Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B29/00—Layered products comprising a layer of paper or cardboard
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B29/00—Layered products comprising a layer of paper or cardboard
  • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B31/00—Preparation of derivatives of starch
  • C08B31/02—Esters
  • C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
  • C09J103/04—Starch derivatives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

• the present invention relates to a modified starch, a process for producing the same, an adhesive composition containing the same, and a pile made using the adhesive composition.
• the carton can be roughly defined as "stiff and thick paper".
• the white board, liner paper, and corrugated paper included in the cardboard differ depending on the kind of paper, but use a considerable amount of paper waste paper.
• it is easy to produce at a high basis weight and efficiently utilize a low-grade raw material, thereby reducing production costs, and improving physical properties and imparting new functionality.
• Korean Patent Laid-Open Publication No. 10-1998-0039253 discloses an adhesive for producing multi-ply paper and a method for producing multi-ply paper using the same. Specifically, it was confirmed that when the slurry liquid adhesive prepared by adding silica sol and clay, which are inorganic substances, to the microgewed general starch used in the conventional method is used between the layers of the multi-ply paper, . However, there is a disadvantage in that there is a difficulty in working using a mixture of inorganic and starch, and a variation in strength is caused by mixing ratio.
• Japanese Patent Application Laid-Open No. 1996-120235 discloses a method in which a starch derivative is made into a low-molecular-weight starch derivative simultaneously with acetylation treatment and a dicarboxylic acid esterification treatment is used in a sheet layer such as a multi-ply. Specifically, by enhancing penetration of the starch into the low molecular weight and enhancing penetration into the paper, strength enhancement effect can be obtained. By treating the combination of acetylation with dicarboxylic acid esterification, the starch gel temperature is lowered to improve interlaminar bond strength and paper surface printability Can be improved.
• the manufacturing cost is increased, and there are disadvantages that various kinds of modified starches must be manufactured because the paper pore varies depending on the kind of the raw material of the multi-ply paper.
• the present invention aims at providing a multi-ply sheet excellent in interlaminar bond strength, compressive strength and stiffness by using the above adhesive composition.
• the present invention provides a modified starch wherein the starch is modified by an esterification reaction with an organic acid.
• the modified starch may have a particle size of 10 to 25 mu m.
• the modified starch may have a starch starch initiation temperature of 60 to 75 ° C.
• modified starch may have a characteristic that the maximum maximum viscosity at 60 to 75 ° C is 500 to 3500 cps.
• the present invention also relates to
• step a) removing the solvent and drying after the reaction of step a) is completed.
• the present invention provides a modified starch having a low starch initiation temperature and a high viscosity by using an ester modification technique using an organic acid, and a process for producing the same.
• the present invention provides an adhesive composition having a low starch-starting temperature by incorporating the modified starch, providing excellent bonding strength, and minimizing environmental contamination.
• the present invention provides a multi-ply paper having an excellent interlaminar bond strength and an excellent compression strength and stiffness by widening the interlayer bonding area by using the above adhesive composition.
• the present invention relates to a modified starch wherein the starch is modified by an esterification reaction with an organic acid.
• the modified starch of the present invention has been developed to solve such a problem.
• the modified starch of the present invention has a low starch initiation temperature and a high viscosity.
• the starch used in the modified starch according to the present invention may be selected from the group consisting of corn starch, corn starch, tapioca starch, potato starch, and sweet potato starch. One or more species can be used.
• the organic acid may be at least one selected from the group consisting of maleic acid, succinic acid, fumaric acid, and acetic acid, and more preferably maleic acid.
• organic acids should be used because starch is hydrolyzed by acid and esterification reaction does not occur.
• the modified starch of the present invention may have a particle size of 10 to 25 mu m, more preferably 10 to 20 mu m. If the particle size is smaller than the above range, there is a possibility of dehydration and loss in the paper manufacturing process. If the particle size is larger than the above range, the nozzle may be clogged in the process.
• the starch modification temperature of the modified starch of the present invention may be 75 ⁇ ⁇ or less, 60 to 75 ⁇ ⁇ . More preferably 60 to 70 ° C. If the initiation temperature of the starch is higher than the above range, the interlayer bonding strength may be reduced due to the micro-starch starch due to the rapid production speed of the paper, or the starch may not be retained in the paper with the micro- A staring initiation temperature is required.
• the modified starch may have a maximum gelatinization viscosity at 60 to 75 DEG C of 500 to 3500 cps, preferably 1000 to 3500 cps, and more preferably 1500 to 3500 cps. If the maximum gelatinization viscosity exceeds the above range, there is a problem that the process efficiency is lowered due to a high viscosity in the process, so that the above range is suitable.
• the esterification may be performed by adding 0.5 to 4 parts by weight of organic acid based on 100 parts by weight of starch, more preferably 1 to 3 parts by weight.
• the gelatinization temperature is not lowered and the effect of the interlayer bonding strength is lowered.
• the gelatinization temperature is lowered. It is not preferable since the dewatering property is lowered when the starch is produced.
• the present invention also relates to
• step a) removing the solvent and drying after the reaction of step a) is completed.
• the slurry may contain 0.5 to 4 parts by weight of organic acid based on 100 parts by weight of the starch.
• an organic solvent and water or a mixture thereof may be used as the solvent, but it is particularly preferable to use water.
• the esterification reaction is preferably carried out at a pH of 6-8.
• the pH decrease rate is lowered under the acidic condition of pH lower than 6.0, and it is not efficient because the lowering rate of the gelatinization starting temperature is lower and the viscosity is lowered under the alkaline condition of pH 8.0 or more.
• the pH is maintained at 7.0 to 8.0.
• a low initiation temperature and a short dewatering time provide favorable results.
• the pH can be adjusted by adding at least one selected from sodium hydroxide and potassium hydroxide.
• step a) The reaction of step a) may be carried out for 2 to 9 hours, preferably for 3 to 5 hours.
• step a) may be carried out at a temperature of 30 to 50 ° C.
• the step (b) may further include a step of filtering and washing the reaction product.
• the adhesive composition may further comprise water, wherein the concentration of the modified starch is preferably 1 to 30% by weight.
• concentration of the modified starch is not limited to the above range.
• the above adhesive composition can be preferably used for multi-ply interlayer bonding.
• the interlaminar bond strength of the multi-ply paper by the adhesive composition may be 75 to 130 ft.lb / in 2 , more preferably 80 to 120 ft.lb / in 2 < / RTI > If the interlaminar bond strength is lower than the above range, there may be a problem that the interlayer bonding of the multilayered paper is weak and the layer separation occurs. If the interlaminar bond strength is out of the above range, the process economical efficiency may be lowered.
• the present invention provides a multi-ply fabric prepared using the adhesive composition of the present invention.
• the method for producing the multi-ply paper may be carried out by a technique known in the art, except that the adhesive composition of the present invention is used.
• water is added to the modified starch of the present invention to prepare an adhesive composition in a slurry state, and the adhesive composition is sprayed so that the adhesive composition is 0.1 to 5 g / m 2 between the multi- For 1 to 3 kg / cm < 2 >, followed by drying at a temperature of 100 to 130 < [deg.] ≫ C.
• the positive starch having a positive substitution degree of 0.06 may be added in an amount of 1 to 3 parts by weight based on 100 parts by weight of the pulp.
• Example 1-3 succinic acid (Example 4-6), fumaric acid (Example 7-9), or acetic acid (Example 10) were added thereto while stirring the starch slurry containing the common starch and water at 40 ° C, -12) were added to 1 part by weight, 2 parts by weight and 3 parts by weight, respectively, of 100 parts by weight of starch.
• succinic acid Example 4-6
• fumaric acid Example 7-9
• acetic acid Example 10
• reaction product was filtered, washed and dehydrated, and dried with a hot air drier to produce modified starch.
• the gelatinized starch was adjusted to about 10% moisture, and its gelatinization temperature and viscosity were confirmed by Brabender viscosity graph. The results are shown in Table 1 below. In Comparative Example 1, the gelatinization temperature, viscosity and dehydration time of the common starch were measured.
• Example 1 Maleic acid One 68.4 1709 177 1280
• Example 2 2 65.0 1678 202 2360
• Example 3 3 62.1 1624 251 3040
• Example 4 are mountain One 68.4 990 215 1540
• Example 5 2 65.2 1092 181 3480
• Example 6 3 63.1 964 208 4580
• Example 7 Fumaric acid One 74.2 735 185 3860
• Example 8 2 73.4 733 206 4440
• Example 10 Acetic acid One 72.9 759 278 2960
• Example 11 2 72.0 781 284 5280
• Example 12 3 71.6 835 335 7240 Comparative Example 1 - - 75.1 1114 200
• the average particle size of the modified starches of Examples 1, 2 and 3 and the starch of Comparative Example 1 was measured using MASTERSIZER 2000 (MALVERN. Ltd, UK). The results are shown in Table 2 below.
• Modified starch was prepared in the same manner as in Example 2 except that the pH was changed to 5.0, 6.0, 8.0, and 10.0 in the esterification reaction.
• Modified starches were prepared in the same manner as in Examples 1 to 3 except that the amount of organic acid added was changed to 0.5, 1.5, 2.5, and 4.0 parts by weight based on 100 parts by weight of starch.
• Example 17 Maleic acid 0.5 70.6 1371 170 1130
• Example 1 1.0 68.4 1709 177 1280
• Example 18 1.5 66.6 1687 182 1930
• Example 2 2.0 65.0 1678 202 2360
• Example 19 2.5 63.7 1703 238
• Example 3 3.0 62.1 1624 251
• Example 20 4.0 60.3 1717 341 3150
• Producing the number 2 and propelled by the spray device between the embodiment of each modified starch of 1 to 1 to 6 were spray such that 3g / m 2 was laminated to a pressure of 2.0kg / cm 2 for one minute 120 °C Dried through a drum dryer, and dried to produce a multi-ply paper.
• Example 21 Used starch Organic acid Input amount (parts by weight) Interlaminar bond strength (ft.lb/in 2 ) Compressive strength (kN / m) Stiffness (kN)
• Example 21 Used starch Organic acid Input amount (parts by weight) Interlaminar bond strength (ft.lb/in 2 ) Compressive strength (kN / m) Stiffness (kN)
• Example 21 Example 1 Maleic anhydride One 84 1.40 89
• Example 22 Example 2 2 99 1.46 92
• Example 23 Example 3 3 110 1.52 104 Comparative Example 2 Comparative Example 1 - - 70 1.36 84

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Biochemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
• Paper (AREA)
• Laminated Bodies (AREA)
• Adhesives Or Adhesive Processes (AREA)

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• 2017
  • 2017-11-17 KR KR1020170154131A patent/KR102016464B1/ko active IP Right Grant
• 2018
  • 2018-10-18 JP JP2020545024A patent/JP7055960B2/ja active Active
  • 2018-10-18 WO PCT/KR2018/012341 patent/WO2019098543A1/ko active Application Filing

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