KR100970332B1 - Preparation method of blend film using recycled waste polyvinylalcohol and blend film obtained thereby - Google Patents

Abstract

The present invention relates to a method for producing a blend film using recycled waste polyvinyl alcohol nonwoven fabric and starch, and to a blend film prepared by the method, and more specifically, the blend film blends starch into recycled waste polyvinyl alcohol nonwoven fabric. Blend solution preparation step of dissolving with water; And a film forming step of forming a film by using the blend solution. As a result, the film can be used to replace existing hybrid array polyvinyl alcohol while maintaining functionality such as strength and elastic modulus.

Polyvinyl Alcohol, Blends, Films, Starches

Description

Preparation method of blend film using recycled waste polyvinylalcohol and blend film obtained

The present invention relates to a method for producing a blend film using recycled waste polyvinyl alcohol nonwoven fabric and starch, and to a blend film produced by the method.

Starch is abundant and inexpensive biodegradable natural polymer in nature, whereby starch particles are formed around the central nucleus formed by the precipitation of small amounts of insoluble matter.

Starch is initially spherical but over time becomes flat or rod-shaped. Starch particles are insoluble in water below 60 ° C, absorb water and expand and gelate.

Continued heating of the starch breaks the structure of the particles and creates a paste of sticky mass. In addition, it has been used in various businesses such as food, clothing, and paper through various reforming and processing reactions, and has been developed as a substitute material for synthetic polymer plastics.

In the production of plastic materials using starch, a method of filling starch into synthetic polymers such as PE, PP, and PS, a method of blending with hydrophilic synthetic polymer, a method using modified starch, and the like have been used. Such starch is a natural polymer that has been generally used as an auxiliary material and is widely used.

Poly (vinyl alcohols) (PVA) was produced by German Herrmann and Hanel (WOHerrmann and W. Hachnel, German Patent, 450, 286 (1924), 1924). The first discovery was made during saponification of poly (vinyl acetate) s).

In addition to polyvinyl acetate, PVA is a polymer produced by saponifying various types of poly (vinyl esters) and poly (vinyl ethers) -based polymers, and has molecular weight and stereoregularity. And very useful polymers widely used in the manufacture of resins, clothing fibers, industrial fibers, food packaging films, liquid and gas separation membranes, polarizing films, and medical polymeric materials, depending on the degree of saponification.

In the domestic PVA market, Tongyang Chemical first began producing commercials at 12,000 tons in 1992 and 24,000 tons in 1996. Tong Yang Chemical's PVA market share reached 40-50% in 1996 and 1997 with 24,000 tons, and sold 7500 tons of domestically and 6,500 to 8,600 tons. Edo production was only up to 16,500 tons.

However, in 1998, Dongyang Chemical's PVA production capacity reached an all-time high of 17,000 tons, and its market share expanded significantly from 45% to 65 ~ 70%. In addition to TDI, Tong Yang Chem has significant significance in that it sets PVA as a prototype of a full-scale organic chemistry business. In particular, PVA is the first attempt to enter specialty chemicals.

Research has continued to use these PVAs as contained in recycled waste PVAs. This research results in cost reduction and energy saving due to resource recycling, and shows the possibility of environmental preservation and development of eco-friendly industry of related companies by recovery and recycling of PVA, which is a non-degradable material.

The water-soluble film uses PVA resin in which saponification degree was adjusted uniformly. The preparation of the solution using a PVA resin, a plasticizer, a surfactant, and the like is the same as the production of other PVA films, but the saponification degree of the PVA resin used at this time is suitably 82 to 92%.

It is known that water solubility is inadequate in saponification degree of 80% or less and 95% or more. In the case of a water-soluble PVA film using a low saponification PVA resin, an inorganic filler such as silicone or talc is added to reinforce toughness and impact resistance. In addition, it is also necessary to shorten the swelling time of the film by giving unevenness to the surface of the film so that it can be quickly dissolved in water under the desired conditions.

Therefore, the inventors have found that the precursors for obtaining PVA so far are the price of polyvinyl acetate, a polymerized monomer of polyvinyl acetate used as a precursor of hybrid array PVA, and thus PVA at a relatively low price by using recycled waste PVA nonwoven fabric. The present invention has been completed in view of the fact that it can be used for various purposes by using a blended starch and adding a lower price.

Accordingly, it is an object of the present invention to provide a method for producing a blend film using recycled waste polyvinyl alcohol nonwoven fabric and starch, and a blend film prepared by the method.

In order to achieve the above object, the present invention is a blend solution manufacturing step of blending starch in a recycled waste polyvinyl alcohol nonwoven fabric and dissolved with water; And a film forming step of forming a film by using the blend solution. The method of manufacturing a blend film using recycled waste polyvinyl alcohol, comprising: a film forming step;

The polyvinyl alcohol nonwoven fabric is preferably a low molecular weight polyvinyl alcohol having molecular variables of number average polymerization degree of 1,000 to 2,000, alternating diad group content of 50 to 55%, and saponification degree of 80.0 to 99.9%.

If the polyvinyl alcohol nonwoven fabric is used beyond the molecular variables such as the number average degree of polymerization, alternating diad group content, and saponification degree, problems such as weakening of the durability of the film and deterioration of polarization in a high temperature and high humidity environment may occur. May be caused.

The blend solution is preferably blended with 10 to 100 parts by weight of starch based on 100 parts by weight of recycled waste polyvinyl alcohol nonwoven fabric, and then dissolved in a concentration of 0.1 to 30 g / dl by adding water.

If the starch content is out of the above range, problems such as deterioration of permeability and physical properties may occur.

At this time, it is preferable to blend recycled waste polyvinyl alcohol and starch, and then add water and mix the mixture to dissolve completely at 80 to 100 ° C. for 2 to 4 hours.

In addition, the film forming step of forming a film uses a general film forming process, and for example, the blend solution may be poured into a stainless steel dish and dried for 1 to 10 minutes.

In addition, the present invention is a recycled waste polyvinyl alcohol, characterized in that consisting of recycled waste polyvinyl alcohol nonwoven fabric and starch having a number average degree of polymerization of 1,000 to 2,000, alternating diad group content of 50 to 55%, and saponification degree of 80.0 to 99.9%. It provides the blend film used.

The thus prepared blend film has a thickness of 40 to 80 μm, a tensile strength of 0.01 to 0.06 GPa, and a tensile modulus of 1 to 4 GPa.

The blend film produced according to the production method of the present invention is very economical because it is possible to produce a PVA blend film at a fairly low price by using recycled waste PVA instead of the conventionally used hybrid array PVA and blending starch.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only for the purpose of clarifying the contents of the present invention, and the present invention is not limited by the examples.

≪ Example 1 >

Beaker blended starch blended with recycled waste PVA with 1700 degree of polymerization, 53.9% of alternator content and 99.0% of saponification degree. The concentration of the solution was 20 g / dl and the weight ratio was 9: 1. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to PVA / starch having a thickness of 80 μm, tensile strength of 0.06 GPa, and tensile modulus of 4 GPa. A blend film was obtained.

<Example 2>

In the beaker, the solution obtained by blending waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% in a beaker was 20 g / dl, and had a weight ratio of 9: 1. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to PVA / starch having a thickness of 70 μm, a tensile strength of 0.05 GPa and a tensile modulus of 3 GPa. A blend film was obtained.

<Example 3>

In the beaker, the solution obtained by blending waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% in a beaker was 20 g / dl, and had a weight ratio of 9: 1. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to PVA / starch having a thickness of 40 μm, a tensile strength of 0.02 GPa, and a tensile modulus of 2 GPa. A blend film was obtained.

<Example 4>

In the beaker, the solution obtained by blending waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% in a beaker was 20 g / dl, and had a weight ratio of 9: 1. At this time, the mixture was mixed using water as a solvent and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to PVA / starch having a thickness of 30 μm, tensile strength of 0.04 GPa, and tensile modulus of 3 GPa. A blend film was obtained.

Example 5

The same number average polymerization degree as that of Example 1 in the beaker was changed to 1700, alternating content of 53.9%, saponification degree of 99.0%, and a concentration of 20 g / dl and a weight ratio of 8: 2. At this time, the mixture was mixed using water as a solvent and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to form PVA / starch having a thickness of 80 μm, a tensile strength of 0.05 GPa, and a tensile modulus of 4 GPa. A blend film was obtained.

<Example 6>

The same number average polymerization degree as that of Example 1 in the beaker was changed to 1700, alternating content of 53.9%, saponification degree of 99.0%, and a concentration of 20 g / dl and a weight ratio of 8: 2. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to PVA / starch having a thickness of 70 μm, a tensile strength of 0.05 GPa and a tensile modulus of 3 GPa. A blend film was obtained.

<Example 7>

The same number average polymerization degree as that of Example 1 in the beaker was changed to 1700, alternating content of 53.9%, saponification degree of 99.0%, and a concentration of 20 g / dl and a weight ratio of 8: 2. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to form a PVA / starch having a thickness of 40 μm, a tensile strength of 0.04 GPa, and a tensile modulus of 2 GPa. A blend film was obtained.

<Example 8>

The same number average polymerization degree as that of Example 1 in the beaker was changed to 1700, alternating content of 53.9%, saponification degree of 99.0%, and a concentration of 20 g / dl and a weight ratio of 8: 2. At this time, the mixture was mixed using water as a solvent and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to PVA / starch having a thickness of 30 μm, tensile strength of 0.04 GPa, and tensile modulus of 3 GPa. A blend film was obtained.

Example 9

In the beaker, the concentration of the mixed solution of waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% was 20 g / dl, and the weight ratio was 7: 3. At this time, water was used as a solvent, mixed, and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes, PVA / starch having a thickness of 80 μm, a tensile strength of 0.04 GPa, and a tensile modulus of 3 GPa. A blend film was obtained.

<Example 10>

In the beaker, the concentration of the mixed solution of waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% was 20 g / dl, and the weight ratio was 7: 3. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to give a PVA / starch having a thickness of 70 μm, a tensile strength of 0.02 GPa, and a tensile modulus of 3 GPa. A blend film was obtained.

<Example 11>

In the beaker, the concentration of the mixed solution of waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% was 20 g / dl, and the weight ratio was 7: 3. At this time, the mixture was mixed using water as a solvent and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to have a thickness of 40 μm, a tensile strength of 0.01 GPa, and a tensile modulus of 2 GPa. A starch blend film was obtained.

<Example 12>

In the beaker, the concentration of the mixed solution of waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% was 20 g / dl, and the weight ratio was 7: 3. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes, PVA / starch having a thickness of 30 μm, a tensile strength of 0.01 GPa and a tensile modulus of 1 GPa. A blend film was obtained.

Example 13

In the beaker, the concentration of the mixture of waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% in the beaker was 20 g / dl, and the weight ratio was 6: 4. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to form PVA / starch having a thickness of 80 μm, a tensile strength of 0.05 GPa, and a tensile modulus of 3 GPa. A blend film was obtained.

<Example 14>

In the beaker, the concentration of the mixture of waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% in the beaker was 20 g / dl, and the weight ratio was 6: 4. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to PVA / starch having a thickness of 70 μm, a tensile strength of 0.03 GPa, and a tensile modulus of 2 GPa. A blend film was obtained.

<Example 15>

In the beaker, the concentration of the mixture of waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% in the beaker was 20 g / dl, and the weight ratio was 6: 4. At this time, the mixture was mixed using water as a solvent and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to form a PVA / starch having a thickness of 40 μm, a tensile strength of 0.01 GPa, and a tensile modulus of 1 GPa. A blend film was obtained.

<Example 16>

In the beaker, the concentration of the mixture of waste PVA and starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% in the beaker was 20 g / dl, and the weight ratio was 6: 4. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes, PVA / starch having a thickness of 30 μm, a tensile strength of 0.01 GPa and a tensile modulus of 1 GPa. A blend film was obtained.

<Example 17>

In the beaker, the solution obtained by blending waste PVA with starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% was 20 g / dl, and had a weight ratio of 5: 5. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, which was then poured into a stainless steel dish and dried for 10 minutes to form PVA / starch having a thickness of 80 μm, a tensile strength of 0.03 GPa, and a tensile modulus of 2 GPa. A blend film was obtained.

&Lt; Example 18 >

In the beaker, the solution obtained by blending waste PVA with starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% was 20 g / dl, and had a weight ratio of 5: 5. At this time, the mixture was mixed using water as a solvent and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to give a PVA / starch having a thickness of 70 μm, a tensile strength of 0.02 GPa, and a tensile modulus of 2 GPa. A blend film was obtained.

&Lt; Example 19 >

In the beaker, the solution obtained by blending waste PVA with starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% was 20 g / dl, and had a weight ratio of 5: 5. At this time, the mixture was mixed using water as a solvent and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to form a PVA / starch having a thickness of 40 μm, a tensile strength of 0.01 GPa, and a tensile modulus of 1 GPa. A blend film was obtained.

Example 20

In the beaker, the solution obtained by blending waste PVA with starch having the same number-average degree of polymerization of 1700, alternating content of 53.9%, and saponification degree of 99.0% was 20 g / dl, and had a weight ratio of 5: 5. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes, PVA / starch having a thickness of 30 μm, a tensile strength of 0.01 GPa and a tensile modulus of 1 GPa. A blend film was obtained.

Comparative Example 1

The beaker was blended with PVA (PVA-217), an oriental chemical raw material with a number-average degree of polymerization of 1700, an alternator content of 54.0%, and a saponification degree of 98.9%, and a concentration of 20 g / dl. 1 was. At this time, water was used as a solvent and mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, which was then poured into a stainless steel dish and dried for 10 minutes to PVA / starch having a thickness of 80 μm, a tensile strength of 0.06 GPa, and a tensile modulus of 5 GPa. A blend film was obtained.

Comparative Example 2

The beaker was blended with PVA (PVA-117), a raw material of Japan's Kuraray, with a number-average degree of polymerization of 1700, alternating condenser content of 54%, and saponification degree of 99.9%. : 1. At this time, water was used as a solvent, mixed and completely dissolved at 100 ° C. for 4 hours to prepare a solution, and then poured into a stainless steel dish and dried for 10 minutes to PVA / starch having a thickness of 80 μm, a tensile strength of 0.07 GPa, and a tensile modulus of 5 GPa. A blend film was obtained.

Claims (4)

Blending a starch solution into a recycled waste polyvinyl alcohol nonwoven fabric and dissolving it with water; And a film-forming step of forming a film by using the blend solution. The polyvinyl alcohol nonwoven fabric of claim 1, wherein the polyvinyl alcohol nonwoven fabric is a low molecular weight polyvinyl alcohol having molecular variables of number average polymerization degree of 1,000 to 2,000, alternating diad group content of 50 to 55%, and saponification degree of 80.0 to 99.9%. Method for producing a blend film using recycled waste polyvinyl alcohol. The recycled blend of claim 1, wherein the blend solution is blended with 10 to 100 parts by weight of starch based on 100 parts by weight of recycled waste polyvinyl alcohol nonwoven fabric, and then dissolved with water at a concentration of 0.1 to 30 g / dl. Method for producing a blend film using waste polyvinyl alcohol. delete