Abstract:
In press molding or embossing a thermoplastic resin for producing a molded product excellent in transferability of microscopic surface asperities and having high quality with high productivity, a preform of a thermoplastic resin is heated to about the hardening temperature of the thermoplastic resin constituting the preform. The preform is embedded between an upper half and a lower half of a mold which are maintained at a temperature of about the hardening temperature of the thermoplastic resin, and then the mold is closed at a low pressure. Carbon dioxide is dissolved in a surface of the preform by charging carbon dioxide between a surface of the mold and the surface of the preform in order to reduce the viscosity of the preform surface. The surface of the mold is brought into contact with the preform having the reduced surface viscosity by increasing a pressing pressure. Then, carbon dioxide is discharged, and a molded product is extracted. Thus, the molded product excellent in transferability of microscopic surface asperities and having high quality can be produced with high productivity.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is a divisional application under 37 CFR 1.53(b) of pending prior application Ser. No. 12/401,346 filed Mar. 10, 2009. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    1. Field of the Invention 
         [0003]    The present invention relates to methods for molding thermoplastic resins by dissolving resin-soluble gases such as carbon dioxide in surfaces of preforms of thermoplastic resins. More specifically, the present invention relates to methods for molding thermoplastic resins using preforms and molds having restrictive temperature conditions. 
         [0004]    2. Description of the Related Art 
         [0005]    Products such as optical recording media and light-transmitting substrates have microscopic surface patterns and are required to have high transferability of the surface patterns. Products such as optical lenses for cameras and printers are required to have low birefringence. Conventionally, these products are manufactured by injection molding of thermoplastic resins such as polycarbonates (referred to as PC hereinafter) and acrylic resins (referred to as PMMA hereinafter). 
         [0006]    Nowadays, these products are required to have lower birefringence or more fine transferability, but there are limitations in manufacturing such products by conventional injection molding. Consequently, specific forming or processing methods such as press molding or embossing have been proposed. 
         [0007]    In press molding, after embedding a preform in a cavity of a mold, isotactic pressing is performed by decreasing the cavity volume in order to uniformly generate a high internal pressure in the cavity. As a result, residual strain in a molded product is decreased because uniform dwelling is accomplished, unlike in injection molding. Furthermore, the transferability of the mold is greatly improved. 
         [0008]    In embossing, generally, a design such as a pattern or a shape is transferred by using a roller or a mold. However, in the present invention, embossing is defined as that only the pattern is transferred by using a press mold (the shape is not transferred). 
         [0009]    Conventionally, in press molding and embossing of a thermoplastic resin preform, the mold and preform are heated to a temperature higher than the hardening temperature of the thermoplastic resin before the molding, as described above, and then the pressure of the mold is increased for pressing. Then, the molded product is extracted from the mold after the mold is cooled to a temperature lower than the hardening temperature of the thermoplastic resin. However, in these processes, the preform is melted again before a pressing process. Therefore, preheating of the resin in the mold and a long cycle time are disadvantageously required, though sufficient transferability of microscopic patterns and low birefringence are achieved. Furthermore, since the preform is repeatedly melted and cooled, the shrinkage ratio during cooling is not constant and the dimensional accuracy decreases. 
         [0010]    Some molding methods in which cavities before an injection process are filled with a gaseous material in order to improve the transferability to molded products have been disclosed. 
         [0011]    Japanese Unexamined Patent Application Publication No. 10 (1998)-128783 relates to a method for preventing solidification or an increase in viscosity of a thermoplastic resin during a resin filling process and for transferring a surface form of a mold to a molded product with high accuracy in injection molding of the thermoplastic resin. The method does not use a complicated apparatus or mold and is economically performed by embedding the melted thermoplastic resin in a cooled mold filled with carbon dioxide under a pressure higher than that when 0.1 wt % or more carbon dioxide is dissolved in the thermoplastic resin, and by molding the thermoplastic resin after lowering the hardening temperature of the thermoplastic resin surface. 
         [0012]    However, Japanese Unexamined Patent Application Publication No. 10 (1998)-128783 does not relate to press molding and embossing. Furthermore, since the hardening temperature of the resin is decreased by filling the mold with carbon dioxide, this method cannot be applied to press molding. 
         [0013]    Japanese Unexamined Patent Application Publication No. 2002-052583 relates to a method of obtaining a molded product having excellent transferability and brilliance. In injection molding, immediately after a resin is injected into a cavity, a carbon dioxide gas is charged to a skin layer of the molded product, where the cavity  1  and the resin are in contact with each other, to move back the skin layer to form a space  13  between the cavity and the skin layer. As a result, growth of the skin layer stops and the carbon dioxide gas is dissolved in the skin layer to soften the skin layer. Then, the skin layer is again molded by increasing the applied pressure on the resin and is cooled to be hardened under dwelling. 
         [0014]    However, the preform prepared by the method in Japanese Unexamined Patent Application Publication No. 2002-052583 cannot be applied to press molding and embossing, because of the different molding principle. 
         [0015]    Japanese Unexamined Patent Application Publication No. 2003-320556 relates to a molding method for efficiently and inexpensively manufacturing a molded product by modifying only the surface portion so as to have necessary properties without using a resin mixed with a modifier in advance. The modifier is dissolved or dispersed in a compressed gas that is soluble in a melted resin to be injected. A mold cavity is filled with the compressed gas and then the melted resin is injected into the mold cavity. 
         [0016]    However, Japanese Unexamined Patent Application Publication No. 2003-320556 relates to a method for filling the mold with the compressed gas in advance though the gas has solubility. Therefore, this method cannot be applied to press molding and embossing. 
       SUMMARY OF THE INVENTION 
     Problems to be Solved by the Invention 
       [0017]    It is a first object of the present invention to increase the productivity in thermoplastic resin molding by decreasing molding cycle time. 
         [0018]    It is a second object of the present invention to provide a molding method or process for obtaining molded products further improved in transferability of microscopic patterns and in birefringence in thermoplastic resin molding. 
         [0019]    It is a third object of the present invention to provide a molding method or process for obtaining molded products excellent in dimensional accuracy in thermoplastic resin molding. 
       Means for Solving Problem 
       [0020]    In order to achieve the above-mentioned objects, a first aspect of the present invention is a method for molding a thermoplastic resin to obtain a molded product excellent in transferability of microscopic surface asperities and in dimensional accuracy with a short molding cycle time by: heating a preform of a thermoplastic resin to about hardening temperature of the thermoplastic resin constituting the preform; embedding the preform between an upper half and a lower half of a mold which are maintained at a temperature lower than the hardening temperature of the thermoplastic resin; closing the mold at a low pressure; dissolving a resin-soluble gas in a surface of the preform by charging the resin-soluble gas between a cavity surface of the mold and the surface of the preform to reduce the viscosity of the preform surface; increasing a pressing pressure of the mold to bring the cavity surface into contact at a high pressure with the preform having the reduced surface viscosity; discharging the remaining resin-soluble gas from the mold; and extracting the molded product. 
         [0021]    A second aspect of the present invention is a method for molding a thermoplastic resin to obtain a molded product having greatly improved transferability of microscopic surface asperities and low birefringence with a short molding cycle time by: heating a preform of a thermoplastic resin to a temperature higher than the hardening temperature of the thermoplastic resin constituting the preform; embedding the preform between an upper half and a lower half of a mold which are heated to a temperature higher than the hardening temperature of the thermoplastic resin; closing the mold at a low pressure; dissolving a resin-soluble gas in a surface of the preform by charging the resin-soluble gas between a cavity surface of the mold and the surface of the preform to reduce the viscosity of the preform surface; increasing a pressing pressure of the mold to bring the mold surface into contact at a high pressure with the preform having the reduced surface viscosity; discharging the remaining resin-soluble gas from the mold; cooling the mold and the resin to a temperature lower than the hardening temperature of the thermoplastic resin; and extracting the molded product. 
         [0022]    A third aspect of the present invention is the method for molding a thermoplastic resin according to the first or second aspect, wherein a degree of decrease in viscosity and a thickness of a layer having the decreased viscosity in the preform surface are strictly controlled by changing the pressure and temperature of the resin-soluble gas charged between the cavity surface of the mold and the preform surface and by changing the contact time of the preform with the resin-soluble gas. 
         [0023]    A fourth aspect of the present invention is a method for molding a thermoplastic resin to obtain a molded product having high transferability of microscopic surface asperities and high quality with a short molding cycle time by: embedding a preform of a thermoplastic resin between a stamper which is maintained at a temperature lower than the hardening temperature of the thermoplastic resin and a lower half of a mold which is maintained at a temperature lower than the hardening temperature of the thermoplastic resin; closing the mold at a low pressure; dissolving a resin-soluble gas in a surface of the preform by charging the resin-soluble gas between a surface of the stamper and the surface of the preform to reduce the viscosity of the preform surface; increasing a pressing pressure to bring the stamper surface into contact at a high pressure with the preform having the reduced surface viscosity; discharging the remaining resin-soluble gas from the mold; and extracting the molded product. 
         [0024]    A fifth aspect of the present invention is a method for molding a thermoplastic resin to obtain a molded product having greatly improved transferability of microscopic surface asperities and high quality with a short molding cycle time by: embedding a preform of a thermoplastic resin between a stamper which is heated to a temperature higher than the hardening temperature of the thermoplastic resin and a lower half of a mold which is maintained at a temperature lower than the hardening temperature of the thermoplastic resin; closing the mold at a low pressure; dissolving a resin-soluble gas in a preform surface by charging the resin-soluble gas between a surface of the stamper and the surface of the preform to reduce the viscosity of the preform surface; increasing a pressing pressure to bring the stamper surface into contact at a high pressure with the preform having the reduced surface viscosity; discharging the remaining resin-soluble gas; cooling the stamper and the resin to a temperature lower than the hardening temperature of the thermostatic resin; and extracting the molded product. 
         [0025]    A sixth aspect of the present invention is the method for molding a thermoplastic resin according to the fourth or fifth aspect, wherein a degree of decrease in viscosity and a thickness of a layer having the decreased viscosity in the preform surface are strictly controlled by changing the pressure and temperature of the resin-soluble gas charged between the stamper surface and the preform surface and by changing the contact time of the preform with the resin-soluble gas. 
         [0026]    A seventh aspect of the present invention is the method for molding a thermoplastic resin according to any one of the first to sixth aspects, wherein the resin-soluble gas is selected from the group consisting of carbon dioxide, nitrogen, methane, ethane, propane, fluorocarbons having fluorine substituted for hydrogen in these hydrocarbons, and mixtures thereof. 
         [0027]    Carbon dioxide charged in the mold is discharged at the instant when the mold is opened after the pressing process. However, when the pressure of carbon dioxide is high, carbon dioxide is preferably discharged from another path just before the mold is opened. 
         [0028]    In the above-described first, second, fourth, and fifth aspects, when the mold temperature is denoted by Tt, the hardening temperature of the resin is denoted by Tf, and the decrease in the resin-hardening temperature by dissolving carbon dioxide is denoted by ΔTco2, the mold temperature Tt is preferably controlled to be in the following range: Tf-ΔTco2≦Tt≦Tf. 
         [0029]    Transferability in a molded product is improved with a value given by Tt-(Tf-ΔTco2). 
       EFFECT OF THE INVENTION 
       [0030]    In the first and fourth aspects of the present invention, the viscosity of preform surfaces is decreased by dissolving carbon dioxide in the preform surfaces. Therefore, press molding or embossing can be performed under conditions in which a mold is maintained at a predetermined temperature lower than a hardening temperature of a thermoplastic resin. With this, the molding cycle time is vastly improved to increase productivity, compared with conventional methods which require heating the mold before a pressing process and cooling the mold in a cooling process. Furthermore, since the resin temperature is not changed by hardening, a molded product can be obtained without a substantial decrease in dimensional accuracy caused by shrinkage of the resin. 
         [0031]    In the second and fifth aspects of the present invention, since the mold is heated before a pressing process and is cooled in a cooling process, as in the conventional press molding or embossing, the molding cycle time is not largely improved. However, the viscosity of the preform surfaces is largely decreased and transferability of microscopic surface asperities is vastly improved. Furthermore, a vast improvement in birefringence is achieved due to strain relaxation. As described in the third and sixth aspects of the present invention, the degree of decrease in viscosity of the preform surface and the thickness of a layer having the decreased viscosity can be strictly controlled by changing the pressure and temperature of carbon dioxide charged between the mold cavity surface and the preform surface and by changing the contact time of the preform with the carbon dioxide. When molding is performed under conditions where the layer having the decreased viscosity becomes thicker than the preform, the viscosity of the entire preform is decreased to reduce internal strain. Therefore, a molded product having low birefringence can be obtained. 
         [0032]    The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and specific objects attained by its uses, reference is made to the accompanying drawings and descriptive matter in which preferred embodiments of the invention are illustrated. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0033]    In the drawings: 
           [0034]      FIG. 1  is a schematic diagram of a press molding apparatus for operating the present invention; 
           [0035]      FIG. 2  is a schematic diagram of a preform, (a) is a plan view, and (b) is a cross sectional view taken along the line A-A′; 
           [0036]      FIG. 3  is a schematic diagram of a molded product, (a) is a plan view, and (b) is a cross sectional view taken along the line B-B′; 
           [0037]      FIGS. 4  ( a ) and ( b ) are schematic diagrams of a press molding process according to a first aspect of the present invention; 
           [0038]      FIGS. 5  ( a ) and ( b ) are schematic diagrams of a press molding process according to a second aspect of the present invention; 
           [0039]      FIG. 6  is a schematic diagram of an embossing apparatus for operating the present invention; 
           [0040]      FIG. 7  is a schematic diagram of a preform, (a) is a plan view, and (b) is a cross sectional view taken along the line C-C′; 
           [0041]      FIG. 8  is a schematic diagram of a molded product, (a) is a plan view, and (b) is a cross sectional view taken along the line D-D′; 
           [0042]      FIGS. 9  ( a ) and ( b ) are schematic diagrams of an embossing process according to a fourth aspect of the present invention; 
           [0043]      FIGS. 10  ( a ) and ( b ) are schematic diagrams of an embossing process according to a fifth aspect of the present invention. 
       
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
       [0044]    Referring to the drawings in particular, examples of the thermoplastic resins used in the present invention include styrene resins (e.g. polystyrene, butadiene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer), ABS resins, polyethylenes, polypropylenes, ethylene-propylene resins, ethylene-ethyl acrylate resins, polyvinyl chlorides, polyvinylidene chlorides, polybutenes, polycarbonates, polyacetals, polyphenylene oxides, polyvinyl alcohols, polymethyl methacrylates, saturated polyester resins (e.g. polyethylene terephthalates, polybutylene terephthalates), biodegradable polyester resins (e.g. hydroxycarboxylic acid condensates such as polylactic acid, diol-dicarboxylic acid condensates such as polybutylene succinate), polyamide resins, polyimide resins, fluoropolymers, polysulfones, polyether sulfones, polyacrylates, polyether-ether ketones, liquid crystal polymers, and mixtures thereof. Resins mixed with various types of inorganic or organic fillers are also included. Among these thermoplastic resins, amorphous resins are most preferable. 
         [0045]    Gases effectively dissolved in surfaces of preforms are preferably used in the present invention as the resin-soluble gas. Specifically, examples of such gases include carbon dioxide, hydrocarbons such as methane, ethane, and propane, fluorocarbons having fluorine substituted for hydrogen in these hydrocarbons, and mixtures thereof. These gases can be used alone or in a combination. In particular, carbon dioxide is most preferable because of its safety, low-cost, ease in handling, and low environmental impacts. 
       Example 1 
       [0046]    This example corresponds to the first aspect of the present invention, and will be described in detail with reference to the drawings.  FIG. 1  shows the whole molding apparatus. In  FIG. 2 , (a) is a plan view of a preform X- 1 , and (b) is a cross sectional view taken along the line A-A′. In  FIG. 3 , (a) is a plan view of a molded product X- 2 , and (b) is a cross sectional view taken along the line B-B′. In  FIG. 4 , (a) shows a molding process, and (b) shows hardening temperature of a resin changing according to the molding process and a mold temperature. 
         [0047]    In the drawings, reference numerals  8   a  and  8   b  denote an upper half and a lower half, respectively, of a mold for press molding. The insides of the upper and lower halves  8   a  and  8   b  are provided with heat exchangers  9   a  and  9   b , respectively, for heating the mold  8   a  and  8   b  by circulating hot water. The lower half  8   b  is provided with a sealing member  10  for guaranteeing airtightness when the mold  8   a  and  8   b  are sealed. Temperature of the mold is controlled by a temperature regulator  6  through temperature regulating lines  7   a  and  7   b.    
         [0048]    The temperature regulator  6  is an in-house product and is composed of pumps  2   a  and  2   b , a heater  3 , a cooler  5 , and electromagnetic valves  4   a ,  4   b ,  4   c ,  4   d ,  4   e , and  4   f . The regulator operates to pump water from a water source  1  by the pump  2   a  to the heater  3  for heating the water or by the pump  2   b  to the cooler  5  for cooling the water, and operates to circulate the water in the heat exchangers  9   a  and  9   b  of the upper and lower halves  8   a  and  8   b  by switching the electromagnetic valves  4   a ,  4   b ,  4   c ,  4   d ,  4   e , and  4   f . For feeding the hot water to the mold  8   a  and  8   b , the electromagnetic valves  4   a ,  4   c , and  4   e  are opened. For feeding the cold water to the mold  8   a  and  8   b , the electromagnetic valves  4   b ,  4   d , and  4   f  are opened. Charging of carbon dioxide into the mold  8   a  and  8   b  is performed by a carbon dioxide generator-injector  21  through a carbon dioxide feeding line  11 . The carbon dioxide generator-injector  21  is an in-house product and is composed of electromagnetic valves  12   a  and  12   b , a pressure sensor  13 , a back-pressure regulating valve  14 , a pressure-relief valve  15 , a temperature sensor  16 , an accumulator  17 , a warmer  18 , a pressure-reducing valve  19 , and a check valve  20 . The generator-injector operates to control pressure of carbon dioxide generated in a carbon dioxide source  22  by using the pressure-reducing valve  19 , to control temperature of carbon dioxide by the warmer  18 , and operates to accumulate carbon dioxide in the accumulator  17 . The pressure is finely controlled by the back-pressure regulating valve  14 , and charge and discharge of carbon dioxide is conducted by using the electromagnetic valves  12   a  and  12   b . For charging carbon dioxide, the electromagnetic valve  12   b  is opened. For discharging carbon dioxide, the electromagnetic valve  12   a  is opened. When the mold  8   a  and  8   b  is closed in the molding process, the pressure of carbon dioxide charged in the mold  8   a  and  8   b  can be maintained by the sealing member  10 . 
         [0049]    The press molding process according to the first, second, third, and seventh aspects of the present invention will be described with reference to  FIGS. 4 and 5 . PMMA (trade name: MGSS, Sumitomo Chemical Co., Ltd.) was used as a resin. The hardening temperature of this resin is about 100° C. The preform X- 1  is shown in  FIG. 2 , and the form of the molded product X- 2  is shown in  FIG. 3 . The preform X- 1  was in the form of a plate having a length of 28 mm, a width of 28 mm, and a thickness of 3 mm. The molded product X- 2  was in a form of a box having a length of 32 mm, a width of 32 mm, a height of 4 mm, and a thickness of 1.5 mm. The center area of the molded product X- 2  had microscopic successive V-grooves  23  having a width of 20 mm and a depth of 5.7 mm. 
         [0050]    The molding process according to the first aspect of the present invention will be described with reference to  FIG. 4 . At first, as shown in (A), PMMA preform X- 1  heated to 80° C. was placed between the upper half  8   a  and the lower half  8   b  which were maintained at 80° C. by the temperature regulator  6  and the temperature regulating lines  7   a  and  7   b . Then, as shown in (B), the upper half  8   a  was closed by immediate proximity of the surface of the preform X- 1 , and carbon dioxide having a pressure of 8 MPa and a temperature of 40° C. was charged between the upper half  8   a  and the preform X- 1  for 1 second from the carbon dioxide generator-injector  21  through the carbon dioxide feeding line  11 . With this, the hardening temperature of the resin surface was decreased by about 60° C., i.e. from about 100° C. of PMMA to about 40° C. Then, as shown in (C), the upper half  8   a  was sealed at a pressure of 50 MPa, and the pressure was maintained for 5 seconds. Then, as shown in (D), carbon dioxide in the carbon dioxide feeding line  11  was discharged. Then, as shown in (E), the upper half  8   a  was opened to extract the molded product X- 2 . Conditions for molding are shown in Table 1, and evaluation of the molded product is shown in Table 2. 
       Example 2 
       [0051]    Molding was performed as in EXAMPLE 1 except that the charging pressure of carbon dioxide was 15 MPa. Conditions for molding are shown in Table 1, and evaluation of the molded product is shown in Table 2. 
       Example 3 
       [0052]    Molding was performed as in EXAMPLE 1 except that the temperature of carbon dioxide was 60° C. Conditions for molding are shown in Table 1, and evaluation of the molded product is shown in Table 2. 
       Example 4 
       [0053]    Molding was performed as in EXAMPLE 1 except that the contact time of carbon dioxide was 5 seconds. Conditions for molding are shown in Table 1, and evaluation of the molded product is shown in Table 2. 
       Example 5 
       [0054]    Molding was performed as shown in  FIG. 5  by using the same apparatus and resin as in EXAMPLE 1. At first, as shown in (A), PMMA preform X- 1  heated to 140° C. was placed between the upper half  8   a  and the lower half  8   b  of the mold which were heated to 140° C. by the temperature regulator  6  and the temperature regulating lines  7   a  and  7   b . Then, as shown in (B), the upper half  8   a  was closed by immediate proximity of the surface of the preform X- 1 , and carbon dioxide having a pressure of 8 MPa and a temperature of 40° C. was charged between the upper half  8   a  and the preform X- 1  for 1 second from the carbon dioxide generator-injector  21  through the carbon dioxide feeding line  11 . With this, the hardening temperature of the resin surface was decreased by about 60° C., i.e. from about 100° C. of PMMA to about 40° C. Then, as shown in (C), the upper half  8   a  was sealed at a pressure of 50 MPa, and the pressure was maintained for 5 seconds. Then, as shown in (D), carbon dioxide in the carbon dioxide feeding line  11  was discharged, and the upper half  8   a  was cooled to 80° C. by the temperature regulator  6  and the temperature regulating lines  7   a  and  7   b . Then, as shown in (E), the upper half  8   a  was opened to extract the molded product X- 2 . Conditions for molding are shown in Table 1, and evaluation of the molded product is shown in Table 2. 
       Example 6 
       [0055]    Molding was performed as in EXAMPLE 2 except that a gas mixture of carbon dioxide and nitrogen in a ratio of 3:1 was used as a resin-soluble gas. Evaluation of the molded product is shown in Table 2. Change in ratio of carbon dioxide and nitrogen can control only transferability of the molded product. 
       Comparative Example 1 
       [0056]    Molding was performed as in EXAMPLE 1 except that carbon dioxide was not charged. Conditions for molding are shown in Table 1, and evaluation of the molded product is shown in Table 2. 
         [0000]    
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                   
                   
                   
                   
                   
                 Resin- 
               
               
                   
                   
                   
                   
                 Resin- 
                   
                 soluble 
               
               
                   
                   
                   
                 Mold 
                 soluble 
                 Resin-soluble 
                 gas 
               
               
                   
                 Resin- 
                 Highest mold 
                 temperature at 
                 gas 
                 gas 
                 contact 
               
               
                   
                 soluble 
                 temperature 
                 extraction 
                 pressure 
                 temperature 
                 time 
               
               
                   
                 gas 
                 (° C.) 
                 (° C.) 
                 (Mpa) 
                 (° C.) 
                 (sec) 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 EXAMPLE 1 
                 CO 2   
                 80 
                 80 
                 8 
                 40 
                 1 
               
               
                 EXAMPLE 2 
                 CO 2   
                 80 
                 80 
                 15 
                 40 
                 1 
               
               
                 EXAMPLE 3 
                 CO 2   
                 80 
                 80 
                 8 
                 60 
                 1 
               
               
                 EXAMPLE 4 
                 CO 2   
                 80 
                 80 
                 8 
                 40 
                 5 
               
               
                 EXAMPLE 5 
                 CO 2   
                 140 
                 80 
                 8 
                 40 
                 1 
               
               
                 EXAMPLE 6 
                 CO 2  + N 2   
                 80 
                 80 
                 15 
                 40 
                 1 
               
               
                 COMPARATIVE 
                 — 
                 140 
                 80 
                 — 
                 — 
                 — 
               
               
                 EXAMPLE 1 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Trans- 
                   
                 Dimensional 
                   
               
               
                   
                 ferability 
                 Birefringence 
                 accuracy 
                 Productivity 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 EXAMPLE 1 
                 Δ 
                 ◯ 
                 ⊚ 
                 ⊚ 
               
               
                 EXAMPLE 2 
                 ◯ 
                 ◯ 
                 ⊚ 
                 ⊚ 
               
               
                 EXAMPLE 3 
                 Δ 
                 ◯ 
                 ◯ 
                 ⊚ 
               
               
                 EXAMPLE 4 
                 ◯ 
                 ⊚ 
                 ⊚ 
                 ◯ 
               
               
                 EXAMPLE 5 
                 ⊚ 
                 ⊚ 
                 Δ 
                 Δ 
               
               
                 EXAMPLE 6 
                 Δ~◯ 
                 ◯ 
                 ⊚ 
                 ⊚ 
               
               
                 COMPARA- 
                 Δ 
                 ◯ 
                 Δ 
                 Δ 
               
               
                 TIVE 
               
               
                 EXAMPLE 1 
               
               
                   
               
               
                 Evaluation criteria 
               
               
                 ⊚ Excellent 
               
               
                 ◯ Good 
               
               
                 Δ Poor 
               
             
          
         
       
     
       Example 7 
       [0057]    This example corresponds to the fourth aspect of the present invention.  FIG. 6  shows an apparatus of this example,  FIGS. 7  ( a ) and ( b ) shows a preform X- 1 , and  FIGS. 8  ( a ) and ( b ) shows a molded product X- 2 . In  FIG. 9 , (a) shows a molding process, and (b) shows hardening temperature of a resin changing according to the molding process and a stamper temperature. Reference numerals  8   a  and  8   b  denote an upper half and a lower half of a mold for embossing, and  8   c  denotes the stamper. Temperature of the stamper is controlled by circulating a heating medium in a heat exchanger  9   a  in the stamper  8   c  by the temperature regulator  6  through temperature regulating lines  7   a  and  7   b . The temperature regulator  6  is an in-house product and is composed of pumps  2   a  and  2   b , a heater  3 , a cooler  5 , and electromagnetic valves  4   a ,  4   b ,  4   c ,  4   d ,  4   e , and  4   f . The regulator operates to pump water from a water source  1  by the pump  2   a  to the heater  3  for heating the water or with the pump  2   b  to the cooler  5  for cooling the water, and operates to circulate the water in the heat exchanger  9   a  of the stamper  8   c  by switching the electromagnetic valves  4   a ,  4   b ,  4   c ,  4   d ,  4   e , and  4   f . For feeding hot water to the stamper  8   c , the electromagnetic valves  4   a ,  4   c , and  4   e  are opened. For feeding cold water to the stamper  8   c , the electromagnetic valves  4   b ,  4   d , and  4   f  are opened. Charging of carbon dioxide into the mold is performed by a carbon dioxide generator-injector  21  through a carbon dioxide feeding line  11 . The carbon dioxide generator-injector  21  is an in-house product and is composed of electromagnetic valves  12   a  and  12   b , a pressure sensor  13 , aback-pressure regulating valve  14 , a pressure-relief valve  15 , a temperature sensor  16 , an accumulator  17 , a warmer  18 , a pressure-reducing valve  19 , and a check valve  20 . The generator-injector operates to control pressure of carbon dioxide generated in a carbon dioxide source  22  by using the pressure-reducing valve  19 , to control temperature of carbon dioxide by the warmer  18 , and operates to accumulate carbon dioxide in the accumulator  17 . The pressure is finely controlled by the back-pressure regulating valve  14 , and charge and discharge of carbon dioxide is conducted by the electromagnetic valves  12   a  and  12   b . For charging carbon dioxide, the electromagnetic valve  12   b  is opened. For discharging carbon dioxide, the electromagnetic valve  12   a  is opened. When the mold  8   a  and  8   b  is closed in the molding process, the pressure of carbon dioxide charged in the mold can be maintained by the sealing member  10 . 
         [0058]    Press molding according to the fourth, fifth, sixth, and seventh aspects of the present invention will be described with reference to  FIG. 9 , (a) and (b) or  FIG. 10 , (a) and (b). PMMA (trade name: MGSS, Sumitomo Chemical Co., Ltd.) was used as a resin. The hardening temperature of the resin is about 100° C. As shown in  FIGS. 7 and 8 , the preform X- 1  and the molded product X- 2  were in the form of a plate having a length of 32 mm, a width of 32 mm, and a thickness of 1.5 mm. The center area of the molded product X- 2  had microscopic successive V-grooves  23  having a width of 20 mm and a depth of 5.7 mm. 
         [0059]    The molding process will be described with reference to  FIG. 9 , (a) and (b). At first, as shown in (A), a preform X- 1  of PMMA at ambient temperature was placed between the lower mold  8   b  at 80° C. and the stamper  8   c  which was maintained at 80° C. by the temperature regulator  6  and the temperature regulating lines  7   a  and  7   b . Then, as shown in (B), the stamper  8   c  was closed by immediate proximity of the surface of the preform X- 1 , and carbon dioxide having a pressure of 15 MPa and a temperature of 40° C. was charged between the stamper  8   c  and the preform X- 1  for 1 second from the carbon dioxide generator-injector  21  through the carbon dioxide feeding line  11 . With this, the hardening temperature of the resin decreased by about 60° C., i.e. from about 100° C. of PMMA to about 40° C. Then, as shown in (C), the upper half  8   a  was sealed at a pressure of 50 MPa, and the pressure was maintained for 5 seconds. Then, as shown in (D), carbon dioxide in the carbon dioxide feeding line  11  was discharged. Then, as shown in (E), the upper half  8   a  was opened to extract the molded product X- 2 . Conditions for molding are shown in Table 3, and evaluation of the molded product is shown in Table 4. 
       Example 8 
       [0060]    Molding was performed as shown in  FIG. 10 , (a) and (b) by using the same apparatus and resin as in EXAMPLE 7. At first, as shown in (A), a preform X- 1  of PMMA at ambient temperature was placed between the lower half  8   b  at 80° C. and the stamper  8   c  which was heated to 120° C. by the temperature regulator  6  and the temperature regulating lines  7   a  and  7   b.    
         [0061]    Then, as shown in (B), the stamper  8   c  was closed by immediate proximity of the surface of the preform X- 1 , and carbon dioxide having a pressure of 8 MPa and a temperature of 40° C. was charged between the stamper  8   c  and the preform X- 1  for 1 second from the carbon dioxide generator-injector  21  through the carbon dioxide feeding line  11 . With this, the hardening temperature of the resin decreased by about 60° C., i.e. from about 100° C. of PMMA to about 40° C. Then, as shown in (C), the upper mold  8   a  was sealed at a pressure of 50 MPa, and the pressure was maintained for 5 seconds. Then, as shown in (D), carbon dioxide in the carbon dioxide feeding line  11  was discharged, and the stamper  8   c  was cooled to 80° C. by the temperature regulator  6  and the temperature regulating lines  7   a  and  7   b . Then, as shown in (E), the upper half  8   a  was opened to extract the molded product X- 2 . Conditions for molding are shown in Table 3, and evaluation of the molded product is shown in Table 4. 
       Comparative Example 2 
       [0062]    Molding was performed as in EXAMPLE 8 except that carbon dioxide was not charged. Conditions for molding are shown in Table 3, and evaluation of the molded product is shown in Table 4. 
         [0000]    
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                   
                   
                   
                   
                   
                 Resin- 
               
               
                   
                   
                   
                   
                 Resin- 
                   
                 soluble 
               
               
                   
                   
                 Highest 
                 Mold 
                 soluble 
                   
                 gas 
               
               
                   
                 Resin- 
                 mold 
                 temperature 
                 gas 
                 Resin-soluble 
                 contact 
               
               
                   
                 soluble 
                 temperature 
                 at extraction 
                 pressure 
                 gas temperature 
                 time 
               
               
                   
                 gas 
                 (° C.) 
                 (° C.) 
                 (Mpa) 
                 (° C.) 
                 (sec) 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 EXAMPLE 7 
                 CO 2   
                 80 
                 80 
                 15 
                 40 
                 1 
               
               
                 EXAMPLE 8 
                 CO 2   
                 120 
                 80 
                  8 
                 40 
                 1 
               
               
                 COMPARATIVE 
                 — 
                 120 
                 80 
                 — 
                 — 
                 — 
               
               
                 EXAMPLE 2 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                 Trans- 
                   
                 Dimensional 
                   
               
               
                   
                 ferability 
                 Birefringence 
                 accuracy 
                 Productivity 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 EXAMPLE 7 
                 ◯ 
                 ◯ 
                 ⊚ 
                 ⊚ 
               
               
                 EXAMPLE 8 
                 ⊚ 
                 ⊚ 
                 Δ 
                 Δ 
               
               
                 COMPARA- 
                 Δ 
                 ◯ 
                 Δ 
                 Δ 
               
               
                 TIVE 
               
               
                 EXAMPLE 2 
               
               
                   
               
               
                 Evaluation criteria 
               
               
                 ⊚ Excellent 
               
               
                 ◯ Good 
               
               
                 Δ Poor 
               
             
          
         
       
     
         [0063]    Since the results of EXAMPLE 6 according to the sixth aspect of the present invention were the same as those in EXAMPLES 2 to 5, the description is omitted. 
         [0064]    While specific embodiments of the invention have been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles. 
       REFERENCE SYMBOLS 
       [0000]    
       
         1: Water source 
           2   a ,  2   b : Pump 
           3 : Heater 
           4   a ,  4   b ,  4   c ,  4   d ,  4   e ,  4   f : Electromagnetic valve 
           5 : Cooler 
           6 : Temperature regulator 
           7   a ,  7   b : Temperature regulating line 
           8   a ,  8   b : Mold 
           8   c : Stamper 
           9   a ,  9   b : Heat exchanger 
           10 : Sealing member 
           11 : Carbon dioxide feeding line 
           12   a ,  12   b : Electromagnetic valve 
           13 : Pressure sensor 
           14 : Back-pressure regulating valve 
           15 : Pressure-relief valve 
           16 : Temperature sensor 
           17 : Accumulator 
           18 : Warmer 
           19 : Pressure-reducing valve 
           20 : Check valve 
           21 : Carbon dioxide generator-injector 
           22 : Carbon dioxide source 
           23 : Microscopic successive V-grooves 
         X- 1 : Preform 
         X- 2 : Molded product