged at 3000 rpm for 40 minutes, and the mass was measured (denoted as C (g)). And the plasticizer absorbency (%) was calculated according to the following formula.

[0607] Plasticizer absorbency (%) = 100 × [{(C - A) / (B - A)} - 1]

[0608] (3) Monomer removal property (residual monomer ratio)

[0609] After taking out the polymerization reactants in the suspension polymerization of vinyl chloride, drying is carried out at 75 °C for 1 hour and 3 hours, and the residual monomer amount at each time point is measured by headspace gas chromatography, and the residual monomer ratio is obtained by the following formula.

[0610] Residual monomer ratio = (residual monomer amount at the time point of drying for 3 hours / residual monomer amount at the time point of drying for 1 hour) × 100

[0611] The smaller this value is, it means that from the time of drying for 1 hour to the time of drying for 3 hours, that is, within 2 hours, the proportion of monomers remaining in the vinyl chloride polymer particles removed due to drying is large, and this value becomes an index indicating the removal goodness of the residual monomer, that is, the monomer removal property.

[0612] (4) Measurement of fish eyes

[0613] Using a roll mixer, 100 parts of the obtained vinyl chloride polymer particles, 35 parts of DOP (dioctyl phthalate), 5 parts of tribasic lead sulfate, and 1 part of zinc stearate are mixed at 150 °C for 7 minutes to produce a sheet with a thickness of 0.1 mm, and the number of fish eyes per 100 mm × 100 mm of this sheet is measured.

[0614] [Table 14]

[0615]

[0616] It can be confirmed that: the average particle size, plasticizer absorbability, monomer removal property, and fish eye values of the vinyl chloride polymer particles of the PVA resins in Examples 6-1 and 6-2 are not inferior to those in Reference Examples 6-1 and 6-2 respectively, and have the performance as a dispersion stabilizing aid for suspension polymerization of the same degree. In addition, it can contribute to saving petroleum resources and suppressing global warming.

[0617] (Synthesis Example 7-2)

[0618] 50 parts of the plant-derived vinyl acetate obtained in Synthesis Example 1-1 above and 50 parts of the usual petroleum-derived vinyl acetate are uniformly mixed and used as raw materials, and polyvinyl acetate is synthesized according to a conventional method. It is made into a methanol solution, and a saponification reaction is carried out using an alkali catalyst, and drying is carried out to obtain PVA (PVA7-1). The average degree of polymerization of this PVA obtained by changing the manufacturing conditions (saponification conditions) within the desired range from Synthesis Example 3-2 is 1,750, and the saponification degree is 98.5 mol%.

[0619] (Synthesis Example 7-3)

[0620] 30 parts of plant-derived vinyl acetate obtained in Synthesis Example 1-1 and 70 parts of ordinary petroleum-derived vinyl acetate were uniformly mixed and used as raw materials to copolymerize ordinary petroleum-derived ethylene. In addition, PVA (PVA7-2) was obtained in the same manner as in Synthesis Example 7-2. The average degree of polymerization of this PVA was 1,720, the degree of saponification was 97.5 mol%, and the content of ethylene units was 4.2 mol%.

[0621] (Synthesis Example 7-4)

[0622] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and a PVA resin (PVA7-3) was synthesized in the same manner as in Synthesis Example 7-2. The degree of saponification of this PVA was 98.7 mol%, and the average degree of polymerization was 1,780.

[0623] (Synthesis Example 7-5)

[0624] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and a PVA resin (PVA7-4) was synthesized in the same manner as in Synthesis Example 7-3. The degree of saponification of this PVA was 98.1 mol%, the average degree of polymerization was 1,680, and the ethylene content was 4.1 mol%.

[0625] (Oxygen barrier property)

[0626] After conditioning the multilayer structures obtained in the examples and comparative examples at 20°C and 85% RH for 5 days, the oxygen permeability was measured (cc / m 2 ·day·atm) using an oxygen permeability measuring device (manufactured by MOCON, MOCON OX-TRAN2 / 21).

[0627] Temperature: 20°C

[0628] Humidity on the oxygen supply side: 85% RH

[0629] Humidity on the carrier gas side: 85% RH

[0630] Carrier gas flow rate: 10 mL / min

[0631] Oxygen pressure: 1.0 atm

[0632] Carrier gas pressure: 1.0 atm

[0633] [Example 7-1]

[0634] (Manufacture of multilayer structure)

[0635] For the obtained PVA7-1, a multilayer structure was manufactured by the following method, and the oxygen barrier property (oxygen permeability) was evaluated.

[0636] 100 parts by mass of the obtained vinyl alcohol polymer was added to water to prepare an aqueous solution (coating agent) having a concentration of 7% by mass of the vinyl alcohol polymer, and then allowed to stand at 20 °C and 60% RH for 1 hour. An anchor coating agent (adhesive) was coated on layer (D) of a stretched polyethylene terephthalate (OPET) film (substrate) having a thickness of 15 μm to form an adhesive component layer on the surface of the OPET film. Using a gravure coater, the above-obtained coating agent was coated on the surface of the adhesive component layer at 40 °C, and then dried at 120 °C to form layer (C). In order to promote the reaction of the anchor coating agent, the aforementioned film was further heat-treated at 160 °C for 120 seconds, whereby a multilayer structure was obtained. The thickness of layer (C) was 2 μm. The oxygen permeability of the obtained multilayer structure is shown in Table 15.

[0637] [Examples 7-2, Comparative Examples 7-1 and 7-2]

[0638] PVA7-2, PVA7-3 and PVA7-4 were used in place of PVA7-1, and otherwise, the same operations as in Example 7-1 were carried out to manufacture a multilayer structure. The results obtained by evaluating the oxygen permeability of the obtained multilayer structure according to the above method are summarized in Table 4.

[0639] [Table 15]

[0640]

[0641] It was confirmed that the oxygen barrier properties of the PVA-containing multilayer structures of Examples 7-1 and 7-2 were not inferior to those of Comparative Examples 7-1 and 7-2, respectively, and had the same degree of barrier properties. The multilayer structure of the present invention and the packaging material having the same have excellent oxygen barrier properties, and can contribute to saving petroleum resources and suppressing global warming.

[0642] (Synthesis Example 8-2)

[0643] 50 parts of the plant-derived vinyl acetate obtained in Synthesis Example 1-1 above and 50 parts of the usual petroleum-derived vinyl acetate were uniformly mixed and used as raw materials to synthesize polyvinyl acetate according to a conventional method. It was made into a methanol solution, and saponification reaction was carried out using an alkali catalyst, followed by drying to obtain PVA (PVA8-1). The average degree of polymerization of this PVA obtained by changing the manufacturing conditions (saponification conditions) within a desired range from Synthesis Example 3-2 was 1,750, and the degree of saponification was 98.5 mol%.

[0644] (Synthesis Example 8-3)

[0645] 30 parts of plant-derived vinyl acetate obtained in Synthesis Example 1-1 and 70 parts of ordinary petroleum-derived vinyl acetate were uniformly mixed and used as raw materials, and ordinary petroleum-derived ethylene was copolymerized. In addition, PVA (PVA8-2) was obtained in the same manner as in Synthesis Example 8-2. The average degree of polymerization of this PVA was 1,720, the saponification degree was 97.5 mol%, and the ethylene unit content was 4.2 mol%.

[0646] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and a PVA resin (PVA8-3) was synthesized in the same manner as in Synthesis Example 8-2. The saponification degree of this PVA was 98.7 mol%, and the average degree of polymerization was 1,780.

[0647] (Synthesis Example 8-5)

[0648] Ordinary petroleum-derived vinyl acetate was used as 100% raw material, and a PVA resin (PVA8-4) was synthesized in the same manner as in Synthesis Example 8-3. The saponification degree of this PVA was 98.1 mol%, the average degree of polymerization was 1,680, and the ethylene unit content was 4.1 mol%.

[0649] [Examples 8-1 and 8-2, Reference Examples 8-1 and 8-2]

[0650] For the obtained PVA8-1 to PVA8-4, they were heated and dissolved in hot water at 95 °C for 2 hours, and adjusted to a coating agent with a solid content concentration of 6%. The coating agent was evaluated by the following method. The results are shown in Table 16.

[0651] [Test of making coated paper using the coating agent]

[0652] Using a wire bar, the coating agent was manually coated on glassine paper with a basis weight of 64 gsm at 20 °C in the form of a coating solution. Then, using a cylinder-type rotary dryer, drying was carried out at 105 °C for 1 minute. The coating amount in terms of the solid content of the coating agent was 1.0 gsm (single-sided). After the obtained coated paper was conditioned at 20 °C and 65% RH for 72 hours, the physical properties of the coated paper were measured.

[0653] [Water resistance strength test of coated paper]

[0654] After about 0.1 g of ion-exchanged water at 20 °C was dropped on the surface (coating agent coating surface) of the coated paper manufactured by the above method, it was wiped with a fingertip, and the dissolution state of the coating agent was observed and evaluated according to the following criteria.

[0655] 〇 - Excellent water resistance strength, no slipping feeling.

[0656] △ - Part of the coating agent was emulsified.

[0657] × - Coating agent dissolution.

[0658] [Evaluation for release paper application: Air permeability resistance measurement]

[0659] In accordance with JIS P 8117:2009, use the Wang Yan type smoothness and air permeability tester to measure the air permeability resistance of the coated paper.

[0660] [Evaluation for release paper application: Toluene barrier property test]

[0661] After coating the coated surface of the coated paper with (5×5 cm) colored toluene (red) dissolved with red food coloring, evaluate the degree of printing through (small red spots and / or overall coloring of the coated surface) on the back side (uncoated surface) according to the following criteria.

[0662] 5 - No spots on the back

[0663] 4 - (One or two) spots are generated

[0664] 3 - A large number of spots are generated (about 10 - 20% of the toluene-coated surface)

[0665] 2 - About 50% of the coated surface is colored

[0666] 1 - The entire coated surface is colored

[0667] [Evaluation for oil-resistant paper application: KIT test, bent KIT test]

[0668] According to TAPPINo. T559cm - 02, conduct the KIT test on the flat part and the bent part of the coated surface. Evaluate by visual inspection. It should be noted that the KIT value of commercially available oil-resistant paper using fluororesin is usually 5 or above, and the oil resistance that is not a problem in general use is 5 or above. Therefore, the oil resistance of the coated paper is preferably 5 or above, and in applications requiring higher oil resistance, it is preferably 7 or above, and more preferably 10 or above.

[0669] In the KIT test of the bent part, place the coated paper with the coated surface facing outwards, and press it from above the bent part under the conditions of a width of 1.0 mm, a depth of 0.7 mm, and a pressure of 2.5 kgf / cm 2 · second to completely fold out the crease. Then, unfold the coated paper and use TAPPINo. T559cm - 02 to measure the oil resistance of the crease part. The measurement is carried out by visual inspection.

[0670] [Table 16]

[0671]

[0672] It can be confirmed that the physical properties of the coated papers with the PVA-containing coating agents in Examples 8-1 and 8-2 are not inferior to those in Comparative Examples 8-1 and 8-2 respectively, and have the same level of performance. The paper coating agent of the present invention and the paper coated therewith have excellent barrier properties and oil resistance, and can contribute to the conservation of petroleum resources and the suppression of global warming.

Claims

1. A vinyl alcohol polymer (X) which is obtained by polymerizing and saponifying a plant-derived vinyl ester monomer (A) and a petroleum-derived vinyl ester monomer (B), wherein the 14 C (radioactive carbon) / C (carbon) is 1.0×10 -14 or more and 1.0×10 -12 or less, and the molar ratio of (A) / (B) is 5 / 95 to 90 / 10.

2. The vinyl alcohol polymer (X) according to claim 1, further comprising an ethylene unit, wherein the content of the ethylene unit is 1 mol% or more and less than 20 mol%.

3. An additive for slurry, comprising the vinyl alcohol polymer (X) according to claim 1 or 2.

4. A drilling mud, containing the additive for slurry according to claim 3.

5. The drilling mud according to claim 4, further containing water and bentonite.

6. A cement slurry, containing the additive for slurry according to claim 3.

7. The cement slurry according to claim 6, further containing a liquid agent and a curable powder.

8. A filling agent for underground treatment, comprising the vinyl alcohol polymer (X) according to claim 1 or 2.

9. The filling agent for underground treatment according to claim 8, wherein the vinyl alcohol polymer (X) comprises another unsaturated monomer (C) capable of copolymerizing with a vinyl ester monomer.

10. The filling agent for underground treatment according to claim 8 or 9, further comprising a plasticizer.

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