KR20120066197A - The environmental-friendly windows profile compositions with enhanced heat resistance and color - Google Patents

Abstract

PURPOSE: A thermoplastic synthetic resin composition is provided to express various colors by high heat deflection temperature, together with excellent physical properties, and to provide doors and windows with excellent workability. CONSTITUTION: A thermoplastic synthetic resin composition comprises 30-60 weight% of acrylic rubber resin, 20-70 weight% of styrene-vinyl cyan copolymer of which average molecular weight is 150,000-400,000, and 3-20 weight% of a copolymer consisting of N-substituted maleimide based monomer, α-alkylstyrene based monomer, a vinyl cyan based monomer, and aromatic vinyl based monomer. The acrylic rubber composition is a copolymer resin, in which rubber containing acryl rubber as a base component is grafted by an aromatic vinyl compound monomer and a vinylcyan based compound monomer.

Description

The environmental-friendly Windows Profile compositions with enhanced heat resistance and color}

The present invention relates to an environment-friendly window material composition and a window material using the same, and more particularly, to an environment-friendly window material composition excellent in heat resistance and colorability and a window material using the same.

Polyvinyl chloride (PVC) resins, which have been widely used as building materials for windows and door frames, have been problematic in that large amounts of environmentally harmful substances, such as dioxins, are generated during combustion or extrusion. In addition, heavy metal ions such as cadmium stearate (Cd-st) and lead stearate (Pb-st), which are used as heat stabilizers, are also regulated by acting as a human hormone disruptor and are the main cause of problems such as sick house syndrome. It is becoming. In addition, polyvinyl chloride resin has a low thermal stability, there is a problem that is difficult to recycle due to discoloration during manufacture in the process of extrusion into the window.

Research has been made to replace such polyvinyl chloride (PVC) resins with ABS resins. Applicant described in the Republic of Korea Patent Publication No. 10-2007-0095142 and Patent Registration 10-0590821, an acrylic copolymer resin consisting of acrylic rubber-styrene monomer-butadiene rubber-vinyl cyan monomer and styrene-vinyl cyan based The resin composition using a copolymer is disclosed.

However, these resins can solve environmental problems by not using pollutants generated from existing polyvinyl chloride (PVC) resins, and unlike PVC, which is made of only white color, it can realize various colors and patterns, but it is used as a building exterior material. In the case of using a good light absorbing color, the surface and the internal temperature of the building exterior material in combination with the rise in atmospheric temperature, there was a problem that the building materials such as distortion, deformation, color discoloration. In addition, the weather resistance of the pigments used to implement a variety of colors has been a problem of discoloration when exposed to the external climate.

Accordingly, there is a demand for a new method that can simultaneously secure physical properties, heat resistance, and weather resistance as a building material due to an increase in the external atmospheric temperature and an increase in the surface temperature of the building material due to various colors.

The problem to be solved in the present invention is to provide a new thermoplastic resin composition which is improved at the same time the heat resistance and weather resistance applied to building materials such as windows and door frames.

Another problem to be solved by the present invention is to provide a building material such as windows and door frames made of a new thermoplastic resin composition at the same time improved heat resistance and weather resistance.

Another problem to be solved by the present invention is to provide a new styrene-based thermoplastic resin composition for windows and doors that can be produced in PVC production equipment and improved heat resistance and weather resistance at the same time.

Another object to be solved by the present invention is to reuse the styrene-based thermoplastic resin composition to provide a styrene-based thermoplastic resin composition for windows or door frames.

In order to solve the above problems, the thermoplastic resin composition of the present invention is 30 to 60% by weight of the acrylic rubber resin, 20 to 70% by weight of the styrene-vinyl cyan copolymer having a weight average molecular weight of 150,000 to 400,000, N-substituted Provided is a thermoplastic synthetic resin composition for windows and doors consisting of 3 to 20% by weight of a copolymer composed of a maleimide monomer, an α-alkylstyrene monomer, a vinyl cyan monomer and an aromatic vinyl monomer.

In the present invention, the acrylic rubber resin refers to a resin obtained by copolymerizing, preferably graft-copolymerized, an acrylic rubber or a rubber containing an acrylic rubber as a main component of an aromatic vinyl compound monomer and a vinyl cyanide compound monomer. .

In the present invention, the rubber containing the acrylic rubber as a main component means that the content of the acrylic rubber is 85% by weight or more. The rubber containing the acrylic rubber as a main component is a rubber containing not more than 15% by weight of other types of rubber, for example, diene rubber, for example butadiene rubber.

In one embodiment of the invention, the acrylic rubber resin is a ternary copolymer obtained by graft copolymerization of an acrylic rubber obtained by cross-polymerizing butyl acrylate or ethylhexyl acrylate with an aromatic vinyl compound and a vinyl cyan compound. In another embodiment, the acrylic rubber resin may be a quaternary copolymer in which a small amount of butadiene rubber and acrylic rubber are mixed and copolymerized with an aromatic vinyl compound and a vinyl cyan monomer. In another embodiment, the acrylic rubber and vinyl cyan resin may be used. It may be a mixture of a resin copolymerized with a monomer and an aromatic vinyl compound monomer, a resin copolymerized with butadiene rubber, a vinyl cyanide monomer and an aromatic vinyl compound monomer, and the mixing may be performed in a latex or powder state. In a preferred embodiment of the present invention, the acrylic rubber resin is an aromatic vinyl is a rubber containing a mixture of acrylic rubber and butadiene rubber in a weight ratio of 85:15 ~ 99: 1, more preferably 90:10 ~ 97: 3 weight ratio And a copolymer resin graft copolymerized with the compound and the vinyl cyan compound.

In a preferred embodiment of the invention, the acrylic rubber resin is the acrylic rubber-acrylonitrile-butadiene rubber-styrene (AABS) copolymer, the composition of the acrylic rubber-butadiene rubber / acrylonitrile / styrene is 40 ~ 70 It is a weight part / 5-20 weight part / 25-40 weight part.

In the present invention, the styrene monomer may be styrene, alpha-methyl styrene, p-methyl styrene, vinyl toluene or a mixture of two or more thereof, as an aromatic vinyl monomer, and monomers copolymerizable with these, for example, acrylic It may include a rate-based monomer. In a preferred embodiment the styrene-based monomer is styrene.

In the present invention, the vinyl cyan monomer is an acrylonitrile, methacrylonitrile, or a monomer copolymerizable with these, for example, a monomer containing methyl methacrylate, acrylate, etc., preferably acrylonitrile to be.

In the present invention, the acrylic rubber resin is 30-60% by weight, more preferably 35-55 parts by weight of the acrylic rubber to satisfy the durability, such as strength and impact resistance required for the thermoplastic synthetic resin for windows and doors Good to do.

In the present invention, the styrene-vinyl cyan copolymer is a copolymer of a styrene monomer and a vinyl cyan monomer.

In the present invention, the styrene-vinyl cyan-based copolymer has a weight average molecular weight of 150,000 or more, so that the final product can maintain physical properties, in particular rigidity, more preferably the weight average molecular weight is 300,000 to 500,000 More preferred.

In the present invention, the styrene-vinyl cyan-based copolymer is more preferably 60 to 80% by weight and 20 to 40% by weight of the composition ratio of styrene and vinyl cyan. 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 styrene-vinyl cyan-based copolymer has a wide molecular weight distribution, more preferably a small amount of low molecular weight and a high molecular weight of 1 million or more are mixed.

In the present invention, the method for producing a copolymer is not particularly limited as long as the molecular weight can satisfy the above range, and can be produced using ordinary emulsion polymerization, block polymerization or suspension polymerization. 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 styrene-vinyl cyan-based copolymer is 20 to 70% by weight, more preferably 25 to so as to meet the stiffness such as tensile strength, flexural strength and elastic modulus required for the thermoplastic synthetic resin for windows and doors It is recommended to use 55% by weight. Specifically, when the amount of the styrene-vinyl cyan-based copolymer is greater than the above range, the impact strength is lowered, and when too small, there is a problem that the workability is lowered.

In the present invention, the copolymer composed of the N-substituted maleimide monomer, the α-alkylstyrene monomer, the vinyl cyan monomer and the aromatic vinyl monomer is preferably composed of an employee bulk copolymer for discoloration stability and strength. In particular, the quaternary block copolymer according to the present invention has good compatibility with acrylic rubber and styrene-vinyl cyan-based copolymer, and has a low melt viscosity, thereby facilitating extrusion and molding of windows and doors at low temperatures such as conventional PVC extruders.

In the present invention, the N-substituted maleimide monomer is N-phenyl maleimide, maleimide. N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-cyclohexyl maleimide , N-chlorophenyl maleimide, N-methylphenyl maleimide, N-bromophenyl maleimide, N-naphthyl maleimide, N-lyryl maleimide, N-hydroxyphenyl maleimide, N-methoxy phenylmaleimide Mead, N-lauryl maleimide, N-hydroxyphenyl maleimide, N-methoxyphenyl maleimide, N-carboxy phenylmaleimide, N-nitrophenyl maleimide, N-benzyl maleimide and small amounts copolymerizable with these It is a monomer containing the monomer of.

In the present invention, the N-substituted maleimide monomer prevents the expression of heat resistance properties and decreases the thermal stability in the quaternary bulk polymer and suppresses the increase in melt viscosity and brittleness, thereby maintaining processability and kneading property when blended with the mixed resin. In addition, it is used in the range of 5 to 60% by weight in the bulk block copolymer to facilitate the heating control.

In a preferred embodiment of the present invention, the α-alkylstyrene monomer, vinyl cyan monomer and aromatic vinyl monomer are used 40-95% by weight, the relative content can be adjusted in consideration of the fluidity and rigidity of the quaternary copolymer. Preferably, the molecular weight of the quaternary copolymer is less than 7 to 150,000, 5 to 60% by weight of N-substituted maleimide, 10 to 70% by weight of α-alkyl styrene monomer, and 5 to 50% by weight of vinyl cyan monomer. It is good to consist of 3-50 weight% of aromatic vinyl monomers.

In the present invention, the copolymer composed of N-substituted maleimide monomer, α-alkylstyrene monomer, vinyl cyan monomer and aromatic vinyl monomer can be combined with heat resistance, durability and discoloration required for thermoplastic synthetic resin for windows and doors. It is preferable to use 3 to 20% by weight, preferably 5-15% by weight.

In another aspect, the present invention, 30 to 60% by weight of the acrylic rubber resin, 20 to 70% by weight of the styrene-vinyl cyan based copolymer having a weight average molecular weight of 150,000 to 400,000, N-substituted maleimide monomer, α-alkyl Provided is a thermoplastic composition for windows and doors comprising an antioxidant, a ultraviolet absorber, and a lubricant in a thermoplastic resin composition consisting of 3 to 20% by weight of a copolymer comprising a styrene monomer, a vinyl cyan monomer, and an aromatic vinyl monomer.

In the practice of the present invention, the antioxidant, the ultraviolet absorber, the lubricant is preferably contained in 0.01 to 1.0 parts by weight of the antioxidant, 0.01 to 1.0 parts by weight of the ultraviolet absorber, 0.3 to 5.0 parts by weight of the lubricant in 100 parts by weight of the thermoplastic resin composition. Do.

In the styrene-based thermoplastic resin composition for windows and doors according to the present invention, the antioxidant, the ultraviolet absorber and the lubricant are added to improve the thermal stability, ultraviolet stability and processability of the product. The antioxidant may be used individually or mixed with a phenolic, phosphorus or sulfur ester, the addition amount is 0.01 ~ 1.0 parts by weight. In addition, in this invention, the ultraviolet absorber used as an additive uses benzotriazole or HALS type, respectively, or it mixes, The addition amount is 0.01-1.0 weight part. Lubricants include ethylene bis stearamide, polyethylene wax or stearic acid, and 0.3 to 5.0 parts by weight is added.

In another aspect, the present invention, 30 to 60% by weight of the acrylic rubber resin, 20 to 70% by weight of the styrene-vinyl cyan based copolymer having a weight average molecular weight of 150,000 to 400,000, N-substituted maleimide monomer, α- Provided is a colored window prepared by extruding an antioxidant, a UV absorber, a lubricant, and a pigment to a thermoplastic resin composition composed of 3 to 20% by weight of a copolymer composed of an alkylstyrene monomer, a vinyl cyan monomer, and an aromatic vinyl monomer.

The colored window according to the present invention is excellent in thermal stability and heat resistance of the window itself, it is possible to color the various colors required by the market.

Styrene-based thermoplastic resin composition for a window frame according to the present invention is an out-of-standard product caused by problems such as color difference or surface defects during the manufacturing process, in order to reduce the recycling of the product, cost reduction and prevention of environmental pollution due to waste resin generation Can be used together. Typically, products outside the specification can be used after mixing with the raw materials, and preferably mixed and reused within 70% by weight.

The styrene-based thermoplastic resin composition for windows and doors according to the present invention may be manufactured using PVC synthetic resin extrusion conditions for window frames using a PVC extrusion apparatus for window frames. In the practice of the present invention, the styrenic thermoplastic resin for the window frame is typically extrudable at an extruder temperature range of 150 ~ 250 ℃ which is the extrusion condition of the PVC for the window frame, a product containing a mixture of up to 70% by weight of scrap in the raw material Can be prepared.

In another aspect of the present invention, the window of the present invention is characterized in that the acrylic rubber is dispersed in a SAN resin containing PMI, the content of the PMI in the window is 0.15 ~ 9.0% by weight.

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

<Extrusion Condition>

The thermoplastic resins produced below were made into window frames through the extrusion machine for the manufacture of windows. Twin screw 95mm (manufactured by Sambu Machinery Co., Ltd.), a PVC extruder, was used as a window frame manufacturing machine and manufactured according to the following extrusion conditions. The model produced was the P chassis BF-115.

Extruder condition

Table 1

(1) liquidity

According to ASTM D 1238 method, the load was measured by 10kg load, and the suitable fluidity range for extruding the window material should be 5 ~ 8g / 10min so that the window shape can be formed.

(2) impact strength

As a Charpy impact strength test, a standard test was carried out at 23 ° C ± 2 with a No. 5 test specimen (type A notch) according to KS M3056 method, and a low temperature test was performed at -10 ° C ± 2. According to the standard of KS F5602, it is more than 12.7 kJ / M ² (standard) and 4.9 kJ / M ² (low temperature) to be used as window profile.

(2) tensile strength

Tensile strength and elongation test was carried out at a temperature of 23 ℃ ± 2 according to the KS M3006 method. According to KS F5602 standard, tensile strength should be 36.8 MN / m ² or more to be used as window profile.

 (4) Weathering test

In order to evaluate long-term weather resistance, 200 hours of UV (A type 310 nm) 0.74 W / m ² (light intensity) irradiation was performed for 200 hours using 8-hour Q-UV (manufacturer; US Q-PANEL). The color difference change after the test for + 3 minutes water spray + 45 ℃ condensation for 3 hours 57 minutes) was measured.

(5) flexural modulus

Flexural modulus test is tested according to KS M 178 standard. The number of specimens shall be five. According to KS F5602 standard, the flexural modulus should be more than 1960 MN / m ² to be used as window profile.

(6) HDT (heat deformation temperature)

Heat deflection temperature test shall be done in Method B as specified in KS M ISO75-2, but the specimens shall be tested in a flat direction. The number of specimens shall be two.

(7) heat discoloration

Heat resistance discoloration test is the length of the test piece L: 100 ± 2.0mm in a constant temperature and humidity device for 24 hours at 25 ± 2 ℃, 50RH% conditions, and then in the dryer condition (temperature 150 ℃, 3 hours) Maintain for a certain time. ΔEab * values are measured using a CR-300 colorimeter.

(8) heat resistance strain

In the heat resistance strain test, the test piece has a length of L: 100 ± 2.0mm and is measured for a certain period of time in a dryer condition (temperature 85 ℃, 3 hours), and then the rate of change of the test piece is measured. It is possible.

Window materials made of conventional polyvinyl chloride resin or conventional ABS-based synthetic resin window composition has problems such as deformation and distortion of windows and doors due to the rise of the surface temperature of the windows due to the increase of the atmospheric temperature and the retention of various colors. Due to the high heat deflection temperature, the windows are high in various color expression and mechanical properties, and are excellent in extruding work as window profiles and provide superior physical properties compared to existing eco-friendly ABS based windows and windows.

Examples 1-6

After mixing the butyl acrylate monomer and the crosslinking agent with the acrylate rubber, which is a rubbery polymer, using an emulsion polymerization method, the pure water as an initiator, an emulsifier and a dispersion medium is first introduced into a polymerization tank, and the temperature is raised to 70 ° C, and the monomer and the crosslinking agent are continuously added while stirring. 30 parts by weight of solid styrene and 10 parts by weight of acrylonitrile were added continuously with a conventional emulsifier, initiator, and the like, and the styrene-acrylonitrile was grafted to acrylic rubber. Copolymer latex was prepared. Separately, 60 parts by weight of polybutadiene latex (solid content basis) was first added to a polymerization tank and heated up to 70 ° C while stirring. When the polymerization was carried out by continuously adding an emulsifier, an initiator, and 30 parts by weight of styrene monomer and 10 parts by weight of acrylonitrile to prepare a copolymer (B) latex grafted with styrene and acrylonitrile to butadiene rubber. Using magnesium sulfate as an electrolyte, 85 parts by weight of the copolymer (A) and 15 parts by weight of the copolymer (B) were mixed and coagulated to prepare AABS resin, which is a quaternary copolymer (C), based on the solid content. silver

 After heating the temperature to 150 ° C. in the polymerization reactor, 44 parts by weight of styrene, 44 parts by weight of acrylonitrile, 10 parts by weight of toluene, and 0.1 parts by weight of tertidodecyl mercaptan as a molecular weight regulator were mixed in a polymerization tank continuously. By addition to the polymerization. At the point where the conversion rate is 70%, the polymer is transferred to a separate tank, warmed to 220 ° C, and then transferred to a devolatilizer to remove the unreacted monomer and toluene by vacuum to -720mmHg. The product thus obtained had a SAN copolymer resin having a weight average molecular weight of 180,000 and a composition of styrene and acrylonitrile ratio of 66/34. In addition, the preparation of the PMI-SAN copolymer was first performed with 20 parts by weight of phenylmaleide and acryl. After mixing 20 parts by weight of nitrile, 50 parts by weight of alphamethylstyrene and 10 parts by weight of styrene are mixed and mixed, followed by polymerization by continuous addition at a polymerization temperature of 100 ° C.

At the point where the conversion rate reached 50%, the polymer was heated to 240 ° C., and the unreacted monomer was removed by vacuum in the devolatilization apparatus to obtain a weight average molecular weight of 100,000 and the ratio of PMI / AMS / ST / AN was 20/50/10. A PMI-SAN copolymer having excellent heat resistance having a / 20 composition is obtained.

 The mixing ratio of the SAN copolymer resin and PMI-based SAN resin and AABS resin as shown in the following table, and the antioxidant is 0.3 parts by weight of antioxidant (Songwon Industrial 6260), ultraviolet absorber (Siba Special Co., Ltd. TINUVIN-P) 0.3 parts by weight , 4 parts by weight of titanium dioxide was added to pelletize the resin produced after uniform mixing. Window profiles were prepared using a PVC extruder using the pelletized synthetic resin composition.

Comparative Example 1

Window profiles were prepared without adding PMI SAN resin as shown in the following table.

Comparative Example 2

A window profile was prepared by adding 20 wt% PMI SAN resin as shown in the following table.

Comparative Example 3

A window profile was prepared by adding 25 wt% PMI SAN resin as shown in the following table.

[Table 2]

[Table 3]

Claims (11)

30 to 60 wt% of acrylic rubber resin, 20 to 70 wt% of styrene-vinyl cyan copolymer having a weight average molecular weight of 150,000 to 400,000, N-substituted maleimide monomer, α-alkyl styrene monomer, vinyl cyan monomer and A thermoplastic synthetic resin composition for windows and doors comprising 3 to 20% by weight of a copolymer made of an aromatic vinyl monomer. 2. The thermoplastic synthetic resin composition according to claim 1, wherein the acrylic rubber resin is a copolymer resin obtained by graft polymerization of an acrylic rubber or a rubber containing an acrylic rubber as an aromatic vinyl compound monomer and a vinyl cyan compound monomer. . The copolymer of claim 1, wherein the copolymer of N-substituted maleimide monomer, α-alkylstyrene monomer, vinyl cyan monomer, and aromatic vinyl monomer is a bulk copolymerized copolymer, and has a molecular weight of less than 7 to 150,000, Thermoplastic for windows and doors comprising 5 to 60% by weight of N-substituted maleimide, 10 to 70% by weight of α-alkylstyrene monomer, 5 to 70% by weight of vinyl cyanide monomer, and 3 to 50% by weight of aromatic vinyl monomer. Synthetic resin composition. The thermoplastic synthetic resin composition of claim 1, further comprising 0.01 to 1.0 parts by weight of antioxidant, 0.01 to 1.0 part by weight of ultraviolet absorber, and 0.3 to 5.0 parts by weight of lubricant. The thermoplastic synthetic resin composition according to claim 1, wherein the thermoplastic synthetic resin composition comprises 70 wt% or less of the scrap of the thermoplastic synthetic resin composition. The acrylic rubber resin of claim 1, wherein the acrylic rubber resin is an acrylic rubber-styrene monomer-butadiene rubber-vinyl cyan monomer copolymer, and a weight ratio of acrylic rubber and butadiene rubber is 85: 15-99: 1. Thermoplastic synthetic resin composition. Styrene-vinyl cyanide copolymer having an acrylic-vinyl cyanide monomer-butadiene rubber-styrene monomer moiety copolymer resin of 30 to 60% by weight, and a weight average molecular weight of 150,000 to 400,000. A thermoplastic synthetic resin composition for windows and doors composed of 20 to 70 wt% of a resin, an N-substituted maleimide monomer, an α-alkyl styrene monomer, an unsaturated nitrile monomer amount, and 3 to 20 wt% of an aromatic vinyl monomer. An acrylic rubber is composed of a thermoplastic resin dispersed in a SAN resin containing PMI, the window characterized in that the content of PMI is 0.15 ~ 9.0% by weight. 10. The window and the window of claim 8, wherein the window is a colored window. According to claim 8, wherein the SAN-containing SAN resin has a molecular weight of less than 7 to 150,000, PMI 5 to 60% by weight, α-alkyl styrene monomer 10 to 70% by weight, vinyl cyan monomer 5 to 50 weight Windows, characterized in that it comprises a block copolymer consisting of 3 to 50% by weight of an aromatic vinyl monomer. The window of claim 8, wherein the acrylic rubber comprises an acrylic rubber and a butadiene rubber in an amount of 85:15 to 99: 1.