KR20110109670A

KR20110109670A - Poly-oxymethylene resin coomposition

Info

Publication number: KR20110109670A
Application number: KR1020100029491A
Authority: KR
Inventors: 강경민; 박성근
Original assignee: 코오롱플라스틱 주식회사
Priority date: 2010-03-31
Filing date: 2010-03-31
Publication date: 2011-10-06
Also published as: WO2011122850A2; WO2011122850A3

Abstract

The present invention is 0.01 to 0.2 parts by weight of porous organic-inorganic hybrid silica compound based on 100 parts by weight of polyoxymethylene resin; And it relates to a polyoxymethylene resin composition comprising 0.01 to 3 parts by weight of a hydrazide compound, according to which the emission amount of not only formaldehyde but also all volatile organic compounds have a slight and excellent functional properties, polyoxymethylene resin It is possible to provide environmentally friendly materials that are harmless to human body while maintaining excellent physical properties and molding processability.

Description

Polyoxymethylene resin composition {POLY-OXYMETHYLENE RESIN COOMPOSITION}

The present invention relates to a polyoxymethylene resin composition, and more particularly, the amount of release of not only formaldehyde but also a total volatile organic compound has a slight and excellent organoleptic property, while maintaining excellent physical properties and molding processability of the polyoxymethylene resin. It relates to a polyoxymethylene resin composition that can provide a harmless and environmentally friendly material.

Polyoxymethylene resin is a crystalline thermoplastic resin that is excellent in mechanical properties such as tensile strength, fatigue resistance and abrasion resistance, and is easily formed and processed, and is used in various fields such as electric products, automobiles, machines, building materials, and sundries.

In the case of such polyoxymethylene resins, formaldehyde released in a molten state and a solid state at room temperature has been a problem. Particularly, formaldehyde is a very harmful substance to the human body. In the presence of a certain concentration of formaldehyde in the air, headache, In addition to respiratory diseases or skin diseases, serious illnesses such as chronic fatigue and indigestion also occur, and is known to be a major cause of sick house syndrome and new car syndrome. Accordingly, various methods for reducing the amount of formaldehyde emitted from the polyoxymethylene resin have been proposed.

Japanese Patent Application Laid-Open No. 1992-063857 discloses a polyoxymethylene resin composition having excellent thermal stability and less discoloration during molding by containing a polyoxymethylene resin with a fatty acid ester of a polyhydric alcohol and an alkaline earth alkaline metal salt. Publication No. 195-173368 discloses a polyhindered phenol in a polyoxymethylene resin, an amine-substituted triazine compound, a metal-containing compound represented by a group consisting of hydroxides, inorganic acid salts and alkoxides of alkali or alkaline earth metals, and polyhydric alcohols. A polyoxymethylene resin composition exhibiting excellent thermal stability by containing fatty acid esters and higher fatty acid amides is disclosed.

Japanese Patent No. 3399483 discloses improved resin compositions formed by uniformly melt kneading polyoxymethylene resins, steric hindrance phenols, amine-substituted triazine compounds, specific metal-containing inorganic compounds, metal salts of fatty acids, fatty acid esters and higher fatty acid amides. It is disclosed to have stability.

Korean Patent No. 0606175 discloses a polyoxymethylene resin composition having a very low formaldehyde odor and excellent thermal stability and color tone during molding by adding a metal salt of carboxylic acid to a polyoxymethylene resin.

However, these conventional methods can only increase the thermal stability of the resin composition or reduce the occurrence of formaldehyde odor, but do not provide a fundamental solution and release other volatile organic compounds known to have a negative effect on the human body. Could not reduce.

Volatile organic compounds such as benzene, ethylene, styrene, and acetaldehyde, which are generated from plastics, volatilize to the atmosphere to produce odors and ozone, as well as skin contact or respiratory inhalation, which can cause nervous system disorders and cancer. Recently, regulations on the concentration of total volatile organic compounds (TVOCs) generated from plastics are being tightened around the world, and demand for eco-friendly materials is increasing rapidly. Accordingly, while maintaining excellent physical properties and molding processability of the polyoxymethylene resin, it is required to develop a material that is harmless to the human body and is environmentally friendly.

The present invention is a polyoxymethylene which can provide a material that is harmless to human body and is environmentally friendly while maintaining excellent physical properties and molding processability of polyoxymethylene resin, because the emission amount of not only formaldehyde but also total volatile organic compounds are insignificant and have excellent functional properties. It is for providing a resin composition.

Moreover, this invention is providing the molded article containing the said polyoxymethylene resin composition.

The present invention is 0.01 to 0.2 parts by weight of porous organic-inorganic hybrid silica compound based on 100 parts by weight of polyoxymethylene resin; And it provides a polyoxymethylene resin composition comprising 0.01 to 3 parts by weight of a hydrazide compound.

Moreover, this invention provides the molded article containing the said polyoxymethylene resin composition.

Hereinafter, a polyoxymethylene resin composition and a molded article including the same according to a specific embodiment of the present invention will be described in detail.

In one embodiment of the invention, 0.01 to 0.2 parts by weight of porous organic-inorganic hybrid silica compound, based on 100 parts by weight of polyoxymethylene resin; And it may be provided a polyoxymethylene resin composition comprising 0.01 to 3 parts by weight of a hydrazide compound.

The present inventors have conducted studies to reduce the amount of formaldehyde and total volatile organic compounds released from such resins while maintaining the physical properties of the polyoxymethylene resin, and as a result, the porous organic-inorganic hybrid silica compound and When the hydrazide-based compound is included in a specific content, the emission amount of not only formaldehyde but also all volatile organic compounds can be drastically reduced, and the sensory properties can be significantly increased through experiments. Accordingly, the use of such a polyoxymethylene resin composition can provide a material that is harmless to the human body and is environmentally friendly while maintaining the excellent physical properties and molding processability of the polyoxymethylene resin, and various industrial fields, for example, to which environmental regulations are applied. The present invention can be applied to interior and exterior materials of automobiles, interior and exterior materials of constructions or household goods, and precision electric and electronic products which are sensitive to the presence of organic compounds.

The polyoxymethylene resin composition may include a polyoxymethylene resin commonly used, but preferably includes a polyoxymethylene resin having a weight average molecular weight of 100 to 1,000,000. In general, polyoxymethylene resin shows a small decrease in free energy at room temperature or high temperature when it is converted from a monomer to a polymer, and a decrease in free energy is insignificant at around 127 ° C. Because of this property, the polyoxymethylene resin can maintain stability due to temperature change during processing. In addition, such a polyoxymethylene resin has a balanced structure can exhibit excellent insulating properties. The polyoxymethylene resin in the weight average molecular weight range is excellent in fatigue resistance, chemical resistance, heat resistance, friction wear characteristics, electrical characteristics, friction wear characteristics, moldability, etc., because of these characteristics of electrical, electrical / electronics, automobiles, various It can be easily applied to accessories of machinery and household goods.

On the other hand, in one embodiment of the invention, the porous organic-inorganic hybrid to 100 parts by weight of the polyoxymethylene resin in order to increase the olfactory sensitivity quality of the final product, or to minimize the generation of non-polar organic materials and volatile organic compounds The silica compound may be included in an amount of 0.01 to 0.2 parts by weight. When the content of the porous organic-inorganic hybrid silica compound is less than 0.01 part by weight, the number of fine pores or functional groups that act is so small that it is difficult to properly capture volatile organic compounds and the like, and when exceeding 0.2 parts by weight of polyoxy The bonding force between the end group of the methylene resin and the resin is weakened to cause decomposition, which causes severe gas to be released and at the same time severe foaming may cause problems in the synthesis process.

The porous organic / inorganic hybrid silica compound may include a silicate compound carrying a metal salt of aluminum silicate hydroxide. Such a porous organic / inorganic hybrid silica compound may be obtained by supporting a metal salt on a silicate compound formed by reacting sodium silicate, aluminum nitrate, urea and the like in an aqueous solution.

The silicate compound carrying the metal salt of the aluminum silicate hydroxide may be represented by the following Formula 1.

[Formula 1]

In Formula 1, the F portion may include a structure of Formula 2, M is phosphorus (P), calcium (Ca), zinc (Zn), iron (Fe), potassium (K), manganese (Mn ), Molybdenum (Mo), silver (Ag), magnesium (Mg) or titanium (Ti), x may be an integer between 1 and 5, y may be an integer between 2 and 7.

[Formula 2]

The porous organic / inorganic hybrid silica compound may have a pore size of 50 nm or less and a surface area of 200 to 2000 m 2 / g. The silica compound having such pore size and surface area appropriately captures formaldehyde and other volatile organic compounds. Can improve the sensory properties of the final product.

On the other hand, in one embodiment of the invention, in order to increase the olfactory sensitivity quality of the final product, or to minimize the generation of non-polar organic materials and volatile organic compounds, the hydrazide system based on 100 parts by weight of the polyoxymethylene resin (hydrazide) compound may be included in an amount of 0.01 to 3 parts by weight. When the content of the hydrazide compound is less than 0.01 parts by weight of the porous to remove formaldehyde or volatile organic compounds (VOCs) The organic / inorganic hybrid silica compound may have low efficiency or may decompose polyoxymethylene resin. In addition, when the content of the hydrazide-based compound exceeds 3 parts by weight, an excessive amount of mold deposit may occur in the manufacturing process, or the color tone of the polyoxymethylene resin may be lowered, thereby reducing the final product. Quality may be degraded.

The hydrazide-based compound may include hydrazide piopionate, thiocarbo hydrazide, dihydrazide oxalate, dihydrazide malonate, dihydrazide succinate, dihydrazide glutarate, Dihydrazide adipate, dihydrazide sebacide, dihydrazide dodecanoic acid, 1,18-octadecane dicarbohydrazide, dihydrazide maleate, dihydrazide fumarate, 7,11 Octadecanediene-1, 18-dicarbohydrazide, dihydrazide adipate, dihydrazide sebacate, dihydrazide dodecanediic acid, dihydrazide terephthalate, dihydrazide terephthalate Or mixtures thereof.

In addition, the hydrazide-based compound may include a compound of formula (3). In Formula 3, R may be alkyl having 1 to 20 carbon atoms, and n may be an integer of 1 to 30.

[Formula 3]

Meanwhile, the polyoxymethylene resin composition may further include one or more additives selected from the group consisting of antioxidants, weathering agents, mold release agents, colorants, sunscreen agents, fillers, plasticizers, adhesive aids, and pressure sensitive adhesives. In addition, the additives may be appropriately adjusted and applied by those skilled in the art according to the physical properties required in the final product, and the additives that can be used are not limited to the examples described below.

Examples of the antioxidant include sterically hindered phenolic, phosphite, thioether or amine compounds. Examples of the weathering agent include benzophenone, benzotriazole or sterically hindered amine compounds. Examples include glass fibers, carbon fibers or potassium titanate fibers, and examples of the filler include silica, clay, calcium carbonate, calcium sulfate or glass beads, and examples of the nucleating agent include talc or clay.

In addition, the colorant may be used without limitation, inorganic pigments and organic pigments used for coloring the resin, such inorganic pigments, such as titanium oxide, titanium yellow, whitening, podium, sulfur lead, composite oxide pigment, zinc sulfide Zinc oxide, barium sulfide, iron oxide, ultramarine blue, blue blue, cobalt blue, calcined pigments, carbonates, phosphates, acetates, carbon black, titanium black, acetylene black, lamp black, or mixtures thereof; As the condensed azo system, disazo system, monoazo system, diketopyrrolopyrrole, isoindolin system, anthraquinone system, heterocyclic system, quinacridone system, thioindigo system, perylone system, perylene system, dioxazine system, phthalocyanine Pigments of the system or mixtures thereof can be used. And such a coloring agent can use 1 type, or 2 or more types of the above-mentioned examples.

Specific examples of the release agent include alcohols such as mineral oil, liquid paraffin, paraffin wax, fatty acids, aliphatic alcohols, trivalent or more polyhydric alcohols, aliphatic amides, fatty acid metal salts, fatty acid esters, esters of the above alcohols and fatty acids, polycarboxylic acids and aliphatic alcohols. Esters, glycols, alkylene oxide adducts to alcohols, alkylene oxide adducts to fatty acids, polyolefin waxes, silicone oils, polyalkylene glycols, and the like.

In addition to the above-described additives, there are a sunscreen, a plasticizer, an adhesion aid or an adhesive, and the like, which are commonly known to be applicable to the plastic resin composition, without being limited thereto.

On the other hand, in the polyoxymethylene resin composition, as confirmed in Experimental Examples 1 to 3 described later, the generation amount (TVOCs) of total volatile organic compounds measured by GC-MS / MS method based on MS300-55 is 300 ppm or less. Formaldehyde concentration measured according to the VDA275 method may be less than 4.50ppm, and sensory index according to the PV3900 evaluation method may be 3 or less.

According to another embodiment of the present invention, a molded article including the polyoxymethylene resin composition may be provided.

As shown in the above description and the experimental example described below, the polyoxymethylene resin composition not only emits a small amount of formaldehyde as well as all volatile organic compounds, but also realizes very good sensory properties. While maintaining the excellent physical properties and molding processability of the resin can provide a material that is harmless to the human body and environmentally friendly.

Accordingly, the polyoxymethylene resin composition may be used in various industrial fields to which environmental regulations are applied, such as automotive interiors, exteriors, architectural interiors, exteriors or household goods, and precision electrical and electronic products sensitive to the presence of organic compounds. have. Specific examples molded using the polyoxymethylene resin composition, such as a speaker grille, a seat belt clip, a ring, and the like for automobiles and small and medium-sized parts for automobiles, which require abrasion resistance properties, such as cosmetics in the cosmetic container closure, various parts And parts for line of factories that manufacture or assemble electrical and electronic products sensitive to the presence of organic compounds, such as springs and gears, rollers for veranda windows, and semiconductors.

According to the present invention, poly ethylene is not only formaldehyde but has a small amount of emission of total volatile organic compounds and has excellent sensory properties, thereby providing a material that is harmless to humans and is environmentally friendly while maintaining excellent physical properties and moldability of polyoxymethylene resin. An oxymethylene resin composition and a molded article including the same may be provided.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

< Example And Comparative example : Polyoxymethylene Production of Resin Compositions>

Example 1 to 10

The polyoxymethylene resin (cocetal, Kolon plastic), porous silica compound (Epoclean-CS (Epoclean), Taesung Environmental Research Institute) and dihydrazide compound (alkanedionic acid dihydrazide, Nippon Fine Chemical Co., Ltd.) After mixing, using a twin screw extruder (manufactured by Automatik, Germany) at 190 ℃ extruded at a rate of 15kg per hour to prepare a polyoxymethylene resin composition.

Comparative example 1 to 6

The polyoxymethylene resin (cocetal, Kolon plastic), porous silica compound (Epoclean-CS (Epoclean), Taesung Environmental Research Institute) and dihydrazide compound (alkanedionic acid dihydrazide, Nippon Fine Chemical Co., Ltd.) A polyoxymethylene resin composition was prepared in the same manner as in Example 1 except that the polyoxymethylene resin composition was applied.

Compositions of the polyoxymethylene resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 Unit (part by weight) Polyoxymethylene resin Porous silica compounds Dihydrazide Compound Example 1 100 0.01 One Example 2 100 0.10 One Example 3 100 0.20 One Example 4 100 0.01 2 Example 5 100 0.05 2 Example 6 100 0.10 2 Example 7 100 0.20 2 Example 8 100 0.01 3 Example 9 100 0.10 3 Example 10 100 0.20 3 Comparative Example 1 100 0 0 Comparative Example 2 100 0.3 0 Comparative Example 3 100 0.5 0 Comparative Example 4 100 0 4 Comparative Example 5 100 0.3 4 Comparative Example 6 100 0.5 4

< Experimental Example : Example 1 to 10 And Comparative example 1 to 6 Polyoxymethylene Measurement of Physical Properties of Resin Compositions>

Experimental Example 1 = Amount of total volatile organic compounds TVOCs ) Measure

The amount of total volatile organic compounds (TVOCs) generated in the polyoxymethylene resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 was measured using a GC-FID apparatus based on the MS300-55 method.

Specifically, the polyoxymethylene resins of Examples 1 to 10 and Comparative Examples 1 to 6 were melt-kneaded to form a chip, and 14.7 g of a molded product obtained by injection molding the chip was placed in a 1 L sealed container. Then, the airtight container is heated in an oven at 80 ° C. for 30 minutes, left at room temperature for 10 minutes, and then injected with 3 L of high purity nitrogen gas (N ₂ 99.999%) to escape the gas through a separate tube attached to the airtight container. It was made. At this time, the exiting gas was collected using a 5L odorless Tedlar bag. The collected gas was analyzed using a GC-FID instrument to determine the concentration of TVOCs.

Experimental Example 2 : Determination of formaldehyde concentration

The concentration of formaldehyde generated in the polyoxymethylene resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 was measured based on the VDA275 method. The specific method is as follows.

The polyoxymethylene resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 were injection molded into 100 mm × 40 mm × 3 mm to obtain 13 to 16 g of specimens. 50 ml of distilled water was added to a 1 L polyethylene flask, and the specimen was After fixedly installed below 10mm from the top of the polyethylene flask, it was left for 3 hours or more in a thermo-hygrostat (human company) of 60 ° C. The polyethylene flask was then held at room temperature for 60 minutes and the sample was removed from the flask. In this process, humidity was measured according to DIN EN 322.

In addition, the amount of formaldehyde dissolved in the distilled water was measured by the ultraviolet absorption method according to the acetylacetone method. At this time, the acetylacetone solution was prepared by adding 4 ml of acetylacetone solution (quasi chemical, 98.5%) to a 1000 ml Erlenmeyer flask and filling distilled water up to 1000 ml, and using formaldehyde using an ultraviolet absorber (GENESYS10UV, Thermo electron corporation). The concentration of was measured.

Experimental Example 3 : Sensory index evaluation

The functional indexes of the polyoxymethylene resin compositions of Examples 1 to 10 and Comparative Examples 1 to 10 and Comparative Examples 1 to 6 were evaluated based on PV3900. The specific method is as follows.

The polyoxymethylene resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 were melt-kneaded to prepare chips, and the chips were injection molded to have a thickness of 5 to 7 mm, an area of 100 cm 2, and 10 to 60 g. The test piece was prepared.

When the weight of the specimen is (10 ± 1) g, (30 ± 3) g, it is placed in a 1 L sealed container, and when (20 ± 2) g, (60 ± 6) g, it is put in a 3 L sealed container. The 1 L container was filled with 50 mL of deionized water, and the 3 L container was filled with 150 mL of deionized water. At this time, the sample contained in the sealed container was not in direct contact with water.

And, if the weight of the specimen is (10 ± 1) g, (30 ± 3) g and aged in the dryer at (23 ± 2) ℃, (20 ± 2) g, (60 ± 6) g Aged in the dryer for (24 ± 1) hours at (40 ± 2) ℃.

Immediately after taking out the airtight container after the aging process, an evaluation group of 10 people smelled and evaluated the average value of the result. At this time, if each evaluation differed by more than 2 grades, re-evaluation was performed.

Sensory index classification criteria Rating Degree of smell 6.0 Disgusting and irresistible smell with irritating and intense smell 5.5 5.0 Irritating and disgusting smell 4.5 4.0 The smell is easily detected and disgusting 3.5 3.0 Odor is easily detected but not disgusting 2.5 2.0 Almost undetectable odor 1.5 1.0 No smell

The results of Experimental Examples 1 to 3 are shown in Table 3 below.

Results of Experimental Examples 1 to 3 Unit (part by weight) TVOCs (ppm) Formaldehyde concentration (ppm) Sensory Index (Grade) Example 1 281.4 4.21 3 Example 2 235.7 3.89 3 Example 3 231.4 3.27 3 Example 4 201.5 1.32 3 Example 5 180.1 1.02 2.5 Example 6 162.8 2.03 2.5 Example 7 150.4 3.19 3 Example 8 152.3 2.10 2.5 Example 9 141.9 1.04 2.5 Example 10 136.7 1.08 2 Comparative Example 1 538.6 5.91 4 Comparative Example 2 551.2 8.62 4 Comparative Example 3 638.1 19.34 4.5 Comparative Example 4 521.5 3.84 3.5 Comparative Example 5 505.7 5.56 4 Comparative Example 6 602.4 13.41 4

As shown in Table 3, the polyoxymethylene resin composition of Examples, the generation amount (TVOCs) of the total volatile organic compounds (TVOCs) measured by GC-MS / MS method based on MS300-55 is 300ppm or less, based on the VDA275 method It was confirmed that the concentration of formaldehyde measured by the above method was 4.50 ppm or less, and the sensory index based on the PV3900 evaluation method was 3 or less.

Therefore, the polyoxymethylene resin composition of the embodiment can reduce the amount of release of not only formaldehyde but also all volatile organic compounds, and can significantly increase the sensory properties, while maintaining the excellent physical properties and molding processability of the polyoxymethylene resin It can provide environmentally friendly material that is harmless to human body.

Claims

Per 100 parts by weight of polyoxymethylene resin,
0.01 to 0.2 parts by weight of porous organic / inorganic hybrid silica compound; And
Polyoxymethylene resin composition comprising 0.01 to 3 parts by weight of a hydrazide compound.

The method of claim 1,
The polyoxymethylene resin is a polyoxymethylene resin composition having a weight average molecular weight of 100 to 1,000,000.

The method of claim 1,
The porous organic-inorganic hybrid silica compound includes a silicate compound on which a metal salt of aluminum silicate hydroxide of Formula 1 is supported, and the F portion of Formula 1 is a poly-containing structure of Formula 2 Oxymethylene Resin Compositions:
[Chemical Formula 1]

(2)

In Chemical Formula 1,
M is phosphorus (P), calcium (Ca), zinc (Zn), iron (Fe), potassium (K), manganese (Mn), molybdenum (Mo), silver (Ag), magnesium (Mg) or titanium (Ti) ),
x is an integer of 1-5, y is an integer of 2-7.

The method of claim 1,
The porous organic-inorganic hybrid silica compound has a pore size of 50 nm or less and a polyoxymethylene resin composition having a surface area of 200 to 2000 m 2 / g.

The method of claim 1,
The hydrazide compound is a polyoxymethylene resin composition comprising a compound of formula
[Formula 3]

In Chemical Formula 3,
R is alkyl having 1 to 20 carbon atoms,
n is an integer from 1 to 30.

The method of claim 1,
A polyoxymethylene resin composition further comprising at least one additive selected from the group consisting of antioxidants, weathering agents, mold release agents, colorants, sunscreen agents, fillers, plasticizers, adhesion aids, and pressure sensitive adhesives.

The method of claim 1,
The polyoxymethylene resin composition whose generation | occurrence | production amount (TVOCs) of total volatile organic compounds (TVOCs) measured by GC-MS / MS method based on MS300-55 is 300 ppm or less.

The method of claim 1,
The polyoxymethylene resin composition whose density | concentration of formaldehyde measured based on the VDA275 method is 4.50 ppm or less, and the sensory index based on PV3900 evaluation method is 3 or less.

Molded article containing the polyoxymethylene resin composition of any one of Claims 1-8.

The method of claim 9,
The molded article includes a speaker grille, a clip for a seat belt, a loop for a seat belt, a stopper for a cosmetic container, various windings and gears, a roller for a balcony window and a part of a semiconductor assembly process line.