KR100823497B1 - Thermoplastic resin composition for profile and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a resin composition for a profile used as a building material such as a window frame, a window frame, more specifically, a terpolymer of a polycarbonate resin, an acrylic monomer-styrene monomer-vinyl cyan monomer, and It is related with the resin composition for profiles containing the resin composition which consists of a styrene- acrylonitrile copolymer with a broad molecular weight distribution. In the resin composition for profiles, an additive including a flame retardant is used to provide flame retardancy and processability to the profile.

The resin composition for a profile according to the present invention has excellent heat insulation, airtightness, water tightness, sound insulation, wind resistance, condensation resistance and flame retardancy comparable to polyvinyl chloride (PVC), which has been used as a conventional profile resin, Disadvantages of PVC resin, for example, use of harmful heavy metals such as cadmium stearate, lead stearate, etc. to compensate for thermal stability, or release of environmental hormone disturbances such as dioxins during extrusion or fire. It is an environmentally friendly resin composition for a profile.

Acrylic High Rubber

Description

Thermoplastic resin composition for profile and manufacturing method therefor {THERMOPLASTIC RESIN COMPOSITION FOR PROFILE AND MANUFACTURING METHOD THEREOF}

The present invention relates to a resin composition for a profile used as a building material such as a window frame, a window frame, and more particularly, a copolymer of a polycarbonate resin, an acrylic rubber-styrene monomer, a vinyl cyan monomer, and a molecular weight. It is related with the resin composition for profiles which consists of a resin composition which consists of a copolymer of a styrene-type monomer-vinyl cyan-type monomer with a wide distribution.

As a conventional synthetic resin for profiles, polyvinyl chloride (PVC) resins have been used due to advantages such as excellent heat insulation, airtightness, water tightness, soundproofing, wind resistance, condensation resistance, and flame resistance. However, in the environmental aspect, in the case of extrusion processing or in the event of a fire, a large amount of toxic chlorine gas (HCl) or toxic dioxins are released, or cadmium stearate (Cd-St) or lead to overcome the low thermal stability of PVC resin. There have been many problems, such as the use of large amounts of heavy metal additives such as stearate (Pb-St).

Accordingly, development of environmentally friendly materials that can replace PVC is continuing. For example, Korean Patent Laid-Open No. 2001-0096666 discloses a resin composition using a mixture of ethylene copolymer, ethylene vinyl acetate, and EPDM rubber. However, the resin can prevent the production of environmental hormone disturbances such as dioxin, but can not meet the physical properties required for the profile resin is a situation that can only replace some of the soft PVC resin.

Accordingly, there is a continuing demand for replacement resins that can solve the environmental problems of PVC resins while satisfying the physical properties required for the profile resins and the flame retardant properties as building materials.

An object of the present invention is to provide a novel profile resin composition that can replace PVC.

Another object of the present invention is to avoid the environmentally harmful substances (dioxin), which is a disadvantage of PVC resin while utilizing the advantages of PVC resin insulation, air tightness, watertightness, sound insulation, wind pressure resistance, dew condensation resistance and flame retardant properties It is to provide a resin composition for a profile consisting of a polycarbonate and a weather resistant resin that does not use a heavy metal stabilizer such as lead or cadmium which is a substance.

Another object of the present invention is to provide a thermoplastic resin composition that can be produced in a conventional PVC production equipment.

Still another object of the present invention is to provide a window frame or window frame made of polycarbonate and weather resistant resin.

Still another object of the present invention is to provide a method for producing a profile for a window frame using polycarbonate and weather resistant resin.

To achieve the above object, the resin composition for a profile according to the present invention is 20 to 70% by weight of a polycarbonate resin; Acrylic rubber-styrene monomer-vinyl cyan monomer copolymer resin 5 to 40% by weight; 1-40 wt% of a styrenic-vinylcyan based copolymer having a molecular weight distribution (Mw / Mn) of 2.5-5.5; Is made of.

In the present invention, in the present invention, the polycarbonate resin is bisphenol-A-polycarbonate resin, tetramethyl-polycarbonate resin, bisphenol-Z-polycarbonate resin, tetrabromer-polycarbonate resin, tetraacrylo -It is preferable to select and use from polycarbonate resin, More preferably, it is preferable to use the bisphenol-A-polycarbonate resin which is good in improving compatibility and impact resistance. In addition, the content of the polycarbonate resin in the resin composition is preferably 20 to 70% by weight. If the content is less than 20% by weight, it is difficult to obtain a desired impact strength and formability. have.

In the present invention, it is preferable that the polycarbonate resin uses a low viscosity polycarbonate to be processed at a conventional PVC extrusion temperature. In the practice of the present invention, the low-viscosity polycarbonate resin preferably has a weight average molecular weight of 18,000-40,000, more preferably about 25,000-35,000. If the molecular weight is high, the polycarbonate is not dispersed, the appearance characteristics do not come out, the impact strength and elongation characteristics are not obtained. If the molecular weight is low, the tensile strength of the final product is not obtained.

In the present invention, the styrene monomer may be used as an aromatic vinyl monomer, styrene, alpha-methyl styrene, p-methyl styrene, vinyl toluene, and a mixture of two or more thereof, and preferably styrene.

In the present invention, the vinyl cyan monomer is acrylonitrile, methacrylo

Nitriles, mixtures thereof, and the like, preferably acrylonitrile.

In the present invention, the styrene-vinyl cyan monomer copolymer has a molecular weight so as to increase the kneading with the polycarbonate, acrylic rubber-styrene monomer-vinyl cyan monomer copolymer, and to be extruded in a PVC resin extruder It is preferable that the distribution is wide, and more preferably the ratio of the weight average molecular weight and the number average molecular weight is 2.5 to 5.5. When the molecular weight distribution is wide and the ratio of the weight average molecular weight and the number average molecular weight is 2.5 to 5.5, the window frame can be manufactured by extruding at the extrusion conditions of the window frame PVC resin, that is, at a relatively low temperature. In order to maintain, extrusion can be performed under the conditions which calibrate using cooling water, and the product excellent in the surface state of a molded article can be manufactured. Although not theoretically limited, if the molecular weight distribution is wide, low molecular weight resins can be melted at low temperatures on the surface to increase the smoothness of the molded products, and high molecular weight resins increase the rigidity of the molded products, thereby improving durability required for the final product. It will be able to hold. However, if the molecular weight distribution is too wide to reach 5.5 or more, a large polymer, that is, a polymer having a molecular weight of 1 million or more, is formed and cannot be melted during extrusion processing. Therefore, a gel or fish-eye is applied to the surface of the window frame. The surface defects such as the phenomenon is generated, and also the low molecular weight is volatilized during the extrusion process, there is a problem that the surface gloss is reduced.

In the present invention, the styrene-vinyl cyan-based copolymer has a weight average molecular weight of 130,000 or more, so that the final product can maintain physical properties, in particular rigidity, more preferably the weight average molecular weight is 150,000 to 500,000 More preferred.

In the present invention, the styrenic-vinyl cyan-based copolymer is preferably used 1-40% by weight, more preferably 5 to 20% by weight, and when the amount is small, the resin when extruded at a low temperature (PVC extruder) Deterioration of dispersion occurs and appearance defect occurs. If too much is added, the appearance is good during extrusion, but the physical property balance is broken so that the elongation and impact properties of the profile to be finally obtained cannot be obtained.

In the practice of the present invention, the styrene-vinyl cyan-based copolymer is more preferably a composition ratio of 60-80% by weight and 20-40% of the styrene-based and vinylcyan-based, respectively. When the content of the vinyl cyanide is high, the thermal stability of the polymer is low, and when the content of the styrene is high, the rigidity of the polymer of the product may be weakened.

In the present invention, the method for producing the styrene-vinyl cyan-based copolymer is not particularly limited as long as it can satisfy the above molecular weight and molecular weight distribution, and can be prepared using conventional emulsion polymerization, block polymerization or suspension polymerization. Can be. In one embodiment of the invention, it is preferable that the styrene-acrylonitrile copolymer use emulsion polymerization or suspension polymerization.

In the present invention, the acrylic rubber-styrene monomer-vinyl cyan monomer copolymer resin is a double bond instead of the polybutadiene used for impact reinforcement in the acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as ABS resin). Resin that has a molecular structure that is not resistant to weathering deterioration by using acrylic rubber that is free of heat, and improves weather resistance compared to conventional ABS resin, and resin properties that significantly reduce the appearance of windows and appearance changes in windows and doors even when used outdoors for a long time. Indicates. In addition, the weatherability is good, and unlike the ABS copolymer, it shows excellent appearance characteristics only by coloring the raw materials without the coating process.

In the practice of the present invention, the acrylic rubber is a rubber produced by polymerization of an acrylic monomer in which the polymer exhibits rubber properties. In the present invention, the acrylic monomer is preferably an alkyl acrylate having 2 to 8 carbon atoms, preferably butyl acrylate or ethylhexyl acrylate, still more preferably butyl acrylate.

In another embodiment of the present invention, the acrylic rubber may be a mixture of the acrylic monomer monomer and the monomer having an ethylenically unsaturated group copolymerizable therewith. In this case, the acrylic monomer in the mixture can be used in the range having a low temperature Tg that the final product can exhibit rubbery properties, preferably 70% by weight or more, more preferably 80% by weight or more is preferably used.

In another embodiment of the present invention, the acrylic rubber may be a mixture of acrylic rubber and butadiene rubber. In the present invention, the butadiene-based rubber is a polymer of conjugated diene-based monomer, the conjugated diene-based monomer may be used butadiene, isoprene, chloroprene, butadiene-styrene, butadiene-methacrylate. The butadiene rubber can be used in a range that satisfies the long-term weather resistance of the final product, preferably 30% by weight or less, more preferably less than 15%.

In the present invention, the acrylic rubber-styrene monomer-vinyl cyan monomer copolymer resin is a resin in which a styrene monomer and a vinyl cyan monomer are copolymerized with acrylic rubber. Although not limited in theory, the styrene monomer and the vinyl cyan monomer copolymerized with the acrylic rubber may be combined with the styrene monomer to improve the kneading property of the copolymer of the styrene monomer having a wide molecular weight distribution and the vinyl cyan monomer. The vinyl cyan monomer is preferably graft copolymerized to an acrylic rubber.

In one embodiment of the present invention, it is preferable that the acrylic rubber-styrene monomer-vinyl cyan monomer copolymer resin uses an acrylic rubber having a high content of acrylic rubber, for example, an acrylic rubber. In one preferred embodiment of the invention, the content of acrylic rubber is preferably at least 30% by weight, preferably at least 40% by weight, even more preferably at least 50%.

In another embodiment of the present invention, the acrylic high rubber is 30 wt%, preferably 50 wt%, more preferably 60 wt% or more of styrene and acrylonitrile in order to reinforce the impact strength It can be used interchangeably with grafted butadiene rubber. In this case, the content of butadiene high rubber is preferably used in less than 30% by weight, preferably less than 15% by weight so as not to lower the long-term weather resistance.

In one embodiment of the present invention, the acrylic rubber-styrene monomer-vinyl cyan monomer can be prepared by conventional emulsion polymerization. In the practice of the invention, the acrylic rubber-styrene monomer-vinyl cyan monomer is prepared by first polymerizing an acrylic monomer such as butyl acrylate to prepare rubber latex, and then graft polymerization of styrene monomer and acrylonitrile. Can be prepared.

In a preferred embodiment of the invention, the composition of each component in the copolymer grafted with styrene and acrylonitrile monomers is acrylic rubber / acrylonitrile / styrene = 40-85 wt% / 5-20 wt% / 10- 40 wt%.

In the present invention, the acrylic rubber-styrene monomer-vinyl cyan monomer copolymer is preferably used 5-40% by weight in the profile resin. If less than 5% of the copolymer is used, the long-term weather resistance is lowered, there may be discoloration problems. If the amount used more than 40%, the impact strength is increased, but the appearance characteristics of the profile during processing decreases.

The resin composition for a profile according to the present invention is 5-30 parts by weight of a flame retardant, 1-6 parts by weight of pigment, 0.01-5.0 parts by weight of antioxidant, in order to satisfy the flame retardant properties required for the profile for building materials. 0.01 to 5.0 parts by weight of ultraviolet absorber, and 0.3 to 5.0 parts by weight of lubricant.

In the present invention, a flame retardant may be added to improve the flame retardancy of the synthetic resin composition. In a preferred embodiment of the present invention, bromine-based flame retardants include decabromer diphenyl oxide (DBDPO), octabromer diphenyl oxide (OBDPO), tetrabromer bisphenol A (TBBA), 2,4,6 tribromerphenoxy Brominated flame retardants such as 1,3,5 trizan (SR-245), brominated aromatic compounds (S-8010, S-4010) and flame retardants of the bromine laminate epoxy oligomer (BEO) type are used. However, these bromine-based flame retardants have advantages such as price competitiveness, thermal stability, and weather resistance, but have a fatal disadvantage of discharging environmental hormone disturbances such as dioxins and furans as the flame retardants are pyrolyzed during fire combustion. Although this property has the advantage of suppressing combustion in a fire, it has a risk of toxic gases (dioxin, furan) that are harmful to the human body as it is combusted with PVC resin. In addition, chlorinated paraffin and chlorinated polyethylene, which are used as chlorine-based flame retardants, have excellent flame retardant properties and weather resistance, but like brominated flame retardants, the flame retardant is pyrolyzed during fire combustion, releasing chlorine gas (HCl), which is deadly to humans It has a disadvantage. In addition, resorcinol di is an oligomeric form of commonly used phosphorus flame retardants triphenyl phosphate (TPP), tricresyl phosphate (TCP), 3-hydroxyphenylphosphine, ammonium polyphosphate, and triphenyl phosphate (TPP). Flame retardants such as phosphate (RDP), bisphenol A diphosphate (BDP), and aromatic phosphate ester oligomers have the advantage of not emitting toxic substances during fire combustion, but they are more competitive than brominated flame retardants in terms of price competitiveness, physical property balance and flame retardant properties. Has the disadvantage of In the present invention, an aromatic phosphate ester oligomer, which is a phosphorus flame retardant, is used, and the amount of the flame retardant is 1 to 30% by weight.

In addition, the antioxidant used as an additive may be used individually or mixed with phenolic, phosphorus or sulfur esters. It is preferable to use 0.01-5.0 weight part of addition amounts.

In the present invention, the ultraviolet absorber used as an additive is preferably 0.01 to 5.0 parts by weight of benzotriazole or HALS, respectively or mixed.

In the present invention, the lubricant used as an additive may be ethylene bis stearamide or polyethylene wax stearic acid, PEwax, acrylic polymer WAX and the like, and 0.3 to 5.0 parts by weight is added. Preferably it is 0.5-2.0 weight part.

Other pigments can be colored and added according to the required color, and it is preferable to use 1-6 parts by weight of the pigment.

The resin composition for profiles according to the present invention can produce a resin composition using a general mixed melt processing apparatus such as a Banbury mixer and an extruder. The above-mentioned resin components for the profile are prepared by uniformly dispersing each other in an extruder and cooling the dispersed melt by a conventional synthetic resin manufacturing method.

In the practice of the present invention, the pellet of the resin composition can be extruded using a conventional PVC extruder. In one embodiment of the invention, the following extrusion conditions can be used.

Profile Extrusion Condition

The extruder used twin screw 95mm (manufacturer Sambu Machinery Co., Ltd.), a PVC extruder, which is a window frame manufacturing machine, and the window frame model produced is p chassis BF-115.

Profile extruder conditions and various test methods

Die temperature (℃) Cylinder temperature (℃) Rpm Pull out speed (m / min) Coolant temperature (℃) Load D1-D4 AD C6 C5 C4 C3 C2 C1 210/195/200/198 195 190 180 160 140 140 160 10 2.1 18 55

Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited to the Examples.

Examples 1-5

It has the composition ratio as shown in Table 1, but adds 4 parts by weight of titanium dioxide, 0.3 parts by weight of antioxidant (Songwon Industry 147BF), and 0.3 parts by weight of UV absorber (TINUVIN-P Co., Ltd.). After mixing sufficiently with a φ = 25mm, extruded in a twin screw extruder in the range of 170 ℃ ~ 250 ℃, cooled, solidified into pellets, and then extruded through the profile release extruder and then KSF 5602 standard (window for synthetic resin) The physical property test was carried out according to the shape member). In addition, the appearance state of the profile (glossiness, shape smoothness) and the like during extrusion were compared and evaluated. In order to evaluate long-term weather resistance, 200 hours (1 cycle test condition: 60 ℃ * 8 hours UV (A type 310nm)) irradiation using a accelerated weather resistance tester (Model: Q-UV manufactured by Q-PANEL, USA) 0.74w / m2 The color difference change after the test was measured for a light intensity intensity + moisture spray for 3 minutes + 45 ° C. * 3 hours and 57 minutes condensation).

Comparative Examples 1 to 5

Specimens were prepared in the same manner as in the compositions and compositions described in Table 1 above.

Example 1

The specimens prepared according to Examples 1 to 5 and Comparative Examples 1 to 5 above were left to stand for 24 hours, and then tensile strength and elongation were measured according to the following method, and pellets were measured for fluidity after drying, and the results are shown in Table 1. It was.

<Test method>

(1) Impact strength: by Charpy impact strength test

According to KS M 3056 method, it was tested by the 5th test piece (type A notch) at the temperature of 23 +/- 2 degreeC. According to KSF 5602 standard, the pass is 12.7 KJ / M2 or higher.

(2) tensile strength and elongation

Tensile strength and elongation tests were measured according to KS M 3006.

According to KSF 5602 standard, tensile strength is over 36.8 MN / m2 and elongation is

Pass 100% or more to pass.

(3) Combustion resistance test is to be done in method A specified in 5.24.1 (A method) of KSM 3015.

According to KSF 5602, combustion will not continue to pass the flame resistance test.

(3) To obtain long-term weather resistance and to obtain a quick laboratory result, the preliminary promotion test is carried out to predict the results. For 200 hours, the profile produced by the existing PVC has a color difference (ΔE) of 2.0 level and the smaller the measured value, the longer the long-term weather resistance. It means good.

Item Example Comparative example One 2 3 4 5 One 2 3 4 5 Composition (A + B + C + D = 100 wt%) A 50 50 60 40 70 50 75 20 60 50 B Midpoint   20 20 20 High viscosity   20 28 19 15 25 25 50 20 10 C 2 One  5 5 30 D D1  10 20 20 20 5 5 30 10 D2 20 20 F 18 12 18 18 12 18 5 30 12 40 G One 3 One 0.5  0.9 0 0 One 4 0 Properties Impact strength 35 42 55 31 55 16.0 45 9.5 32 18.6 The tensile strength 41 42 44 44 52 35 46 43 43 44 Elongation (%) 112 136 117 120 140 23 102 64 110 58 Flame Retardant Properties Flame resistance clear clear clear clear clear clear fail fail clear clear Extrudability Exterior Good Good Good Good Good Bad Bad Bad Bad Bad Long-term weather resistance Color difference (DE) 0.9 1.3 1.4 1.2 0.9 1.9. 0.5 0.7 1.2 3.5

(week)

A) Polycarbonate resin (Samyang Corp .: 3035grade)

B) Acrylic Rubber-Acrylonitrile--Styrene Terpolymer

 (Middle viscosity: BLENDEX 984 (CROMTON, or XC-450 (Kumho Petroleum)

 High viscosity: BLENDEX WX160 (CROMTON, or XC-500 (Kumho Petroleum)

C) acrylonitrile butadiene styrene copolymer

  (High viscosity: HR-130 powder: Kumho Petroleum)

D) Styrene-Acrylonitrile Copolymer

D1 (Kumho Petrochemical H-1163: Weight average molecular weight 400,000

Molecular weight distribution (weight partial molecular weight (Mw) / number average molecular weight (Mn): 4.0

D2 (Kumho Petrochemical SAN 325 weight average molecular weight 110,000, molecular weight distribution 2.0

E) PX-200, aromatic phosphate ester oligomer

Type: L-1000 (Three rayon)

In the above table, the tensile strength and the elongation rate of the Examples 1 to 5 were generally better than those of the comparative example, and the tensile strength and the elongation rate were satisfied as the result of satisfying the PVC profile (KS F 5602). In contrast, the acrylic resin for windows and doors has suitable physical properties as a synthetic resin for windows and windows.

In addition, the thermoplastic resin composition for profile according to the present invention was confirmed that heavy metals were not detected in the certification test of heavy metals of the Institute for Living Environment Testing and the combustion gas test of the Korea Building Materials Testing Institute, and did not emit environmental hormone disturbance substances (dioxin). It became. This is considered a natural result in that the thermoplastic resin composition for a profile according to the present invention does not use heavy metal heat stabilizers, and does not use PVC, which causes such pollutants.

As described above, the present invention provides the advantages of the conventional PVC resin, such as heat insulation, airtightness, watertightness, soundproofing, wind pressure resistance, dew condensation resistance, and flame retardant properties, while maintaining the advantages of PVC during fire combustion. It is a resin that combines the advantages of aluminum windows and PVC windows. In addition, the existing PVC extruder can be used as it is, it is expected that no additional burden economically occurs.

Claims (12)

Polycarbonate resin 20-70 wt%; Acrylic rubber-styrene monomer-vinyl cyan monomer copolymer resin 5 to 40% by weight; A resin composition for window profiles comprising a weight average molecular weight of 130,000 to 400,000 and a molecular weight distribution (Mw / Mn) of 2.5 to 5.5 of a SAN copolymer of 1 to 40% by weight. The method of claim 1, wherein the polycarbonate resin is bisphenol-A-polycarbonate resin, tetramethyl-polycarbonate resin, bisphenol-Z-polycarbonate resin, tetrabromer-polycarbonate resin, tetraacrylo-polycarbonate resin, And a resin composition for a window profile selected from the group consisting of a mixture thereof. The resin composition of claim 1, wherein the polycarbonate resin has a molecular weight of 18,000 to 40,000. delete delete The composition of claim 1, wherein the acrylic rubber is a polymer of C2-C8 alkyl acrylate monomers. The composition of claim 1, wherein the acrylic rubber is acrylic rubber including 30 wt% or less of butadiene rubber. The composition of claim 1, wherein the acrylic rubber-styrene monomer-vinyl cyan monomer copolymer resin is a resin obtained by graft polymerization of styrene and acrylonitrile on acrylic rubber. The composition for a window profile according to claim 8, wherein the weight ratio of acrylic rubber-styrene-acrylonitrile is 40 to 85% by weight, 5 to 20% by weight, and 10 to 40% by weight, respectively. The flame retardant according to claim 1, 5-30 parts by weight, pigment 1-6 parts by weight, antioxidant 0.01-5.0 parts by weight. A window profile composition comprising 0.01 to 5.0 parts by weight of a ultraviolet absorber and 0.3 to 5.0 parts by weight of a lubricant. The resin composition according to claim 10, wherein the flame retardant is selected from the group consisting of bromine flame retardants, chlorine flame retardants, phosphorus flame retardants, and mixtures of two or more thereof. The window profile manufactured using the resin composition of any one of Claims 1-3 and 6-11.