KR101505241B1 - Synthetic resin composition for pvc nontoxic windows, and pvc nontoxic windows - Google Patents

Abstract

The present invention relates to a synthetic resin composition for a PVC non-toxic window and a non-toxic PVC window which are excellent in initial coloring and heat resistance without containing a lead (Pb) stabilizer harmless to human body or a cadmium (Cd) More specifically, as a stabilizer composition peculiar to the present invention, a stabilizer for a synthetic resin is a) a non-toxic metal soap stabilizer; And b) a non-toxic metal-based inorganic stabilizer; A synthetic resin composition for a PVC non-toxic window, and a non-toxic PVC window obtained by kneading and extruding the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a synthetic resin composition for a PVC non-toxic window and a PVC non-toxic window,

The present invention relates to a synthetic resin composition for a PVC non-toxic window and a non-toxic PVC window which are excellent in initial coloring and heat resistance without containing a lead (Pb) stabilizer harmless to human body or a cadmium (Cd) stabilizer at all.

Currently, PVC window frames are used in many buildings as living building materials that are always in contact with our everyday life. However, in general, PVC has a large chlorine group, so chlorine is easily released by external energy such as heat or light, and a radical is formed in a place where chlorine is dropped, and then a double bond is formed. The increase of the double bond is a factor to change the color of the PVC, and when the temperature is raised, the increase of the double bond rapidly progresses, and the color of the PVC becomes red through the red color.

Because of this low heat resistance, processing and molding of PVC is only possible by adding an effective stabilizer to compensate for heat resistance. PVC which has been manufactured and sold so far

Most of the windows are made by adding lead (Pb) stabilizers containing lead (Pb) or cadmium (Cd), which are highly toxic. Lead (Pb) and cadmium (Cd) are not only poisonous to the human body, but also have a long half-life when they enter the human body, causing them to remain in the body for a lifetime. Therefore, it is necessary to use a stabilizer which is harmless to the human body but there have been many limitations in using a non-toxic stabilizer because of technological, quality and price problems.

The present invention solves the problems of the use of the present invention to produce a PVC non-toxic window which does not contain toxic substances such as lead (Pb) and cadmium (Cd).

PVC windows containing lead (Pb) and cadmium (Cd) are not only harmful to workers during manufacturing work, but also internal toxic stabilizers due to friction and abrasion are leaked out after they are installed on buildings and can seriously affect the human body. Therefore, the use of non-toxic stabilizers has already been legislated in developed countries such as Europe and USA, and many non-toxic related technologies have been developed. However, it has not been easy to replace the excellent performance of the lead (Pb) -based stabilizer as a non-toxic stabilizer due to excellent heat resistance and workability or weatherability of lead (Pb) and cadmium (Cd). When the heat resistance is improved, the processability is deteriorated. If the processability and the heat resistance are matched, there is a problem in weather resistance. If the organic additive stabilizer is excessively used to satisfy all of these requirements, it is practically difficult to manufacture a PVC window using a nontoxic stabilizer due to other physical problems or price increase problems.

PVC non-toxic windows may use metal soap stabilizers and tin (Sn) stabilizers. However, tin (Sn) -based compounds that are known to be harmless due to the use of tin (Sn) -based stabilizers or environmental problems due to their odor, There is still a problem in achieving complete non-toxicity. Therefore, in order to manufacture a completely nontoxic window, a non-toxic metal soap system in which a fatty acid having a C ₃ -C ₅₀ alkyl group is bonded to a toxic metal (Ca, Mg, Zn, etc.) is used as a main stabilizer to control various internal and external lubricants Studies have been developed. However, it has been difficult to solve the problems of workability and weatherability by using only a metal soap system, and it has not been possible to obtain satisfactory results for heat resistance and initial coloring.

Especially, European Patent EP1088032 improves the heat resistance performance by adding the organic stabilizers such as calcium acetylacetonate and THEIC (Tris-Hydroxy Ethyl Iso-Cyanurate) in addition to the metal soap stabilizer and enhances the calcium hydroxide to the inorganic stabilizer And in European patent EP1613696, zinc stearate and the organic stabilizer Zinc-Octoate were used together.

In European patent EP 1692220, Zinc caprylate was used together with zinc stearate to improve initial coloration and heat resistance. However, the use of such an organic stabilizer is disadvantageous in terms of plate out (plate out), weather resistance, and economical use of the polymer.

Therefore, there is a continuing need for research on techniques for solving all problems from initial coloring, heat resistance, weatherability and economy.

The present invention was in the continued research on stabilizers for the preparation of a high resolution and non-toxic PVC windows and doors such problems, the present invention, C ₃ -C ₅₀ for a specific stabilizer composition, non-toxic metal (Ca, Mg, Zn, etc.) A non-toxic metal soap type stabilizer to which a fatty acid having an alkyl group is bonded is blended with a non-toxic metal type inorganic stabilizer to complete the invention capable of solving the above-mentioned disadvantages without reducing or using the amount of the organic stabilizer.

That is, an object of the present invention is to provide a synthetic resin composition for PVC-based windows, which is a synthetic resin composition for non-toxic windows.

Another object of the present invention is to provide a non-toxic PVC window which is excellent in initial coloration and heat resistance and also has excellent weather resistance from the above-mentioned synthetic resin composition for a non-toxic window.

According to the present invention, there is provided a PVC-based synthetic resin composition for a window, comprising: a) a non-toxic metal soap stabilizer; And b) a non-toxic metal-based inorganic stabilizer. The present invention also provides a synthetic resin composition for a PVC non-toxic window.

Also, according to the present invention, there is provided a PVC non-toxic window obtained by kneading and extruding the above-mentioned synthetic resin composition for PVC non-toxic window, and having improved heat resistance, weather resistance and initial coloring prevention property.

Hereinafter, the present invention will be described in detail.

First, the PVC synthetic resin composition for a non-toxic window according to the present invention is characterized by having a stabilizer composition unique to the present invention.

That is, the non-toxic metal soap stabilizer (a) having a fatty acid having a C ₃ -C ₅₀ alkyl group bonded to a non-toxic metal (Ca, Mg, Zn, etc.) .

The non-toxic metal soap stabilizer may be a compound in which at least one metal selected from the group consisting of Li, Na, K, Mg, Ca, Al, and Zn is substituted with hydrogen for a fatty acid having an alkyl group having 3 to 50 carbon atoms. This is because, under heat or other harsh conditions, PVC forms radicals as chlorine is released, the radicals become double bonds, and then the color changes or the polymer ages. Therefore, inactivation of the liberated chlorine is an important factor for improving the heat resistance. Zinc stearate, which is known as an organic substance having a typical non-toxicity, quickly captures liberated chlorine and exhibits properties excellent in initial heat resistance.

On the other hand, calcium stearate and magnesium stearate can be used instead of zinc stearate, since calcium stearate and magnesium stearate can be used in place of zinc stearate.

The fatty acid may be saturated or unsaturated, chain, branched, aromatic type or the like.

The non-toxic metallic soap is preferably in the range of 0.1 to 15 parts by weight based on 100 parts by weight of PVC. When added in an amount of less than 0.1 part by weight, it is not melted and carbonized in the processing of PVC, and when it exceeds 15 parts by weight, the gelation time becomes long due to not being melted, resulting in poor workability and difficulty of plate-out PVC dispersion.

The term "inorganic metal inorganic stabilizer" used in the present invention means at least one selected from the group consisting of Li, Na, K, Mg, Ca, Al, and Zn to a compound used as a conventional inorganic stabilizer such as a metal oxide or a hydroxide- Metal or a compound coated with the compound. For example, zinc, magnesium, calcium or a compound thereof may be coated.

The metal oxide or hydroxide-based inorganic material may include, but is not limited to, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, aluminum oxide, aluminum hydroxide, hydroxides, Zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, and zirconium oxide.

Specific coating methods include, but are not limited to, the method of water-soluble salt of zinc, the coating method using electrolysis method, the coating method using high speed milling and high temperature melting method, and the physical method due to grinding and friction have.

The content of the non-toxic metal or the non-toxic metal compound is preferably in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the metal oxide or the hydroxide-based inorganic component, because initial chlorine can be retained to improve heat resistance and prevent initial coloring.

The inorganic non-toxic inorganic stabilizer (b) is preferably in the range of 0.5 to 15 parts by weight based on 100 parts by weight of PVC. When added to the resin for PVC window in the above content range, as described in the following examples, the resin is hardly deformed by heat and provides the resin with mechanical properties such as heat resistance and high dispersibility, non-cohesive property and impact strength I could confirm.

The composition of the present invention can further comprise at least one selected from the group consisting of 1,3-diketone compounds, dihydro-pyridine, polyol, isocyanurate, amino acid derivatives, organic ester of phosphoric acid, epoxy compound, perchlorate and salts of superacid The above-mentioned auxiliary stabilizer (c) may further be contained in the range of 0.1 to 5 parts based on 100 parts by weight of PVC. When the amount of the auxiliary stabilizer is less than 0.1 parts by weight, the PVC does not sufficiently serve as a heat-resistant stabilizer and is carbonized. When the amount of the auxiliary stabilizer exceeds 5 parts by weight, excessive coloring of the auxiliary stabilizer may occur during processing of PVC.

The composition of the present invention may further comprise one or more organic stabilizers selected from Zinc Octoate, Zinc caprylate, Calcium acetylacetonate and THEIC (Tris-Hydroxy Ethyl Iso-Cyanurate) d), based on 100 parts by weight of PVC, in the range of 0.01 to 5 parts by weight.

The PVC in the composition of the present invention may be, but is not limited to, at least one of polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorosulfonated polyethylene, chlorinated polypropylene or copolymers of chlorinated ethylene and vinyl acetate Can be selected.

Further, the composition of the present invention may further comprise 0.5 to 10 parts by weight of a processing aid, 5 to 15 parts by weight of an impact modifier, 2 to 10 parts by weight of TiO ₂ , 10 to 30 parts by weight of calcium carbonate, And 0.1 to 5 parts by weight of an oxidation inhibitor and an ultraviolet ray inhibitor.

The processing aid may be at least one selected from acrylate, methacrylate and acrylonitrile.

The impact modifier may be at least one selected from the group consisting of acrylic and chlorinated polyethylene.

Furthermore, TiO ₂ can be added to compensate for the white pigment and window weatherability, and calcium carbonate can be added to increase impact resistance.

The lubricant may be at least one selected from montan wax, fatty acid ester, triglyceride or partial ester thereof, glycerin ester, polyethylene wax, paraffin wax, metal soap-based lubricant and amide-based lubricant.

The oxidation and ultraviolet ray inhibitor may be at least one selected from the group consisting of a primary antioxidant and a phenolic HALS ultraviolet ray stabilizer. Specifically, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-benzyl-4-methylphenol, stearyl 3- (3-5- (4-methyl-6-tert-butylphenol), 4,4'-thiobis Phenol), 2,5-di-tert-butyl-hydroquinone and 4,4 ', 4 "- (1 -methyl-1-propanyl- Ethyl) -5-methylphenol.

In addition, other inorganic fillers, dyes, pigments, antistatic agents, surface treatment agents, foaming agents, impact modifiers, etc. may also be used.

The above-described synthetic resin composition has an advantage that it does not contain lead or cadmium toxic substances, which are conventionally used as stabilizers. These compositions can be kneaded and extruded to obtain PVC nontoxic windows improved in heat resistance, weather resistance, and initial coloring resistance.

According to the above description, by increasing the initial coloring and mid-and-long-term heat resistance of PVC,

It has excellent chlorine resistance and heat resistance at the same time. It contributes to the improvement of weather resistance by inorganic materials and can exhibit a characteristic of good weatherability. In addition, two or more inorganic stabilizers having different characteristics and different prices are appropriately mixed and used, (Pb) or cadmium (Cd) stabilizers.

FIG. 1 is a photograph showing a lead check result between Example 1 of the present invention and Comparative Example 2 as a prior art.

Hereinafter, the present invention will be described in more detail with reference to Examples. The embodiments according to the present invention can be modified into various other forms, and thus the scope of the present invention is not limited to the embodiments described below.

For reference, in the following examples, the processing aid was a methyl methacrylate-butyl-2-propenoic acid-ethylbenzene polymer, the impact modifier was chlorinated polyethylene, and the lubricant was 1,2-benzenedicarboxylate dialkyl 1,2-benzenedicarboxylic acid dialkyl ester, and the non-toxic metal soap compound is zinc stearate, calcium stearate, and the organic stabilizer is Tris-HydroxyEthyl Iso- Cyanurate and the oxidation and ultraviolet ray inhibitor are tetrakismeethylene methane and tris phosphate. Metal oxides and hydroxide-based inorganic substances include sodium aluminum silicate, Hydrotalcite was used, and auxiliary stabilizers were dibenzoyl methnn e) metal mixture.

< Example >

Example  One

100 parts by weight of PVC, 1 part by weight of a processing aid, 8 parts by weight of an impact modifier, 4 parts by weight of TiO ₂ , 12 parts by weight of calcium carbonate, 0.5 part by weight of a lubricant, 2 parts by weight of a non- , 0.1 part by weight of an ultraviolet ray inhibitor, 1 part by weight of an inorganic metal-based inorganic stabilizer (a stabilizer coated with 10 parts by weight of zinc on 100 parts by weight of a metal oxide or a hydroxide-based inorganic substance) and 0.2 part by weight of an auxiliary stabilizer were mixed using a Henschel mixer After 10 minutes' stirring at 110 ° C, a window profile was prepared using a PVC window extruder (L / D - 25: 1, screw type - Parallel 90 mm) under the following extruder conditions.

Cylinder 1 Temperature (캜) Cylinder 2 Temperature (캜) Cylinder 3 Temperature (캜) adapter
Temperature (℃) die
Temperature (℃) Revolutions
(rpm) Payback speed
(m / min) cooling water
Temperature (℃) 180 175 170 165 190 10 2.0 15

Comparative Example  One

The procedure of Example 1 was repeated except that the metal oxide or hydroxide-based inorganic material in Example 1 was replaced with a metal oxide or hydroxide-based inorganic material in which a zinc or zinc compound was not coated instead of an inorganic stabilizer coated with zinc or a zinc compound Was repeated to produce a window profile.

Comparative Example  2

100 parts by weight of PVC, 1 part by weight of a processing aid, 8 parts by weight of an impact modifier, 4 parts by weight of TiO ₂ , 12 parts by weight of calcium carbonate, 0.5 parts by weight of a lubricant, 2 parts by weight of a non- Was repeated to produce a window profile.

Test Example  1: impact strength

The impact strength test was carried out under the condition of standard temperature (23 ± 2 ° C) and low temperature (-10 ± 1 ° C) for more than 24 hours, respectively, according to KS M 3056. According to the KS F 5602 standard, it must be at least 12.7 kJ / m ² at standard temperature and at least 4.9 kJ / m ² at low temperature. The measurement results are summarized in Table 2 below.

Test Example  2: Tensile yield strength and tensile elongation at break

Tensile yield strength and tensile elongation at break were tested in accordance with KS M 3006 at a standard temperature of 23 ° C ± 2 ° C. According to KS F 5602, tensile yield strength is over 36.8 MN / m ² and tensile elongation at break is 100% or higher. The measurement results are summarized in Table 2 below.

Test Example  3: Hardness

The hardness test was made on a scale R of KS M ISO 2039-2. According to KS F 5602, the hardness must be above 85 to pass. The measurement results are summarized in Table 2 below.

Test Example  4: Vica Softening temperature

The Vika softening temperature test was conducted at 9.80 N in accordance with KS M 3076. According to KS F 5602, the Vika softening temperature must be higher than 83 ° C. The measurement results are summarized in Table 2 below.

Test Example  5: Weatherability

The weathering test was carried out in a XENON-ARC-type apparatus according to KS F 2274, with a spray cycle of 18 minutes in 120 minutes and a black panel temperature of 63 ± 3 ° C for 1,000 hours. The color difference was measured by the color difference meter. According to KS F 5602, it must pass without significant discoloration. The measurement results are summarized in Table 2 below.

Test Example  6: Initial coloring

The color difference value was confirmed by CR-400 colorimetric method to determine the initial coloring. The heat resistance was confirmed by discharging 20 mm every 5 minutes at 200 ° C in a Mathis oven to check the heat resistance. The measurement results are summarized in Table 2 below.

Test Example  7: Non-toxic

Lead lead was checked for lead content to determine lead content. The lead check turns red when lead is present and does not change color when lead is not present. As can be seen from Fig. 1, lead 1 was not detected in lead 1 because lead 1 did not change color. In Comparative Example 2 using the lead stabilizer, lead check resulted in red color of the solution, indicating that lead contained.

Test Items Example 1 Comparative Example 1 Comparative Example 2 Impact strength kJ / m ² Standard temperature (23 ± 2 ℃) 23.6 22.6 23.5 Low temperature (-10 ± 1 ℃) 8.4 7.8 8.5 Tensile yield strength MN / m ² 40.56 41.41 39.35 Tensile elongation at break% 197.3 180.8 184.9 Hardness (HRR) 105.7 106.0 105.3 Vika softening temperature ℃ 95 94 94 Weatherability ΔE 1.11 1.12 1.09 Initial staining
Whether
The initial (L / a / b) 93.50 /
-0.60 /
2.47 92.95 /
-0.39 /
2.69 93.45 /
-0.66 /
2.45 After 20 minutes △ E 2.74 2.89
3.35 After 40 minutes △ E 9.16 10.60 11.43 Non-toxic judgment Non-toxic Non-toxic Lead content

The initial coloring is indicated by the initial value of the extruded article. Also, heat resistance was confirmed through a mathis oven to judge heat resistance. 20 minutes and 40 minutes, the difference in color was indicated by ? E versus the initial color value, which indicated that Comparative Example 1 had a smaller color difference and was superior in heat resistance to Example 1.

In addition, lead was checked for non-toxicity by checking for lead.

The contents of lead, cadmium and mercury in the non - toxic window were not detected in the external organization KCL. However, we did not confirm the window using existing lead. A photograph using the lead check (Figure 1) was attached to confirm the presence of lead.

According to the results shown in Table 2 above, all of the test results show more than the reference value of KS F 5602, and the prevention of the initial staining and the non-toxicity are both found to be excellent.

Claims (17)

A PVC-based polymer resin-based synthetic resin composition for windows,
As the stabilizer for the synthetic resin, a) a non-toxic metal soap stabilizer; And b) a non-toxic metal-based inorganic stabilizer, wherein the b) the non-toxic inorganic stabilizer is a metal oxide coated with at least one non-toxic metal selected from Li, Na, K, Mg, Ca, Based on 100 parts by weight of the PVC-based polymer resin, 0.5 to 15 parts by weight based on 100 parts by weight of the PVC-based polymer resin.
The method according to claim 1,
The a) non-toxic metal soap stabilizer is a compound in which at least one metal selected from Li, Na, K, Mg, Ca, Al and Zn is substituted with hydrogen in a fatty acid having an alkyl group having 3 to 50 carbon atoms, Based on the total weight of the polyolefin-based resin composition, is 0.1 to 15 parts by weight.
delete The method according to claim 1,
Wherein the metal oxide is at least one selected from the group consisting of calcium oxide, magnesium oxide, aluminum oxide, and titanium oxide.
The method according to claim 1,
Wherein the non-toxic metal-free inorganic stabilizer has a non-toxic metal content of 0.01 to 10 parts by weight based on 100 parts by weight of the metal oxide.
delete delete delete The method according to claim 1,
The composition may further comprise at least one auxiliary selected from 1,3-diketone compounds, dihydro-pyridine, polyol, isocyanurate, amino acid derivatives, organic ester of phosphoric acid, epoxy compounds, perchlorate, and salts of superacid Based on 100 parts by weight of a PVC-based polymer resin, 0.1 to 5 parts by weight of a stabilizer.
The method according to claim 1,
The composition may further comprise one or more organic stabilizers selected from Zinc Octoate, Zinc caprylate, Calcium acetylacetonate and THEIC (Tris-Hydroxy Ethyl Iso-Cyanurate) Based on 100 parts by weight of the polymer resin, in the range of 0.01 to 5 parts by weight.
The method according to claim 1,
Wherein the PVC-based polymer resin is at least one selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorosulfonated polyethylene, chlorinated polypropylene, or copolymers of chlorinated ethylene and vinyl acetate. Synthetic resin composition based on polymer resin based non - toxic window.
The method according to claim 1,
Further, it is preferable that 0.5 to 10 parts by weight of a processing aid, 5 to 15 parts by weight of an impact modifier, 2 to 10 parts by weight of TiO2, 10 to 30 parts by weight of calcium carbonate, 0.5 to 10 parts by weight of a lubricant, And 0.1 to 5 parts by weight of an antioxidant, an antioxidant, and an antioxidant, based on the total weight of the polyolefin resin.
13. The method of claim 12,
The processing aid Acrylic resin, acrylate, methacrylate, and acrylonitrile based on the total weight of the polyolefin resin.
13. The method of claim 12,
Wherein the impact modifier is at least one selected from acrylic and chlorinated polyethylene.
13. The method of claim 12,
Wherein the lubricant is at least one selected from montan wax, fatty acid ester, triglyceride, glycerin ester, polyethylene wax, paraffin wax, metal soap-based lubricant, and amide-based lubricant.
13. The method of claim 12,
The oxidation and ultraviolet inhibitor may be selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol, 2,6-di-benzyl- (3-methyl-6-tert-butylphenol), 4-nonylphenol, 2,2'-methylenebis butylphenol), 2,5-di-tert-butyl-hydroquinone, and 4,4 ', 4 "- (1 -methyl-1-propanyl- , 1-dimethylethyl) -5-methylphenol. The synthetic resin composition for a non-toxic window based on a PVC-based polymer resin.
A PVC-based polymer resin non-toxic window which is obtained by kneading and extruding the PVC resin-based synthetic resin composition for a non-toxic window according to any one of claims 1 and 9 to 16 and has improved heat resistance, weather resistance, .

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