KR102486130B1 - Biodegradable resin composition using plant fattyacid possible to recycling for coating paper - Google Patents

Abstract

The present invention relates to a biodegradable resin composition for paper coating based on vegetable fatty acids that can be recycled, and more specifically, to a naturally derived fatty acid, polybasic acid, and organic sulfonic acid metal salt (Metal salts of organic sulfonic acid) and polyhydric alcohol to prepare an ester prepolymer having an ester main chain, and then copolymerizing and crosslinking with the ester resin of the main chain using an acrylic monomer to satisfy alkali dissociation, water resistance, oil resistance and biodegradability. In addition, it relates to a biodegradable resin composition for paper coating based on vegetable fatty acids that enables easy recycling.

Description

Recyclable vegetable fatty acid-based paper coating biodegradable resin composition {BIODEGRADABLE RESIN COMPOSITION USING PLANT FATTYACID POSSIBLE TO RECYCLING FOR COATING PAPER}

The present invention relates to a biodegradable resin composition for paper coating based on vegetable fatty acids, which satisfies alkali dissociation, water resistance, oil resistance and biodegradability, and enables easy recycling.

In modern life, the use of disposable products with excellent performance and low price plastic materials has increased rapidly due to advanced science and technology, quality improvement of living standards and culture, and pursuit of convenience, while various types of waste vinyl, Styrofoam, plastic containers, etc. It is emerging as a cause of serious environmental pollution, such as leakage of environmental hormones due to incineration or landfill and air pollution caused by incomplete combustion of highly toxic dioxin-detection waste.

When used to solve the problem of plastic waste, research is being conducted to solve the problem of convenience and environmental pollution by adding an additional degradability function while maintaining the processability, durability, and mechanical properties of plastic.

Currently, plastic substitutes that have already been developed and commercialized are used as degradable plastics. Biodegradable plastics manufactured by mixing starch with general-purpose plastics such as PE (Polyethylene) and PP (Polypropylene), and pulp-based products using paper, pulp, etc. There are general-purpose plastics, biodegradable resins, and complex decomposition products using decomposition accelerators, but these biodegradable plastics are inexpensive, but have disadvantages such as poor processability and moldability.

Accordingly, a container made of pulp material that can be 100% recycled as a substitute for disposable plastic cups is required. Cardboard paper for paper lacks these physical properties, so it is widely used by reinforcing basic physical properties by coating or laminating PE or PP. It is coated and used on the inside of various food containers for reasons such as excellent elongation and processability and low price, but there is a possibility of releasing environmental hormones due to plasticizers added to plastics during use and disposal, and it is not easily decomposed, so it is incinerated or landfilled. is causing pollution.

Methods to make disposable paper containers from an eco-friendly point of view have been actively proposed recently. Among the existing markets, packaging materials made of polyvinyl alcohol and fluorine-based oil-resistant components emphasized eco-friendliness, but polyvinyl alcohol itself absorbs moisture and has this characteristic. The downside is that water resistance is low.

In order to solve this problem, Patent Document 1 proposed a coated paper cup using PLA (Polylactic acid), but PLA is a plant-based material and has eco-friendly characteristics, but is expensive and recycling of waste paper is not only lacking in technology to follow, but also has water resistance , oil resistance, alkali dissociation and biodegradability were unreliable.

Patent Document 1: Republic of Korea Patent Registration No. 10-1559960 "Method for manufacturing coated paper cups using PLA"

The present invention is to solve the above problems, by reacting naturally occurring fatty acids, polybasic acids, metal salts of organic sulfonic acid, and polyhydric alcohol to produce esters. After preparing an ester-based prepolymer having a main chain, copolymerization and cross-linking with the ester resin of the main chain using an acrylic monomer to satisfy alkali dissociation, water resistance, oil resistance and biodegradability, as well as to realize easy recycling. It is an object of the present invention to provide a biodegradable resin composition for coating fatty acid-based paper.

The present invention is a biodegradable resin composition, based on 100 parts by weight of an ester prepolymer, 40 to 45 parts by weight of acrylic acid as a reactive monomer, 20 to 25 parts by weight of butyl acrylate parts by weight, methyl methacrylate (methyl methacrylate) 10 to 15 parts by weight, ethylene glycol dimethacrylate (Ethylene glycol dimethacrylate) 30 to 35 parts by weight, stearyl acrylate (stearyl acrylate) 5 to 10 parts by weight, 2- 15 to 20 parts by weight of 2-ethylhexyl acrylate, 0.1 to 2 parts by weight of a water soluble initiator, 1 to 5 parts by weight of a neutralizing agent, 2 to 4 parts by weight of a leveling agent A biodegradable resin composition for paper coating based on recyclable vegetable fatty acids, characterized in that it consists of 0.6 to 1.0 parts by weight of part and a defoamer, as a solution to the problem.

Here, the ester-based prepolymer includes 80 to 100 parts by weight of polybasic acid, 5 to 20 parts by weight of metal salts of organic sulfonic acid, and polyhydric acid based on 100 parts by weight of fatty acid. It is preferably composed of 100 to 200 parts by weight of alcohol (Polyhydric alcohol).

On the other hand, the fatty acid is selected from among soybean oil fatty acid, tall oil fatty acid, linseed oil fatty acid, or dehydrated castor oil fatty acid. Used alone or in combination, the polybasic acid is maleic anhydride or itaconic acid, succinic acid, adipic acid, isophthalic acid acid) or lactic acid, used alone or in combination, and the metal salts of organic sulfonic acid are dimethyl-5-sulfoisophthalate sodium salt, 5-so Sodium-5-sulfoisophthalic acid (Dimethyl-5-sulfoisophthalate lithium salt) or lithium 5-sulfoisophthalic acid is used alone or in combination. , The polyhydric alcohol is trimethylol propane or 1,4-butanediol, neopentyl glycol, monoethylene glycol or diethylene glycol (Diethylene glycol) and 1,6-hexanediol (1,6-Hexanediol) are preferably used alone or in combination.

The present invention not only satisfies alkali dissociation, water resistance, oil resistance and biodegradability, but also enables easy recycling, and thus has an effect of enabling coating and application to various paper containers.

The present invention for achieving the above effect relates to a biodegradable resin composition for paper coating based on vegetable fatty acids that can be recycled, and only parts necessary for understanding the technical configuration of the present invention are described, and other parts are described according to the present invention. It should be noted that it will be omitted so as not to obscure the gist.

Hereinafter, a biodegradable resin composition for coating paper based on vegetable fatty acids that can be recycled according to the present invention will be described in detail.

The biodegradable resin composition for coating paper based on vegetable fatty acids that can be recycled according to the present invention includes 40 to 45 parts by weight of acrylic acid, a reactive monomer, butyl, based on 100 parts by weight of an ester-based prepolymer. 20 to 25 parts by weight of butyl acrylate, 10 to 15 parts by weight of methyl methacrylate, 30 to 35 parts by weight of ethylene glycol dimethacrylate, stearyl acrylate ) 5 to 10 parts by weight, 2-ethylhexyl acrylate 15 to 20 parts by weight, water soluble initiator 0.1 to 2 parts by weight, neutralizing agent 1 to 5 parts by weight, leveling 2 to 4 parts by weight of a leveling agent and 0.6 to 1.0 parts by weight of a defoamer.

The ester-based prepolymer has an ester main chain through the reaction of naturally occurring fatty acid, polybasic acid, metal salts of organic sulfonic acid, and polyhydric alcohol. As a resin, it is added to satisfy alkali dissociation, water resistance, oil resistance, etc., based on 100 parts by weight of fatty acid, 80 to 100 parts by weight of polybasic acid, metal salts of organic sulfonic acid 5 to 20 parts by weight and 100 to 200 parts by weight of polyhydric alcohol are mixed.

Here, when the content of each composition constituting the ester-based prepolymer is out of the above range, there is a concern that alkali dissociation, water resistance, and oil resistance may not be satisfied.

On the other hand, the fatty acid is selected from among soybean oil fatty acid, tall oil fatty acid, linseed oil fatty acid, or dehydrated castor oil fatty acid. Used alone or in combination, the polybasic acid is maleic anhydride or itaconic acid, succinic acid, adipic acid, isophthalic acid acid) or lactic acid, used alone or in combination, and the metal salts of organic sulfonic acid are dimethyl-5-sulfoisophthalate sodium salt, 5-so Sodium-5-sulfoisophthalic acid (Dimethyl-5-sulfoisophthalate lithium salt) or lithium 5-sulfoisophthalic acid is used alone or in combination. , The polyhydric alcohol is trimethylol propane or 1,4-butanediol, neopentyl glycol, monoethylene glycol or diethylene glycol (Diethylene glycol) and 1,6-hexanediol (1,6-Hexanediol) can be used alone or in combination, but are not necessarily limited to the above range, and various types of fatty acids, Applications of polybasic acids, organic sulfonic acid metal salts and polyhydric alcohols are possible.

The reactive monomer is copolymerized and crosslinked with a resin having an ester main chain to satisfy the above-described alkali dissociation, water resistance, oil resistance, etc., 40 to 45 weight of acrylic acid as a reactive monomer 20 to 25 parts by weight of butyl acrylate, 10 to 15 parts by weight of methyl methacrylate, 30 to 35 parts by weight of ethylene glycol dimethacrylate, stearyl acrylate (stearyl Acrylate) 5 ~ 10 parts by weight, 2-ethylhexyl acrylate (2-ethylhexyl acrylate) 15 ~ 20 parts by weight are used. Here, if the content of the reactive monomer and the type and content of each monomer constituting it are out of the above range, there is a concern that alkali dissociation, water resistance, and oil resistance may not be satisfied.

Meanwhile, a water soluble initiator, a neutralizing agent, a leveling agent, and a defoamer are additives already known in the art, and detailed description thereof will be omitted. ) is an example of ammonium persulfate, an example of a neutralizing agent is ammonium hydroxide, an example of a leveling agent is polyether-modified polysiloxane, an antifoaming agent Examples of the (defoamer) may include polyether siloxane, etc., but are not necessarily limited to the above types and content ranges, and various types of additives may be used according to the type of paper, use environment, and purpose within a known content range. can be applied as

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited by the examples.

1. Preparation of ester-based prepolymer

(Production Example 1)

Based on 100 parts by weight of dehydrated castor oil fatty acid, which is a fatty acid, 30 parts by weight of succinic acid, which is a polybasic acid, 30 parts by weight of itaconic acid, 40 parts by weight of adipic acid and 20 parts by weight of dimethyl-5-sulfoisophthalate sodium salt, which is a metal salts of organic sulfonic acid, and polyhydric alcohol 43 parts by weight of phosphorus neopentyl glycol, 27 parts by weight of trimethylol propane, 80 parts by weight of 1,4-butanediol, 50 parts by weight of monoethylene glycol Raw materials were prepared by mixing. Then, while injecting nitrogen into the flask, the raw materials were added, the temperature was raised to 220° C., and then the reaction was performed for about 3 to 4 hours. In addition, when the temperature reached 220 ° C., a reflux reaction was performed, and the degree of polymerization was confirmed while measuring the acid value and viscosity. When the target value was reached, the reaction was terminated by lowering the temperature to obtain an ester-based prepolymer.

(Production Example 2)

Linseed oil fatty acid, which is fatty acid: Dehydrated Castor Oil Fatty Acid = 5: 5, based on 100 parts by weight, polybasic acid, succinic acid ) 25 parts by weight, Itaconic acid 25 parts by weight, Adipic acid 25 parts by weight, Maleic anhydride 5 parts by weight and Metal salts of organic sulfonic acid 5 parts by weight of phosphorus dimethyl-5-sulfoisophthalate sodium salt and 30 parts by weight of polyhydric alcohol, neopentyl glycol, 10 parts by weight of trimethylol propane A raw material was prepared by mixing 30 parts by weight of 1,4-butanediol and 30 parts by weight of diethylene glycol. Then, while injecting nitrogen into the flask, the raw materials were added, the temperature was raised to 220° C., and then the reaction was performed for about 3 to 4 hours. In addition, when the temperature reached 220 ° C., a reflux reaction was performed, and the degree of polymerization was confirmed while measuring the acid value and viscosity. When the target value was reached, the reaction was terminated by lowering the temperature to obtain an ester-based prepolymer.

2. Preparation of biodegradable resin composition for paper coating

(Example 1)

Based on 100 parts by weight of the ester prepolymer according to Preparation Example 1, 40 parts by weight of acrylic acid, 20 parts by weight of butyl acrylate, methyl methacrylate (reactive monomer) methyl methacrylate) 10 parts by weight, ethylene glycol dimethacrylate 30 parts by weight, stearyl acrylate 5 parts by weight, 2-ethylhexyl acrylate 15 parts by weight, Water-soluble initiator (Ammonium persulfate, Sigma-Aldrich) 0.1 part by weight, neutralizing agent (Ammonium hydroxide, OCI) 1 part by weight, leveling agent (EFKA 3035, EFKA) 2 parts by weight and antifoaming agent (BYK 1790, BYK) 0.6 part by weight The raw material was prepared in parts. After putting pre-polyester in a 4-necked reactor and raising the temperature to 80° C., distilled water was doped into the reactor while stirring at high speed at 600 rpm of the stirrer to disperse the mixture. In the following process, nitrogen was injected into the reactor, and then the monomer and initiator mixture was dropped at 80° C. for about 1 hour. After that, while the reaction proceeded for more than 3 hours, the conversion rate of the reaction was calculated through solid content and FT-IR measurement by time. When the theoretical solid content was reached, a neutralizing agent was added to neutralize, and after the reaction was terminated, a leveling agent and an antifoaming agent were added to prepare a final coating solution.

(Example 2)

Based on 100 parts by weight of the ester prepolymer according to Preparation Example 2, 45 parts by weight of acrylic acid, 25 parts by weight of butyl acrylate, methyl methacrylate (reactive monomer) methyl methacrylate) 15 parts by weight, ethylene glycol dimethacrylate 35 parts by weight, stearyl acrylate 10 parts by weight, 2-ethylhexyl acrylate 20 parts by weight, Water-soluble initiator (Ammonium persulfate, Sigma-Aldrich) 2 parts by weight, neutralizing agent (Ammonium hydroxide, OCI) 5 parts by weight, leveling agent (EFKA 3035, EFKA) 4 parts by weight and antifoaming agent (BYK 1790, BYK) 1.0 parts by weight The raw material was prepared in parts. The synthesis method and the coating solution preparation method were performed in the same manner as in Example 1.

(Comparative Example 1)

It was prepared in the same manner as in Example 1, but a polylactic acid (PLA) resin was used without using a prepolymer.

(Comparative Example 2)

It was prepared in the same manner as in Example 2, but a polylactic acid (PLA) resin was used without using a prepolymer.

3. Evaluation of biodegradable resin composition for paper coating

The biodegradable resin composition for paper coating according to the above Examples and Comparative Examples was poured onto paper, and then applied using a coating bar to a dry thickness of about 10 μm, and then the coated paper was put into a forced circulation dryer at 110 ° C. dried for minutes. The evaluation was conducted according to the evaluation method shown in [Table 1] below, and the results are shown in [Table 2] below.

evaluation items Assessment Methods water resistance Cobb size, TAPPI T441, after putting a certain amount of coating resin in the measuring machine,
measure moisture absorption oil resistance Kit, TAPPI T559cm-02, grade check after coating resin is applied to the kit The tensile strength ASTM D 412, after preparing the coating resin, a film-type tensile specimen according to ASTM D412
After manufacturing, measure the strength at tensile fracture using UTM heat sealability ASTM D 903, heat sealing according to sealing strength 5 using a heat sealing machine and at room temperature
Peeling measurement for adhesive bonding at a tensile speed of 200 mm/min after leaving for 24 hours alkali dissociative EL 606, a paper packaging material with coated resin applied in accordance with the EL606 standard
Evaluate by test method to check whether impurities are included on the paper surface biodegradable KSM 3100-1, by measuring the amount of carbon dioxide generated under composting conditions for 45 days
Measurement of aerobic biodegradability and disintegration of paper packaging materials with coating resin applied

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 original film condition -tack(△)
- Strongest film strength (●) -tack(△)
- Strongest film strength (●) - tack(○)
- Strong film strength (○) - tack(○)
- Strong film strength (○) Water resistance (g/m ² /2min) 8 8 16 17 Oil resistance (Kit#) 6 6 3 3 Tensile strength (MPa) 15 14 8.7 8.5 Thermal adhesive gf/inch) 530 536 480 180 alkali dissociative has exist has exist doesn't exist doesn't exist biodegradable 64.5 66 62 61

As shown in [Table 2], it can be seen that the biodegradable resin composition for paper coating according to an embodiment of the present invention has excellent water resistance, oil resistance, alkali dissociation and biodegradability as well as physical properties as a coating composition.

As described above, the biodegradable resin composition for coating paper based on vegetable fatty acids that can be recycled according to the present invention has been described through the above preferred examples and its excellence has been confirmed, but those skilled in the art are in the scope of the following claims. It will be understood that various modifications and changes may be made to the present invention without departing from the spirit and scope of the described invention.

Claims (3)

In the biodegradable resin composition,
Based on 100 parts by weight of the ester prepolymer, 40 to 45 parts by weight of acrylic acid as a reactive monomer, 20 to 25 parts by weight of butyl acrylate, methyl methacrylate ) 10 to 15 parts by weight, 30 to 35 parts by weight of ethylene glycol dimethacrylate, 5 to 10 parts by weight of stearyl acrylate, 2-ethylhexyl acrylate 15 to 20 parts by weight, 0.1 to 2 parts by weight of a water soluble initiator, 1 to 5 parts by weight of a neutralizing agent, 2 to 4 parts by weight of a leveling agent and 0.6 to 1.0 parts by weight of a defoamer made of wealth,
The ester-based prepolymer is based on 100 parts by weight of fatty acid, 80 to 100 parts by weight of polybasic acid, 5 to 20 parts by weight of metal salts of organic sulfonic acid, and polyhydric alcohol ( Polyhydric alcohol) 100 to 200 parts by weight,
The fatty acid is selected from soybean oil fatty acid, tall oil fatty acid, linseed oil fatty acid, or dehydrated castor oil fatty acid, alone or used in combination,
The polybasic acid is maleic anhydride or itaconic acid, succinic acid, adipic acid, isophthalic acid or lactic acid ), used alone or in combination,
The organic sulfonic acid metal salts (Metal salts of organic sulfonic acid) are dimethyl-5-sulfoisophthalate sodium salt, 5-sodiosulfo isophthalic acid (Sodium-5-sulfoisophthalic acid, 5-sulfoisophthalate) Used alone or in combination with dimethyl-5-sulfoisophthalate lithium salt or lithium 5-sulfoisophthalic acid,
The polyhydric alcohol is trimethylol propane or 1,4-butanediol, neopentyl glycol, monoethylene glycol or diethylene glycol ( Diethylene glycol), 1,6-hexanediol (1,6-Hexanediol), characterized in that used alone or in combination, a recyclable vegetable fatty acid-based biodegradable resin composition for paper coating. delete delete