KR102415670B1 - Policarbonate multi-layered corrugated board having excellent weatherability and chemically resistant - Google Patents

Abstract

The disclosed content relates to a polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance, which can remarkably improve weather resistance and chemical resistance compared to conventional multi-layer corrugated board while maintaining the uniformity of outer layer thickness by applying a mixture of an ultraviolet absorber and a chemical resistant antioxidant in an optimal ratio. The polycarbonate multi-layer includes: an inner layer comprising a polycarbonate resin; and an outer layer is integrally formed on the upper and lower surfaces of the inner layer by co-extrusion, respectively, wherein the outer layer includes a synthetic resin obtained by synthesizing a polycarbonate resin and a glycol-modified polyethylene terephthalate resin, an ultraviolet absorber, an antioxidant, a chemical resistant antioxidant, and a lubricant.

Description

Polycarbonate multilayer corrugated board with excellent weather and chemical resistance {POLICARBONATE MULTI-LAYERED CORRUGATED BOARD HAVING EXCELLENT WEATHERABILITY AND CHEMICALLY RESISTANT}

The content disclosed in the present specification relates to a polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance.

Unless otherwise indicated herein, the material described in this section is not prior art to the claims of this application, and inclusion in this section is not an admission that it is prior art.

Conventionally, a flat plate made of synthetic resin or the like was mainly used when manufacturing the roof or exterior material of a structure, and polycarbonate was used as the main material of the flat plate. Polycarbonate is an engineering plastic with excellent transparency and mechanical strength, and its use is expanding throughout the industry, and in particular, it is widely used in construction fields such as roofing or exterior materials. However, when polycarbonate exhibiting the above-described physical properties is molded into a flat plate and applied to a livestock house, when exposed to ultraviolet rays or ammonia gas for a long period of time, yellowing occurs or mechanical properties are deteriorated, so that it can be easily damaged from external impact.

In order to improve this problem, Patent Documents 1 and 2 disclose a method of adding an additive such as an antioxidant and a UV stabilizer or further applying a polybutylene terephthalate resin to a polycarbonate resin, but the weather resistance required for livestock use and chemical resistance is still insufficient.

Republic of Korea Patent Publication No. 10-2020-0059503 (2020.05.29) Republic of Korea Patent Registration No. 10-0836363 (2008.06.02)

The disclosed content is to provide a polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance by applying a UV absorber and a chemical antioxidant in an optimal mixing ratio.

In addition, it is not limited to the technical problems as described above, and it is obvious that another technical problem may be derived from the following description.

According to an embodiment of the disclosure, a polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance is integrally formed with an inner layer comprising a polycarbonate resin and upper and lower surfaces of the inner layer by co-extrusion, respectively, polycarbonate resin and glycol It is composed of an outer layer including a synthetic resin synthesized with a modified polyethylene terephthalate resin, a UV absorber, an antioxidant, a chemical resistant antioxidant and a lubricant, and the UV absorber and the chemical resistant antioxidant are mixed in a ratio of 5 to 15: 1 by weight.

In addition, the inner layer may include an upper sheet, a lower sheet provided to be spaced apart from the upper sheet by a predetermined interval, and a plurality of ribs connecting the upper sheet and the lower sheet while maintaining a predetermined interval.

In addition, the inner layer includes an upper sheet, a lower sheet provided to be spaced apart from the upper sheet by a predetermined distance, a plurality of ribs connecting the upper sheet and the lower sheet while maintaining a predetermined interval, and a position between the upper sheet and the lower sheet and may include one or more intermediate sheets crossing the plurality of ribs.

The polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance according to an embodiment of the present disclosure maintains the uniformity of the outer layer thickness by applying the UV absorber and the chemical antioxidant in an optimal mixing ratio, while maintaining the weather resistance and chemical resistance of the conventional multi-layer board. There is an effect that can significantly improve compared to the corrugated plate.

In addition, it is possible to prevent yellowing due to ultraviolet rays, corrosion or cracking due to ammonia gas in the livestock, and damage due to the impact of hail or other objects, thereby ensuring impact resistance and safety.

1 is a state diagram of a polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance according to an embodiment of the disclosed subject matter.
Figure 2 is an enlarged view showing an enlarged area A in the polycarbonate multi-layer corrugated plate of Figure 1.
Figure 3 is an enlarged view showing an enlarged area of the polycarbonate multi-layer corrugated plate according to another embodiment of the disclosed subject matter.
4 is an image taken with an optical microscope of the outer layer thickness of the polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance according to an embodiment of the disclosed subject matter.
5 is a graph showing the weather resistance results of Example 1 and Comparative Example 1 in Experimental Example 1.

Hereinafter, with reference to the accompanying drawings, the configuration and operation effects of preferred embodiments of the disclosed subject matter will be described. For reference, in the following drawings, each component is omitted or schematically illustrated for convenience and clarity, and the size of each component does not reflect the actual size. In addition, the same reference numerals refer to the same components throughout the specification, and reference numerals for the same components in individual drawings will be omitted.

1 is a state diagram of a polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance according to an embodiment of the disclosure, and FIG. 2 is an enlarged view showing area A in the polycarbonate multi-layer corrugated board of FIG. 1 , FIG. 3 is an enlarged view showing an enlarged area of the polycarbonate multi-layer corrugated board according to another embodiment of the disclosed subject matter.

1 to 3, the polycarbonate multi-layer corrugated board 100 having excellent weather resistance and chemical resistance according to an embodiment of the disclosed content is applied to the livestock house 1, and the inner layers 110-1 and 110-2) and an outer layer 120 integrally formed on the upper and lower surfaces of the inner layers 110-1 and 110-2 by co-extrusion, respectively.

The inner layers 110-1 and 110-2 are made of polycarbonate resin, and in this embodiment, the polycarbonate resin has a weight average molecular weight of 20,000 to 30,000 g/mol, a melt flow index of 6 to 8 g/10 min, and a heat deflection temperature of 133 to It may satisfy 138° C. and a flexural modulus of 90 to 95 MPa.

On the other hand, as shown in FIG. 2 , the inner layer 110 - 1 includes an upper sheet 111 , a lower sheet 112 provided to be spaced apart from the upper sheet 111 at a predetermined interval, and the upper sheet 111 and the It may be composed of a plurality of ribs 113 connecting the lower sheet 112 but maintaining a predetermined interval H, and as shown in FIG. 3 , the inner layer 110-2 includes the upper sheet 111 and the upper portion. A lower sheet 112 provided to be spaced apart from the seat 111 at a predetermined interval, a plurality of ribs 113 connecting the upper sheet 111 and the lower sheet 112 while maintaining a predetermined interval H, and the upper portion It is positioned between the seat 111 and the lower sheet 112 and may be composed of one or more intermediate sheets 114 crossing the plurality of ribs 113 . However, since the number of intermediate sheets 114 may vary depending on the design of the inner layer 110 - 2 , the number is not limited to a specific number. As described above, by providing the outer layer 120 on both sides of the inner layers 110-1 and 110-2 and the plurality of ribs 113 on the inner layers 110-1 and 110-2, the impact resistance is improved and the size is increased. Compared to that, the weight is reduced and damage caused by hail or other objects can be prevented, thereby ensuring impact resistance and safety.

The outer layer 120 is integrally formed on the upper and lower surfaces of the inner layers 110-1 and 110-2 by co-extrusion, respectively, and is formed to a thickness of 20-40 μm, preferably 30 μm as shown in FIG. 4 . Preferably, if the thickness is less than 20um, the impact resistance improvement effect is insignificant, and if it exceeds 40um, the weight may be increased and a large load may be applied to the structure. On the other hand, the outer layer 120 may be made of 100 parts by weight of synthetic resin, 1 to 10 parts by weight of a UV absorber, 0.1 to 1 parts by weight of an antioxidant, 0.1 to 1 parts by weight of a chemical resistant antioxidant, and 0.1 to 1 parts by weight of a lubricant. Therefore, it is possible to solve problems such as yellowing by ultraviolet rays or corrosion or cracking due to ammonia gas in the livestock, thereby ensuring impact resistance and safety.

The synthetic resin may be a mixture of 50 to 90% by weight of a polycarbonate resin and 10 to 50% by weight of a glycol-modified polyethylene terephthalate resin (glycol-modified PET resin). In this embodiment, the polycarbonate resin satisfies a weight average molecular weight of 20,000 to 30,000 g/mol, a melt flow index of 6 to 8 g/10 min, a heat deflection temperature of 133 to 138 ° C, and a flexural modulus of 90 to 95 MPa, and glycol-modified polyethylene terephthalate. Resin (glycol-modified PET resin) is ethylene glycol (EG) with terephthalic acid (TPA), cyclohexanedimethanol (1,4-cyclohexanedimethanol, CHDM) as a comonomer, and isosorbide ( It is a resin copolymerized by adding isosorbide, and it is different from the existing PETG resin copolymerized by adding ethylene glycol (EG) with terephthalic acid (TPA) and cyclohexanedimethanol (1,4-cyclohexanedimethanol, CHDM). It is a different material and has excellent chemical and impact resistance as well as extrudability compared to PETG resin.

On the other hand, isosorbide (Isosorbide) is a bio-based monomer (monomer) made by chemically processing starch extracted from plants such as corn and wheat, and is an environmentally friendly material. It may be possible to improve heat resistance, chemical resistance, processability, etc. at a high temperature such as ~110 ℃. Accordingly, the glycol-modified polyethylene terephthalate resin (glycol-modified PET resin) of this embodiment may satisfy a total light transmittance of 90% or more, a haze of 1.0% or less, and a Rockwell hardness of 115HRC or more.

The UV absorber is a material used to improve the weather resistance of the composition and reduce yellowing caused by UV rays generated from the light source. at least one selected from, preferably a benzotriazole type, most preferably 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3- tetramethylbutyl)) (2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))) can be used, but in the range from 250 to 800 nm As long as it is a material that can absorb the wavelength of

These ultraviolet absorbers may be included in an amount of 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the synthetic resin, which is that when the ultraviolet absorber is less than 2 parts by weight, not only discoloration due to ultraviolet rays but also mechanical and physical properties will be reduced. and, when it exceeds 10 parts by weight, deterioration of physical properties may occur.

The antioxidant is a substance added to prevent the resin from being easily oxidized by reacting with air to prevent deterioration in quality. At least one selected from among phenolic, amine, sulfur, phosphate and phosphorus, preferably phenolic, and a phosphate-based mixture in a ratio of 1: 1 to 2 by weight. In the case of mixing and using the above-mentioned substances and ratios, the problem of poor heat resistance stability during compounding can be improved. Among commercially available antioxidants, phenolic antioxidants include Irganox 1076 (BASF), Irganox 1010 (BASF), AO-60/AO-60G (ADEKA), ETHANOX ^® 310 (ALBEMARLE), and phosphate-based antioxidants Irgafos 168 (BASF), ETHAPHOS ^TM 368 (ALBEMARLE), Hostanox ^® P-EPQ ^® FF (Clariant), and the like.

These antioxidants may be included in an amount of 0.1 to 1 parts by weight, preferably 0.3 to 0.5 parts by weight, based on 100 parts by weight of the synthetic resin. This means that when the antioxidant is less than 0.1 parts by weight, the resin is easily oxidized to shorten the service life or when compounding. Thermal stability may be deteriorated, and if it exceeds 1 part by weight, the synergistic effect of using more than necessary may not be so great, and physical properties may be deteriorated.

Chemical-resistant antioxidants improved chemical resistance and It is a substance added to solve the problem that heat resistance stability, which serves as a phenol-based antioxidant, may decrease during compounding. A phenolic, preferably bis[3,3-bis-(4'-hydroxy-3'-tert) -Butylphenyl)butyric acid]-glycol ester (Bis[3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoic-acid]-glycolester) may be used. Bis[3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butyric acid]-glycol ester has a structure having an ester group, and in particular, chemical resistance to salt (Cl) and alcohol resistance It is a unique substance with

On the other hand, when a chemical-resistant antioxidant is added alone to the glycol-modified polyethylene terephthalate resin, a yellowish phenomenon may occur. Preferably, the UV absorber and the chemical antioxidant are most preferably mixed in a ratio of 5 to 15: 1 by weight.

These chemical antioxidants may be included in an amount of 0.1 to 1 parts by weight, preferably 0.3 to 0.5 parts by weight, based on 100 parts by weight of the synthetic resin, which is less than 0.1 parts by weight of the chemical antioxidant, the uniformity of the outer layer thickness is lowered, When it exceeds 1 part by weight, it is not preferable because it may affect not only chemical resistance but also weather resistance and appearance quality, thereby reducing physical properties.

Lubricant is a material used to facilitate processing by improving fluidity when heat-molding resin, and is selected from metal stearate, ester, amide, and paraffin. One or more, preferably a metal stearate-based (metal stearate) may be used. Commercially available lubricants include, for example, Hi-Lube (Shinwon Chemical), Mg-St (Songwon), Ca-St (Songwon), Zn-St (Songwon), AX-71 (ADEKA), Loxiol ^® P-861 (Emery) and others.

These lubricants may be included in an amount of 0.1 to 1 parts by weight, preferably 0.3 to 0.5 parts by weight, based on 100 parts by weight of the synthetic resin, which is that if the lubricant is less than 0.1 parts by weight, moldability may decrease, and when it exceeds 1 part by weight, The synergistic effect of using more than necessary may not be so great.

Of course, in this embodiment, one or more additives selected from a light stabilizer, a blowing agent, a plasticizer, a flame retardant and a pigment may be further used within a range that does not affect the physical properties of the polycarbonate multi-layer corrugated board.

<Example 1>

The composition corresponding to the outer layer described in Table 1 below was pelletized by mixing/melting (240-260° C.) with a twin-screw extruder (Φ32, L/D=40:1). A single screw extruder was used, but the inner layer composition was put in the main extruder, and the prepared pellets were put in the sub extruder, and these were provided to the T-die through a feed block, respectively, to prepare a 3.6 mm thick polycarbonate multi-layer corrugated board.

division ingredient Content (parts by weight) inner layer polycarbonate resin 100 outer layer synthetic resin polycarbonate resin 50 Glycol　modified PET resin 50 antioxidant phenolic 0.1 phosphite 0.2 Chemical-resistant antioxidant phenolic 0.3 UV absorber Benzotriazole type 3 lubricant metal stearate 0.2

<Comparative Examples 1 to 4>

A polycarbonate multi-layer corrugated board was prepared in the same manner as in Example 1, except that the components and component ratios shown in Table 2 were applied.

division ingredient Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 inner layer polycarbonate resin 100 100 100 100 outer layer synthetic resin PC resin 50 50 50 50 Glycol　modified PET resin 50 50 50 50 antioxidant phenolic 0.1 0.1 0.1 0.1 phosphite 0.2 0.2 0.2 0.2 Chemical-resistant antioxidant phenolic 0.3 0.3 0.5 1.0 UV absorber Benzotriazole type One 6 3 3 lubricant metal stearate 0.2 0.2 0.2 0.2

Experimental Example 1. Evaluation of physical and chemical properties

In order to evaluate the physical and chemical properties of the polycarbonate multi-layer corrugated board according to Example 1 and Comparative Examples 1 to 4, an experiment was conducted as follows.

(1) thickness

For the total thickness, the entire width of the specimen was divided into 5 sections at regular intervals, measured using a thickness gauge (CD-S15C, Mitutoyo), and then the average value was calculated.

For the uniformity of the thickness of the outer layer, the deviation of the thickness in the width direction was measured using an optical microscope (BX53M, Olympus).

(2) Appearance quality

The appearance quality due to fume gas and paraffin generation during the manufacturing process of polycarbonate multi-layer corrugated board was checked and evaluated.

(3) Weather resistance

Using a Q-UV tester (QUV/se, Q-LAB), the UV lamp 340nm wavelength, light quantity 0.71W/m2, 1 cycle (UV mode 4hr, condensation 4hr) was set, and the experiment was conducted in 200-hour increments up to 1000 hours. After yellowing index (YI) change amount (ΔYI) was measured according to ASTM E313-73 standard, and an average value thereof was calculated.

(4) chemical resistance

In accordance with the KS M ISO 275 test standard, about 50 ml of a 25w/w% ammonia water test solution was placed in a 500ml beaker, and the specimen was placed at the entrance of the beaker, and the appearance was checked after 24 hours.

division Outer layer thickness uniformity Extrusion and appearance quality weather resistance chemical resistance Example 1 ◎ ◎ ◎ ◎ Comparative Example 1 ◎ ◎ △ ◎ Comparative Example 2 ○ △ ◎ ◎ Comparative Example 3 ○ ◎ ◎ ◎ Comparative Example 4 ○ ○ ○ ○ ◎: Excellent, ○: Average, △: Poor

Referring to Table 3 and Figure 5, in the case of Example 1, it was excellent in all items corresponding to the outer layer thickness uniformity, extrudability and appearance quality, weather resistance and chemical resistance. On the other hand, in Comparative Examples 1 and 2, in which the chemical antioxidant is composed of the same composition ratio, Comparative Example 1, in which the UV absorber is less than 3 parts by weight, has insufficient weather resistance, and Comparative Example 2, in which the UV absorber is more than 3 parts by weight, has extrudability and appearance The quality was insufficient. In Comparative Examples 3 and 4, in which the UV absorber was composed of the same composition ratio, the outer layer thickness uniformity was normal in Comparative Example 3, in which the chemical antioxidant was more than 0.3 parts by weight, and Comparative Example 4, in which the chemical antioxidant was less than 0.3 parts by weight, was all All in the items were mediocre. Therefore, it was found that the mixing ratio of the UV absorber and the chemical antioxidant has a great influence on all items.

The disclosed content is merely an example, and since various changes can be made by those skilled in the art without departing from the gist of the claims claimed in the claims, the protection scope of the disclosed content is limited to the specific It is not limited to an Example.

1: Congratulatory
10: polycarbonate multi-layer corrugated board
100-1, 100-2: inner layer
111: upper sheet
112: lower seat
113: rib
114: middle seat
120: outer layer

Claims (10)

an inner layer comprising a polycarbonate resin; and
An outer layer comprising a synthetic resin synthesized with polycarbonate resin and glycol-modified polyethylene terephthalate resin, a UV absorber, an antioxidant, a chemical resistant antioxidant, and a lubricant, which is integrally formed on the upper and lower surfaces of the inner layer by co-extrusion, respectively; composed,
The UV absorber and chemical antioxidant are mixed in a weight ratio of 5 to 15: 1, and the chemical antioxidant is a phenolic polycarbonate multilayer corrugated board having excellent weather resistance and chemical resistance.
According to claim 1,
The outer layer is 100 parts by weight of a synthetic resin in which 50 to 90% by weight of a polycarbonate resin and 10 to 50% by weight of a glycol-modified polyethylene terephthalate resin are synthesized, 1 to 10 parts by weight of a UV absorber, 0.1 to 1 parts by weight of an antioxidant, chemical oxidation resistance A polycarbonate multilayer corrugated board with excellent weather resistance and chemical resistance comprising 0.1 to 1 part by weight of an inhibitor and 0.1 to 1 part by weight of a lubricant.
According to claim 1,
The polycarbonate resin has a weight average molecular weight of 20,000 to 30,000 g / mol, a melt flow index of 6 to 8 g / 10 min, a heat deflection temperature of 133 to 138 ° C, and a flexural modulus of 90 to 95 MPa.
According to claim 1,
The glycol-modified polyethylene terephthalate resin is a polycarbonate multilayer corrugated board having excellent weather resistance and chemical resistance, which is copolymerized by adding terephthalic acid, cyclohexanedimethanol and isosorbide to ethylene glycol.
According to claim 1,
The UV absorber is at least one selected from benzophenone-based, benzotriazole-based, cyanoacrylate-based, sarichireto-based and nickel complex salt-based polycarbonate multilayer corrugated boards with excellent weather resistance and chemical resistance.
According to claim 1,
The antioxidant is at least one selected from phenol-based, amine-based, sulfur-based, phosphate-based and phosphorus-based polycarbonate multi-layer corrugated board with excellent weather resistance and chemical resistance.
delete According to claim 1,
The lubricating agent is a polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance at least one selected from metal stearate-based, ester-based, amide-based and paraffin-based.
According to claim 1,
The inner layer is
top sheet;
a lower sheet provided to be spaced apart from the upper sheet at a predetermined interval; and
A polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance comprising a; a plurality of ribs connecting the upper sheet and the lower sheet while maintaining a predetermined interval.
According to claim 1,
The inner layer is
top sheet;
a lower sheet provided to be spaced apart from the upper sheet at a predetermined interval;
a plurality of ribs connecting the upper sheet and the lower sheet while maintaining a predetermined interval; and
A polycarbonate multi-layer corrugated board having excellent weather resistance and chemical resistance comprising a; positioned between the upper sheet and the lower sheet, and at least one intermediate sheet crossing the plurality of ribs.

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