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WO2018190662A2 - Composition de liant, article et procédé de fabrication d'article - Google Patents

Composition de liant, article et procédé de fabrication d'article Download PDF

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Publication number
WO2018190662A2
WO2018190662A2 PCT/KR2018/004308 KR2018004308W WO2018190662A2 WO 2018190662 A2 WO2018190662 A2 WO 2018190662A2 KR 2018004308 W KR2018004308 W KR 2018004308W WO 2018190662 A2 WO2018190662 A2 WO 2018190662A2
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WO
WIPO (PCT)
Prior art keywords
binder composition
polylysine
weight
parts
peak
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2018/004308
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English (en)
Korean (ko)
Other versions
WO2018190662A3 (fr
Inventor
김지은
이창석
문준옥
양영렬
오창엽
노항덕
심도용
조광명
최진우
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CJ CheilJedang Corp
Original Assignee
CJ CheilJedang Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180007895A external-priority patent/KR101922644B1/ko
Priority to CA3059688A priority Critical patent/CA3059688C/fr
Priority to EP25206095.9A priority patent/EP4650383A2/fr
Priority to AU2018251522A priority patent/AU2018251522B2/en
Priority to EP18783720.8A priority patent/EP3611225A4/fr
Priority to NZ759003A priority patent/NZ759003B2/en
Priority to UAA201910613A priority patent/UA123976C2/uk
Priority to JP2019555677A priority patent/JP6928759B2/ja
Application filed by CJ CheilJedang Corp filed Critical CJ CheilJedang Corp
Priority to RU2019134450A priority patent/RU2721572C1/ru
Priority to BR112019021452-6A priority patent/BR112019021452B1/pt
Priority to CN201880024991.3A priority patent/CN110520477B/zh
Priority to MYPI2019006031A priority patent/MY191048A/en
Priority to US16/604,988 priority patent/US10961390B2/en
Publication of WO2018190662A2 publication Critical patent/WO2018190662A2/fr
Publication of WO2018190662A3 publication Critical patent/WO2018190662A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/04—Polyamides derived from alpha-amino carboxylic acids

Definitions

  • a binder composition comprising polylysine, an article bound by thermosetting of the binder composition, and a method for producing the article.
  • Articles such as nonwoven fiber insulation and plywood include binders such as urea-formaldehyde resin (UF resin) and phenol-formaldehyde resin (PF resin), as well as fibers and wood powder.
  • binders such as urea-formaldehyde resin (UF resin) and phenol-formaldehyde resin (PF resin), as well as fibers and wood powder.
  • the mixture mixed with the substrates can be produced by molding and thermosetting.
  • Conventional binders are obtained from fossil fuels and release harmful volatile organic compounds (VOCs), such as formaldehyde, even during the manufacture of binders and articles. Therefore, research is being conducted on binders that provide excellent physical properties without using fossil fuels and releasing hazardous substances.
  • VOCs volatile organic compounds
  • the present invention provides a binder composition derived from nature that exhibits excellent physical properties without releasing harmful volatile organic compounds such as formaldehyde.
  • One aspect of the present application is a polylysine; And one or more reducing sugars or derivatives thereof, wherein the polylysine comprises a first peak at 3.2 ppm to 3.4 ppm and a second peak at 3.8 ppm to 4.0 ppm in a 1 H NMR spectrum It is providing the binder composition whose ratio (A: B) of (A) and 2nd peak area (B) is 70: 30-98: 2.
  • Example 1 is a chemical formula and 1H NMR spectrum of polylysine in which an amino group linked to an alpha position used in Example 1 simultaneously contains a repeating unit used for polymerization and a lysine repeating unit linked to an epsilon position.
  • Figure 2 is a graph showing the pH change with time of the aqueous solution containing the thermosetting of the binder composition prepared in Examples 1 to 4.
  • the binder composition according to one aspect of the present application is polylysine; And one or more reducing sugars or derivatives thereof, wherein the polylysine comprises, in the 1 H NMR spectrum, a first peak at 3.2 ppm to 3.4 ppm and a second peak at 3.8 ppm to 4.0 ppm;
  • the ratio (A: B) of A) and the second peak area B is 70:30 to 98: 2
  • the strength and water resistance of the water-insoluble polymer which is a thermosetting binder composition may be improved.
  • the binder composition and its thermosetting water-insoluble polymer can be environmentally friendly as they do not release harmful organic volatiles such as formamide.
  • the ratio (A: B) of the first peak area (A) and the second peak area (B) is 75: 25 to 98: 2, 80: 20 to 98: 2, 85: 15 To 98: 2, 90: 10 to 98: 2, or 95: 5 to 98: 2.
  • Polylysine includes one polylysine or a mixture of two or more polylysines.
  • the polylysine content is 15 to 60 parts by weight, 25 to 60 parts by weight, 35 to 60 parts by weight, 40 to 60 parts by weight, 15 to 50 parts by weight, 25 to 50 parts by weight, 35 to 50 parts by weight of the binder composition solids 50 parts by weight, or 40 to 50 parts by weight. If the polylysine content is too low, excessive amounts of unreacted reducing sugar may remain in the article manufactured using the binder composition, thereby lowering the physical properties of the article. If the polylysine content is too high, the curing of the binder composition may be incomplete, thereby deteriorating the physical properties of the article manufactured using the binder composition.
  • the polylysine may be at least one condensation polymer selected from the group consisting of L-lysine and DL-lysine.
  • the polylysine may be L-polylysine polymerized using only L-lysine as a monomer.
  • the polylysine may be DL-polylysine polymerized using only DL-lysine as a monomer.
  • Another exemplary polylysine may be a polylysine polymerized using L-lysine and DL-lysine as monomers.
  • polylysine polymerized by including DL-lysine as a monomer may be more suitable than polylysine polymerized using only L-lysine as a monomer.
  • the molecular weight of the polylysine may be at least 4,000 g / mol, at least 5,000 g / mol, at least 6,000 g / mol, at least 7,000 g / mol, at least 8,000 g / mol, at least 9,000 g / mol, or at least 10,000 g / mol.
  • the molecular weight of polylysine can be measured using Gel Permeation Chromatography (GPC) as a value relative to the PEG / PEO standard sample.
  • Polylysine may be the result obtained by condensation polymerization of lysine at 130 to 150 ° C. temperature for 6 to 48 hours.
  • Alpha ( ⁇ ) in polylysine is a repeating unit in which an amino group connected to the alpha ( ⁇ ) position carbon of lysine is used for polymerization, and epsilon ( ⁇ ) in polylysine is an amino group linked to the epsilon ( ⁇ ) position carbon of lysine.
  • the repeat unit used is a repeating unit in which an amino group connected to the alpha ( ⁇ ) position carbon of lysine is used for polymerization, and epsilon ( ⁇ ) in polylysine is an amino group linked to the epsilon ( ⁇ ) position carbon of lysine.
  • the alpha ( ⁇ ): epsilon ( ⁇ ) composition ratio in polylysine is from 3.2 ppm to 1M NMR spectrum of polylysine derived from methine (-CH) of repeating units in which the amino group linked to the alpha ( ⁇ ) position is used for polymerization.
  • the first peak area (A) at 3.4 ppm and the amino group linked to the epsilon ( ⁇ ) position are from 3.8 ppm to 4.0 ppm derived from methine (-CH, a carbon in FIG. 1) of the repeating unit used for polymerization. It is determined by the ratio of the 2 peak area B.
  • the ratio (A: B) of the first and second peak areas A and B may be adjusted.
  • the amino group linked to the alpha ( ⁇ ) position of the lysine in the polylysine increases in the content of the repeating unit used for polymerization, i.e., the ⁇ -polylysine repeating unit, in the 1H NMR spectrum of the polylysine at 3.2 ppm to 3.4 ppm
  • the first peak area A of may increase.
  • the content of the repeating units used for polymerization in the amino group linked to the epsilon ( ⁇ ) position of the lysine in the polylysine i.e., the ⁇ -polylysine repeating unit
  • the ⁇ -polylysine repeating unit increases in the 1H NMR spectrum of the polylysine, from 3.8 ppm to 4.0
  • the second peak area B in ppm may increase.
  • the reducing sugar or derivative thereof may have one or more selected from aldehyde groups and ketone groups.
  • the aldehyde group and / or the ketone group may react with the amine group of the polylysine to form an imine bond upon thermosetting of the binder composition including the reducing sugar. And, this imine bond can be cured by reacting with the hydroxyl group of another reducing sugar, and the curing mechanism can be an irreversible reaction.
  • the content of the reducing sugar or derivative thereof is 40 to 85 parts by weight, 40 to 75 parts by weight, 40 to 65 parts by weight, 40 to 60 parts by weight, 50 to 85 parts by weight, 50 to 75 parts by weight based on 100 parts by weight of the binder composition solids. , 50 to 65 parts by weight, or 50 to 60 parts by weight. If the content of the reducing sugar is too high, unreacted reducing sugar may remain in the article manufactured using the binder composition, thereby lowering the physical properties of the article. When the content of the reducing sugar is too low, the curing of the binder composition may be incomplete, thereby lowering the physical properties of the article manufactured using the binder composition.
  • Reducing sugars may be used monosaccharides and disaccharides or combinations thereof, such as maltose, fructose, galactose, lactose, genthiobiose, lutinose, glucose, xylose, but not necessarily within the scope of the present invention It is not limited to these.
  • the reducing sugar may be glucose, xylose, or a combination thereof.
  • the reducing sugar may include glucose in terms of strength and water resistance.
  • the solid content in the binder composition may be 15 to 80 parts by weight, 15 to 75 parts by weight, 15 to 70 parts by weight, 15 to 65 parts by weight, 15 to 60 parts by weight, or 15 to 55 parts by weight based on 100 parts by weight of the binder composition. have.
  • Solids in the binder composition may be water, polylysine and reducing sugars and components other than solids are diluents. If the solid content is too high, the viscosity of the binder composition is increased to reduce workability, and the binder content may be excessively increased in an article manufactured using the binder composition. If the solids content is too low, excess energy may be consumed to remove the water.
  • the binder composition may further comprise one or more additives.
  • Additives include water repellents to increase the water resistance of thermosets, rust preventives to prevent corrosion of thermosets, anti-vibration oils to reduce dust incidence of thermosets, buffers to control pH of thermosets, and couples to improve adhesion of binder compositions. It may be a ring agent and the like, but is not limited thereto, and any additives that can be used for improving physical properties of the binder composition and the thermoset in the art are possible.
  • the content of the additive is 0.1 to 10 parts by weight, 0.1 to 8 parts by weight, 0.1 to 6 parts by weight, 0.1 to 5 parts by weight, 0.1 to 4 parts by weight, 0.1 to 3 parts by weight of 100 parts by weight of the total amount of polylysine and reducing sugar. It may be part by weight, 0.1 to 2 parts by weight, 0.1 to 1 part by weight, or 0.1 to 0.5 parts by weight, but is not necessarily limited to this range and may be adjusted according to the required physical properties.
  • thermoset of the binder composition described above An article according to another aspect of the present application is bound by the thermoset of the binder composition described above.
  • the thermoset of the binder composition described above strongly binds the article as a water-insoluble polymer, thereby improving the strength and water resistance of the article.
  • the article bound by the thermosetting of the binder composition has an absorption thickness expansion ratio of 40% or less, 38% or less, 36% or less, 34% or less, 33% or less, 30% or less, 25% as measured by a test method according to KSF3200. Up to 20%, up to 15%, or up to 12%. An article bound by the thermoset of the binder composition may have excellent water resistance.
  • the article bound by the thermosetting of the binder composition has an internal bond strength of at least 1.4 N / mm 2, at least 1.5 N / mm 2, at least 1.6 N / mm 2 , 1.7 N / measured by the test method according to KSF3200 mm 2 or more, 1.8 N / mm 2 or more, 1.9 N / mm 2 or more, or 2.0 N / mm 2 or more.
  • An article bound by the thermoset of the binder composition may have good internal bond strengths.
  • the article bound by the thermoset of the binder composition may be a heat insulating material, plywood, etc., but is not necessarily limited to these, any article that is bound in a certain form using the binder composition is possible.
  • An article manufacturing method comprises the steps of preparing the binder composition; And thermally curing the binder composition at a temperature of 120 ° C. or higher. Articles made by the above-described article manufacturing method have excellent water resistance and strength.
  • the binder composition may further include one or more selected from fibrous materials and powdery materials.
  • the fibrous material may be inorganic fiber such as rock wool, glass wool, ceramic fiber, etc., short fiber aggregates such as fibers obtained from natural and synthetic resins, and the like, but is not necessarily limited thereto, and any fibrous material may be used as the fibrous material in the art.
  • the powdery material may be wood powder or the like, but is not necessarily limited thereto, and any powdery material may be used as long as it can be used as a powdery material in the art.
  • the fibrous or powdery material is bound by the thermosetting of the binder composition by the thermal curing of the mixture further comprising at least one selected from the fibrous material and the powdery material in the binder composition at a temperature of 120 ° C. or higher.
  • Heat treatment temperature for thermal curing may be 120 ⁇ 300 °C, 130 ⁇ 250 °C, 140 ⁇ 200 °C, or 150 ⁇ 180 °C. If the heat treatment temperature is too low, uncuring occurs, and if the heat treatment temperature is too high, overcure may occur and dust may be generated.
  • the heat treatment time for thermal curing may be 1 to 60 minutes, 5 to 40 minutes, 10 to 30 minutes, or 12 to 18 minutes.
  • the binder composition is thermoset at a temperature of 120 ° C. or higher, a water-insoluble polymer is formed through various curing reactions, such as a Maillard reaction between an aldehyde group / ketone group of a reducing sugar and an amine group of a polylysine, and properties such as water resistance and strength. It can act as an excellent adhesive.
  • Pressing and molding may be performed simultaneously or sequentially during thermosetting to control the properties and shape of the article to be produced.
  • the pressure and time applied during the pressurization are not particularly limited and may be adjusted according to the required density of the article.
  • Polylysine used in the preparation of the binder composition has a number average molecular weight (Mn) of 6,000 g / mol, a weight average molecular weight (Mw) of 8,000 g / mol, and as shown in the 1 H NMR spectrum of FIG.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • FIG. 1 When 400 MHz NMR was measured using deuterium oxide (D 2 O) as a solvent, 3.2 derived from methine (-CH, FIG. At 3.8 ppm to 4.0 ppm derived from methine (-CH, a carbon in FIG. 1) of the repeating unit used in the polymerization, where the amino group linked to the first peak area (A) and the epsilon ( ⁇ ) position at ppm to 3.4 ppm is used.
  • the ratio of the second peak area (B) of 9 was 9: 1.
  • the first peak is denoted c and the second peak is denoted a.
  • the molecular weight of polylysine was measured in gel permeation chromography (GPC) using PEG / PEO standard samples.
  • the ratio of the area (A) of the first peak to the area (B) of the second peak in the 1 H NMR spectrum of the polylysine used to prepare the binder composition was 9: 1, and the number average molecular weight (Mn) 6,000 g / mol, The weight average molecular weight (Mw) is 8,000 g / mol level.
  • the ratio of the area (A) of the first peak to the area (B) of the second peak in the 1 H NMR spectrum of the polylysine used to prepare the binder composition was 9: 1, and the number average molecular weight (Mn) 6,000 g / mol, The weight average molecular weight (Mw) is 8,000 g / mol level.
  • the ratio of the area (A) of the first peak to the area (B) of the second peak in the 1 H NMR spectrum of the polylysine used to prepare the binder composition was 9: 1, and the number average molecular weight (Mn) 6,000 g / mol, The weight average molecular weight (Mw) is 8,000 g / mol level.
  • Polylysine used to prepare the binder composition was the same as Example 1, the ratio of the area (A) of the first peak and the area (B) of the second peak in the 1 H NMR spectrum was 9: 1, and the number average molecular weight ( Mn) 6,000 g / mol, weight average molecular weight (Mw) 8,000 g / mol level.
  • Polylysine used to prepare the binder composition was the same as Example 1, the ratio of the area (A) of the first peak and the area (B) of the second peak in the 1 H NMR spectrum was 9: 1, and the number average molecular weight ( Mn) 6,000 g / mol, weight average molecular weight (Mw) 8,000 g / mol level.
  • Polylysine used to prepare the binder composition was the same as Example 1, the ratio of the area (A) of the first peak and the area (B) of the second peak in the 1 H NMR spectrum was 9: 1, and the number average molecular weight ( Mn) 6,000 g / mol, weight average molecular weight (Mw) 8,000 g / mol level.
  • polylysine and 14.14 g glucose were dissolved in 28.28 g distilled water except that the polylysine was a mixture of L-polylysine and commercially available ⁇ -polylysine (manufactured by Zhengzhou Bainafo Bioengineering Co., Ltd.) of Example 1.
  • the ratio of the area (A) of the first peak to the area (B) of the second peak in the 1 H NMR spectrum of the polylysine was 7: 3, and the number average molecular weight (Mn) was 6,000 g / mol and the weight average molecular weight (Mw). ) 8,000 g / mol level.
  • Polylysine used to prepare the binder composition was the same as Example 1, the ratio of the area (A) of the first peak and the area (B) of the second peak in the 1 H NMR spectrum was 9: 1, and the number average molecular weight ( Mn) 6,000 g / mol, weight average molecular weight (Mw) 8,000 g / mol level.
  • Binder composition (50% solids content, polylysine: 50% solids content) in the same manner as in Example 1 except that 30 g L-polylysine and 150 g xylose were dissolved in 360 g distilled water and then stirred at 80 ° C. for 1 hour and 30 minutes.
  • Xylose 1: 5 weight ratio).
  • Polylysine used to prepare the binder composition was the same as Example 1, the ratio of the area (A) of the first peak and the area (B) of the second peak in the 1 H NMR spectrum was 9: 1, and the number average molecular weight ( Mn) 6,000 g / mol, weight average molecular weight (Mw) 8,000 g / mol level.
  • Polylysine used to prepare the binder composition was the same as Example 1, the ratio of the area (A) of the first peak and the area (B) of the second peak in the 1 H NMR spectrum was 9: 1, and the number average molecular weight ( Mn) 6,000 g / mol, weight average molecular weight (Mw) 8,000 g / mol level.
  • Polylysine used to prepare the binder composition was the same as Example 1, the ratio of the area (A) of the first peak and the area (B) of the second peak in the 1 H NMR spectrum was 9: 1, and the number average molecular weight ( Mn) 6,000 g / mol, weight average molecular weight (Mw) 8,000 g / mol level.
  • the polylysine is a mixture of L-polylysine and commercially available ⁇ -polylysine (manufactured by Zhengzhou Bainafo Bioengineering Co., Ltd.) of Example 1, and the area (A) of the first peak in the 1 H NMR spectrum of the polylysine The ratio of the area B of the second peak was 5: 5.
  • the polylysine is a mixture of L-polylysine and commercially available ⁇ -polylysine (manufactured by Zhengzhou Bainafo Bioengineering Co., Ltd.) of Example 1, and the area (A) of the first peak in the 1 H NMR spectrum of the polylysine The ratio of the area B of the second peak was 3: 7.
  • the ratio of the area A of the first peak to the area B of the second peak in the 1 H NMR spectrum of the polylysine used for preparing the binder composition was 0:10.
  • a commercial medium density fiberboard (manufactured by Hansol Home Deco, interior grade GI 18) was used.
  • a commercial medium density fiber board (manufactured by Hansol Home Deco Co., Ltd., super light grade GSL 18) was used.
  • the filter paper on which the water-insoluble polymer prepared in Examples 1 to 4 was formed was immersed in distilled water at room temperature for 10 minutes to measure color change and pH change, and the results are shown in Table 1 and FIG. 2, respectively.
  • Color change was measured by APHA value and yellow saturation (b *) through a spectrophotometer.
  • Example 1 Example 2
  • Example 3 Example 4
  • APHA 20 84 119 223 Yellow Saturation (b *) 0.64 2.68 3.78 7.09
  • the binder composition of Example 1 having the same content of polylysine and glucose as the water-insoluble polymer obtained using the binder composition of Examples 2 to 4 having a higher glucose content than that of polylysine was used.
  • the water-insoluble polymer obtained by the reaction showed little change in pH and color even after immersion for a certain time. Accordingly, it was confirmed that the water-insoluble polymer obtained using the binder composition of Example 1 is improved in water resistance compared to the water-insoluble polymer obtained using the binder compositions of Examples 2 to 4.
  • Specimens were each prepared using the binder compositions prepared in Examples 5-7.
  • a mixture was prepared by mixing 85 parts by weight of wood fibers (mixing material such as wood fiber, Pinus rigida, and Radius pine) and 15 parts by weight of the binder composition.
  • the prepared mixture was molded under a temperature of 160 ° C. and a pressure of 200 kg / cm 2 . Molding was repeated twice for 30 seconds and three minutes of depressurization. The gas generated during curing was removed and cured by sea pressure. The molded specimen was cured by standing at 160 ° C. for 1 hour.
  • the width and thickness of the specimens were measured in micrometers, and at room temperature using a universal testing machine (UTM). Compressive strength was measured by compressing at a rate of 50 mm per minute and the results are shown in Table 2 below. In addition, the appearance, density and solids content of the binder composition used to prepare the specimens are also shown in Table 2.
  • Example 6 Comparative Example 1 Specimen Properties Exterior Maroon Opaque Maroon Opaque Brown and transparent - Solid content (%) 50 50 50 - Density (kg / m 3 ) 667 741 667 - Flexural Strength (N / mm 2 ) 9.72 4.40 2.50 0.34
  • the specimen prepared using the binder composition of Example 5 having a similar content ratio of polylysine and glucose had a higher flexural strength than the specimen prepared using the binder compositions of Examples 6 to 7 having different content ratios of polylysine and glucose. It could be confirmed that further improvement.
  • Specimens were each prepared using the binder compositions prepared in Examples 5, 8 and Comparative Examples 2-4.
  • a mixture was prepared by mixing 85 parts by weight of wood fibers (mixing material such as wood fiber, Pinus rigida, and Radius pine) and 15 parts by weight of the binder composition.
  • the prepared mixture was molded under a temperature of 160 ° C. and a pressure of 200 kg / cm 2 . Molding was repeated twice for 30 seconds and three minutes of depressurization. The gas generated during curing was removed and cured by sea pressure. The molded specimen was cured by standing at 160 ° C. for 1 hour.
  • the width and thickness of the specimens were measured using a micrometer, and were tested by a universal testing machine (UTM). By compressing at room temperature at a rate of 50 mm per minute using flexural strength was measured and the results are shown in Table 3 below. In addition, the appearance, density and solids content of the binder composition used to prepare the specimens are also shown in Table 3.
  • Curing temperature was measured using a rheometer (Rheometer, Anton Paar Physica). Place specimens between parallel plates with 0.5 mm gap and equilibrate the plates with a constant shear rate of 1.0 s -1 while raising the temperature at a rate of 2 ° C / min in the temperature range of 30 to 160 ° C. One of them was rotated. Curing temperature was measured from the behavior of the specimen material and the results are shown in Table 3 below.
  • the width and thickness of the specimens were measured using a micrometer, and the specimens were immersed in a beaker filled with distilled water. After leaving time, the thickness change of the specimen was measured and the results are shown in Table 3 below.
  • the thickness expansion rate was calculated from the following equation.
  • Thickness Expansion Rate (%) [TT 0 ] / T 0 ⁇ 100
  • T is the thickness of the specimen after immersion for 24 hours
  • T 0 is the initial thickness of the specimen
  • Example 5 For the specimen prepared using the binder composition prepared in Example 5 and Comparative Examples 2 to 4, the weight of the specimen was measured, the sample was immersed in a beaker filled with distilled water, and the weight of the specimen was measured after 24 hours. The temperature of the distilled water was maintained at room temperature, and when measuring the moisture content, as soon as it was taken out of the beaker, only the moisture on the surface of the specimen was removed and the mass was measured. The water absorption rate was calculated from the following equation.
  • W is the thickness of the specimen after immersion for 24 hours and W 0 is the initial thickness of the specimen.
  • W is the weight of the specimen after immersion for 24 hours
  • W 0 is the initial weight of the specimen
  • Example 8 Comparative Example 2 Comparative Example 3 Comparative Example 4 Specimen Properties Exterior Maroon Opaque Reddish brown and transparent Reddish brown and transparent Brown and transparent Yellow and transparent Density (kg / m 3 ) 667 667 667 500 571 Flexural Strength (N / mm 2 ) 9.72 6.71 5.91 3.76 3.29 Curing temperature (°C) 116.37 117.94 118.35 119.56 129.44 Thickness Expansion Rate (%) 51.28 55.34 75.06 80.89 86.67
  • Example 5 As a result of measuring the water absorption of Example 5 and Comparative Examples 2 to 4, the water absorption of Example 5 was measured as 93.54%, while the water absorption of Comparative Examples 2 to 4, respectively, 276.36%, 281.23 %, And 285.36%. That is, as the alpha ( ⁇ ) binding in polylysine increases, the water absorption rate was confirmed to decrease.
  • Evaluation example 3 Measurement of physical properties according to reducing sugars
  • the binder composition prepared in Examples 9 to 11 was mixed with 64.7 kg / m 3 of wood fiber (wood fiber), and then the mixture was press cured for several seconds under a temperature condition of 220 ° C. (MDF). , Medium-Density Fiberboard) specimens were prepared. That is, 64.7 kg of the binder composition was mixed with respect to 1 m 3 of wood fibers.
  • Comparative Example 5 a medium density fiberboard specimen was prepared in the same manner as in Example 8 except that a commercially available UF resin was used.
  • Example 10 Example 11 Comparative Example 5 Specimen Properties Exterior maroon maroon maroon milk white Density (kg / m 3 ) 717 709 802 740 Thickness (mm) 3.03 2.98 2.87 2.74 Internal bonding strength (N / mm 2 ) 1.72 2.04 2.4 1.3 Thickness Expansion Rate (%) 38 32.8 30 40
  • the medium density fiberboard specimens prepared using the binder compositions of Examples 9 to 11 had improved internal bond strength and thickness compared to the medium density fiberboard specimens prepared using the commercially available resins of Comparative Example 5. The expansion rate decreased.
  • the internal bond strength was increased and the thickness expansion rate was decreased after the specimen preparation compared to the binder composition containing the xylose of Example 10, and thus the physical properties were relatively improved. .
  • Specimens were each prepared using the binder compositions prepared in Examples 11-12 and Comparative Example 5.
  • a mixture was prepared by mixing 85 parts by weight of wood fibers (mixing material such as wood fiber, Pinus rigida, and Radius pine) and 15 parts by weight of the binder composition.
  • the prepared mixture was molded under a temperature of 160 ° C. and a pressure of 200 kg / cm 2 . Molding was repeated twice for 30 seconds and three minutes of depressurization. The gas generated during curing was removed and cured by sea pressure. The molded specimen was cured by standing at 160 ° C. for 1 hour.
  • Comparative Example 5 a medium-density fiberboard specimen was prepared in the same manner as in Example 11 except that a commercially available UF resin was used.
  • the physical property measuring method is the same as the physical property measuring method of the said Table 3.
  • the internal bonding strength of the medium density fiberboard specimens prepared using the binder compositions of Examples 11 and 12 provided similar flexural strength to that of the medium density fiberboard specimens prepared using the commercial resin of Comparative Example 5 It was confirmed that the water resistance was improved as the thickness expansion rate and water absorption rate were decreased.
  • the medium density fiberboard specimens according to Examples 11 and 12 have improved flexural strength and a decrease in water absorption compared to the commercial medium density fiberboard specimens of Comparative Examples 6 and 7 to further improve physical properties.
  • Example 11 when comparing Example 11 and Example 12, it was confirmed that the DL-polylysine polymerized by including DL-lysine as a monomer has better water resistance than L-polylysine polymerized using only L-lysine as a monomer. It was.
  • the binder composition of the present invention may have improved strength and water resistance after thermosetting.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Materials For Medical Uses (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne une composition de liant comprenant de la polylysine, et au moins un sucre réducteur ou un dérivé de celui-ci, la polylysine ayant, dans le spectre RMN 1H, un premier pic à 3,2 ppm jusqu'à 3,4 ppm et un second pic à 3,8 ppm jusqu'à 4,0 ppm, le rapport (A:B) de la surface du premier pic (A) à la zone du second pic est de 70:30 à 98:2.
PCT/KR2018/004308 2017-04-13 2018-04-13 Composition de liant, article et procédé de fabrication d'article Ceased WO2018190662A2 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US16/604,988 US10961390B2 (en) 2017-04-13 2018-04-13 Binder composition, article, and method for manufacturing article
RU2019134450A RU2721572C1 (ru) 2017-04-13 2018-04-13 Связующая композиция, изделие и способ производства изделия
AU2018251522A AU2018251522B2 (en) 2017-04-13 2018-04-13 Binder composition, article, and method for manufacturing article
EP18783720.8A EP3611225A4 (fr) 2017-04-13 2018-04-13 Composition de liant, article et procédé de fabrication d'article
NZ759003A NZ759003B2 (en) 2017-04-13 2018-04-13 Binder composition, article, and method for manufacturing article
UAA201910613A UA123976C2 (uk) 2017-04-13 2018-04-13 Зв'язувальна композиція, виріб та спосіб одержання виробу
JP2019555677A JP6928759B2 (ja) 2017-04-13 2018-04-13 バインダ組成物、物品及び物品製造方法
CA3059688A CA3059688C (fr) 2017-04-13 2018-04-13 Composition de liant, article et procede de fabrication d'article
CN201880024991.3A CN110520477B (zh) 2017-04-13 2018-04-13 粘合剂组合物、制品和制造制品的方法
EP25206095.9A EP4650383A2 (fr) 2017-04-13 2018-04-13 Composition de liant, article et procédé de fabrication d'article
BR112019021452-6A BR112019021452B1 (pt) 2017-04-13 2018-04-13 Composição aglutinante, artigo, e método para fabricar um artigo
MYPI2019006031A MY191048A (en) 2017-04-13 2018-04-13 Binder composition, article, and method for manufacturing article

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KR10-2018-0007895 2018-01-22

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JP2020132790A (ja) * 2019-02-22 2020-08-31 株式会社事業革新パートナーズ 樹脂組成物及びその樹脂組成物を使用した成形方法
JP2021127408A (ja) * 2020-02-14 2021-09-02 国立研究開発法人産業技術総合研究所 ε−ポリリジンと還元性を示す糖類を成分とする材料
WO2022136611A1 (fr) * 2020-12-23 2022-06-30 Basf Se Composition de liant comprenant un ou plusieurs polymères d'acide aminé ainsi que des glucides pour articles composites
WO2023247437A1 (fr) * 2022-06-22 2023-12-28 Basf Se Liant pour panneaux à base de bois comprenant un polymère d'acide aminé et un composé de polyaldéhyde
WO2023247450A1 (fr) 2022-06-22 2023-12-28 Basf Se Mat de fibres minérales à base d'un liant comprenant un polymère d'acide aminé et un composé alpha-hydroxy carbonyle

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EP2669325B1 (fr) * 2012-05-29 2016-01-13 Rohm and Haas Company Liants thermodurcissables résistant à la flamme d'origine biologique présentant une meilleure résistance à l'état humide
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020132790A (ja) * 2019-02-22 2020-08-31 株式会社事業革新パートナーズ 樹脂組成物及びその樹脂組成物を使用した成形方法
JP2021127408A (ja) * 2020-02-14 2021-09-02 国立研究開発法人産業技術総合研究所 ε−ポリリジンと還元性を示す糖類を成分とする材料
WO2022136611A1 (fr) * 2020-12-23 2022-06-30 Basf Se Composition de liant comprenant un ou plusieurs polymères d'acide aminé ainsi que des glucides pour articles composites
WO2022136612A1 (fr) * 2020-12-23 2022-06-30 Basf Se Composition de liant comprenant des poly(aminoacide)s pour des articles composites à base de fibres
US11976168B2 (en) 2020-12-23 2024-05-07 Basf Se Binder composition comprising poly(amino acid)s for fiber composite articles
WO2023247437A1 (fr) * 2022-06-22 2023-12-28 Basf Se Liant pour panneaux à base de bois comprenant un polymère d'acide aminé et un composé de polyaldéhyde
WO2023247450A1 (fr) 2022-06-22 2023-12-28 Basf Se Mat de fibres minérales à base d'un liant comprenant un polymère d'acide aminé et un composé alpha-hydroxy carbonyle

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