Source: https://patents.google.com/patent/US20070112135A1/en
Timestamp: 2018-12-17 17:38:22
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Matched Legal Cases: ['art 6', 'art 6', 'art 6', 'art 6', 'art 6', 'art 6', 'art 6', 'art 6', 'art 6']

US20070112135A1 - Polymer mixture and the utilization thereof for injection molded parts - Google Patents
Polymer mixture and the utilization thereof for injection molded parts Download PDF
US20070112135A1
US20070112135A1 US10575477 US57547704A US2007112135A1 US 20070112135 A1 US20070112135 A1 US 20070112135A1 US 10575477 US10575477 US 10575477 US 57547704 A US57547704 A US 57547704A US 2007112135 A1 US2007112135 A1 US 2007112135A1
US10575477
US7371795B2 (en )
The invention relates to a polymer mixture based on the (meth)acrylate (co)polymer components a), b), c), and/or d) according to claim 1, where a test specimen produced from the polymer mixture simultaneously has the following properties: I. a tensile modulus (ISO 527) of at least 2600 MPa, II. a Vicat softening point VSP (ISO 306-B50) of at least 109° C.,
IV. a melt index MVR (ISO 1133, 230° C./3.8 kg) of at least 1.5 cm3/10 min. The invention further relates to injection mouldings and to the use of the polymer mixture for producing injection-moulded parts.
Various thermoplastics have hitherto been used in this sector, examples being PC, ASA, ASA/PC, PMMA and glass fibre-filler polymers, e.g. GF polyamide.
Because the mouldings are generally produced by means of injection-moulding processes, another requirement relevant to component geometry (long flow paths with small layer thicknesses) when thermoplastics are used is good flowability of the plastics melt, with the aim of avoiding rejection of parts. To give the automotive producer a substantially free choice of colour, the plastic should moreover have almost no intrinsic colour and at the same time have high light transmittance.
Although the use of glass fibre-reinforced plastics gives mouldings with good mechanical properties, subsequent painting is required here, as with steel, to achieve uniform glossy Class A surface quality. Polycarbonate has not only high heat resistance but also very good toughness. However, here again surface painting is required because weathering resistance is insufficient, resulting in yellowing, and surface hardness is low. In addition, the inadequate stiffness of this material is problematic for the application mentioned.
a) a low-molecular-weight (meth)acrylate (co)polymer
b) an impact modifier based on crosslinked poly(meth)acrylates
c) a relatively high-molecular-weight (meth)—acrylate (co) polymer,
characterized by a solution viscosity in chloroform at 25° C. (ISO 1628—Part 6) greater than or equal to 65 ml/g and/or
d) a (meth)acrylate (co)polymer other than a)
where each of the individual components a), b), c) and/or d) may be individual polymers or else a mixture of polymers,
where the entirety of a), b), c) and/or d) is 100% by weight,
and where the polymer mixture may also comprise conventional additives, auxiliaries and/or fillers and
IV. a melt index MVR (ISO 1133, 230° C./3.8 kg) of at least 1.5 cm3/10 min, preferably at least 1.65, 2.0, or 3.0 cm3/10 min.
Conventional additives, auxiliaries and/or fillers are to be selected in such a way as to give no, or at most very slight, impairment of the property profile mentioned above.
The yellowness index can be determined to DIN 6167 (illuminant D65, 10° on 3 mm layer thickness) and is to be less than 20, preferably less than 17.
Component a): from 25 to 75% by weight, preferably from 40 to 60% by weight, in particular from 45 to 55% by weight.
Component b): from 10 to 60% by weight, preferably from 10 to 20% by weight.
Component c) and/or d): from 10 to 50% by weight, preferably from 12 to 40% by weight.
Test specimens with very high VSP values in the range from 116 to 120° C. can be obtained if c) is present at from 30 to 45% by weight, preferably from 35 to 40% by weight and d) is preferably absent (see Example 3).
Test specimens with high VSP values, in the range from 114 to 118° C. together with high gloss, R(60°)= from 48 to 50 can be obtained if both c) and d) are present, the constituent proportions preferably being from 10 to 15% by weight of c) and from 15 to 25% by weight of d) (see Example 2).
Test specimens with VSP values in the range from 109 to 113° C. together with a very low level of intrinsic colour, and light transmittance TD65 to DIN 5033/7 in the range from 60 to 65% can be obtained if d) is present at from 30 to 40% by weight, preferably from 33 to 38% by weight and c) is preferably absent (see Example 1).
Component a) is a low-molecular-weight (meth)acrylate (co)polymer, characterized by a solution viscosity in chloroform at 25° C. (ISO 1628—Part 6) smaller than or equal to 55 ml/g, preferably smaller than or equal to 50 ml/g, in particular from 45 to 55 ml/g.
Corresponding copolymers may be obtained in a manner known per se via free-radical polymerization. By way of example, EP-A 264 590 describes a process for preparing a moulding composition from a monomer mixture of methyl methacrylate, vinylaromatic compound and maleic anhydride, and also, where appropriate, from a lower alkyl acrylate, where the polymerization is carried out to 50% conversion in the presence or absence of a non-polymerizable organic solvent and where, beyond at least 50% conversion, the polymerization is continued in the temperature range from 75 to 150° C. in the presence of an organic solvent to at least 80% conversion, and then the low-molecular-weight volatile constituents are evaporated.
JP-A 60-147 417 describes a process for preparing a highly heat-resistant polymethacrylate moulding composition, where a monomer mixture of methyl methacrylate, maleic anhydride and at least one vinyl aromatic compound are fed into, and polymerized in, a polymerization reactor suitable for solution or bulk polymerization at a temperature of from 100 to 180° C. DE-A 44 40 219 describes another preparation process.
By way of example, component a) may be prepared by treating a monomer mixture of, by way of example, 6355 g of methyl methacrylate, 1271 g of styrene and 847 g of maleic anhydride with 1.9 g of tert-butyl perneodecanoate and 0.85 g of tert-butyl 3,5,5-trimethylperoxyhexanoate as polymerization initiator and 19.6 g of 2-mercaptoethanol as molecular weight regulator, and also with 4.3 g of palmitic acid. The resultant mixture may be charged to a polymerization cell and devolatilized for 10 minutes, for example. The material may then be polymerized in a water bath, for example for 6 hours at 60° C., and then 30 hours at 55° C. water bath temperature. After about 30 hours, the polymerization mixture reaches its maximum temperature, about 126° C. Once the polymerization cell has been removed from the water bath, the polymer is also heat-conditioned as appropriate for component a) in the polymerization cell for about 7 hours, for example at 1170° C. in a hot-air cabinet.
Component c) is a relatively high-molecular-weight (meth)acrylate (co)polymer, characterized by a solution viscosity in chloroform at 25° C. (ISO 1628—Part 6) greater than or equal to 65 ml/g, preferably from 68 to 75 ml/g.
Component d) is a further (meth)acrylate (co)polymer other than a), characterized by a solution viscosity in chloroform at 25° C. (ISO 1628—Part 6) of from 50 to 55 ml/g, preferably from 52 to 54 ml/g.
Component d) may have a Vicat softening point VSP (ISO 306-B50) of at least 107° C., preferably from 108 to 114° C. The melt index MVR (ISO 1133, 230° C./3.8 kg) may, by way of example, be in the range greater than or equal to 2.5 cm3/10 min.
I. a tensile modulus (ISO 527) of at least 2600 MPa, preferably at least 2750 MPa, particularly preferably at least 2850 MPa,
II. a Vicat softening point VSP (ISO 306-B50) of at least 109° C., preferably at least 110° C., in particular at least 112° C., e.g. from 110 to
III. an impact strength (ISO 179-2D, flatwise) of at least 17 kJ/m2, preferably 18 kJ/m2, and
IV. a melt index MVR (ISO 1133, 230° C./3.8 kg) of at least 1.5 cm3/10 min, preferably 1.65 cm3/10 min.
The injection mouldings may be used as parts of household devices, of communication devices, of devices for hobbies or for sports, or bodywork parts or parts of bodywork parts in the construction of automobiles, of ships or of aircraft. Typical examples of bodywork parts or parts of bodywork parts of automobiles are spoilers, panelling, roof modules or exterior mirror housings.
Preparation of Component a):
The resultant mixture is charged to a polymerization cell and devolatilized for 10 minutes. It is then polymerized in a water bath for 6 hours at 60° C., and then for 30 hours at 55° C. water bath temperature. After about 30 hours the polymerization mixture reaches its maximum temperature of 126° C. Once the polymerization cell has been removed from the water bath, the polymer is heat-conditioned in the polymerization cell for a further 7 hours at 117° C. in a hot-air cabinet.
The resultant copolymer is clear and almost colourless, and has a VN (solution viscosity number to ISO 1628-6, 25° C., chloroform) of 48.7 ml/g. The flowability of the copolymer was determined to ISO 1133 at 230° C. with 3.8 kg as MVR=3.27 cm3/10 min.
The component b) used comprised: a commercially available impact modifier METABLEN® IR 441 from Mitsubishi Rayon.
The component c) used comprised: a commercially available copolymer of 75% by weight of methyl methacrylate,. 15% by weight of styrene and 10% by weight of maleic anhydride with a solution viscosity number to ISO 1628-6, 25° C., chloroform of 68 ml/g.
The component d) used comprised: a commercially available copolymer of 99% by weight of methyl methacrylate and 1% by weight of methyl acrylate with a solution viscosity in chloroform at 25° C. (ISO 1628—Part 6) of from about 52 to 54 ml/g.
Inventive Examples 1-3 Example 1
Component a): 50% by weight
Component b): 15.6% by weight
Component c): −
Component d): 34.4% by weight
Lubricant: 0.1% by weight of n-octadecanol (based on the entirety of components a) to d))
Component b): 13% by weight
Component c): 15% by weight
Component d): 22% by weight
Component c): 37% by weight
Component d): −
Comparative Examples (Comp. Ex. 4-9) Comparative Example 4:
Commercially available moulding composition composed of 75% by weight of methyl methacrylate, 15% by weight of styrene and 10% by weight of maleic anhydride with a solution visocisty in chloroform at 25° C. (ISO.1628—Part 6) of 68 ml/g (corresponds to component c) in Examples 1-3).
Tensile modulus 2900 3000 3100 1700 3500 3300 2500 3300 3600
VSP [° C.] 111.5 115.8 118.5 93 121 107 105 108 119
IS [kJ/m2] 39 28.5 20.6 70 11 20 53 20 20
MVR [cm3/10 min] 3.5 2.3 1.7 0.8 2 2.8 0.9 3 1.2
TD65/10° [%] 63 58.5 52 90 92 92 92 92 90
Yellowness index 13.09 14.46 15.87 n.d. n.d. n.d. n.d. n.d. n.d.
0.39% >1800 >1800 >1800 n.d. n.d. n.d. n.d. n.d. n.d.
0.50% 722 1345 >1800 n.d. n.d. n.d. n.d. n.d. n.d.
0.50% 210 777 >1800 n.d. n.d. n.d. n.d. n.d. n.d.
0.7 N 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.
1.5 N 1.5 1.1 1.2 n.d. n.d. n.d. n.d. n.d. n.d.
3.0 N 4.2 3.5 3.9 n.d. n.d. n.d. n.d. n.d. n.d.
R(60°) [%] 43.4 49.1 45.8 n.d. n.d. n.d. n.d. n.d. n.d.
1. A polymer mixture comprising the following components:
a) a low-molecular-weight (meth)acrylate (co)polymer with a solution viscosity in chloroform at 25° C. (ISO 1628—Part 6) smaller than or equal to 55 ml/g
c) a relatively high-molecular-weight (meth)acrylate (co)polymer, with a solution viscosity in chloroform at 25° C. (ISO 1628—Part 6) greater than or equal to 65 ml/g and/or
d) a (meth)acrylate (co)polymer other than a) with a solution viscosity in chloroform at 25° C. (ISO 1628—Part 6) of from 50 to 55 ml/g
II. a Vicat softening point VSP (ISO 306 B50) of at least 109° C.,
2. The polymer mixture according to claim 1, wherein the components are present in the following quantitative proportions, their entirety being 100% by weight:
3. The polymer mixture according to claim 1, wherein component a) is a copolymer of methyl methacrylate, styrene and maleic anhydride.
4. The polymer mixture according to claim 3, wherein component a) is a copolymer of
from 50 to 90% by weight of methyl methacrylate,
from 10 to 20% by weight of styrene and
5. The polymer mixture according to claim 1, wherein component b) has a two or three-shell structure.
6. The polymer mixture according to claim 1, wherein component c) is a copolymer of methyl methacrylate, styrene and maleic anhydride.
7. The polymer mixture according to claim 6, wherein component c) is a copolymer of
8. The polymer mixture according to claim 1, wherein component d) is a homopolymer or copolymer of at least 80% by weight of methyl methacrylate and, optionally, up to 20% by weight of other monomers copolymerizable with methyl methacrylate.
9. The polymer mixture according to claim 8, wherein component d) is a copolymer of from 95 to 99.5% by weight of methyl methacrylate and from 0.5 to 5% by weight of methyl acrylate.
10. The polymer mixture according to claim 1, wherein a lubricant is present as auxiliary.
11. The polymer mixture according to claim 10, wherein stearyl alcohol is present as mould-release agent.
12. An injection moulding, comprising a polymer mixture according to claim 1.
13. A method for producing an injection moulding which has the following properties:
IV. a melt index MVR (ISO 1133, 230° C./3.8 kg) of at least 1.5 cm3/10 min comprising utilizing the polymer mixture according to claim 1 to produce the injection moulding.
14. Use of the injection mouldings according to claim 12 as parts of household devices, of communication devices, of devices for hobbies or for sports, or bodywork parts or parts of bodywork parts in the construction of automobiles, of ships or of aircraft.
US10575477 2003-10-17 2004-09-01 Polymer mixture and the utilization thereof for injection molded parts Active US7371795B2 (en)
DE10349142.2 2003-10-17
DE2003149142 DE10349142A1 (en) 2003-10-17 2003-10-17 Polymer blend for production of injection mouldings, e.g. car body parts, contains low-mol. wt. and high-mol. wt. (meth)acrylate (co)polymers and an impact modifier based on crosslinked poly(meth)acrylate
PCT/EP2004/009704 WO2005047392A1 (en) 2003-10-17 2004-09-01 Polymer mixture and the utilization thereof for injection molded parts
US20070112135A1 true true US20070112135A1 (en) 2007-05-17
US7371795B2 US7371795B2 (en) 2008-05-13
ID=34428514
US10575477 Active US7371795B2 (en) 2003-10-17 2004-09-01 Polymer mixture and the utilization thereof for injection molded parts
US (1) US7371795B2 (en)
EP (1) EP1673409B1 (en)
JP (1) JP4718475B2 (en)
KR (1) KR101017235B1 (en)
CN (1) CN100374500C (en)
CA (1) CA2542459C (en)
DE (2) DE10349142A1 (en)
WO (1) WO2005047392A1 (en)
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JP4718475B2 (en) 2011-07-06 grant
CN1863864A (en) 2006-11-15 application
CA2542459C (en) 2012-11-06 grant
CA2542459A1 (en) 2005-05-26 application
CN100374500C (en) 2008-03-12 grant
DE502004003907D1 (en) 2007-07-05 grant
KR101017235B1 (en) 2011-02-25 grant
DE10349142A1 (en) 2005-05-12 application
EP1673409A1 (en) 2006-06-28 application
EP1673409B1 (en) 2007-05-23 grant
WO2005047392A1 (en) 2005-05-26 application
US7371795B2 (en) 2008-05-13 grant
JP2007510009A (en) 2007-04-19 application
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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WICKER, MICHAEL;SCHULTES, KLAUS;ALBRECHT, KLAUS;AND OTHERS;REEL/FRAME:020591/0516;SIGNING DATES FROM 20060205 TO 20060223
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WICKER, MICHAEL;SCHULTES, KLAUS;ALBRECHT, KLAUS;AND OTHERS;SIGNING DATES FROM 20060205 TO 20060223;REEL/FRAME:020591/0516