TW201245232A - Viscosity-imparting agent and manufacturing method for hydrolytic cellulose using the same - Google Patents

Abstract

The present invention provides a viscosity-imparting agent and a manufacturing method for hydrolytic cellulose using the same. At the time of using cellulosic biomass as a raw material for manufacture of hydrolytic cellulose, the cellulosic biomass can be easily divided into molecular level parts by enduing solution containing the cellulosic biomass with appropriate viscosity, etc. As a result, hydrolytic cellulose can be produced effectively. The present invention is a viscosity-imparting agent which is using cellulosic biomass as a raw material for manufacture of hydrolytic cellulose, characterized by containing polyvinyl alcohol polymer which is having alkyl groups with a carbon number of 29 or less and monomer units with a carbon number of 8 or more.

Description

201245232. The invention relates to a viscous imparting agent for producing a hydrolyzable cellulose using a cellulose-based raw material as a raw material, and a method for producing a hydrolyzable cellulose using the same. . [Prior Art] Biomass refers to a renewable resource from living organisms, which can be defined as "renewable, organic resources derived from living organisms and substances other than fossil resources". In this biomass, there is a need to effectively use wood such as thinning wood, rice stems, wheat straw, rice bran, corn or sugarcane, and the stems of oily seeds (empty fruits bunch; EFB). Unutilized plant germplasm. Even in such a plant-based raw material component, a plurality of polysaccharides such as starch are easily decomposed into monosaccharides by an enzyme or the like, and can be used as energy or food. Here, in order to effectively utilize plant-based biomass, it is considered to be extremely important to decompose the high-order ratio of orysin in plant cells into decane or monosaccharide (glucose) as energy or food. However, it is known that most of the cell walls are formed by the cellulose system, and it is difficult to decompose because of having a firm structure. Actually, it has not been effectively utilized. Specifically, the cellulose system has the following multiple structures in the cell wall. Most of the cellulose forming the cell wall has a paracrystal structure called a microfibrilla which is in close contact with a straight line. The cellulose (microfibrils) having such a quasi-crystalline structure are bonded to each other via a non-cellulosic component such as hemicellulose or lignin. These cellulose components (microfibrils) and non-cellulosic components are generally arranged as -4- 201245232 as a fiber which is said to be laminated to form a structure by a nitrogen bond and a cell wall. As a kind of practicality by anatomical microorganisms, in the monosaccharides, or in the turbine, but the hydrolysis, the action of non-efficient water and enzymes is hydrolyzed to decompose the surface structure of the saccharide structure, so before . This method is a strong combination of fibrils (microfibrils) in which the fibrils are larger and flaky. By this, it is not sufficient to decompose the cellulose having an oxygen-producing microorganism. In addition, the use of the touch can also be used, for example, by hair, which can be used, and will come from the plant as described above, which is recognized as a significant delay. A combination of strong binding. Therefore, the efficiency of the decomposition is not high, and the decomposition of the structure is caused by the medium or the yeast. Fibrin becomes a fiber of energy. The cell wall is the cause of the crystal structure, that is, the quasi-crystal structure, because of the solution. This fibril cell wall. In the case of the above-mentioned quasi-crust, the cellulose polymer is cut, and the plant is provided with a strong t cellulose as a means of digesting, and a method of digestion.徊b-determine, using the reaction control to be complex, etc. The reason is to hydrolyze the fiber into a monosaccharide, which is converted into ethanol by chemical decomposition, and chemically straight in the existing internal combustion engine. The molecular structure of cellulose, and the strong structure of cellulose, hinders the internal structure, so that cellulolytic enzymes cannot easily enter the internal structure of the structure due to the enzyme, and it is impossible to directly separate the enzyme from the quasi-crystallization of cellulose. The cellulose is directly derived from the enzyme, and a cellulose having a quasi-crystalline structure is obtained by a method of finely cutting, which is basically a cellulose which is easily hydrolyzed by a hydrolyzed cellulose-based biomass such as an enzyme. 201245232 Slowly hydrates, by which hydration, the chemical action of weakening the hydrogen bond between the polymer chains of adjacent cellulose; and the mechanical power of the cellulose-based biomass by beating, kneading, etc., to cut the fiber The physical role of the polymer chain. As a specific content of this method, there are proposals, for example, (1) stirring of cellulose-based green matter in a container, causing particles to continue to be disturbed by the - surface, and - surface raising of the suspension of the particles = the same: slowly supplying water to hydrate A technique for producing a fine powder (JP-A-2004-526008), and (2) a machine produced by mixing by mixing and stirring a cellulose-based green material with a water-soluble polymer aqueous solution having a viscosity The force is efficiently transmitted to the cellulose polymer chain, such as a technique in which the cellulose polymer bonds are pulled apart from each other and cut off (International Publication No. 2009/124072). However, in the technique of (1), the device for causing the particles of the cellulose-based biomass to exist as a suspension is a complicated matter, and when this technique is used, since it consumes a large amount of energy, it cannot be said that it is High productivity. On the one hand, in the technique of (2), it is confirmed that the cellulose-based biomass has a certain degree of easy hydrolysis property by the use of a water-soluble polymer for imparting an aqueous solution viscosity, but it is intended to be practical. Further improvements in hydrolysis are required. [Prior Art Document] [Patent Document 1] Japanese Patent Publication No. 2004-526008 [Patent Document 2] International Publication No. 2009/124072 Booklet [Draft of the Invention] [Problem to be Solved by the Invention] 201245232 The present invention According to such a case, a viscous imparting agent and a manufacturing method using the viscous imparting are used, and when the cellulose-based raw cellulose is produced, the viscosity of the cellulose-containing raw material is obtained. The cellulose-based cleavage can be easily performed, and as a result, the hydrolyzable fiber can be efficiently produced. [Means for Solving the Problem] The viscous grade of the present invention which solves the above problems is used for the production of a cellulose-based biomass as a viscous material. The property-imparting agent is characterized by containing a polyvinyl alcohol-based polymer having a base group and containing a monomer unit having a carbon number of 8 or more. Since the viscosity imparting agent contains a polyvinyl alcohol as a monomer unit, it can be improved with water and cellulose. Therefore, the viscosity-imparting agent of the present invention can increase the viscosity of the solution and at the same time improve the uniform dispersibility (mixing property) of cellulose when the cellulose-based biomass of this type is mixed. Therefore, by adding the viscous-imparting agent to the fiber-forming material, it is possible to add an aqueous solution which is viscous to the cellulosic biomass to the cellulosic biomass using the viscous-imparting agent, and to polymerize the cellulose. The 'and' is hydrogen-bonded by a water-and polyvinyl alcohol-based polymer chain having a quasi-crystalline structure. Further, the polyvinyl alcohol-based aqueous solution of the hydrolyzable cellulose which is a raw material for the purpose of providing a hydrolyzable cellulose as a raw material provides a suitable molecular grade vitamin. The precipitant, which is a hydrolyzable fiber of a raw material, has an alkyl polymer having a carbon number of 29 or less, and can be extracted into a solution of an aqueous solution and a powder or a granular biomass by containing an intermolecular interaction into water > The shearing force of the mixed raw material particles. That is, the cutting operation can prevent the polymer inter-polymer from entering the polymer chain thus broken by the 201245232 by the efficient entry of the material chains with each other, thereby preventing the person from being A property-imparting agent that crystallizes fibers; The compound chain is effectively cleaved at a molecular level; the secondary substance is a cellulose which is hydrolyzed (glycated). The above-mentioned polyethylene polymer is preferred because the number of carbon atoms in the monomer unit such as the enzyme is "above, and the ratio of the number of carbon atoms in the single bond to the number of oxygen (carbon number / oxygen number) is preferred. /, two or more 5, 〇〇〇 below, soap servant or degree is 100 'on... two ears% or more 99." mole% or less. The rate of early monomer in the fast monomer is 〇.〇5莫耳When the above-mentioned polymer-based polymer and the above-mentioned monomer unit have a structure, the addition point (4) or the intrusion action between the cellulose polymer chains can be more effectively exhibited. The above-mentioned unit is preferably represented by the following formula (1): (1) —ch2—1- (in the formula (1), a straight bond or a branched alkyl group having a carbon number of 8 to 29; The alkyl group having 1 to 8 carbon atoms can exert the viscosity-increasing effect or the intrusion into the bond between the cellulose polymer bonds more effectively by using a polyethylene glycol-based polymer having such a monomer unit. The polyvinyl alcohol-based polymer (4) has an average polymerization degree of 2 Å or more and 5 Å Å or less, and a saponification degree of 6 〇 mol% or more and 99 Å mol% or less, 201245 232 Jiaji makes the Γ rate of 0.05% or more and 5% by mole or less. When the average degree of polymerization, the degree of saponification, and the content of the monomer unit of the above-mentioned polyvinyl alcohol-based polymer (4) are in the above range, it is possible to more suitably dissolve the viscosity-imparting agent and the cellulose-based biomass as water. Sticky and effective. Good uniform mixing, and the polyethylene polymer (4) can easily enter the cracked cellulosic polymer chain. Therefore, by using such a poly-based polymer (Α), cellulose having higher hydrolyzability can be obtained. The polyvinyl alcohol polymer (Α) is preferably obtained by saponifying an unsaturated monomer represented by the following formula (9) and an ethylene I. 1 II Η Ο a. R1 (Π) (In the formula (π), the meanings of R1 and R2 are the same as in the above formula (1)) by 搐pu , +, & white & ώ in the above method When the polyvinyl alcohol-based polymer (A) is added, it is easy to control the degree of deuteration or the content of the monomer in the above-mentioned monomer. The above monomer unit I is right, ν butyl, +, s bis, /, has a polyoxyalkylene group represented by the following formula (π ΐ) and the ratio of the above monomer units to the ancient ^ 3 is also higher.佳为〇·1mol% or more 10 mole% or less” R3 (DI) 4'CH2'CH2~0t+CH2-CH-〇-]rR4 (in formula (III), R3 system thinks #么田甘The carbon number (1) of the alkyl group or the ethyl group; the R4 hydrogen atom or the 10' 40) 〇201245232 has the viscosity of the compound (8)' as the aqueous solution at the above content, and has an olefin: Poly (temperature sensitive gelatini t·, 敏's gelatinization to ❹ (4) ^ g UtiniZatl〇n). Therefore, the viscosity-increasing effect of the viscosity-enhancing agent can be exerted more effectively by the intrusion between the cellulose polymer chains. k w ^ The average degree of polymerization of the above polyvinyl alcohol-based polymer (B) is (10) or more and 4,000 or less, and the saponification is broad, and it is preferably 7 〇 mol% or more and 99.99 mol% or less. By setting the average degree of polymerization and the degree of saponification of the above-mentioned polyvinyl alcohol-based polymer (8) to the above range, the viscosity-imparting agent (aqueous solution of polyvinyl alcohol-based polymer (B)) and cellulose-based biomass can be more Appropriate viscosity, efficient mixing, and the polyethylene polymer@) can easily enter the cracked cellulose polymer chain. Therefore, cellulose having higher hydrolyzability can be obtained by using such a polyvinyl alcohol-based polymer (B)'. The polyvinyl alcohol polymer (B) is preferably obtained by saponifying a copolymer of an unsaturated monomer represented by the following formula (IV) and a vinyl ester monomer. R6 H?=CX +CH2 - CH2-0 士R5 R3 |-CH2-CH-0 七R4 (汉) (In the formula (IV), R3, .R4, m&n are defined as the above formula (ΙΠ) ;r5 is a hydrogen atom or -COOM1. Ml is a hydrogen atom, a metal atom or a hydroxyl group; R6 is a hydrogen atom, a sulfhydryl group or a -CH2-COOM2; an M2 hydrogen atom, an alkali metal atom or an ammonium group; -, -CH2-0-, -CO-, -C0-0-, •CO-NR7· or -c〇-NR7-CH2-. R7 is a hydrogen atom or a carbon number of 1 to 4). -10-201245232 By obtaining the polyvinyl alcohol-based polymer (B) by the above method, it is easy to control the degree of saponification or the content of the above monomer unit. Among the unsaturated monomers represented by the above formula (IV), R5 is a hydrogen atom; X-form is -co-nr7_4_C0_nr7_CH2_, and a hydrogen atom of the 7th atom or an alkyl group having a carbon number of i to 4 is preferred. Since the polyvinyl alcohol-based polymer has the above-described guanamine structure or the like, it is suitable for the cutting operation of the cellulose-based biomass from the viewpoints of viscosity in the case of preparing an aqueous solution, affinity with cellulose, and the like. By. The viscosity imparting agent is preferably in the form of a gel. By using such a gel-like viscosity-imparting agent (a polyvinyl alcohol-based polymer aqueous solution), the mixture can be made into an appropriate viscosity from the initial stage in the cutting step, and the viscosity can be maintained at To a certain extent, efficient production of hydrolyzable cellulose can be carried out. Further, since it is in the form of a gel, the gel-like viscous agent enters between the cut cellulose polymer chains and can be retained, so that recrystallization of the cellulose polymer chain can be prevented, and the cutting energy can be improved. Further, in the gel-like viscosity-imparting agent, the amount of the gelling agent can be reduced by using the polyvinyl alcohol-based polymer having high viscosity in an aqueous solution. In order to solve the above problems, another method for producing a hydrolyzable cellulose using a cellulose-based biomass as a raw material is characterized in that the method comprises: obtaining a sigma-containing viscosity-imparting agent and a cellulose-based raw material. The mixing step of the mixture, the shearing force added to the mixture, and the cutting step of cutting the cellulose-based biomass. -11 - 201245232 According to the method for producing the hydrolyzable fiber, the viscous agent (the aqueous solution of the polyvinyl alcohol oxime compound) and the cellulose-based biomass can be prepared by mixing It has a mixture of suitable spring fields. Further, according to the manufacturing method, since the shearing force boring tool is attached to the mixture, the cellulose polymer chains are easily separated from each other by the sticky aqueous solution, and And the polyethylene sulphur is taken into the η 糸 polymer to efficiently enter the η within the polymer bond having a quasi-crystalline structure.丨' can reduce the hydrogen bond between the polymer chains. That is, according to the hydrolysis method, the method of producing the fibrils and the quasi-sugar, the cellulose in the cellulosic biomass can be made to collate with the g; And, cellulose which is easily hydrolyzed (saccharified) by an enzyme or the like is obtained. Ruler! "Cellulose" is a cellulose which is used as a raw material to cut the cellulose of 斤 斤 仔, which is more hydrolyzable than the raw material. The "aqueous solution" is a solution in which a solution using water as a solvent is used, and a fluid gel is also removed. [Effect of the Invention] As described above, when the cellulose is used to produce hydrolyzable cellulose by using the biomass of the present invention as a raw material, the solution containing the cellulose-based biomass is Λ ^ The viscosity of the Ding Zhou, etc., and the molecular level of the cellulose-based biomass can be cut to produce a hydrolyzable cellulose. Further, it is effective to produce a hydrolyzable cellulose from cellulose according to the gas of the hydrolyzable cellulose of the present invention. ..., ', ', Μ '':, the efficiency rate is good. The invention can be used as a raw material for the plant system, which can be used as a food or energy resource, and can improve the utilization of raw materials. -12- 201245232 . [Embodiment] [Embodiment of the Invention] Hereinafter, the order of the embodiment of the method for producing a viscous imparting agent and a method for producing a hydrolyzable cellulose using the present invention will be described in detail. [Viscosity-imparting agent] The viscosity-imparting agent of the present invention contains a polyvinyl alcohol-based polymer (

Hereinafter, it is referred to as "PVA", and the present is a single unit of an alkyl group having a slave number of 29 or less. X, the monomer unit has a carbon number of 8 or more. That is, the above PVA is a polyphenol containing a vinyl alcohol unit and the above monomer unit. Further, the above PVA may have other monomer units without departing from the gist of the present invention. The alkyl group having a carbon number of 29 or less has a group represented by CnH2n + ](丨$ n ^ 29), and examples thereof include a methyl group, an ethyl 'propyl group, a butyl group, a decyl group, a hexyl group, an octyl group, and a decyl group. , twelve base, sixteen base, eighteen base, twenty base, twenty-six base, twenty-eight base, and the like. The above alkyl group may be linear or may be in the form of a branch. The above monomer unit may have a plurality of the above alkyl groups. Further, the above monomer unit may have a stretching group such as an ethyl group, an aryl group, an aryl group or the like. The soil is a unit having the above-mentioned carbon number of 29 or less, and the unit of the carbon number § or more is, for example, a monomer unit derived from the following: an a-olefin such as undecene, tetradecene, hexadecane or the like; a vinyl ether of hexyl vinyl ether, mercapto vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether or the like; an alkyl (mercapto) acrylamide of octyl acrylamide or the like; 201245232 by the above formula (II) And an alkyl group (meth) acrylamide represented by the above formula (IV) or the like, and an unsaturated monomer such as an oxybutylene unit or an oxypropylene unit represented by the above formula (IV). Further, in the case of the monomer represented by the formula (11), the alkyl group h R ' having a carbon number of 29 or less is in the form of a monomer represented by the formula (IV), and the alkyl group having a carbon number of Μ or less is referred to as R3. . In the present invention, the monomer represented by the formula (π) has a long-chain alkyl group, or the monomer represented by the general formula (Iv) has a m- or oxy-propion unit-like self-priming primary bond. It is a side chain that has a higher hydrophobicity and can impart a suitable viscosity at the hydrolysis temperature of cellulose. The number of carbon atoms in the monomer unit is Π or more, and the ratio of the number of carbon atoms (number of carbon atoms) to the number of oxygen atoms (number of oxygen atoms) in the monomer unit (p. More than 2.5/1. Further, as the upper limit of the ratio, for example, two L00/1, preferably 5 G/1. The term "side scorpion" as used herein means the carbon number of the above-mentioned monomer unit from the ramification of the main chain carbon I t when the above-mentioned early unit is polymerized, not only the side chain but also the main chain. The carbon number including the carbon number. The PVA having a "sex imparting agent" is supplied to the molecules of water and cellulose by the above-mentioned monomer unit (IV). Therefore, in the case of the present invention, when the aqueous solution is prepared, the viscosity of the solution can be increased, and the solution of the cellulose-based raw material can be improved when the aqueous solution is mixed with the powder or the particulate cellulose.

Mixed). J-shaped 丨丄V, etc. Therefore, by using the viscous imparting agent and the fiber ′, it is possible to add a shearing force to the cellulose-based biomass by mixing the appropriate auxin-based particles. That is, -14 - 201245232: The cutting operation of the cellulosic biomass using the viscosity-imparting agent, by means of eight miscellaneous, - making the cellulose polymer chains easy to enter each other into a quasi-crystalline structure ; = internal 'and can weaken the nitrogen bond between the polymer chains. Further, the PVA which interacts with 6 degrees of cellulose enters between the thus-decomposed cellulose structures, and the chains are quasi-crystallized. That is, the root: = opened cellulose polymer = the secondary: the cellulose polymer chain is effectively cut at a molecular level, and is passed to the cellulose which is hydrolyzed (saccharified) by the material. The content of the above monomer unit in the above PVA is preferably 0.05 mol%, more preferably 〇% mol%. One side m "% of moles, more 0.2 moles. / 5 苴 and ... upper limit, preferably 10 mole %, 8 moles / 〇, 5 mole %, 2 mole %, more i rate For the above range, it can be more effective: by making the content of the inclusion:::: body r (denaturation rate), "the king's early body position in the molar number (mole%) The content of the molar number in the early position of each monomer of β may be determined from the above-mentioned monomer or from the ethylene energy-based polymer of the precursor, and may be obtained as a proton turtle. For example, "Ethylene vinegar-based polymer ί:: In the case of the case 1 body, it is fully carried out in a positive form/acetone; after re-precipitation purification of the incoming polymer, a decompression (10) in 5 "c": A sample for analysis is prepared. The sample is dissolved in an olefin"?: it can be measured by protons. In addition, when the PVA is obtained by enriching the acetonitrile polymer, the content of the above monomer unit, -15 - 201245232 Generally, there is no change before and after saponification. The lower limit of the average degree of polymerization (IV) average polymerization degree of the above PVA is preferably 100, more preferably 5, and Danjima is 1,000. On the one hand, as the upper limit Preferably, it is 5,000, and the residence is 4,000. By making the average polymerization in the above-mentioned circumference, water solubility and viscosity increase can be coexisted.

The above PV in the present invention

The average degree of polymerization of ^, 7_, ar ^ k VA is measured in accordance with JIS K 6 7 2 6 .

That is, after the PVA is deuterated and refined, the ultimate viscosity [η] (1/10 liter/g) measured in water of 3 〇t is obtained by the following formula. The average degree of polymerization = ([η] χ 1 〇 3 / 8 29) (ι, ο. 62) The lower limit ‘the degree of saponification of the above PVA is preferably 6 〇 mol 7 〇 mol. More preferably, the molar percentage is more than 99, 99 mole%, and the rifle/〇 is preferably 99.9 mole%. When the degree of saponification is in the above range, it is possible to exhibit good viscosity or water solubility. The degree of saponification of the above PVA in the present month is a value measured in accordance with JIS K6726. The PVA is preferably PVA (4) and PVA (8) having the following specific monomer units. Hereinafter, ρνΑ(Α) and PVA(B) will be described in detail. [PVA (A)] The above PVA (A) ' has the monomer unit (4) represented by the above formula (1) as the monomer unit. The above PVA (A) can effectively improve the intermolecular interaction with water and cellulose by including the above monomer unit (a) having a predetermined size of an alkyl group and a brewing amine group. Therefore, the above pvA(A), -16-201245232 can more effectively exert the viscosity-increasing effect of the viscosity-imparting agent or the intrusion into the cellulose polymer chain. The number of carbon atoms contained in the linear or branched alkyl group represented by the above R1 is 8 or more and 29 or less, preferably 1 to 25 or less, and more preferably 12 or more and 24 or less. By the fact that the carbon number is 8 or more, the mutual interaction of the alkyl groups is enhanced, and the ability to further improve the viscosity is improved. On the other hand, in the case where the carbon number exceeds 29, the water solubility of PVA (A) is lowered, and the cellulose-based green matter particles become difficult to be uniformly dispersed. The above R2 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but is preferably a hydrogen atom or a methyl group from the viewpoint of ease of synthesis and the like. The content of the monomer unit (4) in the PVA (A) is preferably 0.05 mol% or more and 5 mol% or less, more preferably 〇丨 mol% or more and more preferably 0.2 mol% or more. Further, the content ratio is preferably 2 mol% or less, more preferably 1 mol% or less. By increasing the content of the monomer unit (a) in the above range, the tackiness and the like can be more effectively exhibited. The content of the monomer unit (a), for example, the vinyl ester polymer to be measured does not contain the denatured monomer unit other than the above monomer unit (a), and the ruthenium is linear, and further R 2 is a hydrogen atom. , can be calculated by the following method. That is, the area of the peak α (4 7 to 5.2 ppm) from the main chain sulfhydryl group of the vinyl ester copolymer, and the peak of the terminal methyl group derived from the alkyl group R1 are attached to 8 to 1 〇 PPm) The area 'using the following formula' is used to calculate the content ratio of the monomer unit (a) represented by the above formula (1). The content of the above monomer unit (a) (mole 0 / 〇) = [(wave / 3)}] χ 100 the area of the peak β / 3) / {the area of the peak + (the area of the peak β 2012245232 even in the "life When the vinyl ester polymer has a structure other than the above-described structure, the content of the above monomer unit can be easily calculated by appropriately changing the peak or the calculation formula to be calculated. The average polymerization degree of the above PVA (A) is relatively high. It is preferably 200 or more and 5,000 or less, more preferably 500 or more. Preferably, the average degree of polymerization is in the above range, and when the pVA (4) is used as an aqueous solution and mixed with the cellulose-based raw material, the viscosity is appropriate. The mixture is efficiently and uniformly mixed, and as a result, the cellulose polymer chain can be effectively cut and becomes a state in which hydrolysis is easy. The saponification degree of the PVA (A) is preferably 6 〇 mol% or more. % or less, more preferably 80 mol% or more and 99 9 mol% or less, more preferably 96 mol% or more and 99.9 mol% or less. By making the above pvA (the degree of saponification of the crucible is in the above range, the PVA can be used) (A) When used as an aqueous solution and mixed with a cellulose-based raw material, The viscous efficiency is good and the mixture is uniformly mixed, and as a result, the cellulose polymer chain can be efficiently cut, and the state of hydrolysis is easy. Ma Valley (manufacturing method of PVA (A)) The manufacturing method of the above PVA (A) The method of copolymerizing the unsaturated monomer represented by the above formula (II) with a vinyl ester monomer and saponifying the obtained alkyl-modified vinyl ester polymer is preferably carried out. In the above-mentioned copolymerization, the unsaturated monomer represented by the above formula (II) is used in the alcohol solvent or in the absence of a solvent, and specific examples thereof include N-octylacrylamide and N-mercaptopropene. Indoleamine, N_dodepropene, N-octadecyl acrylamide, N-hexadecyl decylamine-18- 201245232 Octyl decyl acrylamide, N-mercaptomethyl methacrylate An amine, N-dodecyl methacrylamide, N-octadecyl decyl acrylamide, N-hexadecyl decyl acrylamide, etc. Among these, N-octadecyl propylene is preferred. Indoleamine, N-octylmercapto acrylamide, N-mercaptoalkyl acrylamide, N-dodecyl decyl acrylamide, N-octadecyl methacrylamide, and N-Ten six A mercapto acrylamide, more preferably N-octadecyl acrylamide, N-dodecyl methacrylamide, and N-octadecyl methacrylamide. As the above vinyl ester monomer, Listed vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, trimethylacetate, versatic acid, vinegar, hexanoic acid, simene Ester, vinyl laurate, vinyl palmitate, ethyl stearate, vinyl oleate, vinyl benzoate, etc., but among these, vinyl acetate vinegar is preferred. The unsaturated form of formula (II) When the monomer and the vinyl ester monomer are copolymerized, it is possible to copolymerize other monomers without impairing the scope of the present invention. As a monomer which can be used, for example, an a-olefin such as methylene, n-butene or isobutylene; B (tetra), ethyl b (tetra), n-propyl ethene, isopropyl shr, 2, 3-two? a vinyl ether of a base ethane (tetra), an isobutyl ethane sulphate, a tertiary butyl propylene acrylonitrile, a methyl propyl propylene oxide, a methacrylonitrile or the like;

Gasification of B / S, fluorinated ethylene and other teeth Xinhua 7 secret uranium π < national I ethylene; allyl acetate .....,,,,,,,,,,,,,, Propyl propylene, hydrazine, fluorinated vinylene, etc. 南 图 图 常 常 常 常 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; -19 -19 -19 -19 Compound acetic acid isopropyl vinegar and the like. Further, the amount of the other monomer used is preferably 2 for the use of the all monomer. MoM% or less, more preferably 5 mol%;; Moer%. When the amount of other monomer units used exceeds 20% by mole, there is a case where it is difficult to visualize the physical properties of the desired PVA. The car is "in, gathering. When the unsaturated monomer represented by the formula (Π) and the vinyl ester are in the early form, the polymerization degree of the obtained ethylene vinegar-based polymer is adjusted, and the like, without damaging the scope of the present invention. It is also possible to carry out the copolymerization in the presence of a chain transfer agent. Examples of the chain transfer agent include trays such as acetonitrile, acetonitrile, and the like; ketones such as acetone and methyl ethyl ketone; thiols such as 2-hydroxyethyl thiol; and ethylene ethoxide. A phosphatide such as a dentate hydrocarbon; a phosphinate such as sodium phosphinate monohydrate, etc., but aldehydes and ketones are preferably used in the above. The chain transfer agent has a chain shift constant and a target, but is generally not more than 10% by mass based on the vinyl ester. 'Based on the degree of polymerization of the polymer of the key transfer agent to be added, the monomer is preferably 0.1% by mass to carry out the unsaturated monomer and vinyl ester represented by the general formula (IJ). The temperature at which the monomers are copolymerized is preferably from 〇 to 20 CTC, more preferably from 3 〇 = 140 C. It is difficult to obtain the polymerization of the V filling knife in the case where the temperature at which the copolymerization is carried out is lower than that of the generation. speed. That is, in the case where the temperature at which polymerization is carried out is higher, it is difficult to obtain a PVA having a specific monomer unit -20 - 201245232 as specified in the present invention. As a method of controlling the temperature production used in the copolymerization to 0 to 200 t, for example, by controlling the polymerization rate, a method of equalizing the heat generated by the polymerization and the exotherm from the surface of the reactor, or by using The method of pressing the outer sleeve of a suitable heat medium, etc. 'But by the safety aspect, the latter method is preferable. As a polymerization method for carrying out copolymerization of an unsaturated monomer represented by the general formula (11) and an ethylene-based monomer, one of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization can. As the method of the combination, any known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or the like, can be employed. Among these, a bulk polymerization method or a solution polymerization in which a polymerization is carried out in a solvent-free or alcohol-based solvent is suitably employed: = In the case of producing a vinyl ester-based polymer having a high degree of polymerization, emulsion polymerization is suitably employed. law. V ′ As the alcohol solvent, decyl alcohol, ethanol, n-propanol or the like can be used, but it is not limited thereto. Further, these solvents may be used in combination of two or more kinds. (5) As the initiator to be used in the copolymerization, a previously known azo initiator, a peroxide initiator, a redox initiator, or the like can be suitably selected in accordance with the polymerization method. As the azo initiator, 2,2'-azobisisobutyronitrile, 2,2,-azobis(2,4-dimethylvaleronitrile, 2,2'-azobis (4) -Methoxy-2,4-dimercaptophthalonitrile), etc., as an over-initiator initiator, may be exemplified by diisopropyl peroxydicarbonate, di-2-hexyl peroxydicarbonate, and diethyl ethoxylate. Carbonate compound such as ethyl ethyl peroxydicarbonate; tertiary butyl peroxy neodecanoate... _ peroxyneodecanoate), α- cumyl peroxy neodecanoic acid =, first-grade butyl-21 - 201245232 thiol oxime a perester compound such as t-butyl per〇xydecanoate; acetonitrile cyclohexylsulfonyl peroxide; 2,4,4-tridecylpentyl-2-peroxyphenoxyacetate . Further, in the above initiator, potassium persulfate, ammonium persulfate, hydrogen peroxide or the like may be combined to prepare an initiator. Further, examples of the redox initiator include a combination of the above-mentioned peroxide and a reducing agent such as sodium hydrogen sulfite, sodium strontium carbonate, tartaric acid, ascorbic acid, and Rongalite. . Further, in the case where the copolymerization of the unsaturated monomer represented by the formula (Π) and the vinyl ester monomer is carried out at a relatively high temperature, decomposition of the self-derivative monomer derived from ethylene can be observed. The resulting pv A coloring and the like. In this case, in order to prevent coloring, an antioxidant such as tartaric acid may be added to the polymerization system, and a vinyl ester system may be added to the vinyl vine monomer, and the vinyl ester obtained by the above copolymerization may be added. The saponification reaction of the polymer can be suitably carried out by using an alkaline catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an alcoholic decomposition reaction or hydrolysis reaction to an acidic catalyst such as benzenesulfonic acid. Examples of the solvent which can be used in the reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as C- and methyl ethyl ketone; and aromatics such as benzene and toluene; A hydrocarbon or the like may be used alone or in combination of two or more. Among these, a sterol or a methanol/methyl acetate mixed solution is used as a solvent, and sodium hydroxide is used as a catalyst, and the saponification reaction is simple and preferable. [PVA (B)] The above PVA (B) contains, as the monomer unit, a monomer unit (b) having a polyoxyalkylene group (POA group) represented by the above formula (III). - 201245232 The PVA (B) contains the above monomer unit (b), so it is sticky when used as an aqueous solution, and has a temperature-sensitive gelation property. Therefore, the uniform dispersibility (mixing property) in the solution of the cellulose-based biomass when the aqueous solution of the above pvA (B) is mixed with the powder or the particulate cellulose-based biomass can be improved. Further, according to the above PVA (B), the amount of the gelling agent used in the production of the hydrolyzable cellulose can be reduced. The above R3 is an alkyl group selected from a methyl group or an ethyl group. Further, R4 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but is preferably a hydrogen atom or an alkyl group having a carbon number of 丨 to 4, more preferably 1 L atom or a methyl group. In the above formula (III), „! and n represent the number of the respective oxygen-and-tropanth units, and satisfy the relationship between 10 and 5SU40. Here, the unit of the number ^ is unit 1, and the unit of number n is The arrangement of the unit cell 丨 and the unit 2 may be either a random shape or a block shape. The above m system satisfies the relationship of the hacker 1 ,, but is preferably 彡 彡 5. Further, the above η system satisfies 5 The relationship between $η^4〇, but preferably ι〇^η^3〇. By making m and η in the above range, the balance between hydrophilicity and hydrophobicity in the above pVA (B) can be obtained. B) The content of the monomer unit (b) of _ is preferably U (4) ears as follows, more preferably from 15% by mole to less than _^% of the ear. When the content of the monomer unit (b) is in the above range, the viscosity increase property and the like can be more effectively exhibited. The average degree of polymerization of the PVA (B) is preferably 1 〇〇. The above 4, 〇〇〇 or less, more preferably 500 or more, and more preferably 〇〇〇, 〇〇〇 or more. By making the average degree of polymerization of the above pvA (B) within the above range, the pVA (... as a water-soluble solution) can be used. 23- 201 The 245232 liquid is mixed with the cellulose-based raw material and uniformly mixed. As a result, it is easy to carry out hydrolysis, and it is easy to carry out the hydrolysis, and the efficiency is good, and the cellulose polymer chain state can be effectively cut. The above PVA (B) The degree of saponification is preferably 7 〇 mol% or more and 99 99 mol% or less, more preferably 80 mol% or more and 99 9 mol%, and more preferably 96 mol% or more and 99.9 mol% or less. When the degree of recombination of the above pvA (8) is in the above range, when PVA (B) is mixed with the cellulose-based biomass as an aqueous solution, it is effective to mix and mix the results with appropriate viscosity, efficiency, and uniformity. The method of producing the PVA (B) is not particularly limited, but the method of producing the PVA (B) is preferably carried out. A method of condensing an unsaturated monomer with ethylene and deuterating the obtained ethylene vinegar polymer. In the following: the polymerization is preferably carried out in an alcohol solvent or without a solvent. The above R5 hydrogen atom or _C00Mi, ... a hydrogen atom, an alkali metal atom or an ammonium group. The sodium atom or the like may be mentioned. Among them, R5 is preferably a hydrogen atom. R6 is a hydrogen atom, a methyl group or a -CKOOM2, a M2 hydrogen atom, an alkali metal atom or an ammonium group. Examples of the atom include a sodium atom, etc. Among them, R6' is preferably a hydrogen atom or a fluorenyl group. As the above X, _〇_, _CH2_〇..._c〇_c〇〇, -CO -NR7- or -CO-NR7-CH2-, R7 is a hydrogen atom or an alkyl group having a carbon number of 丨 to 4. Among these, 'preferably _c〇_nr7_ or _c〇_nr7_CH2·. Hai PO A denatured PV A has the above-described guanamine structure, and is a suitable material by the cutting operation from the viewpoint of the viscosity of the -24-201245232 when it is made into an aqueous solution, affinity with cellulose, and the like. Further, the hydrogen atom of the diterpenoids, the meglumine, is an upper trace R, preferably a T group or an ethyl group. The above X is particularly limited to asymmetry, but the side of the p〇A base is referred to as "*", and the second side is not included. Preferably, the X is 上述L〇NH-氺, _C0_nh_CH2 氺-CONH-* or _c〇_NHCH2_*. More preferably, it can be combined with the monomer '(10) as a hydrogen atom for the polyoxyalkylene mono(methyl) allyl ether, oxyalkylene mono(methyl) vinegar, and ▲ (4), polyoxygen extension single (methyl) acrylic acid can be cited as polyoxyethylene polyoxypropylene single-acrylic amine,: knee & propylene monomethacrylamide, polyoxyethylene polyoxybutylene Early: thin amine, polyoxyethylene polyoxybutylene monomethyl propylene amide amine = B' polyoxypropylene early dilute propyl test, polyoxyethylene polyoxypropylene monodecyl allyl ether, Polyoxyethylene polyoxybutylene monoallyl ether, polyoxyethylene polyoxybutylene monomethyl propylene (IV), polyoxyethylene polyoxypropylene monoethyl _, polyoxyethylene polyoxygen oxyethylene material, polyoxygen Ethylene (tetra) oxypropylene monoglycolic acid vinegar, polyoxyethylene polyoxypropylene monomethacrylic acid, polyoxyethylene polyoxybutylene monoacrylic acid, polyoxyethylene polyoxybutylene monomethyl acrylate Vinegar and so on. The above-mentioned unsaturated monomer in the case where R4 is an alkyl group having 1 to 8 carbon atoms is exemplified by the substitution of the terminal hydroxyl group of the unsaturated monomer exemplified in the case where R4 is a hydrogen atom to a carbon number of 1 to 8. Alkoxy group. Examples of the vinyl ester monomer include the above. In the above copolymerization, it is also possible to copolymerize other monomers in the range which does not impair the purpose of the present invention. As such another monomer, the above-mentioned thing in the case of the copolymerization of PVA (A) is mentioned. The usage rate of the above other monomer -25-201245232 is also the same as that of PVA (A). At the time of the above-mentioned copolymerization, 'the same as the case of the above PVA (A). Use a chain transfer agent. Further, the temperature at the time of the copolymerization, the polymerization, and the initiator and the antioxidant used are also the same as those of the above PVA (A). The saponification method of the obtained copolymer is also the same. (Form of the viscosity-imparting agent, etc.) The viscosity-imparting agent may be a powder containing only the above PVA, and β is an aqueous solution of PVA. Further, other components may be contained in a range that does not impair the effects of the present invention. As the other components, other water-soluble polymers, gelling agents and the like can be mentioned. The viscosity-imparting agent is preferably in the form of a gel. By using such a gel-like viscosity-imparting agent (PVA aqueous solution), the mixture can be made into an appropriate viscosity from the initial stage in the cutting step, and since the viscosity can be maintained to a certain extent, efficiency can be achieved. Manufacture of good hydrolyzable cellulose. Further, since it is in the form of a gel, the gel-like viscosity-imparting agent (pvA) enters between the cut cellulose polymer chains and can be retained, thereby preventing re-crystallization of the cellulose polymer chain and improving Cutting energy. Further, in the gel-like adhesiveness, the amount of the gelling agent can be reduced by using a pure PVA which is pure in an aqueous solution. [Manufacturing Method of Hydrolyzable Cellulose], Method for Producing Hydrolyzable Cellulose Using Cellulose-Based Biomass as Raw Material - to /Package 3 · Obtaining the viscosity-imparting agent (hereinafter also referred to as "pVA aqueous solution") a mixing step of a mixture of cellulose-based biomass; and an additional shearing force to the above mixture, and a cutting step for cutting the cellulose-based biomass preferably comprises: cutting the cellulose system before the mixing step -26-201245232 Biomass raw material 'Cellulose-based raw material cutting step for forming cellulose-based biomass into particles of appropriate size; and preparing an aqueous solution of a viscosity-imparting agent (pvA aqueous solution) and a viscosity-imparting agent (I>; VA aqueous solution) becomes a gelatinous gelation step. The procedure for the production steps of the following hydrolyzable cellulose will be described. (1) Cellulose-based raw material raw material cutting step In this step, in order to carry out an effective treatment in the subsequent step, the cellulose-based raw material is cut to obtain particles of an appropriate size. Here, the cellulose-based raw material to be used is not particularly limited, and a plant-derived biomass can be preferably used. Specific examples thereof include wood such as thinned wood, rice straw, wheat straw, and rice husk. , bagasse, stalks, stalks of pink stalks, EFs of oil stalks, shells of coconut fruits, etc. When the cellulose-based raw material is removed as much as possible, the material is reduced to a particle shape by various cutting methods such as cutting and beating. In the cutting step, for example, a cutter described in Japanese Laid-Open Patent Publication No. 2004-526008, or a device used for producing pulp chips can be suitably used. The size of the cellulose-based green material to be subjected to the cutting step is preferably 2 mm or less, more preferably 丨mm or less, and particularly preferably ΐΟΟμηη or less. Further, it is preferably 2〇μηι or more and 7〇μπι. the following. By making the average particle diameter of the cellulose-derived green particles to 2 mm or less, and subsequent "seeing step" or especially the cutting step can be carried out efficiently, cellulose excellent in hydrolyzability can be obtained in a short time. (2) Aqueous solution preparation step In the present step, the PVA (viscosity-imparting agent) is dissolved in water to form a water -27-201245232 liquid (a cold-liquid viscosity-imparting agent). The concentration of the aqueous pvA solution is particularly limited, but is preferably 3% by mass or more and 30% by mass. /. Hereinafter, it is more preferably 5 mass% to *20 mass% or less. By making the 5 degree of the PVA aqueous solution in the above-mentioned schematic, 水溶液 can impart an appropriate viscosity to the aqueous solution. Therefore, by making the aqueous solution 澧疳yu ^ i > / morning in the above range, the physical force can be effectively transmitted to the cellulose-based biomass through the aqueous solution at the time of kneading, and as a result, by the water, When the cellulose polymer chain is peeled off, the cellulose-based biomass can be effectively cut into the grade of the . In the case where the concentration of the PVA aqueous solution is λΙ: in the case of 3 mass%, the aqueous solution does not have an appropriate viscosity, and the cutting function of physical action cannot be fully exerted. On the other hand, when the concentration of the right PVA aqueous solution exceeds 30% by mass, the viscosity of the aqueous solution is too large, and it is difficult to carry out the workability in the cutting step. Further, the PVA aqueous solution may contain PVA other than the above pvA. In this case, the concentration of the entire pvA containing the pvA is preferably in the above concentration range. Here, the P V A aqueous solution (the viscosity-imparting agent) may dissolve or dissolve other compounds other than PV A or the like. (3) The gelation step is preferably a step of mixing the cellulose-based biomass cerium particles obtained by the cellulose-based biomass raw material cutting step and the viscous-imparting agent (pvA aqueous solution). Gelatinized. By using such a gelled PVA aqueous solution', in the subsequent cutting step, the mixture has high viscosity from the initial stage of kneading, so the physical action of kneading is effectively conducted to the cellulose-based biomass, and the fiber can be made. Prime biomass is cut at a molecular level of -28-201245232. Further, by using a gelatinous aqueous solution of pva, the gelatinous aqueous solution can enter and remain between the cut cellulose poly-chains, thereby preventing re-crystallization of the cellulose polymer chains. Cutting can be improved. The method of gelation of the PVA aqueous solution may, for example, be a method in which various chemical substances (gelling agents) such as borate, titanium acetate, and other metal salts are added, and PVA is crosslinked. Further, the tackifier (the above-mentioned PVA) is excellent in viscosity in an aqueous solution, so that even if the amount of the gelling agent added is reduced or a gelling agent is not used, a moderate viscosity of the aqueous solution can be provided. . That is, the amount of the gelling agent used can be reduced according to the viscosity-imparting agent'. In the case of adding a borate and gelling the PVA aqueous solution, for example, it is possible to add and mix 〇 part by mass or more and 10 parts by mass or less, preferably 〇1 part by mass, per part by mass of the 5% by mass of the pvA aqueous solution. It is carried out by using a saturated aqueous solution of sodium tetraborate or more per part by mass or less. The PVA aqueous solution which is gelatinous in this manner has appropriate viscosity and is mixed with the cellulose-based raw material, and kneading is continued, and the viscosity is hard to rise (harden), so that it can be easily and efficiently. Kneading. Further, the gelled PVA aqueous solution is preferably acidic, and particularly preferably pH 4 or more and 6 or less. (4) Mixing step The PVA aqueous solution obtained in the above step is preferably a PVA aqueous solution which is gel-formed in the gelation step, and a cellulose system which is cut into a preferred size or the like in the cutting step. The biomass is obtained, and a mixture containing the same is obtained. • 29- 201245232 as a cellulose system; ψ & 、, H & θ relative to , .$人, /tc< s罝, although not particularly limited, but with respect to the total amount of fiber of the mixture is more than 5% The mass % or less, the step::: mixed & the amount is preferably 5% by mass or less. Fiber symplectic ", 'car is 10% by mass or more, 40 quality mixed character Xi Xi Bu 4 ', the quality of the mixture is less than 5 mass%, the viscosity of the mixed σ is low, and the right Μ fills the eight (four) eve The cutting function of sexual function can't be filled with sorrow and sorrow. At the same time, due to the sensitive work of Zhang Weigui LW fiber, the processing capacity of the raw material is low, and the operating rate is reduced. Conversely 5 〇 quality. /. Because of the biomass... The mixture of the vitamins and the raw material is more than 7 and the viscosity of the mixture is too high, and the workability is lowered. As the viscosity of the mixture, for example, it is preferably 5·〇Χΐ°4. He. (10) Magic handle "Pa.WT. (5) Cutting step By adding a shearing force to the mixture obtained in the above mixing step, the cellulose-based biomass is cut at a molecular grade (quasi-crystal structure grade). ', ie' by the cellulose having a quasi-crystalline structure, is partially watered, and, again, the PVA enters to weaken the hydrogen bond between the cellulose molecules: plus the additional physical force due to the shearing force, In a state where the intermolecular bonding is weakened, the microstructure of the cell wall is cut because the cellulose polymers are pulled apart from each other.

Here, by using the viscosity-imparting agent of the present invention, the PVA can impart a moderate viscosity to the mixture by virtue of the high affinity with water and cellulose, so that the so-called cellulose intermolecular hydrogen bond can be effectively and effectively exerted. The reduced chemical action; and the physical separation of the cellulose molecules from each other by an additional mechanical operation of the so-called shearing force. Further, by using the viscosity-imparting agent, the PVA easily enters and adheres to the gap of the cellulose polymer chain which is physically pulled apart. Therefore, according to the production method using the above-mentioned pvA -30-201245232, it is possible to prevent the re- quasi-crystallization of the fiber reinforced polymer and the Tokyo polymer chain to produce the hydrolyzable cellulose more efficiently. The shearing compound 'π ^ , and the initial stage of the additional force of the eye, becomes a straight-to-better mixed-effectively performing the molecular grade cutting of the cellulose-based biomass as a mixture in this cutting step The method of adding the shearing force is not particularly limited, and examples thereof include a method of kneading a mixture. Further, the apparatus used in the cutting step is not particularly limited, and a biaxial extrusion molding machine or the like which is generally used for the formation of a thermoplastic resin can be suitably used. The time required for the cutting step is appropriately set depending on the amount of the mixture, etc., but is, for example, 30 minutes or more and 1 hour or less. In addition, in the case of the knife cutting step, it is preferable to adjust the viscosity by appropriately adding an aqueous solution of sodium tetraborate or the like in the case of reducing the viscosity. According to the method for producing a hydrolyzable cellulose, the cellulose which is easily hydrolyzed by the quasi-crystalline structure of the cellulose-based biomass is subjected to the above-described respective steps. (6) Post-step In addition, the hydrolyzed cellulose obtained in this manner is easily saccharified by adding a hydrolyzing enzyme such as cellulase to the mixture, and the produced glucose is eluted in an aqueous solution. Examples of the hydrolyzable enzyme include ceUulase pectinase, hemicellulose, β-polyglucose, xylanase, and mannose. Mannase, amylase, meicelase, Acremonium 5 -31 - 201245232 Cellulase (cellulase obtained from Acremonium CeUulolytieus), and the like. Further, in the case of saccharification, xylose derived from hemicellulose contained in the cellulose-based biomass may be simultaneously eluted in an aqueous solution. At this time, lignin contained in the cellulosic biomass is present as insoluble particles, and the lignin can be separated, for example, by filtration or centrifugation. The saccharide such as soluble glucose which is obtained in this manner can be suitably used as a fuel resource or the like by fermentation. [Examples] Hereinafter, the present invention will be described in detail based on examples, and the present invention is not limited by the description of the examples. With respect to p V A obtained by the following production example, the evaluation was carried out in accordance with the following method. [The content ratio of the monomer unit having a carbon number of 29 or less in PVA (hereinafter also referred to as "denaturation rate") is determined by the method using the above proton NMR, and the solvent is CDC13 and 500 MHz is used. Proton NMR (JEOLGX-500). [Average polymerization degree of PVA] The average degree of polymerization of PVA was determined according to the method described in JIS Κ6726. [Saponification degree of PVA] The degree of saponification of PVA was determined by the method described in jis K6726. <Production of PVA> Production Example 1-1 (Production of PV A1-1) A 3 L reactor equipped with a mixer, a reflux condenser, a gas introduction tube, a monomer dropping port, and an addition port of an initiator, 75 〇g of vinyl acetate-32-201245232 ester, 250 g of methanol, and 1.lgN-octadecyl methacrylamide (having an alkyl group of unsaturated monomer), while performing nitrogen foaming, the system is carried out. The internal nitrogen was replaced by 30 minutes. Further, N-octadecylmercaptopropeneamine was dissolved in decyl alcohol to prepare a monomer solution having a concentration of 5% as a delayed solution, and nitrogen substitution was carried out by foaming with nitrogen. The temperature rise of the reactor was started, and 0.25 g of 2,2'-azobisisobutyronitrile (AIBN) was added to start polymerization at an internal temperature of 6 Torr. The delayed solution was dropped while the monomer composition (ratio of vinyl acetate to N-octadecylmethylpropenylamine) in the polymerization solution was constant, and the polymerization was stopped after cooling for 3 hours at 6 Torr. The total amount of monomers added until the polymerization was stopped was 4.8 g. Further, the solid content concentration at the time of stopping the polymerization was 299% by mass. Then, while adding methanol at a pressure of 30 ° C under reduced pressure, the unreacted vinyl acetate monomer was removed to obtain a methanol solution of the alkyl-denatured Bake-type copolymer (alkyl-denatured PVAc). 35 mass%). Further, in 771.4 g of an alkyl-denatured PVAci sterol solution (200.0 g of alkyl-denatured PVAc in the solution) prepared by adding methanol thereto, 27 9 g of an alkali solution (10% by mass of a methanol solution of sodium hydroxide) was added. Saponification (the alkylation-denatured PVAc concentration of the saponification solution was 25% by mass, and the molar ratio of the sodium hydroxide of the ethyl acetate unit in the alkylation-denatured PVAc) was carried out. Since a gel was formed about 1 minute after the addition of the test solution, the mixture was pulverized in a pulverizer, and left to stand at 40 ° C for 1 hour to carry out saponification, and then added to the residual test of 50 〇 g of acetic acid. After confirming the completion of the neutralization using a phenol phthalein indicator, filtration was carried out to obtain a white solid, and 2,000 g of methanol was added thereto, and the mixture was allowed to stand at room temperature for 3 hours to be washed. After repeating the above washing operation three times, the white solid obtained by centrifugal deliquedng was placed in a drier at 65 ° C for 2 days to dry, and -33-201245232 alkyl denatured PVA (PVAl-l) was obtained. The degree of saponification is 98.5 mol%, and the average polycondensation ratio of PVA1-1 is 0.4 mol%. The degree of joint is 1,700. Production Examples 1-2 to 1-18 (manufactured by PVAl-2 to 1-18) The vinyl acetate and sterol are loaded into the ss, the type of the unsaturated monomer having an alkyl group used in the polymerization or the polymerization condition added, the concentration of the alkyl-denatured PVAc at the time of saponification, and the ratio of The saponification conditions of the molar ratio of the sodium hydroxide of the vinyl acetate unit, etc., are as follows: 丄In the same manner as in Production Example 1, the various saponification conditions are produced.

The base condition is denaturing PVA (PVA1-2 to 1-18). Production Example 1-19 (Production of PVA 1-19) A reactor of 3 L equipped with a feeder, a reflux condenser, a nitrogen introduction tube, and an initiator addition port was charged with 750 g of vinyl acetate, 25 & decyl alcohol, and 5 7.3 g of octadecyl vinyl ether was nitrogen-foamed while undergoing nitrogen substitution in the system for 30 minutes. The temperature rise of the reactor was started, and polymerization was started by adding 2,2,-azobisisobutyronitrile (AiBN) 1.〇g at an internal temperature of 6 〇t>c. After 6 hours of polymerization at 6 〇t, the mixture was cooled and the polymerization was stopped. The solid content concentration at the time of stopping the polymerization was 30.4% by mass. Next, the unreacted vinyl acetate monomer was removed while adding 3 rc under reduced pressure, and a methanol solution of a calcined vinyl ester copolymer (alkyl derivatized PVAc) was obtained (concentration 35). Quality 4). Further, in a solution of 792.9 g of a decyl-modified PVAc sterol prepared by adding sterol (alkyl denaturing PVAc2 〇〇.〇g in solution), a 7 〇g alkali solution (1 〇) was added. "% by mass of sodium hydroxide in methanol / gluten solution" 'saponification (the saponification solution of the base-denatured PVAc concentration is 25% by mass, relative to the molar ratio of the oxime oxide of the vinyl acetate unit in the alkyl-denatured PVAc) 75). Since the gel was formed after adding the alkali solution for about 12 minutes -34-201245232', the pulverizer was pulverized in the pulverizer, and after saponification was carried out at 4 (rc for 1 hour, 500 g of methyl acetate was added to neutralize the remaining Base. After confirming the completion of neutralization by using phenol ugly indicator, it was filtered to obtain a white solid, and 2, 〇〇〇g methanol was added thereto, and it was washed at room temperature for 3 hours. After repeated three times of the above washing operation, it was centrifuged off. The white solid obtained in the liquid is in the dryer at 65C After 2 days of dryness, 'the base is degenerated ργ·Α(ρνΑ1-19). The average polymerization degree of PVA1-19 is 1,700, the degree of saponification is " ο, the molar denaturing rate is 0 · 8 Mo Production Example 1-20 (Production of PVA 1-20) A reactor of 3 L equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and an addition port of an initiator was charged with 900 g of vinyl acetate and 1 〇〇g. Methanol was subjected to nitrogen blowing in the system, and nitrogen substitution in the system was carried out for 3 minutes. The temperature rise of the reactor was started to be 6 在内 at the internal temperature. 〇.25 g of 2,2'-azobisisobutyronitrile was added. AIBN) polymerization was started, and polymerization was carried out for 3 hours at 6 ° C, and then the polymerization was stopped, and the polymerization was stopped. The solid content concentration at the time of the polymerization was stopped was 31 〇 mass %. Then, while adding methanol at a time of 30 ° C under reduced pressure, methanol was added. The unreacted vinyl acetate monomer was removed to obtain a non-denatured polyvinyl acetate (non-denaturing PVAc) decyl alcohol solution (concentration: 3% by mass). Further, 971. lg was not denatured by adding sterol thereto. pvAc sterol solution (no denaturing PVAc 200.0g in solution), adding 27_9g of alkali solution (1〇% by mass) Sodium saponification of sodium oxide (sodium oxide solution) (the non-denaturing PVAc concentration of the saponification solution is 20% by mass, and the molar ratio of ruthenium oxide to 0.03 in the early stage of the non-denatured pvAc). After about 1 minute, a gel was formed, which was pulverized in a pulverizer, and after 40 minutes of saponification was carried out, '500 gram of methyl acetate was added to neutralize the remaining base. Make -35-201245232 phenolphthalein indicator After confirming the completion of the neutralization, filtration was carried out to obtain a white solid, and 2,000 g of methanol was added thereto, and the mixture was allowed to stand at room temperature for 3 hours to be washed. After the above washing operation was repeated three times, the white solid obtained by centrifugation was dried in a drier at 65 ° C for 2 days to obtain a denaturing PVA (PVAl-20). The average degree of polymerization of PVA1-20 was 3,000, and the degree of saponification was 98.5 mol%. -36- 201245232 【1硌】 Saponification conditions NaOH Mohr ratio 2) 1 0.03 0.03 0.03 0.03 0.03 0.0075 0.007 0.005 0.002 0.0078 0.007 0.0068 0.006 0.03 0.03 0.03 0.03 0.0075 0.0075 0.03 PVAc concentration g yr) CN (N Ο (N CS ( N ^Τ) (N iT) CN <N iT) (N CN ι〇CN CN in (N yr) <N <N polymerization rate g 〇〇 inch inch inch inch inch inch inch inch inch inch inch inch 〇 inch inch 0 inch 0 inch inch inch m load υ unsaturated monomer φ|Μ w 00 inch ' 〇 \ inch ΓΟ 1—Η 00 inch · oo — ΓΟ inch rn CN CN 19.3 42.1 1 inch CN rn < N 00 oo 57.3 1 ίΝ Pi 1 ch3 ch3 m κ υ KU 1 CH3 mu 1 CH3 I m ffi u ΓΛ ffi u ffi um ffi u ch3 ffi u CO ffi u ffi u W um ffi u octadecyl vinyl ether & 1 C18H37 C18H37 C,8H37 Ci8H37 C18H37 C,8H37 C18H37 C18H37 C18H37 C18H37 c,2h25 C8H17 C8HI7 CsH,, C10H21 C26H53 C30H61 C18H37 Methanol (before polymerization starts) Sw/ 250 150 Ο 600 900 250 250 450 600 250 250 250 250 250 250 250 250 250 250 0 Vinyl acetate 3 750 850 900 400 100 750 750 550 400 750 750 750 750 750 750 750 7 50 750 750 900 PVA PVA-1 PVA-2 PVA-3 PVA-4 PVA-5 PVA-6 PVA-7 PVA-8 PVA-9 PVA-10 PVA-11 PVA-12 PVA-13 PVA-14 PVA-15 PVA-16 PVA-17 PVA-18 PVA-19 PVA-20 Production Example 1-1 Production Example 1-2 Production Example 1-3 Production Example 1-4 Production Example 1-5 Production Example 1-6 Production Example 1-7 Production Example 1-8 Production Example 1-9 Production Example 1-10 Production Example 1-11 Production Example 1-12 Production Example 1-13 Production Example 1-14 Production Example 1-15 Production Example 1-16 Production Example 1-17 Production Example 1-18 Production Example 1-19 Production Example 1-20. NalvwssCNocw'T:# 二杳? ^^^^^Η-ιί^ιέ^^^^-ΚΝΗΙ^ιίί-Ι-^^Ί^-ΗίΝ^^η^^έ-Ι^^^ΙΚΙ s • Li_ 201245232 [Embodiment 1 -1 ] PV A 1 -1 was added to distillate water to prepare a 10% by mass aqueous solution of pVA by heating to 90 C' while stirring. The Pva aqueous solution is somewhat more viscous than water. After cooling the aqueous solution of io〇g to room temperature, it was mixed with a saturated aqueous solution of 1 mL of boric acid (KUBO3). The obtained aqueous solution was further mixed by adding a saturated aqueous solution of 〇.5 mL of sodium borate in the aqueous solution to make the aqueous solution a viscous gel. The enthalpy 11 of the gel was 6.5. Next, 50 § £ [6 (particles of diameter 20 to 7 (^111) were added as cellulose-based particles to the gel, and kneaded at room temperature using a mixer-type kneader. This mixture was initially It is softer when kneaded, but under continuous kneading, EFB (cellulose-based green matter) absorbs water and the viscosity is slightly increased. This mixture can be easily stretched and kneaded by a roller. It can be observed that when the particles are kneaded for a certain period of time, a part of the mixture is taken out, and the particle size is confirmed. As the cutting step proceeds, the size of the keel is reduced and the cell structure is cut. It is confirmed by microscopy that the cellulose is sufficiently kneaded by kneading. Cut

Cellulase from m cellulolyticus*: Cellulase (from: Meiji-made stocks -38-201245232 Co., Ltd.), as a hydrolyzing enzyme, stirred at a temperature of 5 Torr in a reaction vessel. After adding the enzyme for several ten minutes, the viscosity of this mixture was significantly reduced. This stirring was carried out for 6 hours to obtain a glucose solution. [Examples 1-2 to 1-18, Comparative Example] In the same manner as Example 1-1 except that the PVA was replaced with the other PVA of Table 2, the examples 12 to 118 and the same were carried out. In Comparative Examples 1 to 1-2, a hydrolyzable cellulose aqueous solution was obtained, and finally a glucose solution was obtained. [Evaluation] (Homogeneous mixing property) In Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-2, EFB was added to the gel, and the kneading machine was used to start kneading. The portion of the mixture was taken out after 1 hour. (4) The micromirror was visually observed for the agglomeration of the extracted mixture = EFB, and the case where the particles were not agglomerated was judged as "good", the case where a few aggregates were determined as "slightly agglomerated", and the case where the aggregation was intensely coagulated was judged as " Cohesion." The evaluation results are shown in Table 2. (Glycation efficiency) After adding distilled water to the glucose solution to be used, 4 mL of the sample solution of the glucose solution (5% of the total solution) was taken and sterilized at 100 C for 5 knives. After cooling the sample solution, the mixture was centrifuged at 3,000 rpm for 30 minutes using a centrifugal separator, and the solid matter was filtered and removed, and then the filtrate was subjected to liquid chromatography, and monosaccharides (glucose or the like) were measured. The mass ratio of hydrazine cellulose and hemicellulose to EFB (50 g) used was 50%. The saccharification efficiency (%) was determined by the following formula. The measurement results are shown in Table 2. Saccharification efficiency = [monosaccharide mass in sample solution (g) / {50 (g) X 0.005 χ〇. 5}] χΐΟ〇 (〇 / 0) -39 - 201245232 [Table 2] PVA evaluation results type average polymerization Degree of denaturation saponification degree uniform mixed saccharification efficiency - (mol%) (mol%) - (%) Example 1-1 PVA1-1 1,700 0.4 98.5 Good 88.9 Example 1-2 PVA1-2 2,400 0.4 98.5 Good 89.4 Implementation Example 1-3 PVA1-3 3,000 0.4 98.5 Good 88.2 Example 1-4 PVA1-4 500 0.4 98.5 Good 85.3 Example 1-5 PVA1-5 100 0.4 98.5 Good 82.3 Example 1-6 PVA1-6 1,700 0.4 88 Good 87.3 Example 1-7 PVA1-7 1,700 0.4 80 Good 86.3 Example 1-8 PVA1-8 1,000 0.4 60 Good 83.7 Example 1-9 PVA1-9 500 0.4 10 Slightly agglomerated 80.4 Example 1-10 PVA1-10 1,700 0.08 88 Good 80.3 Example 1-11 PVA1-11 1,700 1.2 88 Good 84.2 Example M2 PVAM2 1,700 2.5 88 Slightly agglomerated 82.5 Example 1-13 PVA1-13 1,700 5.5 88 Slightly agglomerated 80.7 Example 1-14 PVA1 -15 1,700 0.4 98.5 Good 83.5 Example 1-15 PVA1-16 1,7〇〇0.4 98.5 Good 85.5 Example 1-16 PVA1-18 1,700 0.4 88 Good 84 .2 Example 1-17 PVA1-14 1,700 0.4 98.5 Good 75.4 Example 1-18 PVA1-19 1,700 0.8 88 Condensation 74.3 Comparative Example 1-1 PVA1-20 3,000 - 98.5 Good 70.2 Comparative Example 1-2 PVA1-17 1,700 0.4 98.5 Coagulation 63.8 As shown in Table 2, it is understood that Examples 1-1 to 1-6 have a saccharification efficiency of more than 80% due to the use of an alkyl-denatured PVA having a specific monomer unit, and the cellulose can be cleaved to be easily hydrolyzed. status. On the other hand, it was found that Comparative Example 1-1 was not sufficiently denatured to a state in which hydrolysis was easily carried out because P V A used was non-denatured. <Production of PVA> Production Example 2-l (Production of PVA2-l) A reactor of 3 L equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a monomer dropping port, and an initiator addition port was charged with 750 g. Vinyl acetate, 250 g of methanol, 3.3 g of unsaturated monomer having ROA group (the monomer A shown in Table 4, the arrangement of the unit 1 and the unit 2 are in the form of blocks, and the block of the unit 1 is embedded in the unit 2 The section was located on the X side described above, and nitrogen substitution was carried out in the system for 30 minutes while the atmosphere was foamed. Further, the unsaturated group -10-201245232 and the monomer (monomer A) having a POA group are dissolved in decyl alcohol to prepare a monomer solution having a concentration of 2% by mass as a delayed solution, and nitrogen substitution is performed by foaming of nitrogen gas. . The temperature rise of the reactor was started. When the internal temperature became 60 ° C, 0 25 g of 2,2,-azobisisobutyronitrile (AIBN) was added to initiate polymerization. While the retardation solution was dropped, the monomer composition (ratio of vinyl acetate and monomer A) in the polymerization solution was kept constant, and polymerization was continued at 60 ° C for 3 hours, and then the polymerization was stopped by cooling. The total amount of the above monomer solution added until the polymerization was stopped was 75 π. Further, the solid content concentration at the time of stopping the polymerization was 24.4% by mass. Next, while removing methanol from the unreacted vinyl acetate vine monomer by adding methanol at a reduced pressure at 30 ° C, a POA-modified vinyl ester polymer (p〇A-denatured PVAc) was obtained (concentration 35 mass). %) Further, in a solution of 453.4 g of a sterol solution of POA-denatured PVAc prepared by adding sterol (poa-denatured PVAclOO.Og in solution), 55 6 g of an alkali solution (1 〇 mass% of sodium hydroxide) was added. Solution), saponification (the POA denatured PVAc concentration mass of the saponification solution is 20%, and the molar ratio of sodium hydroxide of the vinyl acetate unit in the PvA denatured pvAc is 1). Since the gelation was produced after about a minute of the addition of the alkali solution, the mixture was pulverized in a pulverizer, and after saponification was carried out for 4 hours at rc, 500 g of methyl acetate was added to neutralize the remaining base. The phenolphthalein indicator was used. After confirming the completion of the neutralization, filtration was carried out to obtain a white solid, and 2,000 g of methanol was added thereto and allowed to stand at room temperature for 3 hours to wash. After repeating the above washing operation three times, the white solid obtained by centrifugation was centrifuged in a dryer at 65. C was left to dry for 2 days to obtain p〇A denatured ρνΑ(ρνΑ2 ι). The average degree of polymerization was 丨, 740, the degree of saponification was 98.5 mol%, and the amount of denaturation was 0_4 mol%. " Manufacturing Example 2-2 2-24 (manufactured by PVA2-2 to 2-24) -41 - 201245232 In addition to changing the loading amount of vinyl acetate and methanol, the type of unsaturated monomer having POA group used in polymerization (Table 4) or adding The polymerization conditions such as the amount, the saponification conditions of the POA-denatured PVAc at the time of saponification, the molar ratio of the sodium hydroxide to the vinyl acetate unit, and the like are shown in Tables 3 and 4, and the production example 2 1 The same method to manufacture various p〇a denatured PVA (PVA2-2 to 2-24) Production Example 2-25 (Production of PVA2-25) In a reactor of 3 L equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and an addition port of an initiator, 700 g of vinyl acetate and 3 〇〇g of methanol were charged. Nitrogen foaming was carried out, and nitrogen substitution was carried out in the system for 3 minutes. The temperature of the reactor was started, and the internal temperature was 6 (the addition of g25g of 2, 2'·azobisisobutyronitrile (AIBN) was started. After the polymerization was carried out for 6 hours, the polymerization was stopped by cooling for 3 hours. The solid content concentration at the time of stopping the polymerization was 17% by mass. Then, the unreacted vinyl acetate was removed while adding decyl alcohol at 30 C under reduced pressure. The ester monomer was obtained as a methanol solution of non-denatured polyvinyl acetate (without denatured PVAc) (concentration: 3% by mass). Further, a denaturing PVAci 544 1 g T alcohol solution prepared by adding methanol thereto (no denaturing PvAcl20 in the solution). In 0g), add 55 to test solution (1〇% by mass of sodium hydroxide in decyl alcohol solution), and carry out 4 (the non-denaturing of the solution solution - Ac concentration 20 里 / 〇, relative to acetic acid in denaturing pvAc Vinyl ester Ql) Since a gel is formed after about 1 minute of the addition of the test solution, the mixture is pulverized in a pulverizer, and after saponification is carried out at 4 (rc for 丨 hours, '5 〇〇g acetic acid is added' to neutralize the remaining base. Phenol ugly finger = agent confirmed after the completion of neutralization, the transition to obtain a white solid, where 2,000g of methanol was added and allowed to stand at room temperature for 3 hours, and washed. Repeat the above -42 ^ 201245232 operation three times, the centrifuged liquid obtained The white solid was dried in a drier at 65 ° C for 2 days to obtain a denaturing PVA (PVA 2-25). The average degree of polymerization of PVA2-25 was 1,760, and the degree of saponification was 98.8 mol%. [Table 3] PVA charged 丨) Polymerization rate saponified phase yak acetic acid 6-salt ester methanol (before polymerization starts) Unsatisfied·»Monomer PVAc concentration NaOH Mobi ratio D Species amount (K) (R) - (β (β) (S) - Production Example 2-1 PVA2-1 750 250 A 17.6 35 20 0.1 Production Example 2-2 PVA2-2 400 600 A 13.0 50 20 0.1 Manufacturing Example 2-3 PVA2-3 550 450 A 11.7 30 20 0.1 Manufacturing Example 2-4 PVA2-4 900 100 A 21.5 25 20 0.1 Manufacturing Example 2-5 PVA2-5 950 50 A 14.8 20 20 0.1 Manufacturing Example 2-6 PVA2-6 100 900 A 4.5 80 20 0.1 Manufacturing Example 2-7 PVA2-7 1,000 0 A 8.0 5 20 0.1 Manufacturing Example 2-8 PVA2-8 1,000 250 A 17,6 35 20 0.0075 Production Example 2-9 PVA2-9 750 250 A 17.6 35 20 0.002 Manufacturing Example 2-10 PVA2-10 750 250 A 17.6 35 20 0.001 Manufacturing Example 2-11 PVA2-11 750 250 A 260.0 35 20 0.1 Manufacturing Example 2-12 PVA2-12 750 250 A 83.9 35 20 0.1 Manufacturing Example 2-13 PVA2-13 750 250 A 9.8 35 20 0.1 Manufacturing Example 2-14 PVA2-14 750 250 A 3.9 35 20 0.1 Manufacturing Example 2-15 PVA2-15 750 250 B 17.6 35 20 0.1 Manufacturing Example 2-16 PVA2-16 750 250 C 17.6 35 20 0.1 Production Example 2-17 PVA2-17 750 250 D 17.6 35 20 0.1 Manufacturing Example 2-18 PVA2 -18 750 250 E 17.6 35 20 0.1 Manufacturing Example 2-19 PVA2-19 750 250 F 17.6 35 20 0.1 Manufacturing Example 2-20 PVA2-20 750 250 G 17.6 35 20 0.1 Manufacturing Example 2-21 PVA2-21 750 250 H 17.6 35 20 0.1 Manufacturing Example 2-22 PVA2-22 750 250 I 17.6 35 20 0.1 Manufacturing Example 2-23 PVA2-23 750 250 J 17.6 35 20 0.1 Manufacturing Example 2-24 PVA2-24 750 250 K 17.6 35 20 0.1 Manufacture Example 2-25 PVA2-25 750 250 - 35 20 0.1 1) In all the production examples, 25.25g of 2,2'-azobisisobutyronitrile (AIBN) was used as a polymerization initiator 2) Relative to PVAc The molar ratio of sodium hydroxide (NaOH) in the vinyl acetate monomer unit [Table 4] Monomer R4 R' R° X mn A -ch3 -H -H -ch3 -CO-NH-氺5 20 B - Ch3 •H -H -ch3 -CO-NH-氺0 6 c ch3 -H -H -ch3 -CO-NH-氺8 36 D -c2h5 -H -H -ch3 -CO-NH-CH24 5 20 E - Ch3 •ch3 -H -ch3 -CO-NH-氺5 20 F -CH, -H -H -H 5 20 G -ch3 •H -H -CHrCOONa -CH2_0氺5 20 H -ch3 -H -COONa •ch3 -CO-NH-氺5 20 I -ch3 -H •H -ch3 -CO-NH-氺3 3 J -ch3 -H -H -ch3 -CO-NH-氺12 20 K -ch3 -H -H - Ch3 -CO-NH_ 氺8 50 氺 indicates POA base side -43- 201245232 [ Examples 2-1 to 2-24, Comparative Example 2-1: Examples 2-1 to 2 were carried out in the same manner as in Example 1-1 except that PVA was replaced with PVA1-1 as the other PVA of Table 5. -24 and Comparative Example 2-1, a hydrolyzable cellulose aqueous solution was obtained, and finally a glucose solution was obtained. [Evaluation] The evaluation of the mixing property and the measurement of the saccharification efficiency were carried out by the above method. The results are shown in Table 5. [Table 5] PVA Evaluation Results Type Average Degree of Polymerization Denaturation Rate Saponification Degree Uniform Mixed Saccharification Efficiency - (mol%) (mol%) - (%) Example 2-1 PVA2-1 1,740 0.4 98.5 Good 92.3 Example 2 2 PVA2-2 530 0.4 98.6 Good 82.3 Example 2-3 PVA2-3 1,040 0.4 98.5 Good 88.2 Example 2-4 PVA2-4 2,380 0.4 98.4 Good 93.3 Example 2-5 PVA2-5 3,600 0.4 98.5 Good 90.4 Example 2-6 PVA2-6 90 0.4 98.8 Good 78.4 Example 2-7 PVA2-7 4,600 0.4 98.4 Good 89.3 Example 2-8 PVA2-8 1,730 0.4 92.0 Good 89.8 Example 2-9 PVA2-9 1,750 0.4 74.3 Good 86.3 Example 2-10 PVA2-10 1,740 0.4 52.0 Slightly agglomerated 81.0 Example 2-11 PVA2-12 1,780 3.6 98.6 Slightly agglomerated 88.7 Example 2-12 PVA2-13 1,740 0.2 98.5 Good 79.3 Example 2-13 PVA2- 15 1,740 0.6 98.5 Good 86.4 Example 2-14 PVA2-16 1,730 0.3 98.6 Good 90.2 Example 2-15 PVA2-17 1,780 0.4 98.5 Good 85.7 Example 2-16 PVA2-18 1,740 0.4 98.4 Good 84.3 Example 2-17 PVA2-19 1,740 0.4 98.5 Good 78.9 Example 2-18 PVA2-20 1,740 0.4 98.5 Good Good 80.2 Example 2-19 PVA2-21 1,730 0.4 98.6 Good 81.8 Example 2-20 PVA2-11 1730 10.8 98.5 Condensation 70.5 Example 2-21 PVA2-14 1,740 0.1 98.5 Slightly agglomerated 72.2 Example 2-22 PVA2- 22 1,780 0.4 98.5 Slightly agglomerated 73.4 Example 2-23 PVA2-23 1,740 0.4 98.4 Slightly agglomerated 68.4 Example 2-24 PVA2-24 1,740 0.4 98.5 Slightly agglomerated 71.7 Comparative Example 2-1 PVA2-25 1,760 - 98.8 Condensation 68.4 -44-201245232 As shown in Table 5, it was found that in Example 211249, since the POA-denatured PVA having a specific monomer unit was used, the saccharification efficiency was more than 78%, and the cellulose was cut into a state of being easily hydrolyzed. - square φ, 崎2, because the PVA used is non-denatured, so the cellulose is not cut to a state prone to hydrolysis. [Industrial Applicability] As described above, the viscosity-imparting agent of the present invention is suitably used when the cellulose-based biomass is used as a raw material to produce hydrolyzable cellulose. Therefore, according to the present invention, the plant abundance of β β & can be used as an efficient food or energy source from the raw material of the cut, 44··τ·, 扨4 The feasibility of using raw materials. [Simple description of the diagram] None. [Main component symbol description] None. -45-

Claims (1)

201245232 VII. Patent application scope: 1. A viscous imparting agent which is produced by using a hydrolyzable cellulose which is characterized in that it has a burning base of not more than 29 carbon atoms. The cellulose-based biomass is used as a raw material containing a polyvinyl alcohol-based polymer, and contains a monomer having a carbon number of 8 or more. 2. If the viscosity is the same as that of the patent, the carbon number in # is U or more. And the ratio of the number of carbon atoms to the number of oxygen (carbon number/oxygen number) in the side bond of the monomer unit is more than 2.5/1. 3: The viscosity-imparting agent of the first or second aspect of the patent application scope of the invention, the average degree of polymerization of the polyethylene-based polymer is 1 〇〇 or more, 5 〇〇〇, and the content is more than or equal to 99. · 9 9 mol / 〇 below, the content of the monomer unit is 〇:. 5 moles above i. Mole% or less. The viscosity-imparting agent according to any one of items 1 to 3, wherein the monomer unit is represented by the following formula (1): R2 CH2-c-- (I) Η (1) wherein 'Rl represents a carbon number of 8 to 29 a linear or branched alkyl group; R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The viscosity-imparting agent of the fourth aspect of the invention, wherein the polyvinyl alcohol-based polymer has an average polymerization degree of 200 or more and 5,000 or less, and a degree of saponification of 60 mTorr/〇 or more and 99 99 mol% or less. The content of the unit is 0.05 mol% or more and 5 mol% or less. -46 - 201245232 6. The viscosity-imparting agent of the fourth or fifth jg*#α_文杰丨^ item, wherein the life-enol-based polymer is formed by the following formula (II) and the copolymer of monomer R1 ethylene vinegar monomer, c cl H cnno / hn \ R1 %t / Π f\ (Formula (II) ~ I Xing this formula (1 The viscous imparting agent according to any one of the claims of the present invention, wherein the monomer unit has a polyoxyalkylene represented by the following formula (III) The content rate is 〇"mole% or more i 〇莫耳.〆. to R3, 卜-j-CH2-CH2-〇-|^-fcH2-CH--〇4-R4 (10)) In (Formula (III) Wherein R3 is each independently methyl or ethyl; r4 is a nitrogen or an alkyl group having 1 to 8 carbon atoms; 〇gmg1〇, 5$η'40). 8' is the viscosity-imparting agent according to item 7 of the patent application scope, wherein the average degree of polymerization of the polyethylene-based polymer is 1 〇〇 or more and 4 〇〇〇 is 7 〇 mol% or more and 9” 9 摩尔% or less. Further, R6 3 -CX is a viscosity-imparting agent of the seventh or eighth aspect of the patent, wherein the poly-polymer is a saponification by a saponification of the following formula (IV) A copolymer of a monomer, (17) HC = I R5 (in the formula (IV), β 3 n 4 κ , R , 111 and η have the same definitions as the formula (III); R a hydrogen atom or - C〇〇M丨: M1 is a hydrogen atom or an alkali metal atom; -47- 201245232 R6 is a hydrogen atom, a methyl group or -CH2-COOM2: Μ2 is a hydrogen atom, an alkali metal atom or an ammonium group; X is -〇-, -CH2-0-, -CO-, -C0-0-, -CO-NR7- or -CO-NR7-CH2-: R7 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The viscosity-imparting agent of the ninth aspect of the invention, wherein R5 in the unsaturated monomer represented by the general formula (IV) is a hydrogen atom; X is _c〇_Nr7_ or -CO-NR7-CH2_, and R7 Is a hydrogen atom or a carbon number of 丨 to 4 alkyl. As claimed in the patent scope of the patent range 1 to 1 A method for producing a hydrolyzable cellulose, which is a method for producing a hydrolyzable cellulose using a cellulose-based biomass as a raw material, characterized in that the inclusions are contained. For example, if the application scope is the first viscosity of the viscous work, the mixing step of any mixture of 3 π τ and cellulose-based biomass; additional shearing force to the mixture, cleavage j fiber xin 4 g cutting Step. 7 knife phantom fiber rope cutting -48- 201245232 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: