ACRYLIC SYNTHETIC RESIN PLATE

Abstract: A synthetic acrylic resin plate and production thereof, said resin plate being laminated with acrylic films and having a wrinkle-free, glossy surface which is improved in printability. In more details, said acrylic resin films (F) are partially swelled and dissolved by acrylic monomer contained in synthetic resin supplied through a syrup feeder (6) onto a belt (1'), before the synthetic resin is hardened by polymerization, and then said films (F) are firmly integrated to the acrylic synthetic resin plate while said acrylic monomer makes polymerization (18,9).

Description: ACRYL1C SYNTHETIC RESIN SHEET TECHNICAL FIELD This invention relates to an acrylic synthetic resin sheet on which an acrylic film is integrally laminated. More particularly, this invention relates to an acrylic synthetic resin sheet on which an acrylic film is laminated, characterized in that said acrylic film is partially swollen and dissolved with monomer which is to be polymerized and hardened into the acrylic synthetic resin sheet and the film becomes integral with the sheet when the monomer is polymerized and hardened. BACKGROUND ART Hitherto, patterns or colors have been printed on acrylic synthetic resin sheets by screen printing, painting or offset printing, but these printing operations are complicated and require many workers and moreover printing patterns or colors on a large-sized sheet was nearly impossible by these methods. It is also known to heat-bond an acrylic film on which patterns or colors are printed to an acrylic synthetic resin sheet. In this case, too, a great number of workers are needed and moreover it is also difficult to print patterns or colors on sheets of large size. A prior art, British Patent 1,274,516 discloses production of solid resin articles by pouring a liquid prepolymer in a mold wherein a synthetic resin film is applied to the inner surface of the mold prior to pouring oi said liquid prepolymer, then the liquid prepolymer is poured in the mold and this is heated to produce a solid resin article, a resin film compatible with the prepolymer being used as said synthetic resin film. Furthermore, said British patent discloses in its Examples that methyl methacrylate is used as the liquid prepolymer and polyvinyl chloride is used as the synthetic resin film and that in the case of the final resin being an acrylate resin polyvinyl chloride, polyvinylidene chloride or polycarbonates are preferred as the compatible film. However, in case the final resin is an acrylate resin, use of the films as mentioned above results in wrinkles during production to damage the commercial value. The present invention is directed toward solution of these defects. DISCLOSURE OF INVENTION Said improvement has been attained by an acrylic synthetic resin sheet on which an acrylic film is integrally laminated, characterized in that said acrylic film is partially swollen and dissolved with monomer for acrylic synthetic resin before being polymerized and hardened into a sheet and becomes integral with the polymerized and hardened acrylic synthetic resin sheet. Methyl methacrylate resin sheets can be used as the acrylic synthetic resin sheet in this invention and synthetic resin sheets which comprise copolymers c f at least 90% by weight of methyl methacrylate and other copolymerizable monoethylenically unsaturated compounds and/or polyfunctional compounds may also be used. Suitable monoethylenically unsaturated compounds are methacrylic esters, acrylic esters, styrene, or the like. Suitable polyfunctional compounds are methacrylic esters such as glycol dimethacrylate, diallyl methacrylate, or the like, diallyl phthalate, diethylene glycol bisallyl carbonate and mixtures thereof. Alkyl methacry'ate films are preferred as the acrylic film and examples thereof are those which are produced by polymerizing methyl methacrylate, ethylmethacrylate, butyl methacrylate, propyl methacrylate, alone orb by copolymerizing two or more of them. Furthermore, if necessary, other copolymerizable components such as other acrylates, vinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylonitrile, etc. may be added thereto. These acrylic films are preferably colorless and transparent when ''weather'resistance or surface gloss is desired and those which are printed with patterns or colors are used when the final sheets are to be used as various decorative sheets, partitions, etc. The method for producing the acrylic synthetic resin sheet with which an acrylic film is integrated will be explained below. As shown in FIG. 1, this invention employs a continuous sheet making method, namely, a polymerizable liquid material such as a monomer or monomer-polymer mixture for acrylic synthetic resin is fed from one end of endless belts to the space surrounded by opposite surfaces of two continuous endless belts 1 and 11 which are set in such a manner that the opposite surfaces run in the same direction at the same speed and the continuous gaskets 7 and 7' which run in such state as being put between the two belt surfaces at both side edge portions of the belts, the monomer or monomer-polymer mixture is polymerized and hardened by heating and cooling during its movement with running of the endless belts 1 and 1' and is taken out from another end of the endless belts 1 and I' as an acrylic synthetic resin sheet. In this method3 simultaneously with the feeding of the monomer or the monomer-polymer mixture, an acrylic film is fed between the endless belts 1 and 1' along at least one of the endless belts or prior to the feeding of the monomer or the monomer-polymer mixture said-monomer or monomer-polymer mixture is thinly coated on the surface of the endless belts and the film, sticking to said coated monomer or monomer-polymer mixture, is fed with running of the endless belts. 17 is a device for thinly coating said monomer or monomer-polymer mixture on the surface of the endless belt 1 and as shown in FIG. 2 and FIG. 3, said device comprises container 171 for said monomer or monomer: polymer mixture and a gauze (fabric). Just after the coating device an acrylic film feeding device 15 is provided and as shown in FIG. 4 the acrylic film F is fed through feed roller 151, pinch rollers 152, 152', 152" and 152"' and guide rollers 153 and 153' and is continuously fed with running of belt 1 with being allowed to stick to upper belt 1 by press roller 154. FIG. 5 shows another acrylic film feeding means. Said monomer or monomer-polymer mixture is coated on the surfaces of the lower and upper belts 1 and 1' by coating devices 27 and 27'. Films F and F' are unwound from feeders 251 and 251' and are continuously fed with being allowed to stick to the monomer or monomerpolymer mixture coated on surfaces of both upper and lower belts 1 and 1 through guide rollers 253 and 253', tension regulators 256 and 256', expander rollers 257 and 257' and feed rollers 258 and 258'. 258" and 258 show the state of transfer of feed rollers 258 and 258', respectively. The monomer or monomer-polymer mixture for said acrylic synthetic resin is poured into the space surrounded by the surfaces of the upper and lower belts 1 and 1' at least one of which has said film F and F' allowed to stick thereon and gaskets 7 and 7' from feeding means 6 through gear pump 5. Thus poured monomer or monomer-polymer mixture is transferred together with film F and F' in accordance with running of belts 1 and 1', during which said monomer or monomer-polymer mixture partially swells and dissolves said films F and F'. In the first polymerization zone 18 the monomer or monomer-polymer mixture is heated by spraying hot water of 60 - 95"C on the back surface of the upper and lower endless belts 1 and 1' by spray device 8 and 8'. By this heating said monomer or monomerpolymer mixture for the acrylic synthetic resin is polymerized and hardened into a polymerized and hardened product which becomes integral with said partially swollen and dissolved film F and F'. In the second polymerization zone 9 and 9 said product is heat treated to 115 - 150 cm which is the temperature of endless belts 1 and 1' by far infrared heater 19. Subsequent to the second polymerization zone 9 and 9', said polymerization hardened product between the upper and lower endless belts 1 and 1' is cooled to lower than 105 cm, preferably 100 - 80"C by passing through the first cooling zone 10 and the second cooling zone 11 and thereafter is taken out from another end of the opposite endless belts 1 and 1'. Running speed of the endless belts 1 and 11 is suitably 0.5 - 4.0m/min, Thickness of thus obtained acrylic synthetic resin sheet which is integrated with the acrylic film is preferably 2 - l2mm. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a longitudinal front section of an apparatus for producing the sheet of this invention. FIG. 2 is a section on line II-II of the device for coating monomer for acrylic synthetic resin or monomer-polymer mixture as shown in FIG. 3. FIG. 3 is a longitudinal front section of said coating device. FIG. 4 is a front view of a device for feeding acrylic film FIG. 5 is a longitudinal front section oi a part of the other apparatus for producing the sheet of this invention. BEST MODE- FOR CARRYING OUT THE INVENTION A methyl methacrylate monomer-polymer mixture (syrup) which contained about 30% by weight of methyl methacrylate polymer and had a viscosity of about 10 poises at 25"C was prepared by prepolymerizing methyl methacrylate monomer. In the resultant syrup were incorporated 650 ppm oi azobisdimethylvaleronitrile as a polymerization catalyst and 30 ppm of dioctylsulfosuccinate (Aerosol OT) as a releasing agent. As shown in FIG. 1, the resultant mixture was fed between the surfaces of the endless belts 1 and 1' at a fixed flow rate using gear pump 5 from feeding means 6. The endless belts 1 and 1' were made of polished stainless steel having a thickness of 1.5mm and a width of 1500mm and were given tension between pulleys 3 and 3' by pulleys 2 and 2' of 1600mm in diameter. Tension of the endless belts 1 and 1' was set at 10 kg/mm2 by hydraulic pressure and they ran at a speed of 3 m/min. Film F of a copolymer of 64% by weight of methyl methacrylate and 36% by weight of butyl acrylate which was printed with marble patterns and which had a thickness of 50 u was fed to the upper belt 1 from film feeding device 15. Prior to the feeding of the film F a methyl methacrylate syrup was thinly coated on the surface of the upper belt 1 by the coating device 17. As shown in FIG. 2 and FIG. 3, said coating device 17 comprised syrup container 171 in which a methyl methacrylate syrup was stored and gauze 173 hung down onto the surface of the upper belt 1 from syrup container 171. Said syrup flowed down gauze 173 little by little on the surface of the upper belt 1. As shown in FIG. 4, said film F was fed from feed roller 151 of said film feeding device 15 through pinch rollers 152, 152', 152" and 1521'' and guide rollers 153 and 153' and ran with running of upper endless belt 1 with being allowed to stick to the upper endless belt 1 by press roller 154. As mentioned above, the methyl methacrylate butyl acrylate copolymer film was then fed being held between the running two endless belts 1 and 1' together with the methyl methacrylate syrup supplied from feeding means 6. The distance between the upper and lower endless belts 1 and 1 was kept by roller groups 4 and 4' which were arranged at the interval of 400mm so that the obtained sheet-like methyl methacrylate polymer had a uniform thickness of 3mm. Polyvinyl chloride hollow pipes which had an outer diameter of 13.0mm and a wall thickness of 0.8mm and contained dibutyl phthalate corresponding to 44% by weight of the polymer as a plasticizer were used as gaskets 7 and 7'. The methyl methacrylate syrup fed into the space surrounded by the surface of film F of methyl methacrylate butyl acrylate copolymer which ran sticking to the upper belt 1, the surface of the lower belt 1' and gaskets 7 and 7' moved to the first polymerization zone 18. This first polymerization zone 18 had a length onto and was heated by spraying hot water of 840G in the form of shower onto the back surface of the endless belts 1 and 1' by spraying devices 8 and 8'. Said methyl methacrylate syrup was mostly polymerized and hardened by said heating to obtain a sheet-like polymerization product. The film and methyl methacrylate. butyl acrylate copolymer was partially swollen and dissolved with methyl methacrylate monomer in the methyl methacrylate syrup fed from one end of the two endless belts 1 and 1' during the period before it reached the first polymerization zone 18 and was integrally laminated with the sheet-like polymerization product formed by polymerization and hardening of the methyl methacrylate syrup, in the first polymerization zone 18. The methyl methacrylate sheet-like polymerization product which became integral with the methyl methacrylate butyl acrylate copolymer film in the first polymerization zone 18 moved to the second polymerization zone 9 with running of the two endless belts 1 and lt. The second polymerization zone 9 had a length of 24m and the endless belts 1 and 1' which contacted with said sheet-like polymerization product was heated to 140çC by far infrared heater 19. The temperature at the exit of the second polymerization zone 9 was l270C. Said sheet-like product which left the second polymerization zones 9 and 9' moved to the first cooling zone 10 with running of the endless belts 1 and 1'. The first cooling zone 10 had a length of 5.4m and the sheet-like product was cooled to 103"C at a cooling rate of 14.4 C/min by vertically blowing air to the back surface of endless belts 1 and 1' by a blower. The second cooling zone ll had a length of 3m and said sheet-like product was cooled to 80 OC by blowing and taken out from endless belts 1 and 1'. The taken out methyl methacrylate sheet-like polymerization product 12 which was integrated with the methyl methacrylate.butyl acrylate copolymer film had a thickness of 3 - 0.3mm, had a marble pattern appearance of excellent gloss and had no wrinkles. Furthermore, there occurred no phenomenon of separation of the methyl methacrylate.butyl acrylate copolymer film and the methyl methacrylate sheet-like product. INDUSTRIAL APPLICABILITY As mentioned hereinbefore, according to this invention, acrylic synthetic resin sheet having a good weather resistance and having a gloss surface can be easily obtained. Furthermore, difficulty in printing directly patterns or colors on the conventional acrylic synthetic resin sheet is not seen in printing on the acrylic synthetic resin sheet of this invention. Moreover, as compared with acrylic synthetic resin sheets on which an acrylic film having patterns or colors printed thereon is bonded by heat, etc., wrinkles do not occur on the acrylic film of the sheet of this invention and so the acrylic film is not separated from acrylic synthetic resin sheet. In addition, as compared with acrylic synthetic resin sheets integrated with compatible films other than acrylic films wrinkles are not produced on- the sheet of this invention.

Claims: CLAIMS 1. An acrylic synthetic resin sheet on which an acrylic film is integrally laminated, the improvement comprises said film being partially swollen and dissolved with monomer for acrylic synthetic resin before polymerized and hardened and being integrated with polymerized and hardened acrylic synthetic resin sheet. 2. The sheet of Claim 1, wherein said synthetic resin sheet is a methyl methacrylate resin sheet. 3. The sheet of Claim 1, wherein said synthetic resin sheet is a copolymer of at least 90% by weight of methyl methacrylate and other copolymerizable monoethylenically unsaturated compounds andfor polyfunctional compounds. 4. The sheet of Claim 3, wherein said monoethylenically unsaturated compounds are selected from the group consisting of methacrylic esters and stylene. 5. The sheet of Claim 3, wherein said polyfunctional compounds are selected from the group consisting of glycol dimethacrylate, diallyl methacrylate, diallyl phthalate, diethylene glycol bisallyl carbonate and mixtures thereof. 6. The synthetic resin sheet of Claim 1, wherein the thickness of said sheet is lmm - 15mm. 7. The sheet of Claim 1, wherein said film has thereon a thin layer of synthetic resin having the same composition as that of the acrylic synthetic resin sheet. 8. The sheet of Claim 1, wherein said film is a polymer prepared from monomers selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate and mixtures thereof. 9. The sheet of Claim 1, wherein said film is colorless and transparent. 10. The sheet of Claim 1, wherein said film is printed with patterns or colors. 11. A method of producing anacrylic synthetic resin sheet which comprises feeding onto a moving belt an acrylic film and a polymerizable liquid material; polymerizing and hardening said liquid; thereby obtaining an acrylic synthetic resin sheet on which an acrylic film is integrally laminated, the improvement comprises said film being partially swollen and dissolved with monomer for acrylic synthetic resin before polymerized and hadened and being integrated with polymerized and hardened acrylic synthetic resin sheet. 12. The method of Claim 11, wherein said polymerizable liquid material comprises a monomer or monomer-polymer mixture of methyl methacrylate. 13. The method of Claim 11, wherein said polymerizable liquid material comprises a monomer or monomer-polymer mixture of at least 90% by weight of methyl methacrylate and other copolymerizat: monoethylenically unsaturated compounds and/or polyfunctional combo3 14. The method of Claim 13, wherein said monoethylenically unsaturated compounds are selected from the group consisting of methacrylic esthers, acrylic esters and stylene. 15. The method of Claim 13, wherein said polyfunctional compounds are selected from the group consisting of glycol dimethacrylate, diallyl methacrylate, diallyl phthalate, diethylene glycol bisallyl carbonate and mixtures thereof. 16. The method of Claim 11, wherein said polymerizing comprises two polymerization zones; wherein the first zone is carried out at a tempe rature of 60"C - 95"C and the second zone is carried out at a temperature of 115 C - l50C. 17. the method of Claim 11, wherein said moving belt comprises con tinuous endless belts, polymerization zones and cooling zones.

Inventors: MURASE, HARUO, OHNISHI, KUNIO, TOYOOKA, YASUO, UENO, TADAOMI
Applicants: MITSUBISHI RAYON CO. LTD.
Application year: 1979
Main classification: B32B27
IPC codes: B32B38, C08J5