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Patent US4299886 - Process for surface coating of molded polycarbonate resin product - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA process for surface coating of a molded polycarbonate resin product which comprises coating and heating a primer on the surface of the molded polycarbonate resin product and then coating and hardening a coating material essentially consisting of a hydrolyzed partial condensate of an alkyltrialkoxysilane,...http://www.google.com/patents/US4299886?utm_source=gb-gplus-sharePatent US4299886 - Process for surface coating of molded polycarbonate resin productAdvanced Patent SearchPublication numberUS4299886 APublication typeGrantApplication numberUS 06/187,375Publication dateNov 10, 1981Filing dateSep 15, 1980Priority dateSep 28, 1979Publication number06187375, 187375, US 4299886 A, US 4299886A, US-A-4299886, US4299886 A, US4299886AInventorsShigeru Soejima, Yasuji OhmoriOriginal AssigneeDaicel Chemical Industries, Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (3), Referenced by (13), Classifications (17) External Links: USPTO, USPTO Assignment, EspacenetProcess for surface coating of molded polycarbonate resin product
US 4299886 AAbstract
1. A process for surface coating of a molded polycarbonate resin product which comprises coating and heating a primer on the surface of the molded polycarbonate resin product and then coating and hardening a coating material essentially consisting of a hydrolyzed partial condensate of an alkyltrialkoxysilane, in which the primer comprises a hydrolyzed partial condensate (A) of silane compounds comprising:a phenyltrialkoxysilane of the general formula C6 H5 Si(OR1)3                         (A- 1) in which R1 represents an alkyl group of C1 -C4 ; and an alkyltrialkoxysilane of the general formula R2 Si(OR3)3                                 (A- 2) in which each of R2 and R3 represents an alkyl group of C1 -C4,in the molar ratio of 1:0-10, being the former:the latter ratio. 2. A process as claimed in claim 1, in which the molar ratio between the phenyltrialkoxysilane and the alkyltrialkoxysilane is 1:0-1.
8. A process for surface coating of a molded polycarbonate resin product which comprises coating and heating a primer on the surface of the molded polycarbonate resin product and then coating and hardening a coating material essentially consisting of a hydrolyzed partial condensate of an alkyltrialkoxysilane, in which the primer comprises:a hydrolyzed partial condensate (A) of silane compounds comprising a phenyltrialkoxysilane of the general formula C6 H5 Si(OR3)3                         (A- 1) in which R1 represents an alkyl group of C1 -C4, and an alkyltrialkoxysilane of the general formulaR2 Si(OR3)3 (A- 2) in which each of R2 and R3 represents an alkyl group of C1 -C4 in the molar ratio of 1:0-10, being the former:the latter ratio; a curing catalyst; an epoxy compound; and a ultraviolet absorber. 9. A process as claimed in claim 8, in which the primer further comprises a solution containing a carboxylic acid of the general formula R4 COOH in which R4 represents the hydrogen atom or an alkyl group of C1 -C5. 10. A process as claimed in claim 8, in which the curing catalyst is selected from the group consisting of γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, triethylamine and 1,8-diazabicyclo(5,4,0)undecene-7.
19. A process as claimed in claim 8, in which the primer is heated at 110�-120� C. for 10 min. to 2 hrs.
C6 H5 Si(OR1)3 in which R1 represents a C1 -C4 alkyl group such as methyl, ethyl, propyl or butyl. A typical representive of the phenyltrialkoxysilane is phenyltriethoxysilane.
R2 Si(OR3)3 in which each of R2 and R3 represents a C1 -C4 alkyl group such as methyl, ethyl, propyl or butyl. A typical representative of the alkyltrialkoxysilane is methyltriethoxysilane.
The hydrolyzed partial condensate (A) of the aforementioned silane compounds is a primarily hydrolyzed condensate prepared by heating the phenyltrialkoxysilane or the mixture of the phenyltrialkoxysilane and the alkyltrialkoxysilane in an aqueous solution containing a small amount of an acid for 1-10 hours, while maintaining the temperature at 50�-80� C. under reflux, as disclosed in Japanese Patent Publication No. 49(1974)-15079.
The primer solution can be coated on a molded polycarbonate resin product by such a method as the dipping method, the spraying method, the flow-coating method or the spin-coating method, and then the coated primer solution is heated to give a dried and hardened coated film. There is no specific limitation on the temperature for heating the coated primer solution, so far as the temperature does not exceed the heat-deformation temperature of the base material, namely, the polycarbonate resin. In general, the heating for hardening the coated film is carried out at a temperature in the range of 70�-140� C. and for 50 min. to 12 hrs. The hardening of the coated film is necessarily carried out to the extent where the primer film will not be peeled off when a final coating will be done later. Under these conditions, a satisfactory adhesion can be produced. If the hardening of the primer film exceeds the preferred level, the adhesion between the primer layer and the final coating material layer decreases. Accordingly, it is necessary to select the hardening level in the appropriate range.
There is no specific limitation on the temperature for heating the coated A-E solution, so far as the temperature does not exceed the heat-deformation temperature of the base material, namely, the polycarbonate resin. In general, the heating for hardening the coated film is carried out at a temperature in the range of 60�-130� C. and for 5 min. to 12 hrs. The heating temperature is preferably selected from temperatues in the range of 110�-120� C., and the period preferably is in the range of 10 min. to 2 hrs.
R7 Si(OR8)3 in which each of R7 and R8 preferably represents a C1 -C4 alkyl group such as methyl, ethyl, propyl or butyl. A typical representative of the alkyltrialkoxysilane is methyltriethoxysilane.
The hydrolyzed partial condensate of the alkyltrialkoxysilane can be produced by heating the alkyltrialkoxysilane in an aqueous phase containing a small amount of an acid at 50�-80� C., for 1-10 hrs., as described in U.S. Pat. Nos. 3,389,114 and 3,451,838. A tetraalkoxysilane can be added to the alkyltrialkoxysilane to subject to the partial cohydrolysis for improving the hardness of the coated film. Alternatively, the hydrolyzed partial condensate of the tetraalkoxysilane can be mixed with the hydrolyzed partial condensate of the alkyltrialkoxysilane to imcorporate in the coating material.
The conditions for the heat-hardening procedure are generally selected from temperatures in the range of 50�-140� C. and periods in the range of 15 min. to 12 hrs. Preferred are a temperature of 80�-130� C. and a period of 2-3 hrs.
In 50 parts (by weight; the same hereinafter) of ethanol were dissolved 30 parts of the so obtained solid hydrolyzed partial condensate of phenyltriethoxysilane. To the solution were added 20 parts of acetic acid and 5 parts of γ-aminopropyltriethoxysilane (curing catalyst), and these were well mixed to prepare a primer solution. This primer solution showed the viscosity of 7 cP (centipoise) at 20� C. on the measurement using the Brookfield viscometer.
In the primer solution obtained previously was dipped a polycarbonate resin sheet (100�100�2 mm.) that had been washed and dried in advance. The dipped sheet was then taken out of the solution at the rate of 20 cm./min. with no vibrating action. The so treated sheet was immediately introduced into a hot-air oven and heated at 70� C. for one hr. Then, the heating was continued at 90� C. for 5 hrs.
The sheet thus coated with a primer was dipped in the final coating material, and then taken out of the coating solution at the rate of 20 cm./min. with no vibrating action. The so treated sheet was again immediately introduced into a hot-air oven and heated at 90� C. for 5 hrs. to obtain a polycarbonate sheet having the hardened surface film.
The coated sheet was immersed in hot water maintained at 100� or 60� C., and the so treated sheet was then subjected to the initial adhesive property test described above.
The procedures described in Example 1 were repeated except that the polycarbonate sheet was replaced with a sheet which has been prepared from diethylene glycol bisallylcarbonate through the cast-molding and except that the primer employed in Example 2 was used and hardened at 90� C. for 3 hrs.
In 300 parts (by weight; the same hereinafter) of n-butanol were dissolved 100 parts of the so obtained solid hydrolyzed partial condensate of phenyltriethoxysilane, 6 parts of Epikote 828 (trade name of bisphenol A polyglycidyl ether; available from Shell Chemical Corp.), and 1 parts of Tinuvin 327 (trade name of a ultraviolet absorber of benzotriazole type; available from Ciba-Geigy Corp.). To the solution were added 30 parts of acetic acid. To the resulting solution were added under stirring and cooling to a temperature lower than 20� C., 16 parts of γ-aminopropyltriethoxysilane slowly. To this were further added 7 parts of water, and the mixture was then mixed well to prepare a primer solution.
TABLE 1__________________________________________________________________________            Initial                 abrasion                      Hot Water Immersion Resistance                                        Weatherability                                                    SolventPrimer           Adhesive                 resis-                      100� C.                               60� C.                                        (hrs.)      ResistanceComponent A      Property                 tance                      (hrs.) more than                               (days) more than                                        Adhesion                                             Appearance                                                    (min.)__________________________________________________________________________ExampleNo.1     Phenyltriethoxy- silane             ##STR1##                 1.5  72       10       400  250    15  ##STR2##             ##STR3##                 1.2  72       10       400  250    153  ##STR4##             ##STR5##                 1.7  10        3       250  150    154  ##STR6##             ##STR7##                 1.5  72       10       400  250    155  ##STR8##             ##STR9##                 1.5  72       10       400  250    15Compara-tiveExampleNo.1     None (no coating            --   35   --       --       --   --     -- was given)2     No-primer was used (final coating only)             ##STR10##                 15   --       --       --   --      23     &#947;-Aminopropyltri- ethoxysilane             ##STR11##                 1.9   1        1       100  --      5__________________________________________________________________________
This primer solution showed the viscosity of 10 cP at 20� C. on the measurement using the Brookfield viscometer.
A polycarbonate resin sheet (100�100�2 mm.) was processed in the same manner as described in Example 1 to prepare the sheet coated with both of the so obtained primer and final coating material. In the procedures, the condition for heating the primer-coated sheet to dry was chosen to be 120� C. for 1 hr.
TABLE 2______________________________________              Hot Water           Sol-Ini-               Immersion   Weather-                                  venttial               Resistance  ability Resis-Adhe-      Abra-   100� C.                      60� C.                            (hrs.)  tancesive       sion    (hrs.)  (days)                            Ad-  Ap-  (min.)Pro-       resis-  more    more  he-  pear-                                      moreperty      tance   than    than  sion ance than______________________________________ExampleNo.   ##STR12##          1.5     72    10    1,500                                   1,000                                        157      "       1.2     72    10    1,200                                   1,300                                        "8      "       1.7     10     3    600  500  "9      "       1.5     72    10    1,000                                   1,100                                        "10     "       1.5     10     3    600  500  "11     "       1.7     72    10    800  700  "12     "       1.5     72    10    1,000                                   800  "13     "       1.5     72    10    800  700  "14     "       1.5     72    10    2,000                                   2,000                                        "Compar-ativeEx. No.4   ##STR13##          1.8                            5______________________________________
______________________________________A           B            C          D______________________________________Ex. No.6     PS        &#947;-Aminopropyl-                       Epikote 828                                Tinuvin 327           triethoxy-  6 parts  1 part           silane 16 parts  ##STR14##           &#947;-Aminopropyl- triethoxy- silane 16                       Epikote 828 6 parts                                Tinuvin 327 1 part8  ##STR15##           &#947;-Aminopropyl- triethoxy- silane 16                       Epikote 828 6 parts                                Tinuvin 327 1 part9  ##STR16##           &#947;-Aminopropyl- triethoxy- silane 16                       Epikote 828 3 parts                                Tinuvin 327 1 part10    "         N-&#946;-(amino-                       Epikote 828                                Tinuvin 327           ethyl)-&#947;-amino-                       6 parts  1 part           propyltri-           methoxysilane           16 parts11    "         1,8-Diazabi-                       Epikote 828                                Tinuvin 327           cyclo(5,4,0)-                       6 parts  1 part           undecene-7           0.3 part12    "         &#947;-Aminopropyl-                       &#947;-Glycidoxy-                                Tinuvin 327           triethoxysilane                       propyltri-                                1 part           16 parts    methoxysilane                       6 parts13    "         &#947;-Aminopropyl-                       Epikote 828                                Tinuvin P           triethoxysilane                       6 parts  1 part           16 parts14    "         &#947;-Aminopropyl-                       Epikote 828                                Tinuvin 327           triethoxysilane                       6 parts  1 part           16 partsCom-Ex.No.4     "         &#947;-Aminopropyl-                       Epikote 828                                Tinuvin 327           triethoxysilane                       20 parts 1 part           16 parts______________________________________
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