WO2016021871A1 - Composition for elastic packaging material - Google Patents

Abstract

Provided is a composition for an elastic packaging material, comprising: a mixed binder including a thermoplastic polymer having a DSC melting point of 50-150℃ and a superplasticizer containing a hydrocarbon component obtained from waste oil; and rubber chips.

Description

Elastic Packaging Material Composition

The technology disclosed herein relates to an elastic packaging composition.

Unlike general road pavement methods, pedestrians and playgrounds are packed with elastomers that can absorb shocks using binders made of rubber chips and polyurethane resin. For example, Korean Patent Laid-Open No. 2012-0027763 discloses an elastomeric composition for floor packaging in which a binder, rubber, urethane resin, etc., and wood, a hardener, etc. are added. However, in the case of long-term freezing in the rainy or winter, due to the hydrolysis of the polyurethane resin used as a binder, there is a problem in that the function of the binder is lost and the pavement is broken because the adhesion between the road and the adhesion of the rubber chip is lost. Therefore, there is a need for a new elastic packaging material having excellent bending strength and tensile strength and capable of excellent buffering action.

As described above, the development of a novel elastic packaging composition using a binder that can replace the polyurethane is required.

According to one aspect of the present invention, a differential binder calorimetry (DSC) melting point of 50 ℃ or more and 150 ℃ or less mixed binder containing a thermoplastic polymer and a fluidizing agent containing a hydrocarbon component obtained from waste oil; And it provides an elastic packaging composition comprising a rubber chip.

According to another aspect of the invention, the step of forming a mixed binder by mixing a fluidizing agent containing a hydrocarbon component obtained from waste oil and a thermoplastic polymer having a DSC melting point of at least 50 ℃ and 150 ℃ or less; Mixing the mixed binder with a rubber chip and heating it to a melting point or more of the thermoplastic polymer to form a composition for an elastic packaging material; Depositing the heated elastic packaging composition on a floor to form a laying layer; And a step of completing the paving of the bottom by compacting the laying layer.

1 is a process flow chart showing a bottom paving method using an elastic packaging material composition.

Hereinafter, various embodiments of the present invention will be described in more detail.

The elastic packaging material is a rubber chip such as EPDM or waste tires mixed with a urethane binder to be cast in place or processed into a certain form and can be used as a golf course walkway, a children's playground, a sidewalk block, and the like. Elastic packaging material has the advantage of high shock absorption rate to minimize the impact to prevent safety accidents, to give a comfortable walking feeling to reduce fatigue, to prevent slipping, excellent sound insulation effect, low thermal conductivity, the winter snow melts quickly. However, when the urethane resin is used as the binder as described above in the background art, there is a problem of deterioration of physical properties due to hydrolysis when the packaging material is exposed to moisture. Therefore, in order to solve this problem, when a new mixed binder is mixed with a rubber chip instead of a conventional urethane to make an elastic pavement composition and applied to road pavement, the construction is easy and the completed pavement can be replaced with urethane pavement. have.

An elastic packaging composition according to an embodiment of the present invention is a mixed binder comprising a thermoplastic polymer having a differential scanning calorimetry (DSC) melting point of 50 ℃ or more and 150 ℃ or less and a fluidizing agent containing a hydrocarbon component obtained from waste oil; And rubber chips. The elastic packaging material composition specifically has the following characteristics.

The thermoplastic polymer is a material having a DSC melting point of 50 ° C. or more and 150 ° C. or less, and serves to increase durability of the elastic packaging material. Since the thermoplastic polymer and the fluidizing agent are mixed to form the mixed binder, the higher the strength of the thermoplastic polymer is, the better the durability of the entire elastic packaging material is. However, it is preferable that the material is excellent in workability during processing by the fluidizing agent while maintaining high strength.

The hardness of the thermoplastic polymer is at least Shore D40, preferably at least D50, in order to be mixed with the fluidizing agent which is a liquid to give the overall elastic packaging material adequate strength. Although the upper limit of the hardness of the said thermoplastic polymer is not specifically limited, Usually, it is D70 or less.

In consideration of workability, the thermoplastic polymer has a DSC melting point of 50 ° C. or more and 150 ° C. or less, preferably 60 ° C. or more and 140 ° C. or less, more preferably 70 ° C. or more and 130 ° C. or less, as measured by ASTM D3418. If the melting point is less than the above range, the elastic packaging material may not withstand the high temperature caused by strong sunlight in the summer season and deforms when a person steps on it, and if it exceeds the above range, it may become too fast when it is applied at low temperatures in the winter and construction may not be possible.

The type of the thermoplastic polymer includes a thermoplastic resin and a thermoplastic rubber as long as it is a hard solid thermoplastic polymer satisfying the melting point, and is not particularly limited. The thermoplastic polymer may be a polyolefin such as polyethylene (LDPE, LLDPE, HDPE, etc.) and polypropylene (PP); Ethylene copolymers such as ethylene vinyl acetate (EVA) and ethylene butene copolymer (EB-Co); Polyolefin elastomers (POEs); And styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butadiene-styrene block copolymers (SEBS), styrene-butylene-butadiene-styrene block copolymers Styrene block copolymers such as (SBBS) and styrene-ethylene-propylene-styrene block copolymers (SEPS).

According to the Korean Waste Management Act, substances that are not needed for human life or business activities such as garbage, combustion materials, sludge, waste oil, waste acid, waste alkali, and dead bodies of animals are called "waste". Waste containing more than% is called waste oil and used oil and classified as designated waste. Waste oil is a dark brown opaque oily and gelled weakly acidic substance. Since fine black particles are suspended, the above carbonized impurities cannot be easily removed by a general centrifugation and filtering device. The reason for this is that ① carbon particles produced by hydrocarbon combustion are suspended by being strongly adsorbed to oil as fine particles of 10 ㎛ or less, and ② water, carbon particles, and metal fine particles because some of the free fatty acids in lubricating oil are emulsified with metal components. It is suspended in the oil to hinder the sedimentation sedimentation, ③ the various stabilizers (oxidants, dispersants, etc.) added during the production of lubricating oil hinders the solidification of the residue, which makes the sedimentation of impurities more difficult. Thus, since the waste oil forms a stable colloidal phase of various foreign substances, a purification process for removing the foreign substances is necessary. In the present specification, "waste oil" includes waste lubricant oil, waste animal oil, waste vegetable oil and waste cooking oil in a broader concept in addition to the above definition.

The waste oil may have a hydrocarbon component and various impurities. The hydrocarbon component may include oil fractionated from the waste oil, unsaturated fatty acids, polyalphaolefins (PAO), phosphate esters, and the like. Such impurities include heavy metals, ash, sulfur, carbides, moisture and other solids.

 The fluidizing agent used in the elastic packaging composition according to an embodiment of the present invention may be obtained by removing various impurities such as residues, heavy metals, carbides, etc. except the hydrocarbon component from the waste oil (waste lubricant, waste cooking oil, etc.). The raw material of the mixed binder is economical and environmentally friendly since it is easy to obtain and is obtained from cheap waste oil. The glidant may be fluid at room temperature and have a low viscosity.

When the fluidizing agent is mixed together with the thermoplastic resin having high hardness at room temperature, the melt index (MI) of the whole mixed binder may be very high at a high temperature of about 110 to 130 ° C., so that the workability at a high temperature may be very high. have. In a preferred embodiment, the melt viscosity of the mixed binder may be 100 to 1,000 cps as measured at 140 ℃ by ASTM D1986-91. If the melt viscosity of the mixed binder is less than the above range, the strength of the binder may be too low, and if it exceeds the above range, the construction may take a long time and the construction quality may be poor.

As the waste oil component, a low unsaturation is preferable because of its good weather resistance at the time of outdoor exposure. In general, high-grade lubricating oils such as engine oils are used as paraffin oil or polyalphaolefin (PAO) as the main raw materials, and these have low unsaturation of their own and extremely low unsaturation after use. Therefore, in this case, if the filtration process for removing heavy metals, residues, carbides and the like without additional treatment can be used as the fluidizing agent of the present invention.

On the other hand, in the waste oil, for example, waste cooking oil is mainly produced in the frying process of ramen, snacks, etc. or the frying process of chicken house. However, since the oil has a high degree of unsaturation, the fats of animals or plants are dissolved in the oil during the frying process, and the unsaturation of the waste cooking oil becomes higher due to oxidation due to high heat, and thus it cannot be used as it is for the use of elastic packaging materials exposed to the outdoors for a long time. Thus, the waste oil can be modified by hydrogenation, alkylation, molecular modification, molecular substitution, etc. or combinations thereof known to those skilled in the art to increase the saturation ratio of at least some of the hydrocarbon components obtained from the waste oil.

Preferably, the fluidizing agent may be modified by a method of hydrogenating (hydrogenation) the hydrocarbon component. The hydrogenation refers to a reaction in which the waste oil is saturated with hydrogen atoms added to a double bond of the waste oil by reacting with hydrogen in a high temperature / high pressure reactor. The hydrogenation reaction requires a catalyst and nickel, nickel-copper, copper-chromium, platinum, cobalt-molybdenum and the like can be used. This hydrogenation can improve the stability of the product by converting the unsaturated hydrocarbons of the waste oil into saturated hydrocarbons. In addition, impurities contained in the waste oil may be removed by reacting with hydrogen. For example, sulfur may be removed in the form of H ₂ S, nitrogen in NH ₃ , and oxygen in H ₂ O.

In one embodiment, at least one wax selected from the group consisting of paraffin wax and microcrystalline wax may be added to the mixed binder to lower the melt viscosity and softening point of the composition.

Usually, the required physical properties of binders used in elastic packaging materials are 60-100 dmm for penetration (ASTM D5), flash point (ASTM D92) of 250 ° C or higher, softening point (ASTM D36) of 42 ° C or higher, and elongation (ASTM D113) 100cm or higher. , Melt viscosity (ASTM D1986) 100 ~ 1000cps.

In order to satisfy the required physical properties such as penetration, flash point, softening point, elongation, melt viscosity, and the like, in order to replace the conventional urethane binder, it is preferable that the mixed binder has an appropriate softening point so that the construction is easy and the hardness is high at room temperature. . In addition, it is necessary to properly adjust the content ratio of the thermoplastic polymer and the fluidizing agent. When the total weight of the mixed binder is 100% by weight, the content of the fluidizing agent is 50 to 90% by weight, preferably 60 to 90% by weight. Meanwhile, the wax may be included in an amount of 1 to 5 wt% based on the total weight of the mixed binder, if necessary.

In the elastic packaging material composition, the rubber chip provides elasticity of the bottom to facilitate shock absorption. Examples of the rubber chip may be EPDM, synthetic rubber, soft synthetic resin, waste tires, waste rubber, etc. in the form of chips. The size of the rubber chip may be 1.0 to 5.0 mm. The rubber chip is to give the elasticity of the bottom to facilitate the shock absorption, the size used is appropriately adjusted according to the purpose to be used. For example, an elastic rubber chip having a relatively large particle size is used for a floor where the surface may be somewhat rough, such as a road or a bicycle road, and an elastic particle having a small particle size is preferable in a place where the surface is relatively flat, such as a basketball court or a tennis court. Rubber chips can be used.

In the total elastic packaging material composition, the mixed binder may be used in an amount of 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the rubber chip. When the content of the mixed binder is less than the above range, the binding force of the binder may be weak, and when the content of the mixed binder exceeds the range, the hardness of the elastic packaging material may be too high and the elasticity may be weakened.

In a preferred embodiment, the composition may further comprise a pigment. The pigments thus serve to impart color to the elastic packaging material. The pigment may be an organic pigment or an inorganic pigment. Examples of the organic pigments include azo pigments, phthalocyanine pigments, dye lake pigments, and condensed polycyclic pigments (anthraquinone, thioindigo, perylene, perrinone, quinacridone, dioxazine (Dioxazine), Isoindorinone, Isoindorine, Quinaphtalone, etc.), Nitroso Pigment, Alizarin Lake Pigment, Metal Complex Salt Azomethine Pigment, Aniline Black Pigment, Alkali Blue Pigment, Fluorescent fluorescent pigments. Examples of the inorganic pigments include oxide pigments (titanium dioxide, iron oxide, chromium oxide, iron black, cobalt blue), hydroxide pigments (aluminum white, iron oxide sulfur), sulfides (zinc sulfide, cadmium yellow, Lithopone (BaSO ₄ + ZnS), Cadmium Red, HgS), Chromate (Chrome Yellow, Molybdate Orange, Zinc Chromate, Strontium Chromate), Silicate (White Carbon, Clay, Talc, Umarin Blue), Sulfate (precipitated barium sulfate, bare light powder), Carbonate (Calcium carbonate, lead white), ferrocyanide (Iron Blue), phosphate (manganese violet), carbon (carbon black) and the like.

The pigment may be added in 0.1 to 5.0 parts by weight based on 100 parts by weight of the total elastic packaging material composition. In addition, the pigment may be used in the color of red, brown, black, yellow, green, blue, white or a combination of these colors can be used to impart any desired color to the floor pavement.

According to one embodiment of the present invention, there is provided a floor paving method using the composition described above. 1 is a process flow chart showing a bottom paving method using an elastic packaging material composition. Referring to FIG. 1, a fluidizing agent containing a hydrocarbon component obtained from waste oil in step S1 and a thermoplastic polymer having a DSC melting point of 50 ° C. or higher and 150 ° C. or lower are mixed to form a mixed binder.

In step S2, the mixed binder is mixed with a rubber chip and heated above the melting point of the thermoplastic polymer to form a composition for an elastic packaging material. In step S3, the heated elastic packaging material composition is laid on the floor to form a laying layer. In step S4, the laying layer is compacted to complete the paving of the bottom. If necessary, the method may further include forming a primer layer by applying a primer on the bottom between the step S2 and the step S3 to improve the binding force with the bottom.

The floor may be an unpaved road or a concrete or asphalt concrete floor. When the above-mentioned elastic packaging material composition is melted at a high temperature of about 110 ~ 130 ℃ when installed on the floor packaging flows like water and exhibits high quality construction properties with a rubber chip, it can exhibit high strength and high elasticity. In addition, it is possible to solve the problem of peeling and collapse of the packaging material due to hydrolysis of the conventional urethane resin by replacing the existing elastic packaging material. Thus, the present elastic packaging material composition may have good workability of elastic packaging material and may have excellent physical properties. In addition, when the pigment is mixed with the mixed binder, a mixture of the colored mixed binder and the rubber chip can be made, and various colors can be realized according to the type of the pigment.

Hereinafter, the present invention will be described in more detail with reference to various examples, but the spirit of the present invention is not limited by the following examples.

<Example>

Waste Lubricating Oil-1: The waste engine oil collected from the auto repair shop contained 1.43% residual carbon, 0.04% moisture and sediment, 0.664% ash, 0.30% sulfur and 1% cadmium. Purified oil was obtained by distillation and condensation at 250 ° C. under reduced pressure to remove moisture and low boiling point components contained in the waste engine oil.

Waste cooking oil-1: The waste cooking oil of the chicken house which uses the cooking oil whose main component is Palm oil was collected. First, the foreign matter in the waste cooking oil was separated using a centrifuge, heated and concentrated to 100 ° C. or more, and water was evaporated. Next, the resultant was filtered with a filter to separate foreign substances in waste cooking oil to obtain purified oil. Then, while passing refined oil and hydrogen through a CoMo catalyst-filled catalyst reactor, the average temperature of the catalyst bed was gradually maintained to 370 ° C., after which the liquid product began to be collected and the liquid product was collected for a total of 10 hours. It was. Water was removed from the collected product to complete the hydrogenation reaction.

The properties of the waste lubricating oil refinery (waste lubricant-1) and waste cooking oil refinery (waste cooking oil-1) thus obtained are shown in Table 1 below.

	Density kg / m 3	Pour point ℃	Flash point ℃	Kinematic viscosity (100 ℃) cSt
	ASTM D4052	ASTM D97	ASTM D92	ASTM D445
Waste Lubricant-1	899	-15	250	14.5
Waste Cooking Oil-1	898	25	301	10.30

Next, as shown in Table 2, a solid thermoplastic polymer of polyethylene (PE), polypropylene (PP), and polyolefin elastomer (POE) was prepared. The thermoplastic polymer used is as follows.

PE-1 ~ 4 Polyethylene

PP-1, PP-2: Polypropylene

POE-1, POE-2: Polyolefin Elastomer

PA-1: Polyamide

	Density g / cc	DSC melting temperature ℃	Penetration (100g, 5 seconds, 25 ℃) dmm	Melt Viscosity (140 ℃) cps	Remarks
	ASTM D1505-98	ASTM D3418	ASTM D5	ASTM D1986-91
PE-1	0.92	103	7.0	180
PE-2	0.92	109	2.0	450
PE-3	0.95	118	0.7	350
PE-4	0.95	120	0.1	470
PP-1	0.89	155	<0.1	Insoluble	Homopolymer
PP-2	0.88	130	0.1	4,000	Syndiotactic Copolymer
POE-1	0.87	70	10.0	8,000
POE-2	0.86	38	30	4,500
PA-1	1.02	178	<0.1	Insoluble	Nylon 12

The waste lubricant oil-1, waste oil oil-1 and thermoplastic polymer of Table 1 and Table 2 were mixed in a mixer at 200 ° C. at the same ratio as in Table 3 (the numbers in the table are parts by weight), and are required for the binder of the elastic packaging material. It is shown in Table 3 by measuring the essential physical properties.

	Binder Requirements	Urethane Binder	Comparative Example 1	Example 1	Example 2	Example 3	Example 4	Example 5	Comparative Example 2	Comparative Example 3	Example 6	Example 7	Comparative Example 4	Comparative Example 5
Waste Lubricant-1			90	70	50	70			90	95	90			95
Waste Cooking Oil-1							70	70				40	40
PE-1			10	30	50
PE-2
PE-3							30
PE-4						30		30
PP-1									10	5
PP-2											10
POE-1												60
POE-2													60
PA-1														5
Trespassing	60-100	80	130	80	65	90	90	80	65	170	90	100	150	30
flash point	250 ↑	400	200	260	270	260	270	280	260	200	260	300	290	250
Softening point	42 ↑	none	35	45	48	50	50	52	55	40	50	43	30	70
Shinto	100 ↑	300	300	250	180	250	240	250	200	400	250	250	500	80
Melt viscosity	100-1000	none	50	200	300	230	210	290	2000	1500	900	900	400	5000
Hydrolysis		has exist	none	none	none	none	none	none	none	none	none	none	none	none
Wealth use as binder		part	part	end	end	end	end	end	part	part	end	end	part	part

Permeability (ASTM D5): 100g, 5 seconds, 25 ° C, unit dmm, Flash point (ASTM D92): ° C, Softening point (ASTM D36): ° C, elongation (ASTM D113): 15 ° C, unit cm, Melt viscosity ( ASTM D1986): 140 ℃, unit cps

From the results of Table 3, the optimized composition of the mixed binder to replace the urethane binder can be determined. The underlined and bold values in Table 3 indicate cases that deviate from the required physical properties of each elastic packaging material binder. If one of the required physical properties is not satisfied, the urethane binder cannot be replaced. Elastic packaging composition according to an embodiment of the present invention is excellent in workability and durability when applied to the floor packaging by using a novel and improved mixed binder. It also saves money and is environmentally friendly by using raw materials from waste oil.

<Test Example>

Urethane Binder Replacement Test of Mixed Binder by Using Mixed with EPDM Rubber Chip

An elastic pavement of 10 mm thickness was constructed on 20 cm x 20 cm x 30 mm concrete and asphalt concrete floors. As a comparative example, the urethane resin was mixed with EPDM chips in a mixer at room temperature, evenly applied to the bottom, pushed with a roller, and cured at room temperature for 48 hours. The composition of Example 5 was mixed with EPDM chips in a mixer at 180 ° C. and then Was applied and pushed with a roller to cool and solidify. And the sample was dipped in 40 degreeC water for 10 days, adhere | attached on the floor. Table 4 shows the results of adhesion and flexural strength after submersion in water. The numbers in Table 4 are parts by weight.

Adhesion test: When the tip between the floor and the elastic pavement is opened with tongs, it is considered 'bad' if the elastic pavement remains circular, and 'good' when the pavement is torn.

Flexural strength: When the elastic packaging material peeled off in the above adhesion test was bent 180 °, it was 'good' if it kept round and 'bad' if cracked.

Claims (12)

1. A mixed binder comprising a thermoplastic polymer having a DSC melting point of at least 50 ° C. and at most 150 ° C. and a fluidizing agent containing a hydrocarbon component obtained from waste oil; And

   Elastic packaging composition comprising a rubber chip.
2. According to claim 1,

   The thermoplastic polymer is at least one elastic packaging composition selected from the group consisting of polyolefins, ethylene copolymers, polyolefin elastomers and styrene block copolymers.
3. According to claim 1,

   Wherein said hydrocarbon component is at least one selected from the group consisting of oils fractionated and distilled from said waste oil, unsaturated fatty acids, polyalphaolefins (PAO) and phosphate esters.
4. According to claim 1,

   Wherein the glidant is modified by one or more methods selected from the group consisting of hydrogenation, alkylation, molecular modification, and molecular substitution to increase at least a portion of the saturation rate for the hydrocarbon component.
5. According to claim 1,

   The softening point of the mixed binder is 42 ℃ or more as measured by ASTM D36, the melt viscosity is 100 to 1,000 cps measured at 140 ℃ by ASTM D1986-91.
6. According to claim 1,

   The mixed binder further comprises at least one wax selected from the group consisting of paraffin wax and microcrystalline wax.
7. According to claim 1,

   The rubber chip is at least one elastic packaging composition selected from the group consisting of EPDM, synthetic rubber, soft synthetic resin, waste tires and waste rubber.
8. According to claim 1,

   An elastic packaging composition containing 5 to 40 parts by weight of the mixed binder with respect to 100 parts by weight of the rubber chip.
9. The method according to any one of claims 1 to 8,

   An elastic packaging material composition further comprising a pigment.
10. Mixing a fluidizing agent containing a hydrocarbon component obtained from waste oil with a thermoplastic polymer having a DSC melting point of at least 50 ° C. and at most 150 ° C. to form a mixed binder;

    Mixing the mixed binder with a rubber chip and heating it to a melting point or more of the thermoplastic polymer to form a composition for an elastic packaging material;

    Depositing the heated elastic packaging composition on a floor to form a laying layer; And

    The step of paving the floor layer paving method comprising the step of completing the paving.
11. The method of claim 10,

    And applying a primer on the bottom to form a primer layer.
12. The method of claim 10,

    Wherein said fluidizing agent is modified by hydrogenating said hydrocarbon component.

Images