TWI244487B - Hydrolyzed and condensation-polymerized starch, process for preparing the same, and shaped articles of hydrolyzed and condensation-polymerized starch - Google Patents

Abstract

Hydrolyzed and condensation-polymerized starch obtained by introducing a flexible and linear organic group into at least a part of a main chain of starch, for example, a group represented by -O-(C=O)-O-, -((O-R1)x-(O-(C=O-R2)y)m-Oz-, or -CH2-(C=O)-CHR3-O- into at least a part of a main chain of starch. In each of the formulae, R1 and R2 denote an alkylene group of a carbon number at least 1 or an arylene group of a carbon number at least 6. The symbols x, y, and z denote 0 or 1. The value of x+y equals 1 or 2. The symbol m denotes an integer of 1 to 3100. R3 denotes hydrogen atom, an alkyl group of a carbon number at least 1, an aryl group of a carbon number at least 6, or an alkoxyl group of a carbon number of at least 1.

Description

1244487

V. Description of the invention (1) [Technical field to which the invention belongs] The present month relates to a hydrolyzed and condensed starch, made of #, and a fiber product / sheet made of the hydrolyzed and condensed powder, and formed into a molded product. The hydrolyzed condensation of the present invention]: or very suitable = for example: cosmetic bulking agent, food bulking agent, rice paper, rugged materials, and fiber products, films, sheets It is used in extrusion molding, molding molding and injection molding. Do not pay [Previous technology] No /, there are, plastic starch is an economical polymer, but it cannot be used for general polymer applications such as films, fibers, and molded products. Therefore many starches have been proposed for making thermoplastic articles ^. In terms of starches reconstituted from the above proposals, there are: hydroxyalkyl lakes = triacetam starch or urethanes. The aforementioned substances are produced by reacting urea, epoxide, urethane or isocyanate-forming substances with the methyl hydroxyl group of starch. However, the chemical starch produced by the above-mentioned reprocessing steps is not economically good, and is generally not used for the general purpose. Although there is a branched branch amylopectin in the old one, it is still a huge polymer, so it cannot show its thermoplasticity. In addition, hydrogen bonding between the fluorenyl group and the private group is also the reason that hinders the formation of thermoplasticity. The modification by reacting the fluorenyl hydroxyl group of the powder will change the hydrogen bonding force to

1244487 V. Description of the invention (2) No, starch can show thermoplasticity. On the other hand, chemical starch is produced by heating starch, and once it is cold, it will recover / S chemical starch. Chip chestnut powder is starch which is formed into a paste by heating in the presence of water, and exhibits better thermal stability in appearance. In Japanese Patent Publication No. 7-74241, it is disclosed that starch is added with water, and The hydrolyzed starch is made at room temperature to produce a melt that has been adjusted for drying. However, after adding water, it breaks down. The subsequent condensation method is not disclosed. Furthermore, in Japanese Patent Publication No. 7-57827, a mixing method of starch and biodegradable resin is disclosed. This method is a method of adding starch to water to produce water-decomposed starch at high temperature to produce a melted solution. "The coldness of the heart is that the starch is hydrolyzed, and the molecular weight of the hydrolyzed starch is 1/5 0 0, and the molecular weight of the hydrolyzed starch is described as" the above hydrolysed starch-based dew. " Decompose palace powder. According to show thermoplasticity. In addition, according to the unveiling system, it dropped from 1/2 of the initial stage to. The above results are questionable because no molecular weight is specified. According to the description, the hydrolyzed starch is made to absorb 18% by weight of moisture,

Then, he and his tree were mixed together, and a dumb test piece was made using an injection molding machine. According to records, the deformation of the test piece is reduced due to moisture absorption. However, when compared with ordinary plastics, 8% by weight is obviously a very large value ', which is not an ordinary value. Many methods have been put forward to put starch in the supercritical state of carbonic acid gas and water system, and to add water in the tank for decomposition. For example, 'In Japanese Unexamined Patent Publication No. 11 1 9 2 5 01, it was revealed that "in high density

2066-5094-PF (N) .Ptd Page 6 1244487 V. Description of the invention (3) = Modification of polysaccharides in the body ". However, this proposal is only a method for exposing the macromolecules of starch in a supercritical state of carbonic acid gas and water to hydrolyze them in the tank to become low-molecules below the aggregates, that is, how to be efficient Decomposition of ground water into low molecular compounds is a major issue. Therefore, the method of continuously decomposing high-molecular-weight starch to low-molecular-weight continuous condensation is completely undisclosed. The “recycling method of cross-linked polymer materials” was proposed in the JP 2000-1 2 53 9 6 7 bulletin. In this case, it was revealed that the crosslinked polymer material was supplied to a 1-axis or biaxial extruder, and then the water was decomposed in the above-mentioned extruder to be supercritical water or subcritical water to be hydrolyzed to cut off the cross-linking. = Part of the method. However, it does not disclose a supercritical or subcritical method using carbonate gas and water-based stone acid reflux gas. In addition, a method for recondensing the cut crosslinked portion is not disclosed. Generally speaking, thermoplastic polymers have the property of easily melting and adhering at high temperatures above the softening point. Therefore, in order to prevent sticking, quenching is performed. For example, a known method is to extrude the polymer melted during the production of nylon, polyester, and other sheet-like materials through a nozzle into a card shape, and then use water cooling to quench it. When the temperature drops below the softening point: reuse A cutter performs cutting to prevent the sheet from sticking. However, if the water cooling method is used, it must be dried before re-melting, which is not economically advantageous. No method for preventing the sticking above the softening point of the thermoplastic resin has been disclosed. The object of the present invention is to provide a novel hydrolyzed condensed starch and its inexpensive manufacturing method.

V. Description of the invention (4) [Summary of the invention] The present invention is a hydrolyzed and condensed starch, which is introduced into the main part q of the starch. The following formula (1), formula (2) and formula ⑴ are also available. It is composed of at least one functional group in the group: • 1244487 The purpose of the present invention is to provide a cheap hydrolyzed condensed starch with thermoplasticity, softness, and practically sufficient mechanical properties, and a method for producing the same, particularly It is a hydrolyzed and condensed Tibetan powder that is not easy to stick even above the softening point and its manufacturing method. The object of the present invention is to provide a fiber product, a film and a sheet molded product, and a molded molded product which have sufficient use characteristics and are convenient and biodegradable. -0- (〇0) 1〇 ~-((0 ~ R1) X- (0— (C = 0) —R2) y) m-〇z—; P is U ^ -CHR3- with carbon number i or more 0-. The base ° R2 is carbon number = = ylene) or propylene fire with carbon number 6 or above]. Is an alkylene group of 0 or a propynyl group of 6 or more carbon atoms. x is 2. Treated as hydrogen. :, 1 or 2 ° m is an integer from 1 to 3100. z is 1 or an alkyl group having a carbon number of 1 or more, an aryl group having a carbon number of β or more or an alkoxy group having a reverse number of 1 or more. This invention your daughter ^ starch. '、 There is a state of the above-mentioned hydrolyzed and shrunken / AU \ humidity bar of the present invention :: Condensed starch, by standing at a temperature of 20 ° C, phase 1 ^ by standing for 2 4 hours, and Make it substantially 悝 ^

Style

Page 8 1244487 V. Description of the invention (5) :: The J-score is :: weight " The powder 1 of the present invention is preferably 150 to 400% of expanded H after soaking in water at a temperature of 25 ° C for 1 hour. Too Mingzhi 4 u horse 顼 屮 hammer ㈣ ㈣ X 17 water is the decondensed starch, it is better to show contact and cross sex (t h i 〇 t r 〇 p y). The free-formation formula of the hydrolyzed condensation condensation of the present invention (" the official envy beauty expressed: 2: two: "and powder, the host-~ B moonyl-based compound, the formation formula (2 -A two: ί Γ The energy-based compound and the compound forming the official compound represented by the formula (3) are represented in the group consisting of the state compound 2 to m ~ 35 ... The following reactions are 'or, in water and carbon dioxide gas' Reverse: reacted under the condition that the carbonic acid gas becomes supercritical state or subcritical state, and is produced. 俅 The starch of the hydrolyzed and condensed starch of the present invention is selected and the free product, 彳 M, π Shiyi τ is based on a compound of at least J compounds in the group consisting of a compound that forms a functional group represented by formula (1), a compound that has a functional group represented by form ^), and a compound that forms a formula (:: functional group)喈 喈 extruder is 100 ~ 25 0kg / cm2 (two 9 · 8 ~ 24.5Mpa) I pressure extrusion is better. Fiber ί Ming t hydrolyzed condensation powder, very suitable for forming, The materials of molded film and sheet and molded products make The hydrolyzed and condensed starch, which has thermoplastic properties, is thermoplastic and is not easy to stick at temperatures above =: point. It is better to show the hydrolyzed and condensed starch that touches the main Maoming. A cent has the formula (1), (2), or (3)

1244487 V. Description of the invention (6) The shortcoming of the soft linear organic group is to have & the introduction of formula (1) and formula € 2 makes the presence of rigid glucose as soft as a hinge increases. For the main chain, it is easy to report to the easy chain and it is rarely good with other main chains. The above phenomenon is considered to be the cause of thermoplasticity. By condensing the starch and the compound forming the functional group shown in the hydrolysis reaction, and adding (), formula (2) or formula (3), condensation can be generated to significantly increase the feasibility of the present invention to improve h, f properties and softness Sexual things temporarily Wenliang Geling powder i :: 30%): ... functional? ", By soft"…-the part becomes a small silk ball V. The flexible chain is entangled, and the main thing that the company becomes a silk ball is that the lubricity between the chains of the present invention will become hydraulically decondensed; : The conditional formula (2) or formula (3) described above decomposes the water, and the powder is expressed, and then the powder is dehydrated with a compound that forms the g-energy group of formula (1) * T dehydration σ water decomposition condensation [Embodiment] Part of the hydrolyzed condensation condensation of the present invention is introduced into formula (1), formula (2), which has a structure in the main chain of the main powder of the present invention. Water content of the present invention j) or formula (3) Functionality represented by)): -G-Mn- Repeated mono- ^ starch, which is a divalent functional group having a hydroxyl group at the 104-position. M ^ is the 1-position where glucose is removed. And the functional group represented by formula (3). When expressing an integer of formula (1), formula (2) or an integer, plural M may be an integer on M. When n is 2 or more, in formula (2) The "word" can be different from the same. For example: 1,2-vinyl, 10 2066-5094-PF (N) .ptd 1244487 5. Description of the invention (7) 1,3-propenyl, 1 , 4-butene Linear alkyl enes with 1 or more carbon atoms (usually 12 or less); benzyl, biphenylene, biphenylene alkylene (for example, biphenylene fluorene, 2 , 2-biphenylene propenyl) and other propynyl groups having a carbon number of 6 or more (usually 15 or less). As for R2 in formula (2), for example: 丨, 1-vinyl, 1, 1-propenyl, 1,2-propenyl, ι, ΐ-butenyl'L2-butenyl, 1,3-butenyl, and the like having an alkyl group having an alkyl group having a carbon number of 1 or more (usually 12 or less) Ritual groups; benzyl groups, biphenylene alkylene groups (e.g., biphenylene methylene groups, 2, 2-biphenylene propenyl groups) and other propynes having a carbon number of 6 or more (usually 15 or less)

base. As far as R2 is concerned, when it is an alkylene-based hydrolyzed condensed starch, it has higher flexibility and biodegradability than when it is a propynyl-based hydrolyzed condensed starch. For functional groups represented by formula (2), there are, for example, formula (4): functional groups represented by a bucket ((C = 〇) _R2) factory (X = 〇, y = l, z = 0) 彳 5 ) (0_ (c = 0) _R2) m-〇—a functional group represented by (x = 〇; functional group X: 1 represented by the formula m (0-R1) m_: y = 〇- ZO); Formula (0-Ri-O- (C: 0) -R2) m-: Functional group represented by ㈤, y = 1, z = 0); Formula (8) b) Functional group represented by m—〇_ ( x = i, y = 〇, z = 1 and (9), (0_R1_0_ (c = 〇) functional group represented by W, y = 1, z = 1) °

x = 1 group As for the functional group represented by formula (4) (R2 is an alkylene group), an aromatic ester group (M, for example, an aliphatic ester is a propynyl group); a monoacetic group

1244487 V. Description of the invention (8)-), diester group (m = 2), triester group (m = 3), polyester group (m is an integer of 2 to 3 100, especially an integer of 4 to 3 100 ). ^ For functional groups represented by formula (5), there are, for example, an aliphatic ester 7 group (R2 is an alkylene group), an aromatic ester ether group (R2 is a propynyl group); = l), diester ether group (m = 2), triester ether group (111 = 3), polyester group (m is an integer of 2 to 3 100), especially an integer of 4 to 3 100 ).

As for the functional group represented by formula (6), there are, for example, a monoalkyl ether group ^ is an alkylene group ~ ^: ^ ~ a dialkyl ether group ⑼ is an alkylene group, ^^): a dialkyl group Group (R1 is an alkylene group, m = 3), polyalkylether group (Ri is an alkylene group, m is an integer from 2 to 3100, especially an integer from 4 to 3100); monoaryl scale group (R1 is propenyl, m = 1), diaryl ether (R1 is propenyl, m = 2), triaryl ether (R1 is propenyl, m = 3), polyaryl ether (R1 is Acryl and m are integers of 2 to 3100, especially 4 to 3100). As for the functional group represented by formula (7), t has, for example, a monoalkylene ester group (R1, alkylene group, m = 1), a dialkylene ester group (R1 is an alkylene group, = 2 ^, trialkylene acetate (R1 is alkylene group, m = 3), polyalkylene group Purpose: Yes. Alkylene group, m is an integer of 2 ~ 3100, especially 4 ~ 31〇〇 A monopropenyl fluorenyl group (R1 is propenyl, m = 1), dipropenyl ester earth is acrylic, mi), tripropenyl ester (R1 is propenyl, π3), polypropylene Group (R1 is a propenyl group, mg2 to 3i0 (^ 0 integer, especially an integer of 4 to 3 100). For the functional group represented by the formula (8), there is, for example, a monoalkyldifluorene (R1 is an alkylene group, m = 1), a dialkyldiether group (R1 is an alkylene group,

1244487 V. Description of the invention (9) ----- m) —Carbonyl group (1 ^ is fluorenyl, π = 3), polyhexyl diether i) (R1 t alkylene, fluorene is An integer from 2 to 3100, especially an integer from 4 to 3100. Its acryl two-base (R1 is acryl, hydrazone), dipropenyl ^ is a propenyl, m = 2), tripropenyl diether (Ri is a propenyl group, and a di-tyl group (R1 is a propenyl group, _ ~ 31〇. The number of work is especially an integer of 4 ~ 3 100). The functional group represented by the formula (9) is, Acetyl group ⑶ is an alkylene group, m = 1) group and it has ": a single alkylene group, m = 2),: 栲 栲 |) a monoalkylene group § ether group (R1 is alkylidene ^ ) Monoalkylene ester ether group (R1 is an alkylene group ^ take the branch = ㈣ (" fired group, m is " "3) Do not burn an integer of 4 to 3100); monopropenyl Special 疋), dipropenyl fluorenyl (Rd group (R0 is propenyl, Π ether group (R1 is propenyl, m = 3), earth), tripropenyl fluorenyl, and muscle are 2 to 31. An integer of 〇, especially = dilute base bond group (R1 is propylene to ΑΜ) Φ Xi 5 is an integer of 4 to 3100 in particular. A 'For R, for example Hydrogen eyebrows, methyl ethyl, n-propyl, isopropyl and other lice atom, methyl, and group; phenyl and other alkoxy groups with 6 or more carbon atoms (generally above or below usually 3 or less) Alkoxy groups such as oxy and isopropoxy groups. The number of specific anions obtained by formula (3) is 1 or more (usually 3 or less such as: dimethyl keto group (R3 is hydrogen atom; m group) For example, methyl methoxymethyl ketone group (R3 is a heart group (R3 is a hydrolyzed and condensed powder of the present invention, one or two or more formulas (1, ", It is composed of the functional group represented by the main bond of YT. By introducing) 弋 (2) or formula (3), there are two or more types of formula (1) and formula (2).

2066-5094-PF (N) .ptd 1244487 Description of the invention The force formed by the functional group represented by (10) or formula (3) ο hydrolyzes the condensed starch and Lv 'can be exemplified by: having the formula (1) The functional group and the functional group represented by the formula (2) and the formula C 3) are hydrolyzed and condensed powders having the formula JL-V, 〇 \…. W w M. Ah ^ 4 or the formula (2) Hydrolyzed condensed starch having a functional group and a functional group represented by formula (3); hydrolyzed condensed starch having two or more functional groups represented by formula (2); having two or more functionalities represented by formula (3) The hydrolyzed and condensed starch of the base has the functional group represented by the formula (1), the formula (2) = the functional group represented by the formula and the hydrolyzed group of the base represented by the formula (3). (1) U45 ~ 1,755cnrl: It can be confirmed that the carbon that is not considered to belong to starch can be confirmed by the photometric measurement under the photometer. . When formula (7) and formula (9) are partially introduced into formula (4), formula (5), (for example, o-cresol, functional group represented by w (y = 1), formula (4) should be formed by using a solvent. ). In the hydrolyzed condensed starch that has been served, the concentration of unreversed functional compound ('(5), formula (7) and formula (9) is measured, and after extraction, the Determination of peaks specific to Nei's methyl group

2066-5094-PF (N) .ptd page 14], after extraction from DO ~ 1,740Cnri (polylactic acid), it can be pre-measured by CO stretching vibration due to CO stretching vibration. In particular (for example, it is confirmed by using poly-hydroxyl. In addition, when R3 is a functional compound when R 3 is vinyl), propionate is used to form an unreacted poly α ′ as represented by the above formula (5). From the obtained water content: 1244487 V. Description of the invention (11). When a functional group (X = 1) represented by formula (6), formula (7), formula (8), or formula (9) is introduced into a part of the main chain of starch, a solvent (for example, boiling water) is used from In the obtained hydrolyzed condensed starch, an unreacted compound (for example, n-propanol) forming a functional group represented by formula (6), formula (7), formula (8), and formula (9) may be extracted, and then In NMR measurement, for example, when R1 is a 1,3-propenyl group, a peak specific to the methylenyl group of propanol which is not a starch is measured, and it is confirmed. When a functional group represented by the formula (3) is introduced into a part of the main chain of starch, the formula (3 can be determined by an absorption band of 1,715 to 1,725 cm-1 when measured by an infrared spectrophotometer. The C 0 stretching vibration specific to the functional group represented by) was confirmed. The above-mentioned absorption bands are considered to be compounds that do not belong to starch and form functional groups represented by formula (3) (eg, glycerin). From the viewpoint of the thermoplasticity of the hydrolyzed and condensed powder, the functional groups represented by formula (1), formula (2) or formula (3) are totaled at 100 moles relative to the glucose unit of starch. The amount of the chemical formula is preferably introduced in a ratio of 50 to 100, especially 70 to 100. If the amount of the functional group represented by formula (1), formula (2), and formula (3) is too small, the thermoplasticity of the hydrolyzed condensed starch will decrease; if too much, formula (1), formula ( 2) and the functional group compound represented by the formula (3) may precipitate from the final product. The amount of the functional group represented by formula (1), formula (2) or formula (3) in the main chain of the hydrolyzed and condensed starch is introduced, even if only the available infrared

2066-5094-PF (N) .ptd Page 15 1244487 V. Description of the Invention (12) The amount observed by the line spectrophotometer, that is, several%, can also show its effect. The shoulder value can also be observed with a less sensitive photometer. As the amount of the functional group represented by formula (1), formula (2) or formula (3) introduced into the main chain increases, the thermoplasticity of the hydrolyzed and condensed starch will increase. If the amount of the functional group represented by formula (1), formula (2), and formula (3) is too small, the hydrolyzed condensed starch will become hard; if it is too large, it will tend to become soft.

The hydrolyzed and condensed starch of the present invention can be formed by combining the starch with the compound represented by the functional group represented by formula a (1) and the functional group represented by formula (2): a spoon compound, (formed by formula (4), formula (5), a formula (6), a formula (7 ^ gas (8) or a compound represented by the functional group represented by formula (9)) or a compound forming a functional group represented by / 3) is reacted to produce it. In the case of the main raw material, the conventionally used starch can be used. For example, from the barley, yin yan zi 丄 rye, wheat, wheat, rice and corn snails cattle s # 土 & In the present invention, the raw material starches are not particularly limited to Zhong Ke 4 λ. However, corn starch is preferred because of its economic advantages. Examples of different types vary by type

In terms of the substance of formula (1), w; the functional groups represented, that is, potassium carbonate, carbonic acid gas that forms a carbonic acid group, or carbon dioxide by heating sodium carbonate, hydrogen breaking acid: ^ Gas removal, carbonic acid, hydrogen carbonate, etc. will release carbon compounds. For compounds having a functional group represented by V »χ (4),

1244487 V. Description of the invention (13) For example, the compound represented by formula ⑴) ((: = 0) 4- (0_ (c = 〇) _R3) mi_〇I ^. In the functional group represented by formula (4) ' In the case of a compound that forms an aliphatic mono group (R3 is an alkylene group, m = 1), for example, hydroxy acetaldehyde, hydroxy ethyl aldehyde, hydroxybutyraldehyde, Glyceraldehyde and other hydroxyalkanals. Among the functional groups represented by formula ⑷, to form aromatic monoacetic acid & (R3 is a propenyl group, ra = 1), for example: methylol = via The ethyl group I, the propyl sulfonyl group, the alkynyl aryl group are in the functional group represented by 4) to form a diacetyl group (M), a dimethyl group (m = 3) For polyester-based compounds (m is an integer from 4 to 3100), etc.:,: T 5 its speciality: lactate, hydroxyacetaldehyde dilactate, hydroxy '": 酽 ::' 士 = 早Secret sacrifice fee has been dedicated to hydroxyalkanal and aliphatic carbonic acid. The combination of the functional groups represented by (5) is, for example, formula (12): H— r D— Γ Γ — fM D3, 铷 六 斗, a, C () —R) m — 0H Among the functional groups represented by jin 'for the formation of lipid ... group m compounds' can be exemplified by: --- via propionic acid-: / hydroxypropanoic acid, α-hydroxybutyric acid, cold-hydroxybutyric acid, dihydrazone Hydroxyalkyl carbonic acid and its polycondensates (such as: poly "monoacid i. In the functional group represented by formula (5) to form aromatic compounds, such as aromatic alkynyl) In other words, for example, thoryl fluorene, diethyl ethyl, phenyl carbamic acid, propyl propyl fluorinated carbonic acid, etc.

2066-5094-PF (N) .ptd Page 17 1244487 V. Description of the invention (14) Carboalkyl aryl carbonic acid. The compound forming the functional group represented by the formula (6) includes, for example, a compound represented by the formula (13): H- (0-R1) m-H. Among the functional groups represented by the formula (6), in order to form an alkyl ether group (R1 is an alkylene group, m = 1), for example, methanol, ethanol, propanol, butanol, pentyl Alcohols, alcohols, hexanol, heptanol, octanol, nonanol, etc. As the compound forming the functional group represented by the formula (7), for example, a compound represented by the formula (14): H- (R1-0- (00) -1? 3) 111-011. Among the functional groups represented by the formula (7), an alkylene ether group (R1 is an alkylene group, π = 1), a dialkylamino group (R1 is an ethylamino group, 111 = 2), Acetic ether group (R1 is an alkylene group, m = 3), polyalkylene ether (R1 is an alkylene group, m is an integer of 2 to 3 1 0 0, especially 4 to 3 1 0 0 Integer), for example: ethyl lactate, ethyl dilactate, ethyl trilactate, polylactic acid, propyl lactate, propyl dilactate, propyl trilactate, polypropyl lactate, butyl lactate , Butyl dilactate, butyl trilactate, polybutyl lactate, α-hydroxybutyrate, ethyl diα-hydroxybutyrate, ethyl triα-hydroxybutyrate, polyα-hydroxybutyrate , Propyl α-hydroxybutyrate, bis α-hydroxybutyrate, tri-α-hydroxybutyrate, poly α-hydroxybutyrate, butyl α-hydroxybutyrate, bis α-hydroxybutyrate Alkyl esters of hydroxy acids such as butyl ester, butyl tri α-hydroxybutyrate, and poly butyl α-hydroxybutyrate. Examples of the compound that forms a functional group represented by the formula (8) include a compound represented by the formula (15): H-R4- (C = 0) -0Η, and a compound represented by the formula (16): H- (0- R1) m-0H. -R4-CH2- is equivalent to R1. With the formula (8

2066-5094-PF (N) .ptd Page 18 1244487 V. The functional group represented by the description of the invention (15)), that is, the compound that forms an alkyl ether group, for example, propionic acid, butyric acid ( N-butyric acid, isobutyric acid), valeric acid, hexanoic acid, lauric acid, oleic acid, stearic acid, etc .; aliphatic ethylene carbonate; ethylene glycol, propylene glycol, butanediol, polyethylene glycol, Polypropylene glycol, polybutylene glycol, ethylene glycol • propylene glycol copolymer. For the compound forming the functional group represented by the formula (9), for example, a compound represented by the formula (17): H-RLO- (C = 0) -R5- (C = 0) -0-H. For R5, -R5-CH2-is equivalent to R3 in formula (2). For the compound forming the functional group represented by the formula (9), for example: monoethyl maleate, monopropyl maleate, monobutyl maleate, ethyl succinate, succinic acid Propyl ester, butyl succinate, ethyl fumarate, propyl fumarate, butyl fumarate, ethyl adipate, propyl adipate, butyl adipate, etc .; 5 carbonic acid Alkyl esters. For a compound forming a functional group represented by formula (3), for example, a compound represented by formula (18): X-0-CH2-CH (OH) -CHR3-〇-Y (X and Y are respectively (Represents a hydrogen atom or a fluorenyl group). For the compound forming the functional group represented by the formula (3), for example, dialkyl glycerol such as glycerol, 1-fluorenyl glycerol, etc., and Alkoxy glycerol, or esters of the above substances. Glycerol or its esters are partially introduced into the main chain of starch to form a dimethylketone group (R3 in the formula (3) is a hydrogen atom). 1-Alkyl glycerol and its esters are introduced into the main chain of starch to form an α-alkyl methyl ketone group (R3 in the formula (3) is a thiol group). 1-Alkyloxyglycerol and its S moieties are introduced into the main chain of starch to form α-alkoxyfluorenylfluorenyl ketone group (formula (3)

2066-5094-PF (N) .ptd Page 19 1244487 5. In the description of the invention (16), R3 is an alkoxy group). In terms of esters, for example, you can deduct the fatty organic acids such as ginseng, ginseng, ginseng, oleic acid, and glyceric acid. Esters, diglycerides, etc.) When using esters, organic acids (especially low-molecular-weight organic, deficient, and poor end-product properties) with organic acids such as Na, m, and Zagan are preferred. F. By using ingredients that are already present in natural foods as functional compounds represented by form (1), formula (2), or formula (3), excellent safety and environmental protection can be obtained. Water to decompose and condense the palace powder. "

By mixing the powder and the compound forming the functional group represented by the formula (1), the formula (2), or the formula (3), in the presence of water, the temperature is preferably from 0 to 3 to 5 and preferably from 135 to After reacting at 155 ° C, the functional group represented by formula (1), formula (2) or formula (3) can be introduced into a part of the main chain of starch. If the reaction temperature is too low, the reaction rate will decrease; if it is too high, the resulting hydrolyzed condensed starch will become discolored, resulting in a significant decrease in molecular weight and embrittlement. By using starch and a compound forming a functional group represented by formula (1), formula (2) or formula (3) in the presence of water and carbonic acid gas, the conditions under which the carbonic acid gas becomes a supercritical state or a subcritical state Under conditions (for example, a temperature of 100 ~ 350 ° C, preferably 135 ~ 155 ° C, a reaction maximum pressure of 7.48 ~ 29 · 4MPa, preferably 15. 7 ~ 23 · 5MPa) to make it react, The functional group represented by formula (1), formula (2) or formula (3) can be introduced into a part of the main chain of starch. The existing carbonic acid gas can also be used as a compound that forms a functional group represented by formula (1). Carbonic acid gas will change to a temperature of 3 1 · 1 ° c or more and a pressure of 7 · 4 8 MPa or more.

2066-5094-PF (N) .ptd Page 20 1244487 V. Description of the invention (17) Supercritical state, under the condition of temperature above 31 · 1 ° C, pressure below 7. 48MPa and temperature below 3 1 · 1 It will become subcritical under the conditions of ° C and Mo Li 7 · 48 MPa. Carbon dioxide gas in a supercritical state or a subcritical state can promote the hydrolytic decomposition reaction of the powder, and at the same time, it can contribute to the dehydration condensation reaction of the hydrolyzed starch and the compound forming the functional group represented by formula (1). It also helps to perform the cross-linking reaction as a cross-linking agent. The amount of carbonic acid gas used is based on water, and may be, for example, 0 < P 1 to 3% by weight. The carbonic acid gas acts as a 'catalyst' during the starch decomposition reaction, so it can exert its effect even in a small amount. The reaction table south pressure 'may be, for example, .76 to 300 kg / c in2 (= 7 5 to 29 4 MPa), and preferably 160 to 240 kg / cm2 (= 15.7 to 23.5 MPa). If the pressure is too low, the reaction rate decreases. If the pressure is too high, the obtained = hydrolyzed and condensed powder will discolor, resulting in a significant reduction in molecular weight and embrittlement. The reaction time may be, for example, 1 to 10 minutes, and preferably 3 to 5 minutes. If the time is too long, the resulting hydrolyzed condensed starch will be colored, resulting in a significant decrease in molecular weight and embrittlement. If the time is over two, the reaction rate will be reduced, and no water-containing human starch with sufficient properties will be obtained. '' σ The amount of water used is, relative to, for example, 100 weight of starch, the total amount of water (usually ^ ~ 丨 wide) contained in starch is 30 to 80 parts by weight, and 50 to 7 〇Parts by weight are preferred. If the amount is too small, the reaction rate of starch will decrease. If the amount of water used is too large, the dehydration condensation reaction rate will be reduced, the molecular weight recovery will be reduced, and the molecular weight of the resulting hydrolyzed condensed starch will be reduced:

2066-5094-PF (N) .ptd Page 21 1244487 V. Description of the invention (18)

to. The energy of the official main chain), the type of water condensation (1), the molecules of the chain can give out heat through the guide, and the power is increased by the energy base (2). The formula gives it plasticity to recover 'so the decomposition of starch and starch is performed in an inverse manner, 2) or the decomposition is reduced (1), hydrophobicity. The dehydration step required to hydrolyze the condensed starch is less economical. Compounds forming the surface represented by formula (1), formula (2) or formula (3) are reacted under the above-mentioned conditions, so that starch should be, starch which has been hydrolyzed, and compounds forming functional groups represented by formula (1: 3) Debonding can introduce a functional group represented by formula (3) into a part of the main chain of the palace powder. At the same time as the main role of starch, the branches of the rice flour will be cut off, and the starch will be nearly linear, and the functional group represented by formula (2) or formula (3) and the flexibility will be changed. Makes water decomposed and condensed

Eighty percent of the compound ^ of the functional group represented by formula (1), formula (2) or formula (3) is formed by dehydration reaction with the hydroxyl group of the glucose unit, especially the oxygen group of the methylol group. Side chains to increase the thermoplasticity of the hydrolyzed and condensed powder. ^ The reaction rate between the powder and the compound forming the functional group represented by formula (1), formula (2) or formula (3) can be determined by the TGA · DSC analysis of the hydrolyzed condensed starch and the reduction rate and The water content is calculated by estimating the unreacted compound forming the functional group represented by formula (1), formula (2) or formula (3). earth

Dianfen can be decomposed by heating under the presence of water under high pressure and high shear force. In order to hydrolyze the starch for a short time under high pressure

2066-5094-PF (N) .ptd Page 22 1244487 Fifth, the description of the invention (19) is carried out, and then followed by the condensation reaction of (1), formula (2) or butane, so in the starch and formation formula, A counter-continuous reactor using a compound represented by a functional group represented by water) is preferred. In the form of a 54-port (vent) extruder with 2 openings or attached; in other words, using an extruder, such as a rod, #M u π ^ extruder with an opening is preferred. The ^ U.e) used is composed of screw # &% \. For example, an extruder with 3 openings is better equipped with a shrinkage: ΐ ::: training section and a kneading and compression section. "" "When the vacuum pump suction opening 100 ~~ is a reaction machine, it is better to use, for example, the front pressure of the nozzle. G 挤 -9'8 ~ 24 · 5Mpa) to squeeze six Fen 5 ::: ^ Knife decondensed starch can also be implemented by using a cross-linking agent. The hydroxyl of the condensed starch is decomposed by adding water to improve the water resistance. Even if the degree of stress is not exerted ... the response will decrease: Lian Zhizhang ^ Difficulties ^ swell drought can be determined by

Such as 2 5 C) immersed in water for 1 hour to calculate the weight of dried soybeans / JDL. It is followed by weight determination and absolute _ certain 3 :: agent use example: linoleic acid, multivalent disc acid, Γ: Γ = Γ is already available, for example: two salt of Sanyunna etc .; Polyvalent carbons of acids, phthalic acid, succinic acid, etc. 2066-5094-PF (N) .ptd Page 23

1244487 V. Description of the invention (20) Obituary, polyvalent acid salts of adipic acid, oxalic acid, maleic acid, phthalic acid, succinic acid f, etc .; hydroxy carbonic acid such as lactic acid; lactic acid Hydroxyl groups such as calcium, 6 ^ 'acid-breaking gas, sodium bicarbonate, bicarbonate, etc .; epoxy compounds such as monoglycidyl ether; acids such as succinic anhydride, maleic anhydride, etc. Isocyanates such as alkylidene diisocyanate and 2,4-diisocyanate; silylates such as ethylene trimethylsilane; hexahydro- 丨, 3, 5-tripropyl distillate-s-triazine . The cross-linking agent may be used singly or in combination of two or more kinds. By adding such as 1000 ~ 180 ° c). The powder of the cross-linking agent is used as a reference, and if it is small, the effect of water resistance will be suppressed in water, and if the amount is too large, it will be reduced, so that when the compound of the extruded group is used, and the compound of the group (OK During the reaction, it is possible to (= 15.7MPa) rapid dehydration. See the addition amount of water-decomposition and shrink-mixing, which is 0.01 ~ 3. The water-decomposition becomes smaller, which reduces the water-swellable water-decomposition shrinkage, and (for example, Carbon starch and the shape such as carbonic acid It consists of, for example,

Cross-linking agent is added to Hedian powder and heated (for example, the hydrolyzed condensed starch can be cross-linked to cross-link the hydrolyzed condensed starch before the cross-linking. Swellability, so that the hydrolyzed condensed starch will eventually dissolve and become infinitely large. The addition of a cross-linking agent will reduce the thermoplasticity and fluidity of the powder.

Let the palace powder and the official acid gas represented by the formula (丨) react in the presence of water. The functional gas represented by formula (2) or formula (3)) enter the order nozzle in the presence of water and carbonic acid gas. The front pressure is maintained at 16 kg / cm2, which can cause a part of the methylol groups of the glucose unit to bow when it is momentarily squeezed out into the atmosphere.

1244487, invention description (21) cross-linking of dish acid gas. By the partial carbonic acid crosslinking described above, a hydrolyzed and condensed starch having a sufficient crosslinking density and exhibiting thixotropy above the softening point can be obtained. The above-mentioned cross-linking reaction is due to the cross-linking reaction using the dehydration between the hydroxyl groups, so the more rapidly dehydration, that is, the more decompression from higher pressure and pressure, the cross-linking density of hydrolyzed condensed starch It will become more and more difficult, the water swelling will be lower, the water resistance will also be higher, and the hydrolyzed and condensed powder will become difficult to stick.

For example, 'The cross-linked water-decomposed condensed starch flakes obtained by cutting with a thermal cutter that is in contact with the die of the extruder will fall on the side while being blown with a little air. For example, the state on the bearing JHI set under 1 meter will not stick, so it can be transported directly by the pressure feed ejector. In addition, even if the above sheet is used, the film is blown and expanded from the two sides of a balloon-shaped film 1 meter behind the die by means of a blower and expansion device, it will not stick. The reason why the cross-linked hydrolyzed and condensed starch is not easy to be parented 'is considered to be reversible thixotropy due to cross-linking. The weight-average molecular weight of the hydrolyzed and condensed starch of the present invention may be, for example, from 30000 to 50000, and more preferably from 50000 to 20000. If the molecular weight of the hydrolyzed and condensed starch is too low, the mechanical properties will tend to decrease, while the too high hydrolyzed and condensed starch will have reduced fluidity and difficult to form. 0 The molecular weight of the hydrolyzed and condensed starch will be When the powder and the compound forming the functional group represented by the formula (1), the formula (2), or the formula (3) are reacted, the reaction temperature is increased, or the reaction pressure is increased.

1244487

The hydrolyzed condensation of the present invention is left under the condition of 60% humidity for 24 hours, and the moisture content is preferably 1 to 6% by weight. The hydrolytic condensation of the present invention has a swelling ratio of 150 to 400 after 1 hour. The hydrolyzed condensed starch tends to stick easily to water resistance, while the swelling ratio and flowability tend to decrease. The hydrolyzed condensation of the present invention, such as the dehydrated glucose unit, is, for example, 'crosslinked hydrolyzed condensation. The cross-linked hydrolyzed and condensed will not cut the cross-linking, so it will maintain its original shape because it becomes spherical, and it will easily flow and deform. Deformation is the reversible thixotropic starch. When the powder is used, the percentage of the powder will be too low. The above-mentioned expanded methyl methyl powder and the powder of the powder are superficial. Have to reach a substantial constant system at 25. In addition, the above-mentioned swelling rate of water decomposition can be interlinked to have the ability to show that if only the heating tension is reduced, only the swelling rate of minus ° C is required to be removed. The sheet is condensed by contact. It can be reversibly softened, so after adding a little weight, the relatively balanced medium immersion high will also have powder, and its added water is low. Better. The thixotropic point continues to maintain the weight without any load. The hydrolyzed condensation powder of the present invention is excellent in transparency because there is no particulate powder. The hydrolyzed and condensed starch of the present invention has an excellent value of 30 or less in terms of a haze value obtained by a spectrophotometer with a 1 mm-thick sheet made by thermal addition. For the haze value, Tt (total light transmittance (%)) & Td (diffused transmittance (%)) can be measured using, for example, HGM-2DP manufactured by Suga Tester (Co., Ltd.), Calculated by the haze value (%) = Td / Tt X 100

2066-5094-PF (N) .ptd Page 26 1244487 V. Description of Invention (23). Although the present invention is partially scattered by light, the polymer colorants (pigments, antistatics, etc.) used in the present invention are added due to local differences. Regarding the use of acids and their glycerin for food degradability, etc. High. At the same time, by increasing upwards, the inverse TGA · DSC of the compound of the formula is summed up. 70 weights will be turned into turbidity due to the difference in the decomposed and condensed properties of the synthesized starch, and the rehydration will shrink. Additives, above materials), light-resistant agents, resistance can make the characteristics of the additives alone, when there is a bad effect of adding water to the plasticizer, the expansion of the plasticizer with water will slowly disappear and the additives, dyes, The addition of the agent, the above-mentioned products, etc. will not be caused by the increase of the starch of the present invention. If the film is soaked in water, there will be a slight difference in refractive index. However, by drying, the refractive index will become transparent. To the synthetic starch, additives generally used may also be added, and additives such as bactericides, deodorants, preservatives, insect heat inhibitors, and anticaking agents can be used. It can also be used in combination of two or more kinds to make the timing of use, which can be considered according to the characteristics of the drug and the way of impact when discarded. Adding aliphatic organics to the decondensed starch can increase the thermoplasticity and increase the blending amount, which can make the thermoplasticity more functional (represented by formula (1), formula (2), or formula (3)). The reduction of the obtained hydrolyzed condensed starch was measured to estimate the reduction. For example, starch is blended with 30% by weight of glycerol, and the hydrolyzed condensed starch is decomposed at a constant rate until it reaches a minute (around 270 ° C) for constant rate reduction. The above-mentioned moisture reduction rate is approximately 15% by weight. When the water content reaches a constant equilibrium, the moisture content is 4 ~ 5% by weight.

2066-5094-PF (N) .ptd Page 27, 1244487 V. After the description of the invention (24), about 10% by weight of glycerol is still estimated to be%, propylene glycol, and about 20% by weight, Or it has been formed as a side chain and is introduced into one of the main chains of the palace to make t hair ::::: =======: the raw material of the pipe weaving nr ::: = product and injection Molded products. At noon, the extruded and molded products come into the ί :: Force 2 7 to dissolve the condensed powder, which can be melted and kneaded using, for example, the melting and drawing method. Monofilaments can be obtained by further dissolving the filaments. The above-mentioned monofilaments are twisted and added together: ΐ = blended, and then processed by false capture, can be paid to various fiber products. For 100% use, Laiyou capacity materials are based on the hydrolytic decomposition and shrinkage of melt viscosity of 〇2 0 ～ 4 0 0, the melt viscosity production of Dian Si ^ ... When a 2 mm diameter nozzle flows out for 10 minutes, and the decompression condensation i reaches 100 or more than 50 °, moisture is added, for example, the drawability when it is stepped down. When cooling, 2 π out: the wire is applied with a rectified air flow (air). Utilizing air-cooled cooling has a better drawability, and can also follow the draw ^ τ water to decompose the water contained in the condensed starch. ... stretching at the same time or after drawing. Tensile break of undrawn yarn

1244487

The crack strength is about mol%. From increasing the powder to glass, the unstretched 2g / d or more, the hair is bundled into fibers, and the short fibers obtained from the cutting step are hunted by blending, and the elongation at break is, for example, 'the fiber strength can be increased during hydrolytic decomposition and condensation. It is preferred that the filaments are stretched. Such as the tensile breaking strength of the fiber. After drawing the thread, fill it with oil and curl to). The resulting bales are cut. Short fibers may also be, for example, about 0.2 g / d, and in the case of tensile breaking 3, the unstretched yarn is subjected to unstretched yarn at a temperature above the shift point from the viewpoint of the strength of the unstretched fiber being stretched. After stretching, you can get an example or obtain 3 g / d under the condition of stretching to decompose the condensed starch to perform a bundle of water, and perform thermal stretching, and then serve short fibers (stap 1 e 'usually after cutting Immediately mix and use with other fibers. The spinning yarn using the hydrolyzed and decomposed condensed starch fiber of the present invention can also be twisted and drawn together with other silks. The hydrolyzed and decomposed human starch fiber of the present invention is as usual Monofilaments or spinning filaments can be the same, and woven fabrics can be made using ^. The short fibers of the hydrolyzed and condensed starch of the present invention are the same as ordinary short fibers, and can be needle-punched, suspended and dried, and fiber. A spinning method, a papermaking method, etc. are used to manufacture a nonwoven fabric.

Using the hydrolyzed and condensed starch of the present invention, it is possible to produce films and sheet shaped products. For example, the hydrolyzed condensed starch of the present invention can be extruded and formed by a τ die method to produce films and sheets. When the film or sheet is manufactured by the T-die method, the thickness of the obtained film or sheet can be controlled by adjusting the extrusion ΐ and the pulling speed. The films and flakes of the hydrolyzed and condensed starch of the present invention can also be produced by an inflation method. When manufacturing a film or sheet by air inflation method, in terms of viscosity, the operation is based on a μm value.

2066-5094-PF (N) .ptd Page 29 1244487 V. Description of the invention (26) Moisturizing in Bu 10, especially 1 ~ 5 Do you want to make the moisturizing in the present invention? Starch is preferred. The extrusion temperature of the water-decomposed condensed starch is fine = the melting point of the powder or film is 20 or less. (: Within the range of 3 ^, it is better to decompose the condensed starch with water by using the τ die method or air inflation v ^ mi80 ° c. The film or sheet of the condensed starch can be dehydrated with the present invention by dehydration or Stretched sheet. The temperature at which the stretched film is stretched by adding water to the present invention is preferably in the range of stopping from the film or sheet of glass c. "From 30 to 30 t above In the present invention, a vacuum-molded sheet such as a hydrolyzed and condensed starch can be used to manufacture a molded sheet. The sheet can be made by using a sheet of 0.2 mm to 2 mm. For example, the thickness of the door μ can be increased by infrared rays and moved. To Nasuke 俨, Λ, ..., the temple is heated to the glass transition point to ... two plastic molds and the sheet can be shaped like a mold ^, and then the mold is executed to attract the well-known peak% tensile fracture The non-stretched polylactic acid of elongated household fire-resistant resin is not practical, and it is: J [2 to 3% at very small temperature, fragile and partially stretched. However, = vacuum molding is performed. Molding, although the deformation is large, the edge portion of the eight puller will remain unstretched The part is almost unstretched, so the hydrolyzed part of the present invention is fragile and not practical. For this, the unstretched sheet whose length is at room temperature (for example, 5 / starch, is stretched and stretched) Partially used for practical purposes 5 C) is more than 20%, so it has the mechanical properties of Litian II without problems even if it is not below. Exemption Example 1: It has the functional group represented by formula (3 to explain the present invention in detail.) Hydrolytic condensation

V. Description of the invention (27) The powder contains 100 parts by weight of corn starch, 70 parts by weight of ion-exchanged water combined with 1 to 13% by weight of water contained in starch, and 50 parts by weight of glycerol. 1 part by weight and 10 parts by weight of butanediol were mixed and supplied to a uniaxial extruder with 45 mm three openings. Open through the opening and dewater it with a water-sealed pump and an oil diffusion pump. The screw of the extruder is designed by the process of supply, mixing, compression, dewatering from the opening, kneading, dewatering from the opening, kneading, dewatering from the opening, and compression. Can get good mixing results. '' The mixing effect of the screw is based on the mixing of 2 parts by weight of polyethylene containing carbon black in 100 parts by weight of colorless and transparent polypropylene. There are parts to be confirmed. Observation with an optical microscope confirmed that polyethylene was approximately uniformly dispersed in polypropylene with a size of about 30 microns. Under the maximum heating temperature of 15 (TC, pressure of 2 30kg / cm2 (= 22.5MPa), the powder is decomposed with water. Then, the dehydrated starch and glycerol are rapidly opened to dehydrate and polymerize. Total residence time It is 3 points, and the feed rate of the raw material is 50 kg / hour. The generated hydrolyzed condensed starch is filtered through a 100 mesh filter, and extruded through a nozzle with a diameter of 1 mm. Sheets. The resulting hydrolyzed · _ 合 殿 粉 片片 system showed a M 丨 value of 8 0. 0) is a good thermoplastic 10 years 〇 Using the obtained water with Fourier transform infrared decomposition decomposition condensation When the starch flakes were made into a thin film and FT-IR measurement was performed with a photometer, it was confirmed that

1244487

It is considered to be 1,724 · 9cm-1's sucking appearance "Death this bang. ^ ^ ^ ^ Old and closed ▼ There is a c unique to the B moon dagger base expressed by the formula (3) that is not belonging to the palace fan. ^^ MTD ,,-] ⑶ stretching vibration. Using the infrared spectrophotometer to measure 仃 FT-IR measurement of surname a L ^, @ ^, 疋 ,,, σ as shown in Figure 1 For the sake of comparison, we will add the moisture content to the newcomer y ^ knife solution ^ Aiki powder which uses infrared spectrophotometry. The degree is calculated in <# 1 R ^ 定 之 / 定 定 结果 'as the raw material used Corn starch was performed with a ί, leaf-transformed infrared spectrophotometer?-The measurement results of the R measurement are compared with those shown in Fig. 2, Fig. 1, and Fig. 2. The absorption of water-decomposed condensed starch i3294cnfl

The hydrogen-bonded O-fluorene, 292 9cm-1 absorption is C-H of CH2 group, and 1724.9cm absorption is monomethylfluorene-based ◦ = 〇, 1646cm-1 absorption system indicates the existence of crystal water. In Figure 2, the absorption of 3 2 9 5cnr1 of corn starch is hydrogen-bonded 0-Η, the absorption of 2929cm-1 is CH-based C-Η, and the absorption of 1 646cnr1 indicates the existence of crystal water. In corn starch, there is no absorption near 1 724. 9 cm-1 indicating the presence of dimethyl ketone group 00. In the F T-IR measurement, a Fourier transform infrared spectrophotometer manufactured by p r k i η-E 1 m r was used. Examples 2 and 3: The hydrolyzed condensed starch having a functional group represented by formula (3) is the same as Example 1 except that the residence time is changed to 3 minutes (Example 2) and 5 minutes (Example 3). When a sheet was formed, as in Example 1, it was confirmed that a hydrolyzed and condensed starch having a functional group represented by the formula (3) having thermoplasticity had been introduced. < Forming of sheet >

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V. Description of the invention (29) Using a τ die with a slit of 0.5mm to mask the extrusion to produce a film thickness of about 4. . : Tensile fracture strength and tensile elongation at break of the sheet at a temperature of 160t / m. As expected, it shows Ke practical strength. The constant $ moisture content after the temperature = kg; μ #? 4 hours eve μ h e t \ + Humidity after the humidity is placed at 0 ℃ is shown below.

< Forming of the film > 9 The unstretched sheet of Example 3 was made at 90 times, and a uniaxially stretched film with a film thickness of 100 μm was produced. The tensile breaking strength of the film was " N / _2, tensile break: =: shows practical strength. 4 The elongation is reduced at 25 / 〇f. 1 •• has the official sweet powder represented by formula (1) &g; the hydrodecomposition condensation lake of this base will produce carbonate U & Sr in addition to the use of -_A ^ f # pore body ^ acid gas to accept 10 parts by weight to replace the second knowledge and enter the reaction, the rest of the media $ 丨 1 Ｍ Ba ye w A Bai Xingbei Example 1 Same 0 water knife solution Integrate 丨 Dian Fen, payroll system Ning 0 Shi ”" Yunyou is using infrared spectrophotometry

Kou Dingjin measured the day guard, and found a new absorption of carbonic acid & unique CO stretching vibration in the absorption band of 1,745 ~ 1 7 W n ^ ^ ^ ’5cm

1 It is confirmed that the functional group represented by formula (1) (C = 0) -〇- has been introduced into a part of the main chain of starch 1244487 V. Description of Invention (30). The above-mentioned absorption bands do not belong to starch. The M I value of the obtained hydrolyzed and condensed powder was 2 3. Example 5: A hydrolyzed condensed starch having a functional group represented by formula (5), except that the reaction is carried out by replacing polyglycerol with polyα-hydroxypropionic acid converted to the same molar number as the molar units This is the same as that of the first embodiment. After extracting unreacted poly-α-hydroxypropionic acid from the obtained hydrolyzed condensed starch with o-cresol, it can be measured at 1,73 0 to 1,74 0 cm-1 by measuring with an infrared spectrophotometer. A new absorption of CO stretching vibration, which is unique to the ester group, was found in the absorption band, and it was confirmed that it has been introduced in a part of the main chain of starch (0- (C = 0) -CH (CH3)) m-0- Functional group. The above-mentioned absorption bands do not belong to starch. The unreacted poly? -Hydroxypropionic acid was extracted from the obtained hydrolyzed condensed starch and then subjected to NMR analysis to detect a peak indicating the presence of a methyl group of the poly? -Hydroxypropionic acid. Example 6: Hydrolytic Condensation Powder with Functional Groups Represented by Formula (6) Except for using n-propanol of the same mole number instead of glycerol for the reaction, the remaining steps are the same as in Example 1. After extracting unreacted n-propanol from the obtained hydrolyzed condensed starch with boiling water, NMR analysis can be used to detect the presence of fluorenyl groups that represent n-propanol that is not starch.

2066-5094-PF (N) .ptd Page 34 1244487 V. Description of the invention (31) The peak value, and it was confirmed that the functional group represented by 0-CH2-CH2-CH2_ has been introduced into a part of the main chain of starch. Example 7: In addition to the decomposition of condensed starch with the formula (5), in addition to using poly alpha which is half less than half the number of moles, add water to o-phenol analysis and confirm that the absorption confirmation that it is in use has been confirmed (CH3). Extracted and measured the non-functional infrared bands found in the lake, found in the palace powder) m " ° ~ are all unreacted with the starch extraction belongs to the main starch, and the spectrophotometry is represented by the main chain of the ester) and formula (6) The n-propanol of the functional group represented by the saliva number and the molar unit 4 were converted, and the reaction was performed in place of glycerol instead of glycerol, which is the same as in Example 1. After taking out the unreacted n-propanol from boiling water and then reusing the poly-α-hydroxypropionic acid, the peak indicating the presence of the methyl group of n-propanol can be separated by NMR, and a part of the bond can be introduced. 〇—CH2-CH2-CH2- The hydrolyzed and condensed starch obtained can be measured by a meter, and the new absorption of CO stretching vibration unique to 73,0 ~ 1,740cm-1, and medium One part was introduced into the s-energy group of (0— (c20) —CH. Examples 8 to 11: Cross-linking was performed in the hydrolyzed and condensed starch produced in Example 1 by changing the amount of trimerization and the amount of sodium to be added. Add and use a single-shaft kneading extruder to knead at 13 ° C, and then use a dry-type cutting machine to produce a sheet. The results of measuring the water swelling properties of the manufactured sheet are shown below. Flakes with small water swelling properties, even when granulated by a thermal cutter, are not 2066-5094-PF (N) .ptd page 35 1244487 5. Description of the invention (32) will stick. Also, The same thin sheet as in Example 1 was produced. Addition of Trimer Dish Acid Fishing Water Swellability Example 8 0.03% by weight Solutions, Example 9 ◦ embodiment infinite _% 160% 05 wt% 63 096 Example 10 1 wt% 20¾ & lt Embodiment Example 113 by weight; molded article of manufacture >

The hydrolyzed and condensed starch of Example 8 was used to produce a body-stretched sheet with a thickness of 1 mm, and it was heated to 90 ° (on the glass transition point g) by an infrared heater, and then moved to a vacuum molding mold at normal temperature. Then, the Liby vacuum pump sucks it from the bottom of the mold, so that the sheet is shaped into the shape as indicated, and then is trimmed with a mold with a blade to produce a mold driver:; 〇 :. Mould: ⑼, is the bottom and the tomb of the opening R is 5mm, m is 5cm on one side, and the bottom is 3cm on the other side. Use ㈣ "to determine whether there is poor shrinkage due to different depths. That ^ depth, the above thin U did not produce cracks or

This phenomenon is very good. The hydrolyzed condensation of the functional group represented by the formula f. Example 12: Formula (8) is the same as in Example 1 except that n-butanediol of the same mole number is used instead.

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V. Explanation of the Invention (33) Except for glycerol, the rest of the steps are the same as in Example 1. After extracting unreacted n-butanediol from the obtained hydrolyzed and condensed starch with boiling water, the peak of the presence of a methylenyl group representing n-butanediol which is not a starch can be detected by NMR analysis, and it can be confirmed that A functional group represented by 0-ch2-ch2-ch2-ch2-0- is introduced into a part of the main chain of starch. < Softening point, breaking temperature > Each of the hydrolyzed and condensed starches obtained in Example 12 was used DSC6200 manufactured by Seiko Electronics Co., Ltd. and SSC5 manufactured by Seiko Electronics Co., Ltd. As a result of analysis, the softening point was 4 2 to 8 0 ° C, and the breaking temperature was 2 7 8 to 2 9 9 ° C. < Biodegradability > 丨 _ The flakes obtained in Examples 1 to 12 were put into a commercially available household waste fertilizer treatment machine, and a portion of the samples were taken periodically every 8 hours to measure the samples. Decrement. The biodegradability of the flakes was evaluated by its reduction rate. The temperature of the waste fertilizing treatment was maintained at 40 to 50 t, and wheat flour was used as a nutrient component for the inoculum for the waste fertilizing treatment. No matter which sample was used, after 48 hours, no hydrolyzed and condensed starch could be sampled, so it showed good biodegradability.

: Manufacture of fibrous products. The hydrolyzed and condensed starch with an MI value of 32 produced in Example 12 was melted with an extruder, and measured by a gear pump, while using a mouthful of 幵 y2 and spraying temperature. Wire drawing and oiling (〇i 1 ing ') were performed at 180 ° C to produce a circular undrawn yarn. Observe the evaporation of water during the drawing,

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It does not affect t at the hot plate temperature it of the cutting wintering Λ. Next, the above-mentioned fibers were added at a draw ratio of 4 · 4 times, and the I-coat was made into a drawn yarn of the fiber 2OD / i6F of the present invention. The similar measurement in the atmosphere of the above-mentioned fibers did not show a melting point. %. The applied strength is 1. 8g / d, and the tensile elongation at break is 22. [Industry's profitability] The strength of the test moon and moon * is thermoplastic, so it decomposes the condensed starch, which is different from starch. It can be used as a substitute material of Γ thermoplastic resin. The material 1 of the molded product of the present invention; no; starch is different because it is used for manufacturing various materials, and i, because it has biodegradability like starch-like, it can be easily biodegraded in composite materials.

1244487 Brief description of the diagram The first diagram is a graph showing the measurement results obtained by using a Fourier transform (F o u r e r t r a n s f 0 r m a t i ο η) infrared hydrolysis spectrophotometer manufactured in Example 1 of the present invention. Fig. 2 is a graph showing measurement results obtained by using a Fourier transform infrared spectrophotometer for the hydrolyzed and condensed starch produced in Example 1 of the present invention and corn starch used as a raw material.

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Claims (1)

1244487 6. Scope of patent application 1. A hydrolyzed and condensed starch. A part of the main chain of starch is introduced with a group consisting of functional groups represented by the following formula (1), formula (2) and formula (3). Consisting of at least one kind of functional group: Formula (1) · -0- (c = o) -〇-; Formula (2):-((Ο-π) x- (0- (C = 0) -R2 ) y) m-Oz-; Formula (3): -CH2- (C = 0) -CHR3-〇-; (In Formula (2), R1 is alkylene or carbon number of 1 or more R 6 is a propynyl group of 6 or more; R 2 is a propenyl group having a carbon number of 1 or more or X 6 is 0 or 1; y is 0 or 1; x + y is 1 or 2; m is 1 An integer of ~ 3100; z is 0 or 1, and in formula (3), R3 is a hydrogen atom, an alkyl group having 1 or more carbon atoms, an aryl group having 6 or more carbon atoms or an alkoxy group having 1 or more carbon atoms). 2. The hydrolyzed and condensed starch according to item 1 of the scope of the patent application, wherein a functional group represented by formula (1) is introduced. 3. The hydrolyzed condensed starch according to item 1 of the scope of the patent application, wherein a functional group represented by the following formula (4) is introduced as a functional group represented by the formula (2): Formula (4): -(0- (C = 0) -R2) m- (when x in the formula (2) is 0, y is 1, and z is 0). 4. The hydrolyzed condensed starch according to item 1 of the scope of the patent application, wherein the functional group represented by the following formula (5) is introduced as the functional group represented by the formula (2): Formula (5): -(0- (C-20) -R2) m-0- (when X in formula (2) is 0, y is 1, and z is 1). 5. Hydrolyzed condensed starch as described in item 1 of the scope of patent application, 2066-5094-PF (N) .ptd Page 40 1244487 VI. The scope of the application for a patent The functional group represented by the following formula (6) is introduced as the functional group represented by the formula (2): Formula (6) ):-(0-F) m- (when X in Formula (2) is 1, y is 0, and z is 0). 6. The hydrolyzed condensed starch according to item 1 of the scope of the patent application, wherein a functional group represented by the following formula (7) is introduced as a functional group represented by the formula (2): Formula (7): -(O-R1 -.- (C: 0) -R2) m-; (when x in the formula (2) is 1, y is 1, and z is 0). 7. The hydrolyzed condensed starch according to item 1 of the scope of the patent application, wherein a functional group represented by the following formula (8) is introduced as a functional group represented by the formula (2): Formula (8): -(0-R ”m-0-; (when X in the formula (2) is l, y is 0, and z is 1.) 8. Hydrolyzed condensed starch as described in item 1 of the scope of patent application, Among them, the functional group represented by the following formula (9) is introduced as a functional group represented by the formula (2): Formula (9):-(0-^-0- (C = 0) -R2) m (When x in the formula (2) is 1, y is 1, and z is 1.) 9. The hydrolyzed and condensed starch according to item 1 of the patent application scope, wherein the formula is introduced by formula (3) The functional group represented by the formula 10. The hydrolyzed condensed starch as described in claims 1, 2, 3, 4, 5, 6, 7, 8 or 9 wherein the hydrolyzed condensed starch is submitted Link status. 2066-5094-PF (N) .ptd Page 41 1244487 6. Scope of patent application * 11. Hydrolysis as described in item 1, 2, 3, 4, 5, 6, 7, 8 or 9 of the scope of patent application Condensed starch, wherein the hydrolyzed condensed starch is left at a temperature of 20 ° C and a relative humidity of 60% for 24 hours, so that the moisture content that has substantially reached a constant weight equilibrium is 1 to 6% by weight. 12. The hydrolyzed and condensed starch according to item 1, 2, 3, 4, 5, 6, 7, 8 or 9 in which the hydrolyzed and condensed powder is soaked in water at a temperature of 25 ° C for 1 hour. The subsequent expansion ratio is 150 ~ 40 0%. 1 3. The hydrolyzed and condensed condensed powder according to item 1, 2, 3, 4, 5, 6, 7, 8 or 9 of the scope of the patent application, wherein the hydrolyzed and condensed condensed powder exhibits thixotropy (thi X 〇tr 〇py). jp 1 4. A method for producing hydrolyzed condensed starch, including the following steps: a group of starch and compounds selected to form functional groups represented by the following formula (1), formula (2), and formula (3) At least one compound in the presence of water and reacted at 100 ~ 350 ° C: Formula (1) · ~ 0- (C-0); Formula (2):-((0-R1) X -(0- (C: 0) -R2) y) m-Oz-; Formula (3): -CH2- (C = 0) -CHR3-0-; (In formula (2), R1 is carbon number 1 Above alkylene or propynyl having 6 or more carbons; R2 is alkylene having 1 or more carbons or propidyl having 6 or more carbons; X is 0 or 1; y is 0 or 1; x + y is 1 or 2; m is an integer from 1 to 3100; z is 0 or 1, in formula (3), R3 is a hydrogen atom, an alkyl group having 1 or more carbon atoms, an aryl group or carbon having 6 or more carbon atoms Number of 1 or more alkoxy). 1 5. —A method for producing hydrolyzed condensed starch, including the following steps 2066-5094-PF (N) .ptd Page 42 1244487 Use Dianfen and A from the following: / 4⑴⑻ 千 官: At least one compound in the group consisting of compounds of the following formula (1), formula (2) and " & / flb group, in water and carbon dioxide In the presence of the name π ^ 4 π 口 4 &% ^, the reaction of carbon dioxide gas is carried out under the condition that the carbon dioxide gas is in a supercritical state or a sub-L boundary state: (C-0) -0- 2) Formula (3) ((〇-R1) X- (0- (C-20) -R2 CH2- (00) -CHR3-0-; (In formula (2), 'R1 is an alkylene group having a carbon number of 1 or more or a propylene group having a number of 6 or more; R2 is an alkylene group with a carbon number of 1 or more or a propenyl group with a carbon number of 6 or more' X is 0 or 1; y is 0 or 1; X + y is 1 or 2; 冚 is an integer of 丨 ~ 'z is 0 or 1. In formula (3), R3 is a hydrogen atom and a carbon number of 1 or more; Group, aryl group having 6 or more carbon atoms or alkoxy group having 1 or more carbon atoms). 1 6 · The method for producing a hydrolyzed and condensed condensed powder as described in item 14 or 15 of the scope of the patent application, wherein starch and optionally are used to form the above formula (1), formula (2) and formula (3) When at least one compound of the group consisting of the compound of the functional group shown by) is reacted, it is extruded by using an extruder with a pressure in front of a nozzle of 100 to 250 kg / cm2 (kg / cm2). 1 A · A fiber product composed of hydrolyzed and condensed starch as described in item 1, 2, 3, 4, 5, 6, 7, 8, or g of the scope of patent application. 1 8 · A film or sheet shaped product, which is composed of the hydrolyzed and condensed starch as described in item i, 2, 3, 4, 5, 6, 7, 8 or 9 of the scope of patent application. 1244487 VI. Scope of patent application 1 9. A molded article composed of hydrolyzed and condensed starch as described in the scope of patent application No. 1, 2, 4, 5, 6, 7, 8 or 92066-5094- PF (N) .ptd Page 44