KR100992398B1 - Filament nonwoven fabric - Google Patents

Abstract

PURPOSE: A biodegradation filament nonwoven fabric using a biodegradation nanocomposite resin, and a manufacturing method and a product thereof are provided to have a good expandable feature and a good compatibility feature. CONSTITUTION: A method for manufacturing a biodegradation filament nonwoven fabric using a biodegradation nanocomposite resin comprises the following steps. A nanocomposite resin including palm oil 12 weight%~15 weight%, PLA 14 weight%~15 weight%, and white mica 65 weight%~73 weight% is manufactured. The first compounding is for dispersing or spreading 0.5 weight%~2 weight% of a biodegradation nanocomposite resin, and 98 weight%~99.5 weight% of a resin of PBS, PBSA, and PBA resins. A biodegradation filament nonwoven fabric is post-processed.

Description

Biodegradable composite filament nonwoven fabric using biodegradable nanocomposite resin, its manufacturing method and product {Filament nonwoven fabric}

 The present invention relates to a biodegradable composite long fiber nonwoven fabric using a biodegradable nanocomposite resin, in particular, the difference in single yarn phenomenon and melting point in the production of long fiber nonwoven fabric due to poor compatibility and crosslinkability (PLA melting point: 155 ℃, PBS, PBSA, PBA melting point: 90 ℃ ~ 110 ℃) to overcome the phenomenon of using a biodegradable nanocomposite resin to a biodegradable composite long-fiber nonwoven fabric having excellent crosslinkability and compatibility, and a method and a manufacturing method thereof.

In general, long-fiber nonwovens are mostly used in disposable products such as masks, flower wrappers, shopping bags, industrial materials.

The long-fiber nonwoven resin is mostly composed of non-degradable PP or PET, which is decomposed over 100 years when disposed, which not only causes environmental problems, but also requires the development of a resin that can replace it as the oil is depleted. It is becoming.

Currently developed plant-derived biodegradable aliphatic resins, PLA (Poly Lactic Acid), PBS, PBSA, and PBA are widely known as low-carbon green products, but due to the disadvantages of being decomposed by temperature and moisture, they are thermally decomposed and hydrolyzed during production. There is a problem that occurs rapidly, and there is no compatibility, there was a difficulty in developing a resin that can replace the long-fiber nonwoven fabric using PP or PET that has been used until now.

The present invention has been made to solve the conventional problems as described above, the purpose of which is, biodegradable excellent compatibility and crosslinkability by utilizing a resin selected from PLA resin, PBS, PBSA, PBA and biodegradable nanocomposite resin The purpose is to be able to obtain a long-fiber nonwoven fabric.

Another object of the present invention is to improve the productivity of the biodegradable long-fiber nonwoven fabric by maintaining a stable flow of the MI width of the biodegradable nanocomposite of the present invention at a constant temperature.

In addition, the present invention is decomposed when the long-fiber non-woven fabric made of the 100% aliphatic biodegradable nano-composite resin, and can be a future non-degradable alternative product that can meet the low-carbon green products by reducing greenhouse gases and environmental loads The purpose is to.

Biodegradable composite long fiber nonwoven fabric of the present invention for achieving the above object,

A first step of preparing a nanocomposite resin having a content of palm oil in a natural oil of 10% by weight to 15% by weight, a PLA content of 12% by weight to 15% by weight, and a weight of 65% to 73% by weight of mica;

A second step of compounding for dispersing and diffusing 0.5 wt% to 2 wt% of the biodegradable nanocomposite resin prepared in the first step and 98 wt% to 99.5 wt% of the PBS, PBSA and PBA resins;

90% to 95% by weight of PLA resin, 4.8% to 9.95% by weight of PBS, PBSA, PBA resin, and 0.2% to 0.05% by weight of biodegradable nanocomposite compounded in the second step Compounding the third step;

A fourth step of extruding the long fiber by setting the biodegradable nanocomposite resin composed of the resin selected in the first step, the second step, and the third step from the first screw 200 ° C. to the die temperature 220 ° C .;

A fifth step of forming a biodegradable composite long fiber nonwoven fabric by simultaneously crystallizing the resin extruded and stretched by the fourth step simultaneously with pressing and fusion by an instantaneous temperature touch method;

A sixth step of post-processing the biodegradable composite long fiber nonwoven fabric of the fifth step; It is manufactured by a manufacturing method consisting of.

The present invention utilizes a biodegradable nanocomposite resin in which a biodegradable composite long fiber nonwoven fabric is branched into a biodegradable resin in neutral and weakly acidic nanosized pores in a PLA resin which is incompatible with other resins and has problems in workability. Thus, there is an advantage that the crosslinkability and compatibility is smooth. That is, biodegradable PLA resin flows into the pores in the neutral or weakly acidic nano-sized inorganic minerals (such as muscovite) pores, which have excellent compatibility and crosslinkability with PLA resins, forming branches and forming PLA resin, PBS, PBSA, PBA. To make the resin compatible

In addition, the melt index (MI: melt index) width of the biodegradable composite resin is kept constant, the productivity is good, there is an effect of excellent workability during post-processing.

Therefore, biodegradable synthetic resins can be replaced with various products such as mask, shopping bag industry materials, flower wrapping paper, and dustproof clothing, which are disposable products market made of non-degradable synthetic resin.

Figure 1 is a biodegradable composite long fiber nonwoven fabric manufacturing process according to the present invention.

As shown in the drawings, the manufacturing step of the biodegradable composite resin long fiber nonwoven fabric using the biodegradable nanocomposite resin of the present invention comprises six steps.

If you list them in order,

First step: preparing biodegradable nanocomposite resin;

Second step: a first compounding step for dispersing and diffusing the biodegradable nanocomposite resin and an alternative resin among PBS, PBSA and PBA;

Third step: second compounding the PLA resin and the second step;

Fourth step: long fiber extrusion stretching step;

Fifth step: crystallization step simultaneously with pressing and fusion by the instantaneous temperature touch method;

Sixth step: post-processing step; to be.

As described above, the manufacturing method of the biodegradable composite resin long fiber nonwoven fabric using the present invention biodegradable nanocomposite resin consisting of a total of six steps will be described in detail for each step.

First stage

The first step is a biodegradable nanocomposite manufacturing step, the composition ratio of the content of palm oil in natural oil 10% to 15% by weight, PLA content 12% to 15% by weight, mucosa 65% to 73% by weight [Patent Registration No. 10-0655914]]

The reason why the neutral and weakly acidic inorganic minerals (Dolomite) is used is that weakly acidic (PH6) PLA resins can weaken the chain structure of each other when compounded with inorganic minerals such as Talc and CaCo₃ Tio₂, which are strong alkalis. .

2nd step

The second step is a first compounding step for dispersion and diffusion with the biodegradable nanocomposite resin prepared in step 1 and an alternative resin among PBS, PBSA and PBA resins, which must be passed before proceeding to step 3 to be described later. As described above, the step is a process that greatly affects the dispersion and diffusion of the biodegradable nanocomposite resin. If this process is not carried out, the production of long fiber will result in radioactive degradation and single yarn phenomena.

Composition ratio of proceeding the second step is 0.5% to 2% by weight of the biodegradable nanocomposite resin prepared in the first step and 98% to 99.5% by weight of the selected resin of PBS, PBSA, PBA resin.

Extrusion conditions for compounding are carried out between 155 ℃ ~ 170 ℃. This is because branched PLA resin in biodegradable nanocomposite resin has melting point of 155 ℃ when screw temperature and die temperature is less than 155 ℃ under extrusion temperature condition, and it is sufficiently dispersed below melting point when crosslinking with alternative resin among PBS, PBSA and PBA. Not only is it poor in crosslinkability, but when it is 170 ° C. or higher, the selected resin among PBS, PBSA, and PBA may have thermal melting point before the biodegradable resin is sufficiently dispersed and crosslinked due to melting point of less than 110 ° C.

In the present invention, if the content of the biodegradable nanocomposite is 0.2% by weight or more based on the total weight of the biodegradable nanocomposite, there may be a single yarn phenomenon during orientation stretching, and if it is less than 0.05%, the resin selected from PLA resin, PBS, PBSA, PBA, and Poor compatibility and crosslinkability.

In addition, if the content of the selected resin of PBS, PBSA, PBA in the biodegradable nano-composite resin of the present invention is less than 9.8% by weight of the total weight, PLA properties are strong, brittle properties appear, and if more than 9.95% PLA resin and Due to the low melting point, which is the characteristic of the resin selected from PBS, PBSA, and PBA resins, which are crosslinked resins, the heat resistance temperature may be 100 ° C. or lower, resulting in deterioration of workability due to heat deformation.

3rd step

The third step is the secondary compounding of the PLA resin and the resin of the second step, the general resin working process of the screw and the extrusion die temperature of the compound and the PLA resin compounded in the second step between 155 ℃ ~ 170 ℃ Proceed as in At this time, it is important to dehumidify and dry the water content of the compounded resin below 50 ppm.

The composition ratio of the resin is 90% to 95% by weight of PLA resin, 4.8% to 9.95% by weight of the selected resin among PBS, PBSA and PBA resins, and 0.05% to 0.2% of the biodegradable nanocomposite resin through the second step. It is carried out in the ratio of weight%.

Among the PBS, PBSA, and PBA, the selected resin is selected from a resin having a MI (melt index) of 15 g to 20 g. If the MI of PBS, PBSA, PBA is less than 15g, the biodegradable composite resin's MI (220 ℃) can be less than 30g. If the MI is more than 20g, the biodegradable composite's MI (220) ℃) is more than 50g to make long-fiber nonwovens productivity difficult and monofilament can occur.

The MI range of the biodegradable composite resin containing the biodegradable nanocomposite resin developed through the first, second, and third steps of the present invention can secure stability, but it is possible to obtain stability of PLA single resin, PBS, PBSA, When producing long-fiber nonwoven fabric from PBA resin as the single resin, the change of MI is severe due to the rapid rise of MI due to the temperature increase, which causes difficulty in spinning or single yarn phenomenon.

Experimental Example 1

A. MI of each resin according to temperature change is shown in Table 1.

Here, the MI measurement is a resin extruded for 10 minutes by moving an orifice (inner diameter 2.09mm, height 8mm) in which a melt is defined at a constant temperature (PLA, PBS, composite resin: 190 ° C to 230 ° C) and a constant load (2.16kg). It is the value which measured the weight (g) of.

division 190 ℃ 200 ℃ 210 ℃ 220 ℃ 230 ℃ Remarks PLA Around 7g Around 10g Around 15g Around 30g Around 65g PBS Around 8g Around 15g Around 22g Around 33g Around 45g Compound Resin 6 g 12g 20g 32 g 39 g

B. MI variation of each resin according to temperature change is shown in Table 2.

Experimental Example 2

A. MI change according to temperature (220 ℃, 230 ℃) of composite resin according to PBS MI is shown in Table 3.

At this time, the MI measurement is: 10 at a constant temperature (PBS: 200 ℃, biodegradable composite resin: 220 ℃ and 230 ℃), a fixed load (2.16 kg) by moving the orifice (inner diameter 2.09mm, height 8mm) prescribed the melt It is the value which measured the weight (g) of resin extruded for a minute.

Table 3 below shows the change in the MI according to the temperature (220 ℃, 230 ℃) of the composite resin compounded with PBS when the MI is 10g, 15g, and 30g.

Condition MI at composite resin 220 ℃ MI at 230 ℃ When using PBS MI 10g 19 g 28 g When using PBS MI 15g 32 g 45 g When using PBS MI 30g 48 g 72 g

As shown in Experimental Example 1 and Experimental Example 2, the MI fluctuation width was the smallest at around 220 ° C. in the biodegradable long fiber nonwoven spinning condition, so that the composite resin spinning property was excellent at this time and the single yarn phenomenon could be prevented.

That is, the spinning temperature of the biodegradable composite resin showed excellent merchandise that the MI was 32g around 220 ° C. As shown in Experiment 1, the PLA MI was 65g, the PBS was 45g, and the composite resin was 39g in Example 1 at 230 ° C. As a result, it was possible to prevent thermal decomposition and control single yarn phenomenon, which are disadvantages of biodegradable resins.

4th step

The fourth step is a long-fiber extrusion stretching step, the extrusion stretching the biodegradable composite resin passed through the first step, the second step, and the third step. At this time, it is preferable to set the temperature from the first screw 200 ℃ to the die temperature 220 ℃ to prevent thermal decomposition, but there may be a change depending on some mechanical conditions and production systems.

In addition, the biodegradable composite resin should have a MI of about 30g at 220 ° C. Of course, the extrusion pressure may vary slightly depending on the screw pressure, the screw structure.

Experimental results show that the smaller the variation of MI at 220 ℃ and 230 ℃, the better the radioactivity and preventing pyrolysis.

MI variation width according to temperature (220 degreeC-230 degreeC) like Experimental example 1 is as follows.

division Fluctuation width (220 ℃ ~ 230 ℃) PLA 35 g PBS 12g Compound Resin 7 g

In the present invention, the temperature condition according to the stretching of the production conditions is one of the important conditions that can prevent the draw ratio and single yarn phenomenon.

In this context, the cooling temperature of the biodegradable composite resin passed through the die should not be less than 55 ℃. This is because the biodegradable composite resin has a glass transition temperature below the glass transition temperature of 55 ° C or less depending on the cooling temperature.

Preferably the direct temperature of the resin temperature passed through the die is 90 ℃ ~ 110 ℃. This shows excellent stretchability up to 4 to 6 times in orientation stretching. That is, when the direct temperature of the resin is 110 ° C or higher, the resin is close to 155 ° C, which is the melting point of the PLA resin. As a result, crystallinity may be weakened in crystallization after orientation stretching or may cause monoclinic phenomenon during orientation stretching.

Biodegradable composite resin filament non-woven fabric can be produced from 1.5 denier to 3 denier in mono thread thickness, and produced in a similar way to ordinary resin, and from 15g to 200g per '㎡ depending on production speed and extrusion conditions. Nonwoven fabric production is possible.

Stretching conditions are stretched 4 to 6 times by instantaneous stretching between the resin direct temperatures of 90 ° C. to 110 ° C., which can prevent single yarn phenomena due to stretching rather than multistage stretching.

Multi-stretch can be stretched between 55 ℃ ~ 110 ℃ due to the characteristics of PLA resin, but when it is oriented stretching step by step, partly crystallization and partly single crystal may occur due to amorphousness. At the same time, workability and physical properties are excellent.

5th step

The biodegradable composite long-fiber nonwoven fabric, which is instantaneous oriented crystalline, passes through two press-forcing rolls to achieve embossing and crystallization.

Crystallization conditions in the present invention are carried out in the same manner as the patent (patent registration No. 10-0833583), but in accordance with the instantaneous temperature touch method. That is, the temperature of the two polishing rolls or the embossing rolls is set at 100 ° C to 110 ° C, and the direct temperature of the biodegradable composite long fiber nonwoven fabric is made to be 90 ° C to 110 ° C. It is crystallized by passing through a processing roll or an embossing roll. Of course, the crystallization temperature conditions can be adjusted according to the spinning speed and the rotating speed of the polishing roll, but if the direct temperature of the biodegradable composite long fiber nonwoven fabric is below 90 ° C., the nonwoven long fiber may be peeled off and if the crystallization temperature is above 110 ° C. Can be weakened.

6th step

If the heating wire is directly closed on the biodegradable composite long-fiber nonwoven fabric, the biodegradable long-fiber nonwoven fabric can be melted on the heating wire, so the direct temperature is 90 ° C on the biodegradable composite long-fiber nonwoven fabric by indirect sealing method coated with silicone on the sealing heating wire. Seal between ~ 110 ℃.

The long-fiber nonwoven fabric made of biodegradable composite resin is made of PBS, PBSA, and PBA, which makes the post-processing work smooth and increase the tensile strength and impact strength.

The physical properties of the biodegradable long fiber nonwoven fabric produced by the above-described manufacturing method of the present invention were measured, and the results of comparing the numerical values with those of PP and PET products, which are general non-degradable materials, are shown in Table 5.

TEST ITEM Unit 20 30 50 70 100 note


PP Unit weight g / ㎡ 20.4 30.5 50.7 70.3 100.9 Tensile
Strength MD Kg / 5 cm 3.5 4.8 10.1 13.8 15.2 CD Kg / 5 cm 1.6 2.7 6.8 9.8 11.3 Elongation MD % 22.1 18.3 29.1 30.5 27.2 CD % 28.3 25.5 35.1 38.5 30.4 tear
strength MD Kg.f 0.39 0.52 0.92 1.64 2.61 CD Kg.f 0.22 0.29 0.58 1.04 1.45 Thickness mm 0.18 0.26 0.38 0.48 0.59


P
E
T Unit weight g / ㎡ 20.3 30.4 50.7 69.9 100.9 Tensile
Strength MD Kg / 5 cm 7.1 10.2 14.6 22.2 30.1 CD Kg / 5 cm 2.8 4.9 6.8 12.5 17.1 Elongation MD % 18.6 19.5 19.7 17.7 16.5 CD % 17.1 18.0 18.4 17.1 16.3 tear
strength MD Kg.f 0.31 0.49 0.86 0.92 1.75 CD Kg.f 0.13 0.27 0.45 0.57 1.23 Thickness mm 0.08 0.12 0.19 0.2 0.27 Biodegradable
Compound Resin Unit weight g / ㎡ 19.7 29.2 48.8 69.8 99.5 Tensile
Strength MD Kg / 5 cm 4.8 6.0 9.7 12.8 15.4 CD Kg / 5 cm 2.7 3.2 6.0 7.6 8.9 Elongation MD % 29.8 31.0 41.5 42.1 38.9 CD % 31.0 35.0 38.7 39.5 36.7 tear
strength MD Kg.f 0.35 0.42 0.48 0.85 0.90 CD Kg.f 0.16 0.21 0.31 0.39 0.51 Thickness mm 0.10 0.16 0.20 0.24 0.29

As shown in Table 5, the biodegradable long fiber nonwoven fabric of the present invention was found to have properties comparable to those of general non-degradable products.

1 is a biodegradable composite long fiber nonwoven fabric manufacturing process according to the present invention

Claims (10)

A first step of producing a nano-composite resin of 14% to 15% by weight of palm oil, 14% to 15% by weight of PLA, 65% to 73% by weight of mica; A second step of primary compounding for dispersing and diffusing 0.5 wt% to 2 wt% of the biodegradable nanocomposite resin prepared in the first step and 98 wt% to 99.5 wt% of the selected resin among PBS, PBSA and PBA resins; 90% by weight to 95% by weight of PLA resin, 4.8% by weight to 9.95% by weight of the optional resin of PBS, PBSA, PBA resin, and 0.05% by weight to 0.2% by weight of the first compounded compound; Step 3; A fourth step of extruding the long fiber by setting the screw and die temperature at 200 ° C. to 220 ° C. through the third step of the biodegradable nanocomposite resin; A fifth step of forming a biodegradable composite long fiber nonwoven fabric by simultaneously crystallizing the resin extruded and stretched by the fourth step simultaneously with pressing and fusion by an instantaneous temperature touch method; A sixth step of post-processing the biodegradable composite long fiber nonwoven fabric of the fifth step; Biodegradable composite long fiber nonwoven fabric manufacturing method using a biodegradable nanocomposite resin consisting of. According to claim 1, wherein the compound and the PLA resin compounded in the second step is the same as the general resin working process between the screw temperature and the extrusion die temperature of 155 ℃ ~ 170 ℃, the water content of the compounded resin is 50ppm Method for producing a biodegradable composite long fiber nonwoven fabric using biodegradable nanocomposite resin, characterized in that the drying under dehumidification. The biodegradable composite using biodegradable nanocomposite resin according to claim 1, wherein the third step uses a resin having a MI (melt index) of 15 to 20 g among the selected resins among PBS, PBSA, and PBA. Long fiber nonwoven fabric manufacturing method. According to claim 1, wherein the cooling temperature of the biodegradable nanocomposite resin passed through the die in the fourth step is the biodegradability using the biodegradable nanocomposite resin, characterized in that the direct temperature of the resin within 55 ℃ to 110 ℃. Composite long fiber nonwoven fabric manufacturing method. According to claim 1, wherein the stretching conditions in the fourth step is a biodegradation utilizing a biodegradable nanocomposite resin, characterized in that the stretching to 4 to 6 times by instantaneous stretching between the resin direct temperature 90 ℃ ~ 110 ℃. Method for producing a composite long fiber nonwoven fabric. The biodegradable nanocomposite resin according to claim 1, wherein the biodegradable nanocomposite resin is formed by an indirect sealing method coated with silicon on a sealing heat wire, and the direct temperature of the biodegradable composite long fiber nonwoven fabric is sealed at 90 ° C to 110 ° C. Method for producing biodegradable composite long fiber nonwoven fabric utilized. delete delete delete delete

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