[1]It relates to an article and articles made by the method of binding a binder composition comprising a poly-lysine, yeolgyeong product of the binder composition.
BACKGROUND
[2]Such as formaldehyde resin binders and fibers, wood powder, such as (PF resin, Phenol-Form aldehyde resin) - non-woven fiber insulation, article, such as plywood, urea-formaldehyde resin (UF resin, Urea-Form aldehyde resin), phenol a mixture of a base material can be produced by molding and curing heat. Conventional binder is obtained from fossil fuels and binders manufacture and article release harmful VOCs such as formaldehyde (VOC, Volatile Organic Compound) After the production of. Therefore, do not use fossil fuels, there is ongoing research on binders that provide excellent properties even without emitting harmful substances.
Detailed Description of the Invention
SUMMARY
[3]
The present invention is to provide a binder composition of a natural origin which, without emitting harmful volatile organic compounds such as formaldehyde, exhibits excellent properties.
Problem solving means
[4]
One aspect of the present application are poly-lysine; And at least one reducing sugar or a derivative thereof, in which the polylysine, 1H NMR spectrum, and a second peak of the first peak and the 3.8 ppm to 4.0 ppm in the 3.2 ppm to 3.4 ppm, a first peak area (a) and a second percentage of the peak area (B) (a: B) is 70:30 to 98: 2, to provide a binder composition.
Brief Description of the Drawings
[5]
1 is a formula and a 1H NMR spectrum of the poly-lysine comprising the repeating unit used for the lysine amino group is a polymerization repeating unit position and attached to the epsilon amino group is used for the polymerization is connected to the alpha-site used in Example 1 at the same time.
[6]
Figure 2 is a graph illustrating the pH change with time of the aqueous solution containing the yeolgyeong product of the binder composition prepared in Example 1-4.
Best Mode for Carrying Out the Invention
[7]
Creative spirit of the present application will be discussed below (inventive concept) is illustrated in the bar, reference to specific embodiments, which may have various embodiments and can apply a wide range of conversion, will be described in detail in the Detailed Description. This, however, is by no means to restrict the creative scope of the present application to the particular embodiments, it should be understood to include any transformation, equivalents or substitutes that are included in the technical scope of the creative scope of the present application.
[8]
As used below are merely used to describe particular embodiments, and are not intended to limit the present creative ideas. Expression in the singular number include a plural forms unless the context clearly indicates otherwise. In the following, "includes The" or "gajida" and the term is that which you want to indicate that the features, numbers, steps, operations, elements, parts, components, materials, or one that exists combinations thereof described in the specification, one or at least the presence or addition of other features or, numbers, steps, operations, elements, parts, components, materials or combinations thereof and are not intended to preclude. "/" Is used below may be interpreted as an "and" may be interpreted to have "or" depending on the situation.
[9]
First, the term of the second and so on throughout the specification can be used in describing various elements, but elements shall not be restricted by the term. These terms are only used to distinguish one element from the other.
[10]
It is further described in detail with respect to the binder composition according to the illustrative embodiment below.
[11]
Binder composition according to one aspect of the present application is polylysine; And at least one reducing sugar or derivatives thereof, poly-lysine, 1H NMR in the spectrum, and a second peak of the first peak and the 3.8 ppm to 4.0 ppm in the 3.2 ppm to 3.4 ppm, the first peak area ( a) and the ratio (a in the second peak area (B): B) is 70:30 to 98: 2; the, the strength and water resistance of the water-insoluble polymer yeolgyeong product of the binder composition can be improved by. In addition, the binder composition and the water-insoluble polymer yeolgyeong storage thereof does not emit hazardous organic volatile substances such as formamide can be environmentally friendly. In the 1H NMR spectrum of poly-lysine, a first ratio of the peak area (A) and a second peak area (B) (A: B) is 75: 25 to 98: 2, 80:20 to 98: 2, 85: 15 to 98: 2, 90: 10 to 98: 1, or 95: 5 to 98: may be 2 days. Polylysine is a mixture of poly-lysine or two or more of one kind of polylysine.
[12]
Polylysine content of binder composition solids to 100 parts by weight based on 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, from 35 to 50 parts by weight, or 40 to 50 parts by weight may be an. When the poly-lysine content is too low may be the unreacted reducing sugar in the articles it made using the binder composition is lowered physical properties of the article by an excess residue. The physical properties of this polyamide articles prepared by using the binder composition as a lysine content is too high, incomplete curing of the binder composition may be degraded.
[13]
Specifically, the poly-lysine may be at least one condensation polymer selected from the group consisting of L- lysine and DL- lysine.
[14]
Specifically, the poly-lysine may be in the L- polylysine polymerization of the monomer only L- lysine. In addition, the poly-lysine may be a polymerization of the monomer only DL- lysine DL- polylysine. Another exemplary one of polylysine can be a polylysine polymerization by the L- and DL- lysine lysine monomers.
[15]
In the water-resistant side it is polymerized polylysine including DL- lysine in the monomer may be adapted compared to the polymerized lysine and L- lysine only to monomers.
[16]
The molecular weight of the poly-lysine may be greater than or equal to 4,000g / mol or more, 5,000g / mol or more, 6,000g / mol or more, 7,000g / mol or more, 8,000g / mol or more, 9,000g / mol or more, or a 10,000g / mol. The molecular weight of polylysine can be measured using gel permeation chromatography (GPC, Gel Permeation Chromatograhy) by a relative value for the PEG / PEO standard sample.
[17]
Polylysine may be a result obtained by condensation polymerization of a lysine at 130 to 150 ℃ temperature conditions for 6 to 48 hours.
[18]
Polylysine in the alpha (α) is in the alpha (α) and the repeating unit used for the amino group are polymerized connected to position carbon, is a poly-lysine in the epsilon (ε) is an amino group attached to the epsilon (ε) where the carbon of the lysine polymerization of lysine It is a repeating unit used.
[19]
Polylysine in the alpha (α): Epsilon (ε) is the composition ratio, in the 1H NMR spectrum of poly-lysine, to 3.2ppm derived from alpha-methine (-CH) of the repeating unit used for the amino group is attached to the polymerization (α) position the at 3.8ppm to 4.0ppm derived from the first peak area (a) and methine (-CH, a carbon of FIG. 1) of the repeating units used in the epsilon (ε) amino group is attached to the position in the polymerization 3.4ppm It is determined by the ratio of the two peak area (B).
[20]
On the other hand, in the 1H NMR spectrum of the poly-lysine is obtained by controlling the condensation reaction conditions as the polylysine, the ratio (A: B) of the first peak area (A) and a second peak area (B) can be adjusted.
[21]
Polylysine within the repeating unit used for the amino group is attached to the polymerase alpha (α) of the lysine in position, that is, if the content of α- polylysine repeating unit increases, in the 1H NMR spectrum of poly-lysine, from 3.2ppm to 3.4ppm it is possible to increase the area of ​​the first peak (a) of. Also, polylysine within the repeating unit used for the amino group is attached to the polymerizing epsilon (ε) of the lysine at position, that is, poly-ε- lysine is increased when the content of the repeating unit, in the 1H NMR spectrum of poly-lysine, 3.8ppm to 4.0 a second peak area (B) in ppm can be increased.
[22]
Reducing sugars or derivatives thereof may have at least one selected from an aldehyde group and ketone group. The reducing sugar may be an aldehyde group and ketone group selected aldehyde group at the time of heat curing of the binder composition containing a reducing sugar as by including at least one and / or the ketone formed from the imine bond by reacting with the amine group of polylysine. And, this imine bond may be cured by reaction with a hydroxyl group of another reducing sugar, the curing mechanism can be a non-reversible reaction.
[23]
The content of reducing sugar or derivatives thereof is a binder composition solids content 100 parts by weight based on from 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 It can be 50 to 65 parts by weight, or 50 to 60 parts by weight. To the unreacted residual reducing sugar within the article made by the content of reducing sugar is too high, use of the binder composition can be the physical properties of the article decreases. If the content of reducing sugar is too low, the physical properties of articles made by using the binder composition as the curing of the binder composition is incomplete can be lowered.
[24]
Reducing sugar is maltose, fructose, galactose, lactose, Gen thio agarobiose, Rutino trehalose, glucose, and a monosaccharide and disaccharide, or a combination thereof, such as xylene agarose can be used, but if the range does not deviate from the object of the present invention must be It is not limited to these.
[25]
As a specific example, the reducing sugar may be agarose, or a combination thereof to glucose, xylene.
[26]
Also, the reducing sugar in the strength and water resistance side may include glucose. In the binder composition solids content is 15 to 100 parts by weight of the binder composition 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 weight can Buil have. In the binder composition solids is polylysine and the non-reducing sugar and solid matter component may be water diluent. The solid content is too high, increase the viscosity of the binder composition to degrade the workability, the binder content can be excessively increased in the article to be produced by using the binder composition. If the solid content is too low, there is excess energy to be consumed to remove the water.
[27]
Binder composition may further comprise one or more additives. The additive coupling for attachment to improve the dust-proof oil, yeolgyeong buffer, a binder composition for adjusting the pH of the cargo to reduce the dust generation rate of corrosion inhibitor, yeolgyeong cargo to prevent corrosion of the water repellent agent, yeolgyeong cargo to increase the water resistance of yeolgyeong cargo agent or the like, but not limited to these, if an additive that can be used to improve physical properties of the binder composition and yeolgyeong cargo in the art, it is possible both. The content of the additive with respect to polylysine and the total sum 100 parts by weight of reducing sugars, respectively 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, 0.1 to 2 parts by weight, 0.1-1 parts by weight, or 0.1 to 0.5 parts by weight but not necessarily limited to such a range may be adjusted according to the required physical properties.
[28]
Article according to another aspect of the application is bound by yeolgyeong product of the above-mentioned binder composition. Yeolgyeong product of the above-described binder composition is improved in strength and water resistance of the article to the article as a water-soluble polymer binder strongly fire.
[29]
Bound by yeolgyeong goods article of the binder composition is absorbed thickness expansion coefficient measured by a test method according to KSF3200 is 40% or less, 38% or less, 36% or less, 34% or less, 33% or less, 30%, 25% or less, or 12%, 20%, 15% or less. The bound product by yeolgyeong product of the binder composition can have excellent water resistance. Further, the coupling products by yeolgyeong product of the binder composition is the internal bond strength measured by a test method according to KSF3200 1.4 N / mm 2 or more, 1.5 N / mm 2 or more, 1.6 N / mm 2 or more, 1.7 N / mm 2 or more, 1.8 N / mm 2 or more, 1.9 N / mm 2 or more, or 2.0 N / mm 2 may be equal to or greater than. The article can have a good internal bond strength of the binding by yeolgyeong product of the binder composition. By yeolgyeong cargo bound article of binder composition is possible if all goods, but the like insulation material, plywood is not necessarily limited to, by using the binder composition binds to a certain type.
[30]
[31]
Article manufacturing method according to another aspect of the present application may include the steps of preparing the above-described binder composition; And a binder composition yeolgyeong solidifying step at a temperature above 120 ℃; includes. Prepared in the above-described method for manufacturing goods article has an excellent water resistance and strength.
[32]
The binder in the article production process composition can further include one or more selected from the group consisting of fibrous materials and powder materials.
[33]
Fibrous material or the like is short-fiber aggregate of fibers, and the like obtained by the inorganic fibers, natural and synthetic resins, such as rock wool, glass wool, ceramic fibers, but are not necessarily limited to these as long as they can all be used as the fibrous material in the art. Powder material, but wood powder or the like is not necessarily limited to these as long as they can all be used as the powdery material in the art.
[34]
The fibrous or powdery material is bound by yeolgyeong product of the binder composition by the fibrous material and the mixture further comprises at least one selected from a powdery material in the binder composition As the heat cured at more than 120 ℃ temperature. Heat treatment temperature for heat curing may be 120 ~ 300 ℃, 130 ~ 250 ℃, 140 ~ 200 ℃, or 150 ~ 180 ℃. If the heat treatment temperature is too low microscope upset occurs, and the heat treatment temperature is too high, the fruit stalk upset occurs may result in dust. The heat treatment time for heat curing can be 1-60 minutes, 5-40 minutes, 10-30 minutes, or 12-18 minutes. The heat treatment time is too short, the microscope upset occurs, and there is a heat treatment time of the dust can be generated by excessively long fruit stalk upset occurs. When the binder composition heat cured at more than 120 ℃ the temperature of the distribution of the amine groups of the aldehyde / ketone group and polylysine of reducing sugar can be via a variety of curing reaction, such as Gouraud (Maillard) reaction the insoluble polymer is formed, physical properties such as water resistance, strength this may serve as an excellent adhesive.
[35]
The pressed and molded at the time of thermal curing is carried out simultaneously or sequentially and can adjust the physical properties and shape of the article of manufacture. Applied during the pressing pressure, time is not particularly limited and may be adjusted depending on the density of the required article.
Mode for the Invention
[36]
The present application by the present examples and comparative examples below are described in more detail. However, the embodiment is not limited to these and the scope of the present application serves to illustrate the present application.
[37]
Example 1
[38]
The binder composition was dissolved in 3.42g of a polymerization temperature from 150 ℃ thermal condensation polymerization for 48 hours by the method of L-lysine to L- monomer is polylysine and 3.42g 38.86g glucose in distilled water (solid content 15%, and total poly lysine were prepared to 1 ratio by weight): glucose = 1. Applying a binder composition onto a 2g filter paper placed in a moisture balance (Moisture Balance) and heated at 160 ℃ for 15 minutes. Of the product of the binder composition yeolgyeong brown water-insoluble polymer it was formed on the filter paper.
[39]
And the polylysine has a number average molecular weight (Mn) 6,000g / mol, a weight average molecular weight (Mw) 8,000g / mol level used in the preparation of the binder composition, of Fig 1 as seen in the H NMR spectrum, the polylysine deuterium oxide (D 2 when the O) by using a solvent as determined by 400MHz NMR, alpha (α), 3.2 to an amino group attached to the position derived from the repeated methine (-CH, carbon c in Fig. 1) of the unit used in the polymerization ppm to 3.8ppm to 4.0ppm at derived from the first peak area (a) and methine (-CH, a carbon of FIG. 1) of the repeating units used in the epsilon (ε) amino group is attached to the position in the polymerization 3.4ppm a second ratio of the peak area (B) of 9: 1. The first peak is represented by c, and the second peak is denoted by a in FIG.
[40]
Of polylysine molecular weight was measured by GPC (Gel Permeation Chromatography) using the PEG / PEO standard sample.
[41]
Example 2
[42]
1.72g L- polylysine with glucose 5.14g of the example 1 and the binder composition by the same method (15% solid content, a poly-lysine: glucose = 1: 3 weight ratio), except that dissolved in 38.86g of distilled water was prepared.
[43]
Applying a binder composition onto a 2g filter paper placed in a moisture balance (Moisture Balance) and heated at 160 ℃ for 15 minutes. Of the product of the binder composition yeolgyeong brown water-insoluble polymer it was formed on the filter paper.
[44]
The poly-lysine used in the production binder composition 1 was 1, the number average molecular weight (Mn) 6,000g / mol,: H NMR spectrum in the ratio of the area of the first peak (A) and a second peak area (B) of the 9 the weight average molecular weight (Mw) 8,000g / mol level.
[45]
Example 3
[46]
1.71g L- polylysine with glucose 8.58g of the example 1 and the binder composition by the same method (15% solid content, a poly-lysine: glucose = 1: 5 weight ratio), except that dissolved in 58.28g of distilled water was prepared. Applying a binder composition onto a 2g filter paper placed in a moisture balance (Moisture Balance) and heated at 160 ℃ for 15 minutes. Of the product of the binder composition yeolgyeong brown water-insoluble polymer it was formed on the filter paper.
[47]
The poly-lysine used in the production binder composition 1 was 1, the number average molecular weight (Mn) 6,000g / mol,: H NMR spectrum in the ratio of the area of the first peak (A) and a second peak area (B) of the 9 the weight average molecular weight (Mw) 8,000g / mol level.
[48]
Example 4
[49]
0.8g L- polylysine with glucose 8g the Example 1 and the binder composition by the same method (15% solid content, a poly-lysine: glucose = 1: 10 weight ratio), except that dissolved in 49.30g of distilled water was prepared. Applying a binder composition onto a 2g filter paper placed in a moisture balance (Moisture Balance) and heated at 160 ℃ for 15 minutes. Of the product of the binder composition yeolgyeong brown water-insoluble polymer it was formed on the filter paper.
[50]
The poly-lysine used in the production binder composition 1 was 1, the number average molecular weight (Mn) 6,000g / mol,: H NMR spectrum in the ratio of the area of the first peak (A) and a second peak area (B) of the 9 the weight average molecular weight (Mw) 8,000g / mol level.
[51]
Example 5
[52]
12.22g L- polylysine with glucose 12.22g the Example 1 and the binder composition by the same method (50% solid content, a poly-lysine: glucose = 1: 1 by weight), except that dissolved in 24.44g of distilled water was prepared.
[53]
The polylysine is the same manner as in Example 1, used in the production binder composition 1, the ratio of the area of the first peak in the H NMR spectra (A) and a second peak area (B) of 9: was 1, and the number average molecular weight ( Mn) 6,000g / mol, a weight average molecular weight (Mw) 8,000g / mol level.
[54]
Example 6
[55]
6.11g L- polylysine with glucose 18.33g the Example 1 and the binder composition by the same method (50% solid content, a poly-lysine: glucose = 1: 3 weight ratio), except that dissolved in 20.5g distilled water was prepared.
[56]
The polylysine is the same manner as in Example 1, used in the production binder composition 1, the ratio of the area of the first peak in the H NMR spectra (A) and a second peak area (B) of 9: was 1, and the number average molecular weight ( Mn) 6,000g / mol, a weight average molecular weight (Mw) 8,000g / mol level.
[57]
Example 7
[58]
15.27g 7.64g L- lysine and poly-glucose is the Example 1 and the binder composition by the same method (50% solid content, a poly-lysine: glucose = 1: 0.5 weight ratio), except that dissolved in 22.91g of distilled water was prepared.
[59]
The polylysine is the same manner as in Example 1, used in the production binder composition 1, the ratio of the area of the first peak in the H NMR spectra (A) and a second peak area (B) of 9: was 1, and the number average molecular weight ( Mn) 6,000g / mol, a weight average molecular weight (Mw) 8,000g / mol level.
[60]
Example 8
[61]
14.14g was dissolved in the poly-lysine and the 14.14g glucose 28.28g distilled water, except that a mixture of the poly-lysine is the first embodiment of L- lysine and poly-ε- commercial polylysine (Zhengzhou Bainafo Bioengineering Co., Ltd, Ltd.) example 1 and the binder composition by the same method (50% solid content, a poly-lysine: glucose = 1: 1 weight ratio) was prepared.
[62]
The poly-lysine 1 ratio of the H NMR spectrum in the area of the first peak (A) and a second peak area (B) of 7: 3 was a number-average molecular weight (Mn) 6,000g / mol, a weight average molecular weight (Mw ) is 8,000g / mol level.
[63]
Example 9
[64]
Was dissolved 30g L- polylysine and 150g glucose 360g of distilled water, for 1 hour at 80 ℃ 30 minutes and the binder composition in the same manner as in Example 1 except that the stirring (50% solid content, a poly-lysine: glucose = 1 : 5 by weight) was prepared.
[65]
The polylysine is the same manner as in Example 1, used in the production binder composition 1, the ratio of the area of the first peak in the H NMR spectra (A) and a second peak area (B) of 9: was 1, and the number average molecular weight ( Mn) 6,000g / mol, a weight average molecular weight (Mw) 8,000g / mol level.
[66]
Example 10
[67]
After 30g to 150g xylene and L- polylysine agarose is dissolved in 360g of distilled water, and the binder composition (50% solids content in the same manner as in Example 1, except in that 80 ℃ stirring for 1.5 hours, polylysine: in xylene Osu = 1: 5 was prepared by weight).
[68]
The polylysine is the same manner as in Example 1, used in the production binder composition 1, the ratio of the area of the first peak in the H NMR spectra (A) and a second peak area (B) of 9: was 1, and the number average molecular weight ( Mn) 6,000g / mol, a weight average molecular weight (Mw) 8,000g / mol level.
[69]
Example 11
[70]
It was prepared 30g is L- polylysine with glucose, 30g of Example 1 and the binder composition by the same method (1 weight ratio of solids content 50%, polylysine: glucose = 1), except that dissolved in 60g distilled water.
[71]
The polylysine is the same manner as in Example 1, used in the production binder composition 1, the ratio of the area of the first peak in the H NMR spectra (A) and a second peak area (B) of 9: was 1, and the number average molecular weight ( Mn) 6,000g / mol, a weight average molecular weight (Mw) 8,000g / mol level.
[72]
Example 12
[73]
The 48 hours thermal condensation polymerization method, the polymerization by the DL- lysine in the form of the monomer 30g DL- polylysine and 30g of glucose at a temperature 150 ℃ dissolved in 60g distilled water, the binder composition (50% solids content, DL- polylysine: glucose = 1: 1 weight ratio) was prepared.
[74]
The polylysine is the same manner as in Example 1, used in the production binder composition 1, the ratio of the area of the first peak in the H NMR spectra (A) and a second peak area (B) of 9: was 1, and the number average molecular weight ( Mn) 6,000g / mol, a weight average molecular weight (Mw) 8,000g / mol level.
[75]
Comparative Example 1
[76]
No binder material was used 100 parts by weight of wood fiber as it is.
[77]
Comparative Example 2
[78]
It was prepared with 16.5g 16.5g polylysine glucose the binder composition (solid content ratio by weight 1 to 50%, polylysine: glucose = 1) dissolved in 33g of distilled water.
[79]
The polylysine is the first embodiment of L- lysine and poly-lysine and poly-ε- commercial mixture of (Zhengzhou Bainafo Bioengineering Co., Ltd, Ltd.), of the poly-lysine first area (A) of the first peak in H NMR spectrum and It was the 5: 2 ratio of the peak area (B) of 5.
[80]
Comparative Example 3
[81]
It was prepared with 18.3g 18.3g polylysine glucose the binder composition (solid content ratio by weight 1 to 50%, polylysine: glucose = 1) was dissolved in 36.6g distilled water.
[82]
The polylysine is the first embodiment of L- lysine and poly-lysine and poly-ε- commercial mixture of (Zhengzhou Bainafo Bioengineering Co., Ltd, Ltd.), of the poly-lysine first area (A) of the first peak in H NMR spectrum and ratio of the second peak area (B) of 3: 7 was.
[83]
Comparative Example 4
[84]
Ε- commercial polylysine (Zhengzhou Bainafo Bioengineering Co., Ltd manufacture) and 16g glucose 16g The binder composition was dissolved in distilled water (solid content 50%, polylysine: glucose = 1: 1 weight ratio) was prepared.
[85]
The poly-lysine used in the production binder composition 1 ratio in the H NMR spectral area of the first peak (A) and a second peak area (B) was of 0:10.
[86]
Comparative Example 5
[87]
Commercial production of urea by direct-formaldehyde resin (UF resin) was used as a binder composition.
[88]
Comparative Example 6
[89]
It was used in a commercial density fiber board (Hansol Decoration 社 manufacture, interior-grade GI 18).
[90]
Comparative Example 7
[91]
It was used in a commercial density fiber board (Hansol Decoration 社 manufacture, super lightweight GSL 18).
[92]
[93]
Evaluation Example 1: polylysine and evaluated according to the composition of the reducing sugar
[94]
Experiments were conducted by the following items for evaluation of the physical properties according to the content ratio of polylysine and a reducing sugar.
[95]
[96]
a) Water resistance rating
[97]
Examples 1 to the non-water-soluble polymer is formed of a filter paper at room temperature prepared from 4 litters measure color change and a pH change in distilled water for 10 minutes respectively and the results are shown in Table 1 and FIG.
[98]
Color change was measured APHA value and the yellow color saturation (b *) color system with the spectral side.
[99]
TABLE 1
division Example 1 Example 2 Example 3 Example 4
RIGHT HERE 20 84 119 223
Yellow saturation (b *) 0.64 2.68 3.78 7.09

[100]
Since pH changes are small as not cure the remaining amount of binder composition that improve dissolution and excellent water resistance is, the more a color change less is excellent in water resistance.
[101]
Table 1 and 2, using the binder composition of the embodiment the content of the poly-lysine and glucose compared to the water-insoluble polymer obtained by the glucose content using a binder composition of high-Examples 2 to 4, the same Example 1 compared to the poly-lysine water-insoluble polymers are obtained by a change in pH and a color change was less even after a certain period of time submerged. Accordingly, Example 1 was confirmed to fire the water resistance is improved as compared to the water-soluble polymer is a water-insoluble polymer obtained by use of a binder composition obtained using the binder compositions of Examples 2 to 4.
[102]
Psalms production
[103]
Carried out using the binder composition prepared in Example 5 to 7 to prepare a sample, respectively.
[104]
Wood fiber (wood fiber and mixed materials such as pitch pine (Pinus rigida), radiator pine (Pinus radiate)) was prepared by mixing 85 parts by weight of the mixture 15 parts by weight of the binder composition. Prepared mixture 160 ℃ temperature and 200kg / cm 2 was molded under a pressure of. Molding was repeated two times for 3 minutes and 30 seconds pressure depressurizing. By depressurizing it was removed in a gas generated during the curing and hardening. The molded specimen was cured by standing at 160 ℃ for 1 hour.
[105]
On the other hand, the wood fiber in Comparative Example 1 to prepare a specimen in the same manner using 100 parts by weight.
[106]
[107]
b) Bending strength (Flexural bending strength), appearance, density measurements
[108]
Examples 5 to 7 with respect to the prepared specimens to the use of a binder composition and comparative wood fiber of Example 1 manufactured by, measured the specimen width and thickness with a micrometer, using a universal testing machine (UTM, Universal Testing Machine) at room temperature by compressing at a rate of 50 mm per minute, measuring the flexural strength and the results are shown in Table 2 below. In addition, the solid content of the binder composition is also used on the exterior of the specimen, density, and sample prepared is shown in Table 2.
[109]
TABLE 2
division Example 5 Example 6 Example 7 Comparative Example 1
Psalms properties Exterior Reddish brown opaque Reddish brown opaque Brown Transparent -
The solid content (%) 50 50 50 -
Density (kg / m 3 ) 667 741 667 -
Bending strength (N / mm 2 ) 9.72 4.40 2.50 0.34

[110]
As shown in Table 2, Examples 5 to 7 prepared by using the binder composition of the sample was significantly improved bending strength compared to a sample prepared by using only the wood fiber of Comparative Example 1.
[111]
In addition, the produced amount of polylysine with glucose ratio Using a similar Example 5 binder composition of the specimen bending strength compared to the samples produced using the polylysine and the binder compositions of Examples 6 to 7, the content ratio is different in glucose It was found more improved.
[112]
Thus, in Table 1 and is more, the content of the poly-lysine and glucose when the second similarity is determined that the curing reaction speed is faster fire improved water resistance and strength of the water-soluble polymer. In other words, the more similar to the amount of poly-lysine and glucose in physical properties of the water-soluble polymer light was further improved.
[113]
[114]
Evaluation Example 2: poly-lysine in the alpha (α): the epsilon (ε) measuring the physical properties of the composition
[115]
In the present application a poly-lysine in the alpha (α): the experiment was performed by the following items to evaluate the binder according to the epsilon (ε) ratio.
[116]
[117]
Psalms production
[118]
Was prepared in Example 5, and Comparative Example 8 using the binder composition prepared in Examples 2 to 4 specimens, respectively.
[119]
Wood fiber (wood fiber and mixed materials such as pitch pine (Pinus rigida), radiator pine (Pinus radiate)) was prepared by mixing 85 parts by weight of the mixture 15 parts by weight of the binder composition. Prepared mixture 160 ℃ temperature and 200kg / cm 2 was molded under a pressure of. Molding was repeated two times for 3 minutes and 30 seconds pressure depressurizing. By depressurizing it was removed in a gas generated during the curing and hardening. The molded specimen was cured by standing at 160 ℃ for 1 hour.
[120]
[121]
a) the appearance, density, bending strength (Flexural bending strength) measurement
[122]
Example 5, Example 8, and it was compared with Examples 2 to with respect to the prepared specimen using the binder composition prepared in four, using a micro-meter measures the sample width and thickness of the universal testing machine (UTM, Universal Testing Machine) and by using a compression at room temperature at a rate of 50 mm per minute, measuring the flexural strength and the results are shown in Table 3. In addition, the solid content of the binder composition is also used on the exterior of the specimen, density, and sample prepared is shown in Table 3.
[123]
[124]
b) a curing temperature measurement
[125]
Times by using the typical rheological properties meter (Rheometer, Anton Paar Physica) was measured cure temperature (curing temperature). Placing the specimen between the flat plate (parallel plate) with a 0.5mm gap, while the temperature was raised to 2 ℃ / min rate at 30 ~ 160 ℃ temperature region, 1.0s -1 flat plate at a constant shear rate (shear rate) of It was one of the rotation. By measuring the cure temperature (curing temperature) from the behavior of the sample material and the results are shown in Table 3.
[126]
[127]
c) measuring the thickness expansion coefficient
[128]
Example 5, Example 8, and was compared with Examples 2 to with respect to the prepared specimen using the binder composition prepared in four, using a micro-meter measures the sample width and thickness, followed by immersion of the specimen in a beaker filled with distilled water 24 hours, then allowed to stand to measure the thickness change amount of the sample and the results are shown in Table 3. The thickness expansion coefficient was calculated from the following equation (1).
[129]

[130]
The thickness expansion rate (%) = [TT 0 ] / T 0 × 100
[131]
Wherein, T is a thickness, T of the sample after 24 hours immersion 0 is the initial thickness of the specimen.
[132]
[133]
d) water absorption measurement
[134]
Example 5 and Comparative Examples 2 to with respect to the specimens prepared by using the binder composition prepared in 4, were measured weight of the sample, by immersion the sample in a beaker filled with distilled water to measure the weight of the specimen after 24 hours. The temperature of the distilled water was maintained at a room temperature, when measuring the moisture content was measured by weight and then removed, only the right out of the beaker water of the specimen surface. Water absorption was calculated from the following equation (2).
[135]

[136]
Water absorption (%) = [WW 0 ] / W 0 × 100
[137]
Wherein, W is the sample thickness after 24 hours of immersion, W 0 is the initial thickness of the specimen.
[138]
Here, W is the sample weight after 24 hours immersion, W 0 is the initial weight of the specimen.
[139]
TABLE 3
division Example 5 Example 8 Comparative Example 2 Comparative Example 3 Comparative Example 4
Psalms properties Exterior Reddish brown opaque Maroon transparent Maroon transparent Brown Transparent Yellow Transparent
Density (kg / m 3 ) 667 667 667 500 571
Bending strength (N / mm 2 ) 9.72 6.71 5.91 3.76 3.29
Curing temperature (℃) 116.37 117.94 118.35 119.56 129.44
The thickness expansion rate (%) 51.28 55.34 75.06 80.89 86.67

[140]
[141]
As shown in Table 3, the poly-lysine in the alpha (α): As in the epsilon (ε) ratio increased the alpha (α) content improved the physical properties of the binder yeolgyeong cargo. Exemplary specimens of Examples 5 and 8, it was confirmed that it has a low curing temperature the flexural strength is increased compared to the sample of Comparative Example 2-4. As it is polylysine in alpha (α) content is increased by the start curing at low temperatures it is determined that the degree of curing bending strength improves with increasing.
[142]
Further, in Example 5 and a water absorption of Comparative Example 2 to a result of measuring a water absorption of 4, Example 5, while measurement by 93.54%, Comparative Example 2, a water absorption of 1 to Comparative Example 4, respectively, 276.36%, 281.23 It was measured in% and 285.36%. That it is, as the polylysine coupled within the alpha (α) is increased was confirmed that the water absorption decreased.
[143]
[144]
Evaluation Example 3: The physical properties measured in accordance with the type of reducing sugar
[145]
To the binder for evaluation of physical properties according to the type of reducing sugar it was carried out an experiment of entry.
[146]
[147]
Psalms production
[148]
Examples 9 to the binder composition prepared in 11 wood fiber (wood fiber) compared to 64.7kg / m 3 were mixed by introducing the mixture density fiber board of the cured press (press) for a second temperature under conditions 220 ℃ (MDF a, Medium-Density Fiberboard) specimens were prepared. In other words, the wood fiber 1m 3 and mixed with the binder composition against 64.7kg.
[149]
Comparative Example 5 was prepared in the density fiber board of the specimen in the same manner as in Example 8 except for using a commercially available UF resin.
[150]
[151]
Density of measuring properties of the fiber board material
[152]
By measuring the wood and on the basis of the Korea Industrial Standards (KSF3200) Examples 9 to 11 and Comparative Example 5 The physical properties of medium density fiber board prepared by using the binder of the density fiber board of the results are shown in Table 4.
[153]
TABLE 4
division Example 9 Example 10 Example 11 Comparative Example 5
Psalms 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 bond strength (N / mm 2 ) 1.72 2.04 2.4 1.3
The thickness expansion rate (%) 38 32.8 30 40

[154]
As shown in Table 4, Examples 9 to compared to the density fiber board specimen of manufacturing a density fiber board specimen of the produced using a binder composition of 11, using a commercially available resin of Comparative Example 5 in better internal bond strength the thickness this expansion was reduced.
[155]
Exemplary binder composition containing glucose of Example 11 is a bar properties hayeotneun the internal bond strength and coefficient of thermal expansion decreases the thickness after the specimen production was confirmed that relatively more improved as compared with the binder composition containing trehalose in xylene of Example 10 .
[156]
[157]
Evaluation Example 4: polylysine measuring physical properties according to the type
[158]
An experiment was carried out as described below for the binder according to the evaluation types polylysine.
[159]
[160]
Psalms production
[161]
Carried out using the binder composition prepared in Examples 11 to 12 and Comparative Example 5 was prepared in the specimen, respectively.
[162]
Wood fiber (wood fiber and mixed materials such as pitch pine (Pinus rigida), radiator pine (Pinus radiate)) was prepared by mixing 85 parts by weight of the mixture 15 parts by weight of the binder composition. Prepared mixture 160 ℃ temperature and 200kg / cm 2 was molded under a pressure of. Molding was repeated two times for 3 minutes and 30 seconds pressure depressurizing. By depressurizing it was removed in a gas generated during the curing and hardening. The molded specimen was cured by standing at 160 ℃ for 1 hour.
[163]
Comparative Example 5 was prepared in the density fiber board of the specimen in the same manner as in Example 11 except for using a commercially available UF resin.
[164]
[165]
Density of measuring properties of the fiber board material
[166]
Based on the Korea Industrial Standards (KSF3200) in Example 11, Example 12 and Comparative Example 5 Comparative density fiber board and of the produced using the binder of Example 6 and the density of the commercially available 7 for the timber and medium density fiber board (MDF) by measuring the physical properties of the fiber board it is shown in the following Table 5 as a result.
[167]
The physical properties measurement method was the same as the method for measuring the physical properties of Table 3.
[168]
Table 5
division Example 11 Example 12 Comparative Example 5 Comparative Example 6 Comparative Example 7
Psalms properties Density (kg / m 3 ) 840 790 770 630 620
Flexural strength (MPa) 27.9 27.3 29.1 26.5 25.2
Internal bond strength (MPa) 0.36 0.48 0.28 0.18 0.59
The thickness expansion rate (%) 38.9 11.9 47.1 9.3 45.6
Moisture absorption rate (%) 1.67 1.00 2.96 6.38 4.76

[169]
Referring to Table 5, Example 11, of the produced using a binder composition of 12 density fiber board specimen is provided in Comparative Example 5, the bending strength is similar to the density fiber board specimen of the produced using a commercially available resin, while the internal bond strength was confirmed and enhanced, that bar water resistance is improved hayeotneun reduced thickness expansion and moisture absorption.
[170]
In addition, Examples 11 and density fiber board of the specimen by 12 Comparative Example 6 and the bending strength is improved compared to the density of the fiber board samples of commercially available 7, there were physical properties in the water absorption decreased to find out more improved.
[171]
Furthermore, Example 11 and Example 12, when viewing the comparison, determine the water resistance is superior as compared to the polymerization L- lysine and poly DL- only the polylysine is L- lysine polymerization including DL- lysine in the monomer the monomer It was.
Industrial Applicability
[172]
Binder composition of the present invention may have an improved strength and water resistance after thermal curing.

Claims

[Claim 1]Polylysine; And at least one reducing sugar or a derivative thereof, in which the polylysine, 1H NMR spectrum, and a second peak of the first peak and the 3.8 ppm to 4.0 ppm in the 3.2 ppm to 3.4 ppm, a first peak area (a) and a second percentage of the peak area (B) (a: B) is 70:30 to 98: 2, the binder composition.
[Claim 2]
The method of claim 1, wherein the deny 15 to 60 parts by weight said polylysine content in the binder composition solids based on 100 parts by weight, the binder composition.
[Claim 3]
According to claim 1, wherein the molecular weight of the polylysine 4,000g / mol or more, a binder composition.
[Claim 4]
The method of claim 1, wherein the poly-lysine is at least one condensation polymer selected from the group consisting of L- lysine and DL- lysine, binder composition.
[Claim 5]
The method of claim 1, wherein the polylysine is a condensation polymerization of the resultant lysine at 130 to 150 ℃ temperature conditions for 6 to 48 hours, and the binder composition.
[Claim 6]
The method of claim 1 wherein said reducing sugar with at least one selected from an aldehyde group and a ketone group, the binder composition.
[Claim 7]
The method of claim 1 wherein the amount of the reducing sugar or its derivatives binder composition solids to 100 parts by weight based on 40 to 60 parts by weight, the binder composition.
[Claim 8]
The method of claim 1 wherein the reducing sugar is trehalose or a combination thereof to glucose, xylene, binder composition
[Claim 9]
The method of claim 1, wherein, in the binder composition solids content is 15 to 80 parts by weight, the binder composition based on 100 parts by weight of the binder composition.
[Claim 10]
Wherein the first to eighth article being bound by the yeolgyeong product of the binder composition according to any one of items.
[Claim 11]
The step of preparing a binder composition according to any one of claims 1 to 8; And yeolgyeong solidifying step the binder composition at a temperature above 120 ℃; article manufacturing method comprising a.
[Claim 12]
11. The method of claim 10 wherein the article manufacturing method in which the binder composition further comprises one or more selected from the group consisting of fibrous materials and powder materials.