WO2018190662A2

WO2018190662A2 - Binder composition, article, and method for manufacturing article

Info

Publication number: WO2018190662A2
Application number: PCT/KR2018/004308
Authority: WO
Inventors: 김지은; 이창석; 문준옥; 양영렬; 오창엽; 노항덕; 심도용; 조광명; 최진우
Original assignee: 씨제이제일제당(주)
Priority date: 2017-04-13
Filing date: 2018-04-13
Publication date: 2018-10-18
Also published as: WO2018190662A3

Abstract

Provided is a binder composition comprising polylysine, and at least one reducing sugar or a derivative thereof, wherein the polylysine has, in the 1H 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, wherein the ratio (A: B) of the area of the first peak (A) to the area of the second peak is 70:30 to 98:2.

Description

Binder Compositions, Articles, and Methods of Making Articles

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. 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.

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.

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 inventive concept of the present application described below may apply various transformations and have various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the inventive idea of the present application to specific embodiments, but should be understood to include all transformations, equivalents, or substitutes included in the technical scope of the inventive idea of the present application.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the inventive concepts. Singular expressions include plural expressions unless the context clearly indicates otherwise. Hereinafter, terms such as "comprise" or "have" are intended to indicate that there is a feature, number, step, action, component, part, component, material, or combination thereof described in the specification, one or the same. It is to be understood that the foregoing does not exclude in advance the possibility of the presence or addition of other features, numbers, steps, operations, components, parts, components, materials, or combinations thereof. "/" Used below may be interpreted as "and" or "or" depending on the situation.

Terms throughout the specification, such as first and second, may be used to describe various components, but the components should not be limited by the terms. The terms are used only to distinguish one component from another.

Hereinafter, a binder composition according to an exemplary embodiment will be described in more detail.

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; When 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. In addition, the binder composition and its thermosetting water-insoluble polymer can be environmentally friendly as they do not release harmful organic volatiles such as formamide. In the 1H NMR spectrum of polylysine, 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.

Specifically, the polylysine may be at least one condensation polymer selected from the group consisting of L-lysine and DL-lysine.

Specifically, the polylysine may be L-polylysine polymerized using only L-lysine as a monomer. In addition, 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.

In terms of water resistance, 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 (α) in polylysine is a repeating unit in which an amino group connected to the alpha (α) position carbon of lysine is used for polymerization, and epsilon (ε) in polylysine is an amino group linked to the epsilon (ε) position carbon of lysine. The repeat unit used.

The alpha (α): epsilon (ε) 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 (α) position is used for polymerization. The first peak area (A) at 3.4 ppm and the amino group linked to the epsilon (ε) 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.

On the other hand, in the 1H NMR spectrum of polylysine obtained by adjusting the condensation reaction conditions of polylysine, the ratio (A: B) of the first and second peak areas A and B may be adjusted.

If the amino group linked to the alpha (α) position of the lysine in the polylysine increases in the content of the repeating unit used for polymerization, i.e., the α-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. In addition, when the content of the repeating units used for polymerization in the amino group linked to the epsilon (ε) position of the lysine in the polylysine, i.e., the ε-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. When the reducing sugar includes at least one selected from an aldehyde group and a ketone group, 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.

For example, the reducing sugar may be glucose, xylose, or a combination thereof.

In addition, 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.

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. In addition, 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 according to another aspect of the present application 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.

In the article manufacturing method, 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 ℃, 130 ~ 250 ℃, 140 ~ 200 ℃, or 150 ~ 180 ℃. 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. If the heat treatment time is too short, uncuring occurs, if the heat treatment time is too long, over-curing may occur, dust may occur. When 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.

The present application is described in more detail through the following examples and comparative examples. However, the examples are provided to illustrate the present application and the scope of the present application is not limited to these examples.

Example One

Binder composition in which 3.42 g of L-polylysine and 3.42 g of glucose were polymerized in 38.86 g of distilled water polymerized using L-lysine as a monomer by thermal condensation polymerization at a temperature of 150 ° C. for 48 hours (solid content 15%, total poly Lysine: glucose = 1: 1 weight ratio). 2 g of the binder composition was applied on filter paper placed in Moisture Balance and heated at 160 ° C. for 15 minutes. A brown water-insoluble polymer, a thermoset of the binder composition, was formed on the filter paper.

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. 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 (ε) position at ppm to 3.4 ppm is used. The ratio of the second peak area (B) of 9 was 9: 1. In FIG. 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.

Example 2

A binder composition (solid content 15%, polylysine: glucose = 1: 3 weight ratio) was prepared in the same manner as in Example 1 except that 1.72 g L-polylysine and 5.14 g glucose were dissolved in 38.86 g distilled water.

2 g of the binder composition was applied on filter paper placed in Moisture Balance and heated at 160 ° C. for 15 minutes. A brown water-insoluble polymer, a thermoset of the binder composition, was formed on the filter paper.

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.

Example 3

A binder composition (solid content 15%, polylysine: glucose = 1: 5 weight ratio) was prepared in the same manner as in Example 1 except that 1.71 g L-polylysine and 8.58 g glucose were dissolved in 58.28 g distilled water. 2 g of the binder composition was applied on filter paper placed in Moisture Balance and heated at 160 ° C. for 15 minutes. A brown water-insoluble polymer, a thermoset of the binder composition, was formed on the filter paper.

Example 4

A binder composition (solid content 15%, polylysine: glucose = 1: 10 weight ratio) was prepared in the same manner as in Example 1 except that 0.8 g L-polylysine and 8 g glucose were dissolved in 49.30 g distilled water. 2 g of the binder composition was applied on filter paper placed in Moisture Balance and heated at 160 ° C. for 15 minutes. A brown water-insoluble polymer, a thermoset of the binder composition, was formed on the filter paper.

Example 5

A binder composition (50% solids, polylysine: glucose = 1: 1 weight ratio) was prepared in the same manner as in Example 1 except that 12.22 g L-polylysine and 12.22 g glucose were dissolved in 24.44 g distilled water.

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.

Example 6

A binder composition (50% solids, polylysine: glucose = 1: 3 weight ratio) was prepared in the same manner as in Example 1 except that 6.11 g L-polylysine and 18.33 g glucose were dissolved in 20.5 g distilled water.

Example 7

A binder composition (50% solids, polylysine: glucose = 1: 0.5 weight ratio) was prepared in the same manner as in Example 1 except that 15.27 g L-polylysine and 7.64 g glucose were dissolved in 22.91 g distilled water.

Example 8

14.14 g 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 ε-polylysine (manufactured by Zhengzhou Bainafo Bioengineering Co., Ltd.) of Example 1. A binder composition (50% solids content, polylysine: glucose = 1: 1 weight ratio) was prepared in the same manner as in 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.

Example 9

Binder composition (50% solids content, polylysine: glucose = 1) in the same manner as in Example 1 except that 30 g L-polylysine and 150 g glucose were dissolved in 360 g distilled water and then stirred at 80 ° C. for 1 hour and 30 minutes. : 5 weight ratio) was prepared.

Example 10

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).

Example 11

A binder composition (50% solids content, polylysine: glucose = 1: 1 weight ratio) was prepared in the same manner as in Example 1 except that 30 g L-polylysine and 30 g glucose were dissolved in 60 g distilled water.

Example 12

Binder composition in which 30 g DL-polylysine and 30 g glucose dissolved in 60 g distilled water polymerized using DL-type lysine as a monomer by thermal condensation polymerization method at a temperature of 150 ° C. for 48 hours (50% of solid content, DL-polylysine: Glucose = 1: 1 weight ratio).

Comparative example One

100 parts by weight of wood fibers were used without binder material.

Comparative example 2

A binder composition (50% solids content, polylysine: glucose = 1: 1 weight ratio) in which 16.5 g polylysine and 16.5 g glucose was dissolved in 33 g distilled water was prepared.

The polylysine is a mixture of L-polylysine and commercially available ε-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.

Comparative example 3

A binder composition (50% solids content, polylysine: glucose = 1: 1 weight ratio) in which 18.3 g polylysine and 18.3 g glucose was dissolved in 36.6 g distilled water was prepared.

The polylysine is a mixture of L-polylysine and commercially available ε-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.

Comparative example 4

A binder composition (50% solids content, polylysine: glucose = 1: 1 weight ratio) in which 16 g of commercially available ε-polylysine (manufactured by Zhengzhou Bainafo Bioengineering Co., Ltd.) and 16 g of glucose were dissolved in distilled water was prepared.

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.

Comparative example 5

Commercially prepared commercial urea-formaldehyde resin (UF resin) was used as it is as a binder composition.

Comparative example 6

A commercial medium density fiberboard (manufactured by Hansol Home Deco, interior grade GI 18) was used.

Comparative example 7

A commercial medium density fiber board (manufactured by Hansol Home Deco Co., Ltd., super light grade GSL 18) was used.

Evaluation example One: Polylysine Evaluation according to the composition of reducing sugar

In order to evaluate the properties according to the content ratio of polylysine and reducing sugar, the following items were tested.

a) water resistance evaluation

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.

구분division	실시예 1Example 1	실시예 2Example 2	실시예 3Example 3	실시예 4Example 4
APHAAPHA	2020	8484	119119	223223
황색채도(b)Yellow Saturation (b )	0.640.64	2.682.68	3.783.78	7.097.09

The smaller the pH change, the better the water solubility of the binder composition remaining without curing, and the better the water resistance.

Referring to Table 1 and FIG. 2, 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.

Specimen Fabrication

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.

On the other hand, using 100 parts by weight of wood fibers of Comparative Example 1 to prepare a specimen.

b) Flexural strength, appearance and density measurements

For the specimens prepared using the binder compositions prepared in Examples 5 to 7 and wood fibers of Comparative Example 1, 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.

구분division		실시예 5Example 5	실시예 6Example 6	실시예 7Example 7	비교예 1Comparative Example 1
시편 물성Specimen Properties	외관Exterior	적갈색불투명Maroon Opaque	적갈색불투명Maroon Opaque	갈색투명Brown and transparent	--
	고형분 함량(%)Solid content (%)	5050	5050	5050	--
	밀도(kg/m³)Density (kg / m ³ )	667667	741741	667667	--
	굴곡강도(N/mm²)Flexural Strength (N / mm ² )	9.729.72	4.404.40	2.502.50	0.340.34

As shown in Table 2, the specimen prepared using the binder composition of Examples 5 to 7 significantly improved the bending strength compared to the specimen prepared using only the wood fiber of Comparative Example 1.

In addition, 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.

Therefore, according to Tables 1 and 2, it is determined that the more similar the content of polylysine and glucose is, the faster the curing reaction rate is, thereby improving the water resistance and strength of the water-insoluble polymer. That is, the more similar the content of polylysine and glucose, the better the physical properties of the water-insoluble polymer.

Evaluation example 2: Polylysine of mine Alpha (α): epsilon (ε) Measurement of physical properties according to composition ratio

In the present application, experiments of the following items were performed to evaluate the binder according to the alpha (α): epsilon (ε) composition ratio in polylysine.

Specimen Fabrication

Specimens were each prepared using the binder compositions prepared in Examples 5, 8 and Comparative Examples 2-4.

a) measurement of appearance, density, and flexural strength;

For the specimens prepared using the binder compositions prepared in Examples 5, 8, and Comparative Examples 2 to 4, 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.

b) Curing temperature Measure

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.

c) thickness expansion rate measurement

For the specimens prepared using the binder compositions prepared in Examples 5, 8 and Comparative Examples 2 to 4, 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

Where T is the thickness of the specimen after immersion for 24 hours, and T ₀ is the initial thickness of the specimen.

d) water absorption rate measurement

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.

Water Absorption Rate (%) = [WW ₀ ] / W ₀ × 100

Where W is the thickness of the specimen after immersion for 24 hours and W ₀ is the initial thickness of the specimen.

Where W is the weight of the specimen after immersion for 24 hours, and W ₀ is the initial weight of the specimen.

구분division		실시예 5Example 5	실시예 8Example 8	비교예 2Comparative Example 2	비교예 3Comparative Example 3	비교예 4Comparative Example 4
시편 물성Specimen Properties	외관Exterior	적갈색불투명Maroon Opaque	적갈색투명Reddish brown and transparent	적갈색투명Reddish brown and transparent	갈색투명Brown and transparent	노란색투명Yellow and transparent
	밀도 (kg/m³)Density (kg / m ³ )	667667	667667	667667	500500	571571
	굴곡강도 (N/mm²)Flexural Strength (N / mm ² )	9.729.72	6.716.71	5.915.91	3.763.76	3.293.29
	경화온도 (℃)Curing temperature (℃)	116.37116.37	117.94117.94	118.35118.35	119.56119.56	129.44129.44
	두께 팽창률 (%)Thickness Expansion Rate (%)	51.2851.28	55.3455.34	75.0675.06	80.8980.89	86.6786.67

As shown in Table 3, as the alpha (α) content was increased in the poly (lysine) alpha (α): epsilon (ε) composition ratio, the physical properties of the binder thermoset improved. It was confirmed that the specimens of Examples 5 and 8 had a lower curing temperature and increased flexural strength than the specimens of Comparative Examples 2 to 4. As a result, as the alpha (α) content in the polylysine increases, the bending strength is improved as curing begins at a low temperature and the degree of curing increases.

In addition, 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 (α) binding in polylysine increases, the water absorption rate was confirmed to decrease.

Evaluation example 3: Measurement of physical properties according to reducing sugars

Experiments of the following items were carried out to evaluate the binder properties according to the type of reducing sugar.

Specimen Fabrication

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.

In 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.

Medium density Measurement of physical properties of fiberboard material

Based on the Korean Industrial Standards (KSF3200) for wood and medium density fiber boards, the physical properties of the medium density fiber boards manufactured using the binders of Examples 9 to 11 and Comparative Example 5 were measured and the results are shown in Table 4 below.

구분division		실시예 9Example 9	실시예 10Example 10	실시예 11Example 11	비교예 5Comparative Example 5
시편 물성Specimen Properties	외관Exterior	적갈색maroon	적갈색maroon	적갈색maroon	유백색milk white
	밀도(kg/m³)Density (kg / m ³ )	717717	709709	802802	740740
	두께(mm)Thickness (mm)	3.033.03	2.982.98	2.872.87	2.742.74
	내부결합강도(N/mm²)Internal bonding strength (N / mm ² )	1.721.72	2.042.04	2.42.4	1.31.3
	두께 팽창률(%)Thickness Expansion Rate (%)	3838	32.832.8	3030	4040

As shown in Table 4, 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.

In the binder composition containing glucose of Example 11, 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. .

Evaluation example 4: Polylysine Property measurement by type

In order to evaluate the binder according to the polylysine type, the following experiment was performed.

Specimen Fabrication

Specimens were each prepared using the binder compositions prepared in Examples 11-12 and Comparative Example 5.

In 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.

Medium density Measurement of physical properties of fiberboard material

Based on the Korean Industrial Standard (KSF3200) for wood and medium density fiberboard (MDF), the commercial medium density of the medium density fiberboard prepared using the binders of Examples 11, 12 and 5 and Comparative Examples 6 and 7 The physical properties of the fiberboard were measured and the results are shown in Table 5 below.

The physical property measuring method is the same as the physical property measuring method of the said Table 3.

구분division		실시예11Example 11	실시예12Example 12	비교예 5Comparative Example 5	비교예 6Comparative Example 6	비교예 7Comparative Example 7
시편 물성Specimen Properties	밀도(kg/m³)Density (kg / m ³ )	840840	790790	770770	630630	620620
	굴곡강도(MPa)Flexural Strength (MPa)	27.927.9	27.327.3	29.129.1	26.526.5	25.225.2
	내부결합강도(MPa)Internal bonding strength (MPa)	0.360.36	0.480.48	0.280.28	0.180.18	0.590.59
	두께 팽창률(%)Thickness Expansion Rate (%)	38.938.9	11.911.9	47.147.1	9.39.3	45.645.6
	수분 흡수율(%)Water absorption (%)	1.671.67	1.001.00	2.962.96	6.386.38	4.764.76

Referring to Table 5, 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.

In addition, it can be seen that 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.

In addition, 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.

Claims

Polylysine; And

One or more reducing sugars or derivatives thereof,

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, wherein the first peak area (A) and the second peak area (B) The binder composition having a ratio (A: B) of 70:30 to 98: 2.
The binder composition of claim 1, wherein the polylysine content is 15 to 60 parts by weight based on 100 parts by weight of the binder composition solids.
The binder composition of claim 1, wherein the polylysine has a molecular weight of at least 4,000 g / mol.
The binder composition of claim 1, wherein the polylysine is at least one condensation polymer selected from the group consisting of L-lysine and DL-lysine.
The binder composition of claim 1, wherein the polylysine is a condensation polymerization product of lysine at a temperature of 130 to 150 ° C. for 6 to 48 hours.
The binder composition of claim 1, wherein the reducing sugar has at least one selected from an aldehyde group and a ketone group.
The binder composition according to claim 1, wherein the content of the reducing sugar or derivative thereof is 40 to 60 parts by weight based on 100 parts by weight of the binder composition solids.
The binder composition of claim 1, wherein the reducing sugar is glucose, xylose, or a combination thereof.
The binder composition according to claim 1, wherein the solid content in the binder composition is 15 to 80 parts by weight based on 100 parts by weight of the binder composition.
An article bound by thermosetting of the binder composition according to claim 1.
Preparing a binder composition according to any one of claims 1 to 8; And

And thermally curing the binder composition at a temperature of 120 ° C. or higher.
The method of claim 10 wherein the binder composition further comprises one or more selected from fibrous materials and powdery materials.