KR101276294B1 - Starch based hot melt adhesiven with improved compatibility and adhesion strength - Google Patents

Abstract

PURPOSE: A hot melt adhesive is provided to have excellent adhesion and workability and to improve compatibility and adhesion without including a plasticizer. CONSTITUTION: A hot melt adhesive consists of starch, thermoplastic polymer, and composition including a tackifier. The amount of the starch is 20-60 wt% or more. The amount of the thermoplastic polymer is 20-200 parts by weight based on 100.0 parts by weight of starch. The amount of the tackifier is 25-150 parts by weight based on 100.0 parts by weight of starch and is mixed of an aliphatic hydrocarbon resin and a hydrogenated hydrocarbon resin.

Description

Starch based hot melt adhesiven with improved compatibility and adhesion strength

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to starch-based hot melt adhesives, and more particularly, to starch-based hot melt adhesives which contain at least a predetermined amount of starch and impart excellent adhesion and workability.

Adhesion refers to a state in which two surfaces are bonded by an attractive force between molecules, atoms, and ions. Adhesion is widely applied in our daily lives not only for daily necessities such as tapes and bonds, but also for automobiles and cutting-edge semiconductor devices. In recent years, the demand for adhesives in each field has been diversified due to the remarkable industrial development.

The polymer adhesive may be classified into a chemical reaction type, a solvent type, a hot melt type and the like according to the solidification process. Among them, hot melt adhesive is a representative example that is easy to use and can meet the requirements of the emerging environment.

Hot melt adhesive (hot melt adhesive) is a solid material at room temperature without melting or dispersing in a solvent to melt only 100% of the heat in an adhesive to use as a liquid. Hot-melt adhesives were first developed by DuPont in the 1960s as an ethylene-vinylacetate resin (EVA), and have the advantages of high productivity, eco-friendly features, broad applicability, and re-adhesion through process automation. The growth rate is high. The hot melt adhesive is applied to the surface to be adhered in a molten state and then cooled and solidified by dissipating heat to and around the surface of the adherend. Hot melt adhesive is characterized by a small working space and fast adhesion speed without the need for drying process compared to other solvent adhesives or water dispersion adhesives. High-speed adhesion enables the automation and productivity increase of the production line, and it has considerable economical efficiency such as improvement of productivity, reduction of labor cost, and reduction of raw material amount due to control of coating amount. Hot melt adhesives have been applied in many fields such as packaging, bookbinding, construction, woodworking, automotive, textile, electrical / electronics, etc.

Conventional commercial hot melt adhesives generally include ethylene-vinylacetateyl series, polyolefin series, styrene block copolymerization series, polyamide series, polyester series, urethane series (reactive hotmelt), and the like, and the base resin is a hotmelt adhesive. Among the physical properties of the most important adhesion and cohesion has a big impact. Conventional commercial hot melt adhesives are mainly composed of petroleum-based materials, so the lack of environmentally friendly properties, manufacturing costs can be increased due to external factors such as supply and demand of petroleum-based materials, depletion of petroleum-based materials, etc. I have a problem. Therefore, in consideration of environmental friendliness, stable supply of supplies, cost value, etc., it is necessary to replace all or part of the basic resin, which is a major component of the hot melt adhesive, with biomass, in particular starch, which can be infinitely regenerated.

In addition, conventional commercial hot melt adhesives use plasticizers to improve compatibility (or mixing) and processability and enhance the adhesion of the final product in the manufacturing process, where part of the base resin is replaced with starch and contains plasticizers. In the hot melt adhesive, bubbles are generated in the melting process, and thus, adhesion is not uniform, and there is a concern that unwanted physical property changes such as color change may occur.

The present invention was derived to solve the conventional problems, and an object of the present invention is to provide a starch-based hot melt adhesive excellent in adhesion and workability even if a substantial amount of the base resin is replaced with starch. It is also an object of the present invention to provide a hot melt adhesive with improved compatibility and adhesion even without a plasticizer.

In order to solve the above object of the present invention, the present invention is a composition comprising a starch, a thermoplastic polymer, and a tackifier, wherein the starch is contained in 20 to 60% by weight based on the total weight of the composition, the thermoplastic polymer 20 to 200 parts by weight based on 100 parts by weight of starch, ethylene-vinyl acetate copolymer (Ehtylene Vinyl Acetate Copolymer, EVA), polyvinyl acetate (Polyvinyl acetate), polyvinyl alcohol, ethylene- acrylic acid copolymer, and It is composed of one or more selected from the group consisting of ethylene-methacrylic acid copolymer, the tackifier is included in 25 to 150 parts by weight relative to 100 parts by weight of starch, composed of a combination of aliphatic hydrocarbon resin and hydrogenated hydrocarbon resin It provides a starch-based hot melt adhesive, characterized in that.

The hot melt adhesive according to the present invention contains about 20 to 60% by weight of starch which is biomass that can be infinitely regenerated, which is less harmful, more environmentally friendly, and reduced compared to a hot melt adhesive containing a petroleum-based substance as a main component. It has manufacturing costs and is less sensitive to depletion of petroleum resources. In addition, the hot-melt adhesive according to the present invention contains hydrocarbon resins different from each other as a tackifier, and even when no plasticizer is included, compatibility between the components does not deteriorate and excellent adhesion and workability are provided. It can be applied to various fields such as woodworking and textiles.

1 is a photograph showing the hot melt adhesive prepared in Preparation Example 22, Figure 2 is a photograph showing the hot melt adhesive prepared in Preparation Example 28.

The present invention relates to a starch-based hot melt adhesive, wherein the starch-based hot melt adhesive according to the present invention consists of a composition comprising starch, a thermoplastic polymer, and a tackifier. In addition, the starch-based hot melt adhesive according to the present invention may optionally include a plasticizer, preferably may further comprise an auxiliary additive. Hereinafter, the present invention will be described by dividing the components of the starch-based hot melt adhesive according to the present invention.

Starch

The hot melt adhesive according to the present invention comprises starch in an amount of about 20 to 60% by weight, preferably about 25 to 55% by weight, more preferably about 30 to 50% by weight, based on the total weight of the composition. If the starch content is less than 20% by weight, the adhesive strength may drop below the required level in the field where the hot melt adhesive is used, and workability may be deteriorated.When the starch content exceeds 60% by weight, the adhesion strength is rapidly decreased and melted. The viscosity is very high and workability may deteriorate.

Starch is not greatly limited in kind, and includes, for example, corn starch, waxy corn starch, tapioca starch, potato starch, sweet potato starch, rice starch, wheat starch and the like. In addition, the starch includes an unmodified starch or a specific modified starch, and is preferably an unmodified starch in consideration of adhesion, workability, manufacturing cost, and the like of the hot melt adhesive. Unmodified starch is a starch obtained from a conventional starch production process, and is a modified starch (eg, acid-treated starch, oxidized starch, acetyladione) whose physical properties (viscosity, thermal stability, freeze thaw stability) have been changed by chemical treatment and heat treatment. Starch phosphate, acetyl phosphate starch, octenyl pumpkin starch, phosphate starch, monophosphate starch, phosphate starch, starch acetate, hydroxypropyl phosphate starch, hydroxypropyl starch, etc.). to be. Specific modified starches used in the composition for hot melt adhesives of the present invention include acid modified starch, Oxidized Starch, Starch Acetate, Starch Octenyl Succinate, and the like. have. Based on the above, the starch according to the present invention is an unmodified starch, acid modified starch, oxidized starch, oxidized starch, starch acetate, and octenyl succinate starch. It may be composed of one or more selected from the group consisting of.

Thermoplastic Polymer

The thermoplastic polymer functions to control the adhesion and cohesion of the hot melt adhesive, and the thermoplastic polymer used in the present invention is not particularly limited as long as it contains a vinyl group or a hydroxyl group, for example, ethylene-vinylacetate air. Ethylene Vinyl Acetate Copolymer (EVA), Polyvinyl Acetate (Polyvinyl Acetate), Polyvinyl Alcohol (Polyvinyl Alcohol), Ethylene-Acrylic Acid Copolymer, and Ethylene Methacrylic Acid Copolymer Can be configured.

The content of the thermoplastic polymer in the hot melt adhesive according to the present invention is about 20 to 200 parts by weight, preferably about 30 to 150 parts by weight, more preferably about 40 to 120 parts by weight, based on 100 parts by weight of starch. If the content of the thermoplastic polymer is less than 20 parts by weight, the adhesive strength of the hot melt adhesive is drastically reduced and there is little flow, which makes the work hard. In addition, when the content of the thermoplastic polymer is more than 200 parts by weight, there is a fear that the adhesive strength of the hot melt adhesive falls below the level required in the field, and the flowability of the hot melt adhesive is so great that workability may deteriorate.

Tackifier ( Tackifier )

When the hot melt adhesive is composed only of starch and thermoplastic polymer, hot-tack adhesive is poor in hot-tack and wetting, and the viscosity is high, so that the operation is not easy. Therefore, the hot melt adhesive according to the present invention further includes a tackifier.

In the hot melt adhesive according to the present invention, the tackifier is a low molecular weight resin, and when used in combination with a starch and a thermoplastic polymer, which is a basic component, lowers the melt viscosity and improves workability. It improves the wettability and the adhesive force on the surface of the adherend of the hot melt adhesive, it is possible to control the solidification time and the like. In addition, the tackifier according to the present invention is composed of a combination of an aliphatic hydrocarbon resin and a hydrogenated hydrocarbon resin in order to improve compatibility between starch and other resins, that is, mixing.

At this time, the aliphatic hydrocarbon resin (Aliphatic hydrocarbon resin) is a resin containing an aliphatic hydrocarbon as the main monomer, commercial products Hikorez A-1100, Hikorez A-1100S, Hikorez C-1100, Hikorez of Kolon Emulsifier (Korea) R-1100, Hikorez R-1100S, Hikorez T-1080, Hikorez T-1095, Hikorez T-1100, Hikorez T-3100, Hikorez H-2200, Hikorez H-2300 and the like. In addition, in the present invention, the aliphatic hydrocarbon resin is preferably an aliphatic hydrocarbon modified with an aromatic hydrocarbon. The aliphatic hydrocarbon resin modified with the aromatic hydrocarbon is prepared by copolymerizing an aliphatic olefin and an aromatic olefin, preferably Trans-1,3-pentadiene, cis-1,3-penta Cis-1,3-pentadiene, 2-methyl-2-butene, cyclopentadiene, isoprene, piperylene, dicyclopentadiene (dicyclopentadiene, DCPD), cyclopentene, methylcyclopentene, and at least one aliphatic olefin selected from the group consisting of dihydrodicyclopentadiene and styrene, vinyltoluene, methylstyrene, coumarone, indene, and methyl It is composed of a copolymer of one or more aromatic olefins selected from the group consisting of indenes, more preferably aliphatic chain hydrocarbons (hydrocarbons having 4 to 10 carbon atoms), aliphatic ring hydrocarbons (for example cyclopentadiene, disa Chloropentadiene) and aromatic hydrocarbons (for example, hydrocarbons having 8 to 10 carbon atoms) as monomers. Commercial products of aliphatic hydrocarbon resins modified with aromatic hydrocarbons include Hikorez T-1080, Hikorez T-1095, Hikorez T-1100, Hikorez T-3100, Hikorez H-2200, Hikorez H-2300, etc. There is this.

In addition, the hydrogenated hydrocarbon resin (Hydrogenated hydrocarbon resin) is a hydrogenated hydrocarbon resin by the hydrogenation reaction, it can be subdivided into hydrogenated aliphatic hydrocarbon resin, hydrogenated aromatic hydrocarbon resin, hydrogenated aliphatic / aromatic hydrocarbon resin, etc. Sukorez D-300, Sukorez D-390, Sukorez SU-90, Sukorez SU-100, Sukorez SU-100S, Sukorez SU-110, Sukorez SU-120, Sukorez SU- 130, Sukorez SU-200, Sukorez SU-210, Sukorez SU-220, Sukorez SU-230, Sukorez SU-230S, Sukorez SU-400, Sukorez SU-420, Sukorez SU-490, Sukorez SU-500, Sukorez SU- 525 and Sukorez PX-95. In the present invention, the hydrogenated hydrocarbon resin (Hydrogenated hydrocarbon resin) is preferably a hydrogenated hydrocarbon resin modified with an ester-containing acrylic monomer. Hydrogenated hydrocarbon resin modified with the ester group-containing acrylic monomer is prepared by copolymerizing unsaturated hydrocarbons such as aliphatic olefins (for example, aliphatic chain hydrocarbons or aliphatic hydrocarbons) or aromatic olefins with ester group-containing acrylic monomers. This is hydrogenated, preferably Trans-1,3-pentadiene, cis-1,3-pentadiene, 2-methyl-2- Butene (2-methyl-2-butene), cyclopentadiene, Isoprene, Piperylene, Dicyclopentadiene (DCPD), Cyclopentene (Cyclopentene), Methylcyclopentene, Di At least one unsaturated hydrocarbon selected from the group consisting of hydrodicyclopentadiene, styrene, vinyltoluene, methylstyrene, coumarone, indene, and methylindene, methylacrylate, ethyl It was hydrogenated to a methacrylate, butyl acrylate, hexyl acrylate, octyl acrylate, methyl methacrylate, and copolymers of an ester group-containing acrylic monomer selected from the group consisting of meta-butyl methacrylate. Commercial products of the hydrogenated hydrocarbon resin modified with the ester group-containing acrylic monomer include Sukorez PX-95 of Kolon Emulsifier Co., Ltd. (South Korea). In addition, the hydrogenated hydrocarbon resin modified with the ester group-containing acrylic monomer is more preferably aliphatic chain hydrocarbons (hydrocarbons having 4 to 10 carbon atoms), aliphatic ring hydrocarbons (for example cyclopentadiene, dicyclopentadiene) and The copolymer produced by copolymerizing the ester group-containing acrylic monomer is hydrogenated.

In addition, the hot melt adhesive according to the present invention may further include a rosin-based resin, a terpin-based resin, or an aromatic hydrocarbon resin in addition to the aliphatic hydrocarbon resin and the hydrogenated hydrocarbon resin as a tackifier. Commercial products of the aromatic hydrocarbon resin (Aromatic hydrocarbon resin) as Hikotack P-110S, Hikotack P-120, Hikotack P-120HS, Hikotack P-120S, Hikotack P-140, Hikotack P-140M of Kolon Emulsifier (Korea) , Hikotack P-150, Hikotack P-160, Hikotack P-90, Hikotack P-90S, Hirenol PL-1000, Hirenol PL-400. In addition, commercial products of the rosin-based resins include Komotac KF382S, Komotac KF392S, Komotac KF452S, Komotac KF462S, Komotac KS-2090, Komotac KS-2100, Komotac KS-2110, Komotac KZ223S and Komotac KZ224S. Etc.

The content of the tackifier in the hot melt adhesive according to the present invention is about 25 to 150 parts by weight, preferably 35 to 120 parts by weight, more preferably 40 to 100 parts by weight relative to 100 parts by weight of starch. If the content of the tackifier is less than 25 parts by weight, the effect of lowering the melt viscosity due to the addition of the tackifier may be insufficient, and thus the workability of the hot melt adhesive may not reach a satisfactory level, and the adhesive strength of the hot melt adhesive may be satisfied. If the content of the tackifier exceeds 150 parts by weight, the adhesive strength of the hot melt adhesive rapidly decreases, and the rate of decrease of the melt viscosity due to the excess of the tackifier is not large. There is a risk of reducing the overall physical properties of the hot melt adhesive.

Plasticizer

Since the hot melt adhesive according to the present invention contains hydrocarbon resins different from each other as a tackifier, even when no plasticizer is included, the hot melt adhesive has excellent adhesion and workability without compromising compatibility between components. When the plasticizer is used to improve the compatibility of starch and other resins, that is, mixing properties, in the manufacture of starch-based hot melt adhesives, bubbles are generated during the melting process and browning of the final product. The adhesive preferably does not contain a plasticizer, and even when the plasticizer is used, its amount is preferably limited in order to improve compatibility and adhesion.

Plasticizers are used to impart flexibility and adhesion to polar polymers, and the types of plasticizers according to the present invention are not particularly limited, for example, sorbitol, ethylene glycol, glycerin, glycerin diacetate, and penta. It may be composed of one or more selected from the group consisting of erythritol. The content of the plasticizer in the hot melt adhesive according to the present invention is about 0.5 to 50 parts by weight, preferably 1 to 35 parts by weight, more preferably 2 to 20 parts by weight based on 100 parts by weight of starch. If the content of the plasticizer is less than 0.5 parts by weight, the effect of the addition of the plasticizer is insignificant. If the content of the plasticizer is more than 50 parts by weight, the generation and browning of bubbles are so severe that the quality of the product is greatly reduced and the excessive use of the plasticizer is required. There is a risk of economic deterioration. When the content of the plasticizer is 2 to 20 parts by weight with respect to 100 parts by weight of starch, it is possible to minimize the generation and browning of bubbles and at the same time expect a certain level of compatibility improvement by adding the plasticizer.

Auxiliary additives

The hot melt adhesive according to the present invention may further include auxiliary additives in addition to starch, plasticizer, thermoplastic polymer, tackifier, and adhesion promoter, and the auxiliary additive may change the physical properties of the hot melt adhesive or impart specific functions to the hot melt adhesive. .

The auxiliary additive included in the hot melt adhesive according to the present invention may be composed of one or more selected from the group consisting of waxes, polybutenes, oils, fillers, and antioxidants.

The wax is added to lower the melt viscosity, to improve the wettability on the nonpolar surface, to prevent blocking, to adjust the solidification time, and specifically, paraffin wax or polyethylene wax. Polybutene is added to improve water resistance or to impart flexibility. The oil is added to give flexibility, to improve processes such as melt kneading. Filler is a substance applied for the purpose of anti-aging, reinforcement and increase in the practical use of rubber or plastic, and is used to control the flowability of hot melt adhesive. The type of filler is not particularly limited and may be composed of one or more selected from, for example, calcium carbonate, clay, bentonite, or calcium stearate. Antioxidant may be added when using a material containing a structure that can be easily oxidized due to poor thermal stability can improve the change in viscosity, yellowing, deterioration of adhesion and degradation of durability due to oxidation and decomposition. The type of antioxidant is not particularly limited, and specific examples thereof include phenols, aromatic amines, citric acid, or ascorbic acid.

In addition, the hot melt adhesive according to the present invention is not significantly limited in its use, and in particular, can be applied to many fields such as packaging, bookbinding, construction, carpentry, automotive, textile, electrical / electronics, the content of starch, The content of the tackifier, the content of the adhesion promoter and the like can be adjusted.

In addition, the hot melt adhesive according to the present invention can be produced by a variety of methods, for example, it may be prepared by melt kneading by kneader, melting and extrusion by an extruder. At this time, the melting temperature is not particularly limited, for example, may be melted at 110 ~ 200 ℃.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to clearly illustrate the present invention and do not limit the scope of protection of the present invention.

1. Explanation of analysis method

(1) 180 ° Peel Shear Adhesion Strength

In order to evaluate the 180 ° peeling strength of the hot melt adhesive, an edge made of a wood-based particle board and an ABS resin (acrylonitrile butadiene styrene copolymer) was bonded using an edge bander, a hot melt adhesive applicator, to prepare an adhesive specimen. It was. At this time, the use temperature of the hot melt adhesive was about 175 ~ 180 ℃. After the adhesive specimens were prepared and about 24 hours had elapsed, the average stress was measured for a section using an Instron Universial Testing Machine, and the average value was repeated eight times to obtain 180 ° peeling. Taken by strength. At this time, the load cell and the speed conditions of the Instron universal material tester were 5 kN and 10 mm / min, respectively.

2. Containing Starch Hot melt  Manufacture of adhesives

(1) Changes in Physical Properties of Hot Melt Adhesives with Varying Starch Content

Production Example 1

100 g of unmodified corn starch, 100 g of pentaerythritol as a plasticizer, 500 g of ethylene-vinylacetate copolymer as a thermoplastic polymer, and an aliphatic hydrocarbon resin as a tackifier (Product name: Hikorez H-2300 Supplier: Kolon Emulsification, Korea) 300g was added to a kneader (kneader, kneader) and melt kneaded at 170 to 180 ° C. to prepare a hot melt adhesive.

At this time, Hikorez H-2300, a tackifier, is an aliphatic hydrocarbon resin modified with an aromatic hydrocarbon, specifically, a resin obtained by copolymerizing an aliphatic olefin or diolefin and an aromatic olefin.

Preparation Examples 2 to 9.

A hot melt adhesive was prepared in the same manner as in Preparation Example 1 except that corn starch content, plasticizer content, or thermoplastic polymer content was changed.

Table 1 shows the kinds and contents of the components used in Preparation Examples 1 to 9, and the 180 ° peeling strength of the hot melt adhesive.

division Starch (g) Plasticizer (g) Thermoplastic polymer (g) Tackifier (g) 180 ° peeling adhesive strength (kgf) Unmodified Corn Starch Pentaerythritol Ethylene-Vinyl Acetate Copolymer Hikorez H-2300 Production Example 1 100 100 500 300 8.2 Production Example 2 200 100 400 300 7.0 Production Example 3 300 50 350 300 8.5 Production Example 4 300 100 300 300 8.7 Production Example 5 400 50 250 300 9.5 Production Example 6 400 100 200 300 9.8 Production Example 7 400 150 150 300 9.4 Production Example 8 500 100 100 300 7.2 Production Example 9 650 100 50 300 6.1

As shown in Table 1, when the starch content is 65% by weight or more based on the total weight of the hot melt adhesive and the content of the thermoplastic polymer is less than 20 parts by weight based on 100 parts by weight of the starch, the adhesive strength of the hot melt adhesive decreases rapidly and the flowability is almost It wasn't so smooth. In addition, when the starch content is less than 20% by weight based on the total weight of the hot melt adhesive and the content of the thermoplastic polymer is more than 200 parts by weight based on 100 parts by weight of the starch, the adhesive strength of the hot melt adhesive is slightly lowered and the flowability is too high, so that the hot melt adhesive may be Flowing phenomenon occurred.

(2) Changes in Physical Properties of Hot Melt Adhesives with Various Plasticizer Contents

Production Example 10.

Kneader 400g unmodified corn starch, 250g ethylene-vinylacetate copolymer (EVA) as a thermoplastic polymer, and 200g aliphatic hydrocarbon resin (Trade name: Hikorez H-2300; supplier: Kolon Emulsification, Korea) as a tackifier (Kneader, kneader) and melt kneading at 170 ~ 180 ℃ to prepare a hot melt adhesive.

Production Example 11.

400 g of unmodified corn starch, 50 g of pentaerythritol as a plasticizer, 250 g of ethylene-vinylacetate copolymer as a thermoplastic polymer, and an aliphatic hydrocarbon resin as a tackifier (Product name: Hikorez H-2300 Supplier: Kolon Emulsification, Korea) 200g was added to a kneader (kneader, kneader) and melt kneaded at 170 to 180 ° C. to prepare a hot melt adhesive.

Production Example 12.

A hot melt adhesive was prepared in the same manner as in Preparation Example 11, except that 100 g of pentaerythritol was used as a plasticizer.

Production Example 13.

A hot melt adhesive was prepared in the same manner as in Preparation Example 11, except that 200 g of pentaerythritol was used as a plasticizer.

Table 2 shows the kinds and contents of the components used in Preparation Examples 10 to 13, and the 180 ° peeling strength of the hot melt adhesive.

division Starch (g) Plasticizer (g) Thermoplastic polymer (g) Tackifier (g) 180 ° peeling adhesive strength (kgf) Unmodified Corn Starch Pentaerythritol Ethylene-Vinyl Acetate Copolymer Hikorez H-2300 Production Example 10 400 - 250 200 6.3 Production Example 11 400 50 250 200 9.4 Production Example 12 400 100 250 200 9.3 Production Example 13 400 200 250 200 8.3

As shown in Table 2, when the hot melt adhesive does not contain a plasticizer as a component, the adhesive force drastically decreased. This is believed to be due to poor compatibility of starch and other resins due to no addition of plasticizer.

(3) Changes in Physical Properties of Hot Melt Adhesives with Changes in Tackifiers

Production Example 14.

400 g unmodified corn starch, 100 g pentaerythritol as a plasticizer, 200 g ethylene-vinylacetate copolymer (EVA) as a thermoplastic polymer, and an aliphatic hydrocarbon resin as a tackifier (Product name: Hikorez H-2300 Supplier: Kolon Emulsification, Korea) 100g was added to a kneader (kneader, kneader) and melt kneaded at 170 to 180 ° C. to prepare a hot melt adhesive.

Preparation Examples 15 to 20.

A hot melt adhesive was prepared in the same manner as in Preparation Example 14, except that the content of the tackifier was changed.

Table 3 shows the kinds and contents of the components used in Preparation Examples 14 to 20, and the 180 ° peeling strength of the hot melt adhesive.

division Starch (g) Plasticizer (g) Thermoplastic polymer (g) Tackifier (g) 180 ° peeling adhesive strength (kgf) Unmodified Corn Starch Pentaerythritol Ethylene-Vinyl Acetate Copolymer Hikorez H-2300 Production Example 14 400 100 200 100 7.2 Production Example 15 400 100 200 200 10.1 Production Example 16 400 100 200 300 9.8 Production Example 17 400 100 200 400 9.5 Production Example 18 400 100 200 500 9.1 Production Example 19 400 100 200 600 7.5 Production example 20 400 100 200 700 5.5

As shown in Table 3, when the content of the tackifier is less than 25 parts by weight based on 100 parts by weight of starch, the adhesive strength of the hot melt adhesive is not greater than an appropriate level, and the content of the tackifier is greater than 150 parts by weight relative to 100 parts by weight of starch. In this case, the adhesive force decreased drastically.

(4) Change of Physical Properties of Hot Melt Adhesive According to Combination of Tackifiers

Production Example 21.

400 g of unmodified corn starch, 100 g of pentaerythritol as a plasticizer, 214 g of ethylene-vinylacetate copolymer (EVA) as a thermoplastic polymer, and an aliphatic hydrocarbon resin as a tackifier (Product name: Hikorez H-2300 Supplier: Kolon Emulsification, Korea) 214 g was added to a kneader (kneader, kneader) and melt kneaded at 170 to 180 ° C. to prepare a hot melt adhesive.

Preparation Examples 22 to 28.

A hot melt adhesive was prepared in the same manner as in Preparation Example 21, except that the amount of the plasticizer, the use of the plasticizer, and the type and content of the tackifier were changed.

Table 4 shows the types and contents of the components used in Preparation Examples 21 to 28, and the 180 ° peeling strength of the hot melt adhesive.

division Starch (g) Plasticizer (g) Thermoplastic polymer (g) Tackifier (g) 180 ° peeling adhesive strength (kgf) Unmodified Corn Starch Pentaerythritol Ethylene-Vinyl Acetate Copolymer Hikorez H-2300 Sukorez PX-95 Production Example 21 400 100 214 200 - Production Example 22 400 100 214 150 50 Production Example 23 400 100 214 100 100 Production Example 24 400 100 214 50 150 Production example 25 400 100 214 - 200 Production Example 26 400 50 214 150 50 Production Example 27 400 10 214 150 50 Production Example 28 400 - 214 150 50

* Hikorez H-2300 (Supplier: Kolon Emulsification, Korea): Hikorez H-2300, a tackifier, is an aliphatic hydrocarbon resin modified with an aromatic hydrocarbon, specifically a resin obtained by copolymerizing an aliphatic olefin or a diolefin and an aromatic olefin. to be. At this time, the aliphatic olefin or Diolefin (Trans-1,3-pentadiene), cis-1,3-pentadiene (Cis-1,3-pentadiene), 2- 2-methyl-2-butene, cyclopentadiene, isoprene, piperylene, dicyclopentadiene (DCPD), cyclopentene, methyl Cyclopentene, dihydrodicyclopentadiene, and the like, and aromatic olefins include styrene, vinyltoluene, methyl styrene, coumarone, indene, methyl indene, and the like.

* Sukorez PX-95 (Supplier: Kolon Emulsification, Korea): Sukorez PX-95, a tackifier, is a hydrogenated hydrocarbon resin modified with an ester-containing acrylic monomer, specifically, trans-1,3-pentadiene (Trans-1 , 3-pentadiene), cis-1,3-pentadiene, 2-methyl-2-butene, cyclopentadiene, isoprene ( Aliphatic hydrocarbons such as isoprene, piperylene, dicyclopentadiene (DCPD), cyclopentene, methylcyclopentene, dihydrodicyclopentadiene, and methyl acrylate, ethyl acrylate, butyl acryl The copolymer obtained by copolymerizing (meth) acrylates, such as a rate, hexyl acrylate, octyl acrylate, methyl methacrylate, and butyl methacrylate, is hydrogenated by the hydrogenation reaction.

As shown in Table 4, when both Hikorez H-2300 and Sukorez PX-95 are used as the tackifier, the use of the plasticizer has a great effect on the adhesive strength of the hot melt adhesive, unlike the case where only Hikorez H-2300 is used as the tackifier. It was confirmed that it was not harmful.

In addition, Figure 1 is a photograph showing a hot melt adhesive prepared in Preparation Example 22, Figure 2 is a photograph showing a hot melt adhesive prepared in Preparation Example 28. As shown in FIG. 1, when a plasticizer is used to prepare the hot melt adhesive, bubbles are generated during the melting of the components, and the final hot melt adhesive is browned. On the other hand, as shown in FIG. 2, when the hot melt adhesive is prepared by using Hikorez H-2300 and Sukorez PX-95 as a tackifier and simultaneously using no plasticizer, no bubbles are generated and no discoloration occurs.

(5) Changes in Physical Properties of Hot Melt Adhesives According to Manufacturing Methods

Production Example 29.

400 g of unmodified corn starch, 214 g of ethylene-vinyl acetate copolymer (EVA) as a thermoplastic polymer, and 150 g of hydrophobic hydrocarbon resin (product name: Hikorez H-2300; supplier: Kolon Emulsification, Korea) as a tackifier 50 g of a genified hydrocarbon resin (product name: Sukorez PX-95; supplier: Kolon Emulsification, Korea) was added to a kneader (kneader, kneader) and melt kneaded at 170 to 180 ° C. to prepare a hot melt adhesive.

Production Example 30.

Except that 100g of aliphatic hydrocarbon resin (product name: Hikorez H-2300; supplier: Kolon Emulsification, Korea) and 100g of hydrogenated hydrocarbon resin (product name: Sukorez PX-95; supplier: Kolon Emulsion, Korea) were used as tackifiers. Hot melt adhesive was prepared in the same manner as in Preparation Example 29.

Production Example 31.

400 g of unmodified corn starch, 214 g of ethylene-vinyl acetate copolymer (EVA) as a thermoplastic polymer, and 150 g of hydrophobic hydrocarbon resin (product name: Hikorez H-2300; supplier: Kolon Emulsification, Korea) as a tackifier 50 g of a genified hydrocarbon resin (product name: Sukorez PX-95; supplier: Kolon Emulsification, South Korea) was introduced into a hopper of an extruder, melted at 170 to 180 ° C, and extruded to prepare a hot melt adhesive.

Production Example 32.

Except that 100g of aliphatic hydrocarbon resin (product name: Hikorez H-2300; supplier: Kolon Emulsification, Korea) and 100g of hydrogenated hydrocarbon resin (product name: Sukorez PX-95; supplier: Kolon Emulsion, Korea) were used as tackifiers. Hot melt adhesive was prepared in the same manner as in Preparation Example 31.

Table 5 shows the preparation method of the hot melt adhesive used in Preparation Examples 29 to 32, the type and content of components constituting the hot melt adhesive, and the 180 ° peeling strength of the hot melt adhesive.

division Manufacturing method Starch (g) Thermoplastic polymer (g) Tackifier (g) 180 ° peeling adhesive strength (kgf) Unmodified Corn Starch Ethylene-Vinyl Acetate Copolymer Hikorez H-2300 Sukorez PX-95 Production Example 29 Kneader 400 214 150 50 10.6 Production Example 30 Kneader 400 214 100 100 10.4 Production Example 31 Extruder 400 214 150 50 10.6 Preparation Example 32 Extruder 400 214 100 100 10.2

As shown in Table 5, when the hot melt adhesive was prepared by using a kneader and an extruder, there was no significant difference in the adhesive strength of the hot melt adhesive.

Although the present invention has been described through the above embodiments as described above, the present invention is not necessarily limited thereto, and various modifications can be made without departing from the scope and spirit of the present invention. In addition, many modifications may be made to adapt a particular situation and material to the teachings of the invention without departing from the essential scope thereof. Accordingly, the protection scope of the present invention should not be construed as being limited to the particular embodiments disclosed as the best mode contemplated for carrying out the invention but to cover all embodiments falling within the scope of the appended claims.

Claims (13)

A composition comprising starch, a thermoplastic polymer, and a tackifier,
The starch is included in 20 to 60% by weight based on the total weight of the composition,
The thermoplastic polymer is contained in 20 to 200 parts by weight based on 100 parts by weight of starch, and ethylene-vinyl acetate copolymer (Ehtylene Vinyl Acetate Copolymer, EVA), polyvinyl acetate (polyvinyl acetate), polyvinyl alcohol (polyvinyl alcohol), ethylene-acrylic acid A copolymer, and at least one member selected from the group consisting of ethylene-methacrylic acid copolymers,
The tackifier is 25 to 150 parts by weight based on 100 parts by weight of starch, starch-based hot melt adhesive, characterized in that composed of a combination of aliphatic hydrocarbon resin and hydrogenated hydrocarbon resin.
The starch-based hot melt adhesive according to claim 1, wherein the aliphatic hydrocarbon resin is an aliphatic hydrocarbon resin modified with an aromatic hydrocarbon.
According to claim 2, wherein the aliphatic hydrocarbon resin modified with an aromatic hydrocarbon is trans-1,3-pentadiene (Trans-1,3-pentadiene), cis-1,3-pentadiene (Cis-1,3-pentadiene ), 2-methyl-2-butene, 2-cyclopentadiene, cyclopentadiene, isoprene, piperylene, dicyclopentadiene (dicyclopentadiene, DCPD), cyclopentene ( Cyclopentene), at least one aliphatic olefin selected from the group consisting of methylcyclopentene, and dihydrodicyclopentadiene and 1 selected from the group consisting of styrene, vinyltoluene, methylstyrene, coumarone, indene, and methylindene A starch-based hot melt adhesive, characterized in that a copolymer of at least two aromatic olefins.
The starch-based hot melt adhesive according to claim 1, wherein the hydrogenated hydrocarbon resin is a hydrogenated hydrocarbon resin modified with an ester group-containing acrylic monomer.
The hydrogenated hydrocarbon resin modified with the ester group-containing acrylic monomer is trans-1,3-pentadiene, cis-1,3-pentadiene (Cis-1). , 3-pentadiene, 2-methyl-2-butene, cyclopentadiene, isoprene, piperylene, dicyclopentadiene (DCPD) , At least one unsaturated hydrocarbon and methyl acrylate selected from the group consisting of cyclopentene, methylcyclopentene, dihydrodicyclopentadiene, styrene, vinyltoluene, methylstyrene, coumarone, indene, and methylindene Hydrogenated copolymer of an ester group-containing acrylic monomer selected from the group consisting of ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, methyl methacrylate, and butyl methacrylate. Starch-based hot-melt adhesive.
The starch-based hot melt adhesive according to claim 1, wherein the composition does not contain a plasticizer.
The composition of claim 1, wherein the composition further comprises a plasticizer,
The starch-based hot melt adhesive, characterized in that the plasticizer is contained in 1 to 50 parts by weight relative to 100 parts by weight of starch.
The starch-based hot melt adhesive according to claim 7, wherein the plasticizer is composed of at least one selected from the group consisting of sorbitol, ethylene glycol, glycerin, glycerin diacetate, and pentaerythritol.
The composition of claim 1, wherein the composition further comprises an auxiliary additive,
The auxiliary additive is included in less than 10 parts by weight based on 100 parts by weight of starch and starch-based hot melt adhesive, characterized in that composed of one or more selected from the group consisting of wax, polybutene, oil, filler, and antioxidant.
The starch-based hot melt adhesive according to claim 9, wherein the wax is paraffin wax or polyethylene wax.
The starch-based hot melt adhesive according to claim 9, wherein the filler is composed of one or more selected from calcium carbonate, bentonite, or calcium stearate.
The starch-based hot melt adhesive according to claim 9, wherein the antioxidant is citric acid or ascorbic acid.
The method according to any one of claims 1 to 8, wherein the starch is unmodified starch, acid modified starch, Oxidized Starch, Starch Acetate, and Octenyl Succinate Starch ( Starch Octenyl Succinate) starch-based hot melt adhesive, characterized in that composed of one or more selected from the group consisting of.

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