• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A rubber-modified styrene type polymer excellent in transparency and excellent in impact strength and moldability, is presented. A rubber-modified styrene type polymer comprising from 1 to 15 parts by weight of a dispersed phase made of a rubber-like elastic material and from 99 to 85 parts by weight of a continuous phase made of a polymer comprising from 35 to 75 wt % of styrene type monomer units and from 65 to 25 wt % of (meth)acrylate type monomer units, wherein the rubber-like elastic material is a styrene (30 to 50 wt %)-butadiene (70 to 50 wt %) block copolymer, the weight average molecular weight (Mw) of the polystyrene portions of this block copolymer is from 45,000 to 75,000, and the ratio (Mw/Mn) of Mw to the number-average molecular weight (Mn) is from 1.20 to 1.80.
    公开号:US20010003769A1
    申请号:US09/739,658
    申请日:2000-12-20
    公开日:2001-06-14
    发明作者:Takeshi Yamada；Tetsuya Shinmura
    申请人:Denki Kagaku Kogyo KK；
    IPC主号:C08F287-00
    专利说明:
    [0001] 1. Technical Field of the Invention [0001]
    [0002] The present invention relates to a rubber-modified styrene type polymer excellent in transparency, impact strength and moldability. [0002]
    [0003] 2. Prior Art [0003]
    [0004] A styrene type polymer is a synthetic resin excellent in transparency, moldability and rigidity and has been widely used as a molding material for e.g. household articles, electric appliances and packages. And, as the application fields have expanded, it has been demanded to improve the impact strength of the styrene type polymer. A styrene type polymer containing a rubber-like elastic material as dispersed particles in order to improve the impact strength of the styrene type polymer, i.e. a rubber-modified styrene type polymer, is known. However, such a rubber-modified styrene type polymer has been poor in transparency as compared with a styrene-type polymer not modified with rubber, and it has had a drawback that it can not be used in a field where the transparency is particularly required. [0004]
    [0005] On the other hand, a technique is also known to improve the impact strength by blending a styrene-butadiene block copolymer to a polystyrene. However, such a styrene type polymer composition has a drawback that due to a heat history during the molding, the styrene-butadiene block copolymer undergoes crosslinking to form a so-called gelled substance, which deteriorates the appearance of the molded product. Further, such a styrene type polymer composition also has a drawback that the cost is high. [0005]
    [0006] Also known is a technique to obtain a transparent rubber-modified styrene type polymer excellent in impact strength, which comprises styrene, methyl methacrylate and a styrene-butadiene block copolymer. However, such is not yet sufficient to satisfy the demand of the market which requires excellent transparency. [0006] PROBLEMS TO BE SOLVED BY THE INVENTION
    [0007] It is an object of the present invention to provide a rubber-modified styrene type polymer which is excellent in the transparency of a sheet or a film as an injection molded product or an extrusion molded product and which is excellent also in the impact strength and moldability. [0007] MEANS TO SOLVE THE PROBLEMS
    [0008] The present inventors have conducted a research strenuously to accomplish such an object and as a result, has found it possible to obtain a rubber-modified styrene type polymer having excellent transparency by employing, as a rubber-like elastic material for forming a dispersed phase of a rubber-modified styrene type polymer, a styrene-butadiene block copolymer wherein the weight average molecular weight (Mw) of the polystyrene portions is from 45,000 to 75,000, and the ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight (Mn) is from 1.20 to 1.80, whereupon the present invention has been accomplished. Namely, the present invention provides a rubber-modified styrene type polymer excellent in transparency, impact strength and moldability, comprising from 1 to 15 parts by weight of a dispersed phase made of a rubber-like elastic material and from 99 to 85 parts by weight of a continuous phase made of a polymer comprising from 35 to 75 wt % of styrene type monomer units and from 65 to 25 wt % of (meth)acrylate type monomer units, wherein the rubber-like elastic material is a styrene-butadiene block copolymer comprising from 30 to 50 wt % of styrene monomer units and from 70 to 50 wt % of butadiene monomer units, the weight average molecular weight (Mw) of the polystyrene portions of the styrene-butadiene block copolymer is from 45,000 to 75,000, and the ratio (Mw/Mn) of the weight average molecular weight to the number-average molecular weight (Mn) is from 1.20 to 1.80. [0008]
    [0009] Now, the present invention will be described in detail. [0009]
    [0010] The rubber-like elastic material to be used in the present invention is a styrene-butadiene block copolymer. And, in order to obtain the excellent transparency of the rubber-modified styrene type polymer, it is necessary that the weight ratio of the styrene monomer units to the butadiene monomer units of the styrene-butadiene block copolymer is 30-50:70-50. Further, it is also necessary that the styrene-butadiene block copolymer has the weight average molecular weight (Mw) of the polystyrene portions within a range of from 45,000 to 75,000. If Mw is less than 45,000 or exceeds 75,000, the transparency of the rubber-modified styrene type polymer tends to be poor. Further, the ratio (Mw/Mn) of Mw to the number average molecular weight (Mn) is from 1.20 to 1.80. If it departs from this range, it is also impossible to obtain the excellent transparency of the rubber-modified styrene type polymer. [0010]
    [0011] The molecular weight of the polystyrene portions was determined by measuring GPC of the polystyrene obtained by subjecting the styrene-butadiene block copolymer to ozone decomposition by a method disclosed in a literature “RUBBER CHEMISTRY AND TECHNOLOGY”, Vol.58, p.16 (Y. Tanaka, et. Al., 1985) and obtaining the molecular weight corresponding to each peak from a calibration curve prepared by using standard polystyrene. [0011]
    [0012] The styrene-butadiene block copolymer to be used in the present invention can be obtained by polymerizing a styrene monomer and a butadiene monomer under specific conditions in an organic solvent by using an organic lithium compound as an initiator. As the organic solvent, a known organic solvent, for example, an aliphatic hydrocarbon such as butane, pentane, hexane, isopentane, heptane, octane or isooctane, an alicyclic hydrocarbon such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane or ethylcyclohexane, or an aromatic hydrocarbon such as benzene, toluene, ethylbenzene or xylene, may be employed. The organic lithium compound is a compound having at least one lithium atom bonded in the molecule, and ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium or t-butyl lithium may, for example, be used. And, the weight average molecular weight (Mw) of the polystyrene portions of the styrene-butadiene block copolymer can be controlled by adjusting the ratio of the amount of the initiator to the amount of the styrene monomer and the butadiene monomer. Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polystyrene portion of the styrene-butadiene block copolymer, can be controlled by adding a deactivator such as an organic acid such as acetic acid or stearic acid, an alcohol such as ethanol or butanol or water while adjusting the amount or the timing of the addition during the polymerization. [0012]
    [0013] The rubber-like elastic material contained in the rubber-modified styrene type polymer of the present invention is from 1 to 15 parts by weight. If the rubber-like elastic material is less than 1 part by weight, the excellent impact strength can hardly be obtainable, and if it exceeds 15 parts by weight, the transparency and moldability tend to deteriorate, such being undesirable. [0013]
    [0014] Now, the styrene type monomer and the (meth)acrylate type monomer as the polymer units for forming the continuous phase to be used in the present invention, will be described. The styrene type monomer to be used in the present invention may, for example, be styrene, α-methylstyrene, p-methylstyrene or p-t-butylstyrene. However, preferred is styrene. These styrene type monomers may be used alone or may be used in combination of two or more of them. On the other hand, the (meth)acrylate type monomer may, for example, be methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate or octyl acrylate. However, preferred is methyl methacrylate or n-butyl acrylate. These (meth)acrylate type monomers may be used alone or may be used in combination of two or more of them. [0014]
    [0015] The weight ratio of the styrene type monomer units to the (meth)acrylate type monomer units which form the continuous phase of the rubber-modified styrene type polymer of the present invention, is 35-75:65-25, preferably 42-59:58-41. If the weight ratio of the styrene type monomer units to the (meth)acrylate type monomer units is outside the range of 35-75:65-25, the transparency of the rubber-modified styrene type polymer deteriorates. [0015]
    [0016] For the rubber modified styrene type polymer of the present invention, a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method, which is commonly used for the preparation of a styrene type polymer, may be employed. Further, either a batch system polymerization method or a continuous system polymerization method may be employed. [0016]
    [0017] In such a polymerization method, as the polymerization initiator, an azo compound such as azobis butyronitrile or azobiscyclohexane carbonitrile, or an organic peroxide such as benzoyl peroxide, t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxide, dicumyl peroxide or ethyl-3,3-di-(t-butylperoxy)butyrate, may be employed. Further, as a molecular weight modifier, t-dodecylmercaptan, n-dodecylmercaptan or 4-methyl-2,4-diphenylpentene-1 may be added, and as a plasticizer, butylbenzyl phthalate may, for example, be added, as the case requires. [0017]
    [0018] The rubber-modified styrene type polymer of the present invention may be processed into various molded products by a method such as injection molding, extrusion molding, compression molding or vacuum molding and practically used. Further, as the case requires, an additive such as an antioxidant, a weather resistant agent, a lubricant, a plasticizer, a colorant, an antistatic agent, a mineral oil or a flame retardant, may be incorporated at an optional stage such as prior to the initiation of the polymerization, during the polymerization reaction, during the post treatment of the polymer, or during the granulation, molding or processing of the polymer. The method for blending the additive is not particularly limited. However, various molded products of the styrene type polymer or its composition can be obtained, for example, by preliminarily mixing the rubber-modified styrene type polymer with the additive by a known blender such as Banbury mixer or a Henschel mixer, palletizing the mixture by an extruder and processing it by a method such as injection molding, extrusion molding or compression molding. Further, in order to improve the surface properties of a film or a sheet, an antistatic agent or a lubricant such as silicone may be coated on the surface. [0018] EXAMPLES
    [0019] Now, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to these Examples. [0019]
    [0020] In the following description, “parts” and “%” mean “parts by weight” and “wt %”, respectively. [0020] Example 1
    [0021] 6.0 parts of a styrene-butadiene block copolymer A (content of styrene monomer units: 40%, Mw of polystyrene portions: 46,500, Mw/Mn=1.27) was dissolved in a monomer mixture comprising 58.5 parts of styrene, 36.0 parts of methyl methacrylate and 5.5 parts of n-butyl acrylate, and 0.04 part of benzoyl peroxide as a polymerization initiator and 0.2 part of t-dodecylmercaptan as a chain transfer agent, were added thereto. The mixture was heated at 90°C. for 8 hours with stirring and then cooled to stop bulk polymerization. Then, to the reaction mixture, 0.2 part of dicumyl peroxide was added afresh as a polymerization initiator. 0.001 part of sodium dodecylbenzene sulfonate and 0.5 part of calcium tertiary phosphate were added as suspension stabilizers to 200 parts of pure water, and the mixture was dispersed therein with stirring. And, this mixture was heated and polymerized at 100°C. for 2 hours, at 115°C. for 3.5 hours and at 130°C. for 2.5 hours. [0021]
    [0022] After completion of the reaction, washing, removal of water and drying were carried out to obtain a rubber-modified styrene type polymer in the form beads. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0022] Example 2
    [0023] 6.0 parts of a styrene-butadiene block copolymer B (content of styrene monomer units: 40%, Mw of polystyrene portions: 46,300, Mw/Mn=1.71) was dissolved in a monomer mixture comprising 58.5 parts of styrene, 36.0 parts of methyl methacrylate and 5.5 parts of n-butyl acrylate, and 0.04 part of benzoyl peroxide as a polymerization initiator and 0.2 part of t-dodecylmercaptan as a chain transfer agent were added thereto. The mixture was heated at 90°C. for 8 hours with stirring and then cooled to stop bulk polymerization. [0023]
    [0024] Thereafter, the operation was carried out in the same manner as in Example 1 to obtain a rubber-modified styrene type polymer. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0024] Example 3
    [0025] A rubber-modified styrene type polymer was obtained in the same manner as in Example 1 except that as the styrene-butadiene copolymer, a styrene-butadiene block copolymer C (content of styrene monomer units: 40%, Mw of polystyrene portions: 73,500, Mw/Mn=1.26) was employed. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0025] Example 4
    [0026] A rubber-modified styrene type polymer was obtained in the same manner as in Example 1 except that as the styrene-butadiene copolymer, a styrene-butadiene block copolymer D (content of styrene monomer units: 40%, Mw of polystyrene portions: 73,300, Mw/Mn=1.72) was employed. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0026] Example 5
    [0027] A rubber-modified styrene type polymer was obtained in the same manner as in Example 1 except that as the styrene-butadiene copolymer, a styrene-butadiene block copolymer E (content of styrene monomer units: 40%, Mw of polystyrene portions: 62,500, Mw/Mn=1.52) was employed. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0027] Example 6
    [0028] 6.0 parts of a styrene-butadiene block copolymer E (content of styrene monomer units: 40%, Mw of polystyrene portions: 62,500, Mw/Mn=1.52) was dissolved in a monomer mixture comprising 54.5 parts of styrene and 45.5 parts of methyl methacrylate, and 0.04 part of benzoyl peroxide as a polymerization initiator and 0.2 part of t-dodecylmercaptan as a chain transfer agent were added thereto. The mixture was heated at 90°C. for 8 hours with stirring and then cooled to stop bulk polymerization. [0028]
    [0029] Thereafter, the operation was carried out in the same manner as in Example 1 to obtain a rubber-modified styrene type polymer. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0029] Comparative Example 1
    [0030] 6.0 parts of a styrene-butadiene block copolymer F (content of styrene monomer units: 40%, Mw of polystyrene portions: 43,300, Mw/Mn=1.51) was dissolved in a monomer mixture comprising 58.5 parts of styrene, 36.0 parts of methyl methacrylate and 5.5 parts of n-butyl acrylate, and 0.04 part of benzoyl peroxide as a polymerization initiator and 0.2 part of t-dodecylmercaptan as a chain transfer agent were added thereto. The mixture was heated at 90°C. for 8 hours with stirring and then cooled to stop bulk polymerization. Thereafter, the operation was carried out in the same manner as in Example 1 to obtain a rubber-modified styrene type polymer. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0030] Comparative Example 2
    [0031] A rubber-modified styrene type polymer was obtained in the same manner as in Example 1 except that as the styrene-butadiene copolymer, a styrene-butadiene block copolymer G (content of styrene monomer units: 40%, Mw of polystyrene portions: 77,700, Mw/Mn=1.51) was employed. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0031] Comparative Example 3
    [0032] A rubber-modified styrene type polymer was obtained in the same manner as in Example 1 except that as the styrene-butadiene copolymer, a styrene-butadiene block copolymer H (content of styrene monomer units: 40%, Mw of polystyrene portions: 63,200, Mw/Mn=1.16) was employed. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0032] Comparative Example 4
    [0033] A rubber-modified styrene type polymer was obtained in the same manner as in Example 1 except that as the styrene-butadiene copolymer, a styrene-butadiene block copolymer I (content of styrene monomer units: 40%, Mw of polystyrene portions: 63,000, Mw/Mn=1.86) was employed. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0033] Comparative Example 5
    [0034] A rubber-modified styrene type polymer was obtained in the same manner as in Example 1 except that as the styrene-butadiene copolymer, a styrene-butadiene block copolymer J (content of styrene monomer units: 40%, Mw of polystyrene portions: 40,900, Mw/Mn=1.86) was employed. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0034] Comparative Example 6
    [0035] [0035] 6.0 parts of a styrene-butadiene block copolymer J (content of styrene monomer units: 40%, Mw of polystyrene portions: 40,900, Mw/Mn=1.86) was dissolved in a monomer mixture comprising 54.5 parts of styrene and 45.5 parts of methyl methacrylate, and 0.04 part of benzoyl peroxide as a polymerization initiator and 0.2 part of t-dodecylmercaptan as a chain transfer agent were added thereto. The mixture was heated at 90°C. for 8 hours with stirring and then cooled to stop bulk polymerization. Thereafter, the operation was carried out in the same manner as in Example 1 to obtain a rubber-modified styrene type polymer. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. Comparative Example 7
    [0036] 0.7 part of a styrene-butadiene block copolymer E (content of styrene monomer units: 40%, Mw of polystyrene portions: 62,500, Mw/Mn=1.52) was dissolved in a monomer mixture comprising 58.5 parts of styrene, 36.0 parts of methyl methacrylate and 5.5 parts of n-butyl acrylate, and 0.04 part of benzoyl peroxide as a polymerization initiator and 0.2 part of t-dodecylmercaptan as a chain transfer agent were added thereto. The mixture was heated at 90°C. for 8 hours with stirring and then cooled to stop bulk polymerization. Thereafter, the operation was carried out in the same manner as in Example 1 to obtain a rubber-modified styrene type polymer. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0036] Comparative Example 8
    [0037] 17.0 parts of a styrene-butadiene block copolymer E (content of styrene monomer units: 40%, Mw of polystyrene portions: 62,500, Mw/Mn=1.52) was dissolved in a monomer mixture comprising 58.5 parts of styrene, 36.0 parts of methyl methacrylate and 5.5 parts of n-butyl acrylate, and 0.04 part of benzoyl peroxide as a polymerization initiator and 0.2 part of t-dodecylmercaptan as a chain transfer agent were added thereto. The mixture was heated at 90°C. for 8 hours with stirring and then cooled to stop bulk polymerization. Thereafter, the operation was carried out in the same manner as in Example 1 to obtain a rubber-modified styrene type polymer. The composition of the obtained rubber-modified styrene type polymer is shown in Table 1, and its physical properties are shown in Table 2. [0037]
    [0038] The respective physical property values were obtained by using as a test sample a molded product obtained by extruding the rubber-modified styrene type polymer obtained in each Example (or Comparative Example) by a single screw extruder (PMS40-28, manufactured by IKG Company) at a cylinder temperature of 220°C. to obtain pellets, followed by injection molding of these pellets by a 2 ounce in-line screw injection molding machine (manufactured by Niigata Tekkosho) at a cylinder temperature of 220°C. However, for MFR, the above pellets were employed. [0038]
    [0039] The methods for measuring the respective composition values and the respective physical property values are as follows. [0039]
    [0040] (1) Izod impact strength: In accordance with ASTM D256, a notch with a depth of 2.54 mm was imparted to a test piece of 12.7×64×6.4 mm in thickness, and the measurement was carried out at an impact rate of 3.46 m/sec. [0040]
    [0041] (2) Elongation: In accordance with ASTM D638, the measurement was carried out by using type 1 dumbbell with a chuck distance of 114 mm and a tensile rate of 5 mm/min. [0041]
    [0042] (3) MFR: In accordance with JIS K7210, the measurement was carried out at a temperature of 200°C. under a load of 5 Kgf. [0042]
    [0043] (4) Haze: In accordance with ASTM D1003, the measurement was carried out by using a test piece of 30×90×2 mm in thickness. [0043]
    [0044] (5) Total light transmittance: In accordance with ASTM D1003, the measurement was carried out by using a test piece of 30×90×2 mm in thickness. [0044]
    [0045] (6) Content of the rubber-like elastic material in the rubber-modified styrene type polymer: Obtained by measuring the absorbance at 960 cm[0045] −1 and 910 cm−1 by an infrared absorption spectrum method which is commonly used for a rubber-modified polystyrene.
    [0046] (7) Proportion of the constituting units of the continuous phase of the rubber-modified styrene type polymer: The rubber-modified styrene type polymer was dissolved in toluene, followed by centrifugal separation, and the supernatant was taken, and methanol was added thereto, and the resin content thereby insolubilized was precipitated, collected by filtration and dried and used as a test sample, and by means of FT-NMR, the weight ratio of the styrene type monomer units and the (meth)acrylate type monomer units were measured. [0046] TABLE 1 Proportion of constituting units (wt %) Content ofStyrene type (meth)acrylate rubber-like monomer type monomer elastic materialStyrene MMA n-BA (wt %)Example 1 58.2 36.2 5.8 5.7 Example 2 58.4 35.9 5.7 5.8 Example 3 58.3 36.0 5.7 5.8 Example 4 58.6 35.8 5.6 5.7 Example 5 58.7 35.9 5.4 5.9 Example 6 54.4 45.6 — 5.8 Comparative 58.6 36.0 5.4 5.8 Example 1 Comparative 58.5 36.2 5.3 5.8 Example 2 Comparative 58.6 35.8 5.6 5.7 Example 3 Comparative 58.6 36.0 5.4 5.9 Example 4 Comparative 58.6 36.2 5.2 5.7 Example 5 Comparative 54.3 45.7 — 5.9 Example 6 Comparative 58.3 36.2 5.5 0.6 Example 7 Comparative 58.4 36.1 5.5 16.7 Example 8
    [0047] [0047]TABLE 2 Izod Total impact Elonga- light strength tion MFR Haze transmittance (Kg · cm/cm) (%) (g/10 min) (%) (%) Example 1 9.0 60 6.8 1.9 90 Example 2 9.1 60 6.9 1.8 90 Example 3 9.0 60 6.7 1.9 90 Example 4 9.0 60 6.8 1.8 90 Example 5 9.0 60 6.9 1.7 90 Example 6 9.0 60 3.8 1.9 90 Comparative 9.1 60 6.8 5.8 88 Example 1 Comparative 9.0 60 6.7 5.5 88 Example 2 Comparative 9.0 60 6.8 5.7 88 Example 3 Comparative 9.1 60 6.8 5.6 88 Example 4 Comparative 9.0 60 6.8 5.9 88 Example 5 Comparative 9.0 60 3.7 5.7 88 Example 6 Comparative 2.3 15 9.7 2.0 90 Example 7 Comparative 14.6 75 2.1 17.7 85 Example 8 EFFECTS OF THE INVENTION
    [0048] According to the present invention, it is possible to provide a rubber-modified styrene type polymer excellent in transparency, impact strength and moldability. [0048]
    权利要求:
    Claims (1)
    [1" id="US-20010003769-A1-CLM-00001] 1. A rubber-modified styrene type polymer comprising from 1 to 15 parts by weight of a dispersed phase made of a rubber-like elastic material and from 99 to 85 parts by weight of a continuous phase made of a polymer comprising from 35 to 75 wt % of styrene type monomer units and from 65 to 25 wt % of (meth)acrylate type monomer units, wherein the rubber-like elastic material is a styrene-butadiene block copolymer comprising from 30 to 50 wt % of styrene monomer units and from 70 to 50 wt % of butadiene monomer units, the weight average molecular weight (Mw) of the polystyrene portions of the styrene-butadiene block copolymer is from 45,000 to 75,000, and the ratio (Mw/Mn) of the weight average molecular weight to the number-average molecular weight (Mn) is from 1.20 to 1.80.
    类似技术:
    公开号 | 公开日 | 专利标题
    US3162696A|1964-12-22|Interpolymerized compositions comprising alkenyl aromatic monomers and elastomeric ethylene copolymers
    EP0721476A1|1996-07-17|Maleimide-modified high heat abs resins
    US4699947A|1987-10-13|Weather and impact resistant resin composition and process for its preparation
    US6214278B1|2001-04-10|Rubber-modified styrene copolymer
    US6162870A|2000-12-19|Rubber-modified styrene polymer
    US3300545A|1967-01-24|Blends of polystyrene and a graft copolymer of a styrene-methyl methacrylate type mixture on a rubbery polymer of a conjugated 1, 3-diene
    US4228256A|1980-10-14|Transparent blends of resinous copolymers and grafted elastomers
    US4778850A|1988-10-18|Thermoplastic moulding materials made from vinyl chloride polymers and graft polymers and having improved properties
    EP0096527B1|1989-04-26|A process for producing a rubber-modified thermoplastic resin
    KR101432597B1|2014-08-21|Method for producing a thermoplastic having highly heat resistance and scratch resistance
    EP0403902B1|1994-10-05|Styrene-based resin composition
    KR101856465B1|2018-06-19|The environmental-friendly Windows Profile compositions with enhanced heat resistance and color
    CA1165035A|1984-04-03|Thermoplastic moulding compositions of celluloseesters
    KR100657739B1|2006-12-13|High Impact, High Gloss Weatherable Resin Composition And Method For Preparing The Same
    JP2016507630A|2016-03-10|High impact polystyrene with high modulus and resistance to environmental stress cracking
    JP4467088B2|2010-05-26|Rubber-modified styrenic polymer
    JPH11322863A|1999-11-26|Rubber-modified styrene-based polymer
    JP4137256B2|2008-08-20|Flame retardant resin composition
    US3794697A|1974-02-26|Modified styrene polymers providing impact-resistant molded articles
    US5196483A|1993-03-23|Rubber compositions with a high elastic modulus
    US3712934A|1973-01-23|Weatherable,high impact,thermoplastic resin composition
    JP4467657B2|2010-05-26|Molded body for packaging electronic parts
    KR20030051990A|2003-06-26|Styrenic Thermoplastic Resin Composition with High Melt Strength
    JP2001131240A|2001-05-15|Rubber-modified styrene polymer and method for preparing same
    JPH06166729A|1994-06-14|Rubber-modified aromatic vinyl copolymer resin and its production
    同族专利:
    公开号 | 公开日
    US6403707B2|2002-06-11|
    US6214278B1|2001-04-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4080406A|1976-04-12|1978-03-21|Union Carbide Corporation|Rubber-modified impact polystyrenes|
    KR880014684A|1987-05-11|1988-12-24|엔.타이스 머레트|Method for reducing the breakdown between source / drain and channel stop and reducing P + / N + intrusion|
    JP3353844B2|1992-03-31|2002-12-03|大日本インキ化学工業株式会社|Method for producing rubber-modified copolymer resin and rubber-modified copolymer resin composition|
    JPH07330996A|1994-06-03|1995-12-19|Nippon Steel Chem Co Ltd|Rubber-modified aromatic vinyl resin composition|
    JP3516506B2|1995-03-02|2004-04-05|三井化学株式会社|Transparent rubber-modified styrenic resin composition and method for producing the same|JP3935509B2|1997-02-12|2007-06-27|ワイ． チャン，ユージーン|Methods and products for polymer analysis|
    US7223460B2|2005-01-12|2007-05-29|Nova Chemicals Inc.|Rubber modified styrenic copolymers and their use in disposable card applications|
    ES2654377T3|2008-10-07|2018-02-13|Ross Technology Corporation|Spill resistant surfaces with hydrophobic and oleophobic boundaries|
    JP5858441B2|2010-03-15|2016-02-10|ロス テクノロジー コーポレーション．Ｒｏｓｓ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏｒｐｏｒａｔｉｏｎ|Plunger and method for obtaining a hydrophobic surface|
    BR112013021231A2|2011-02-21|2019-09-24|Ross Tech Corporation|superhydrophobic and oleophobic coatings with low voc bonding systems|
    EP2791255B1|2011-12-15|2017-11-01|Ross Technology Corporation|Composition and coating for superhydrophobic performance|
    EP2864430A4|2012-06-25|2016-04-13|Ross Technology Corp|Elastomeric coatings having hydrophobic and/or oleophobic properties|
    法律状态:
    2002-05-24| STCF| Information on status: patent grant|Free format text: PATENTED CASE |
    2003-02-25| CC| Certificate of correction|
    2005-11-11| FPAY| Fee payment|Year of fee payment: 4 |
    2009-11-12| FPAY| Fee payment|Year of fee payment: 8 |
    2013-11-11| FPAY| Fee payment|Year of fee payment: 12 |
    优先权:
    申请号 | 申请日 | 专利标题
    US09/251,487|US6162870A|1997-08-18|1999-02-17|Rubber-modified styrene polymer|
    US09/639,114|US6214278B1|1999-02-17|2000-08-16|Rubber-modified styrene copolymer|
    US09/739,658|US6403707B2|1999-02-17|2000-12-20|Rubber-modified styrene type copolymer|US09/739,658| US6403707B2|1999-02-17|2000-12-20|Rubber-modified styrene type copolymer|
    [返回顶部]