JP2008158135A - Manufacturing method of reflection sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a reflection sheet having a high reflectance suitable for reflective material which can be used for backlight of liquid crystal display device or the like. <P>SOLUTION: A composition sheet containing a polypropylene resin (A) of ≥50 vol% and <90 vol% and a hole-forming material (B) incompatible with the polypropylene resin of ≥10 vol% and <50 vol% is biaxially oriented; holes are formed and thereafter, the heat contraction of ≥10% is performed in both of the longitudinal and lateral directions or in either of the longitudinal direction and lateral direction to manufacture the reflection sheet. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a reflective sheet of a resin composition having holes therein, and more particularly to a method for producing a reflective sheet suitable for a reflective material used for a backlight of a liquid crystal display device.

Since the liquid crystal itself does not emit light, a light source is required to use the liquid crystal as a display device. A liquid crystal display device is composed of a liquid crystal panel composed of a liquid crystal, an alignment plate, an electrode, a polarizing plate, and the like, and a device for irradiating the panel with light, generally a lighting device called a backlight, and directs light from the lamp toward the screen A reflective sheet is used for efficient reflection.
In general, the backlight of a liquid crystal display device is roughly classified into two types: an edge light type backlight and a direct type backlight.

  The edge light type backlight is a backlight that is often used in a small liquid crystal display device used in a mobile phone, a portable information terminal, and the like. An edge-light type backlight is a light source such as a light emitting diode or a cold cathode ray tube, a light guide plate formed of a transparent resin such as acrylic resin in a wedge shape, and a reflection disposed on the side of the light guide plate opposite to the liquid crystal panel. Often composed of materials. In the edge light type backlight, light from a light source such as a light emitting diode or a cold cathode ray tube disposed on the end face of the light guide plate is incident from the end face of the light guide plate. Light incident on the light guide plate exits from the side surface of the light guide plate in the process of passing through the light guide plate. Light exiting from the liquid crystal panel side of the light guide plate illuminates the liquid crystal panel, but light exiting from the side opposite to the liquid crystal panel side of the light guide plate cannot illuminate the liquid crystal panel A light reflecting plate is installed on the side of the light guide plate opposite to the liquid crystal panel, and the light coming out from the side of the light guide plate is reflected to the liquid crystal panel to effectively use the light from the light source. Usually, the liquid crystal panel is irradiated.

  The direct type backlight is a backlight in which a plurality of light source lamps such as cold cathode ray tubes are arranged side by side on the opposite side of the display surface of the liquid crystal panel, and is used for a large-screen liquid crystal display device used in large televisions. It is done. In large-screen liquid crystal display devices, the brightness of the light source lamp is limited when trying to increase the brightness of the edge-light type backlight to a level that satisfies the brightness, so a direct-type backlight that uses multiple light source lamps is usually used. ing. Since the light from the light source lamp is also irradiated on the side opposite to the liquid crystal side, it is possible to effectively irradiate the liquid crystal panel with the light from the light source by providing a reflective sheet on the side opposite to the liquid crystal side of the light source lamp. This is generally done for backlights.

  Recently, not only televisions but also personal computers often display moving images, and liquid crystal display devices are required to be brighter. For this reason, in the backlight used for the liquid crystal display device, a reflection sheet having a reflectance of 90% or more is often used. In order to make the liquid crystal display device brighter, the output of a light source such as a cold cathode ray tube tends to increase. For this reason, the temperature of the backlight in use tends to be higher. For this reason, the resin used for the reflective sheet is required to have a heat resistance of approximately 80 ° C., which is close to the heat resistant temperature of the liquid crystal substance. For this reason, the reflective sheet used for the backlight of a liquid crystal display device is required to be a reflective sheet of a resin composition that is easily formed into a sheet and excellent in heat resistance. Furthermore, in a backlight used for a large-screen liquid crystal display device such as a large television, a large-area reflective sheet is illuminated with intense light over a long period of time. For this reason, there is a demand for a reflective sheet that is less likely to undergo discoloration or alteration due to light from the light source, and that does not easily undergo deformation such as warping due to temperature rise or moisture absorption over a long period of time.

  It is well known that a resin sheet containing pores and bubbles inside is reflected in light and appears white or shows pearly luster when irradiated with light. The reason why the resin containing holes and bubbles in the interior reflects light well is considered as follows. Since the refractive index of the resin is approximately 1.4 to 1.6 and the refractive index of air is about 1, the reflectance of light generated by the difference in refractive index between the resin and air is about 4% per reflection. Only. However, in a resin sheet containing a large number of holes and bubbles inside, there are a large number of interfaces between the resin and air inside, so that the light irradiated to the sheet is reflected many times inside the sheet. As a result, in the resin sheet containing a large number of holes and bubbles inside, the irradiated light is mostly reflected inside the sheet, and as a result, the reflectivity of the entire sheet is considered to increase.

  In addition, since many holes and bubbles contained in the resin often have different shapes and sizes, the light reflected at the interface between the holes and bubbles is not reflected in one direction. The direction of the reflected light is different for each hole or bubble. For this reason, reflection when light is applied to a resin sheet containing a large number of holes and bubbles therein tends to be diffuse reflection in which incident light is reflected in all directions. As a sheet of a resin composition containing pores and bubbles inside, (1) by stretching the resin to which the inorganic powder is added, the interface between the resin and the inorganic powder is cleaved, and pores are formed inside the resin. There are known ones formed and (2) one obtained by dissolving a pressurized inert gas in a resin and then foaming it by reducing the pressure to form bubbles inside the resin.

  As the resin sheet of (1), for example, in Patent Document 1, a polyethylene terephthalate resin containing 5 to 30 wt% of fine calcium carbonate is melt extruded and biaxially stretched, and the void ratio calculated from the density is 7 to 30. % White polyethylene terephthalate sheet is disclosed. In such a reflection sheet, since inorganic powder such as calcium carbonate and barium sulfate is contained in a large ratio of several tens of volume% of the entire reflection sheet, a part of the inorganic powder may protrude from the surface of the reflection sheet. . When such a reflection sheet is used for an edge light type Levek light, there is a possibility that the surface of the light guide plate is damaged by the partially protruded inorganic powder in the step of attaching the reflection sheet to the light guide plate. In addition, the inorganic powder may be detached from the surface or end surface of the reflecting sheet and adhere to the reflecting sheet surface or the surface of the backlight, which may appear as dots on the liquid crystal screen and impair the image quality of the display screen. .

As the resin sheet of (2), for example, in Patent Document 2, an inert gas such as carbon dioxide gas is dissolved in a thermoplastic polyester under a pressurized atmosphere, and then heated and foamed under normal pressure. A light reflecting sheet containing fine bubbles is disclosed. This is a resin reflection sheet that does not contain inorganic powder, but in order to dissolve the inert gas in the resin sheet, it is necessary to place the resin sheet in a pressurized inert gas atmosphere for a certain period of time, Since a process of taking out a resin sheet in which an inert gas is dissolved and returning it to normal pressure and then foaming it by heating is necessary, the manufacturing process tends to be large and complicated. In Patent Document 2, pores are formed by fine foaming of polyester. Although it is fine foaming, the pore diameter is 5 to 10 μm even if it is small. In order to obtain high reflection performance, it is necessary to contain a lot of fine bubbles. Therefore, the sheet thickness becomes as thick as 0.8 to 1.2 mm. For liquid crystal displays, a sheet that is thinner and has excellent reflection performance is desired. When a thick sheet is wound into a roll, the winding diameter increases and problems such as winding are also caused. In some cases, the sheet must be supplied in the form of a single sheet, which complicates handling for commercialization.
With respect to diffuse reflection, reflection in which the angle at which light is incident on the reflection surface and the reflection angle are symmetric is called regular reflection, and the reflection surface has a mirror shape. As the regular reflection by the resin sheet, (3) a polyester resin sheet whose surface is coated with a material having a high reflectance such as silver by a method such as vapor deposition is known.

  In the reflective sheet of (3), metal particles such as silver covering the surface of the resin sheet are easily agglomerated by the heat of the light source lamp in use or oxidized by an acidic gas component contained in a trace amount in the atmosphere. It is known that discoloration of metals such as silver and a decrease in reflectance occur. For this reason, the metal surface such as silver covering the surface of the sheet is coated with a resin to prevent contact with the atmosphere, and the surface of the resin sheet is thinly coated with metal or resin multiple times. Therefore, the manufacturing process tends to be a large and complicated process. The reflection sheet in this example is a sheet that causes specular reflection, but in a direct type backlight used for a large screen liquid crystal display device such as a large television, light from a light source lamp in which a plurality of light source lamps are arranged is used. It is known that spots are likely to occur in the brightness of the liquid crystal screen due to interference. For this reason, a reflection sheet that causes diffuse reflection is often used for the direct type backlight.

The reflection sheets of (1) and (2) above are reflection sheets that cause diffuse reflection. However, the light guide plate is damaged by inorganic particles added in large quantities to the reflection sheet as described above, and the problem of inorganic particles falling off. There is a demand for a reflection sheet that diffuses and reflects, which solves problems such as a large manufacturing process.
As a white resin sheet in which pores are formed without adding inorganic particles, Patent Document 3 discloses a white biaxially stretched polyolefin sheet containing 65 to 93% by weight of polypropylene and 5 to 20% by weight of an incompatible resin. Although disclosed, it can be used as a white sheet used for printing paper, labels, etc., but it is difficult to obtain a high reflectivity that can be used for backlights of liquid crystal display devices. .

  Patent Document 4 discloses a resin composition containing 50% by volume or more and less than 80% by volume of a polypropylene resin and 20% by volume or more and less than 50% by volume of a resin phase-separated from the polypropylene resin at a temperature at which the polypropylene resin can be stretched. A reflective sheet is disclosed. For this, a reflection sheet having a high reflectance of 90% or more is provided with an ordinary simple resin drawing production apparatus without containing inorganic powder. However, recent liquid crystal display devices require higher reflection performance, and there is a strong demand for a reflection sheet having a high reflectance even at 1%. It is said that even if the difference is 1%, the performance is substantially improved by 2 to 3 times due to the effect of repeated reflection.

Japanese Patent Publication No. 6-89160 Japanese Patent No. 2925745 Japanese Patent No. 3139510 International Publication No. 2005/096036

An object of this invention is to provide the method of manufacturing the reflection sheet which consists of a resin composition which does not contain a large amount of inorganic powder, Comprising: The sheet | seat which has a higher reflectance.
In addition, there is a case where the term is used in such a manner that a film having a thickness of 200 μm or less is referred to as a film and a film having a thickness exceeding 200 μm is referred to as a sheet. That's it.

As a result of intensive studies to solve the above problems, the present inventors have found that in a reflective sheet comprising a polypropylene resin and a hole forming material that is incompatible with the polypropylene resin, the heat of the sheet at a specific temperature. Obtaining the knowledge that a sheet having a shrinkage rate below a specific value has high reflection performance, found a method for producing a sheet having such a specific heat shrinkage rate, and led to the present invention. It was.
That is, this invention is a manufacturing method of the reflective sheet as follows.

(1) Biaxial composition sheet containing 50% by volume or more and less than 90% by volume of polypropylene resin (A) and 10% by volume or more and less than 50% by volume of pore forming material (B) incompatible with polypropylene resin A method for producing a reflective sheet, comprising stretching and forming holes, and performing thermal shrinkage of 10% or more in both the longitudinal direction and the transverse direction, or in either the longitudinal direction or the transverse direction.
(2) The reflection according to the above (1), wherein after the hole is formed, heat shrinkage of 20% or more is performed in both the vertical direction and the horizontal direction, or in either the vertical direction or the horizontal direction. Sheet manufacturing method.
(3) The method for producing a reflective sheet as described in (1) or (2) above, wherein the hole forming material (B) is an inorganic material.
(4) The reflective sheet according to any one of (1) to (3), wherein the hole forming material (B) includes at least one selected from the group consisting of calcium carbonate, barium sulfate, and titanium dioxide. Manufacturing method.
(5) The hole forming material (B) is a resin, and the elastic modulus of the resin is higher than that of the polypropylene resin (A) at a temperature at which the polypropylene resin (A) can be stretched. The manufacturing method of the reflecting sheet as described in 2).
(6) The method for producing a reflective sheet as described in any one of (1), (2) and (5) above, wherein a polycarbonate resin is included as a resin incompatible with the polypropylene resin.
(7) The above-described (1) to (6), wherein the stretching ratio of biaxial stretching is 1.5 times or more in each of the MD direction and TD direction, and the area stretching ratio is from 3 times to 50 times The manufacturing method of the reflective sheet in any one of.
(8) The reflecting sheet according to (7) above, wherein the stretching ratio of biaxial stretching is 2 times or more in each of the MD direction and the TD direction, and the area stretching ratio is 4 times or more and 30 times or less. Manufacturing method.
(9) Biaxial stretching is a longitudinal and transverse sequential biaxial stretching method, and the relationship between MD and TD stretch ratios is MD ≦ TD, and after transverse stretching, the transverse direction is equal to the transverse stretching ratio at a temperature near the transverse stretching temperature. The method for producing a reflective sheet according to any one of the above (1) to (8), wherein a relaxation heat treatment is performed to cause thermal shrinkage of 10% or more in the direction.
(10) The reflective sheet according to (9), wherein after the transverse stretching, a relaxation heat treatment is performed to perform thermal shrinkage of 20% or more in the transverse direction with respect to the transverse stretching ratio at a temperature near the transverse stretching temperature. Production method.

  According to the method for producing a reflective sheet of the present invention, it is possible to obtain a reflective sheet that exhibits a higher reflectance than conventional reflective sheets having the same basis weight and density.

The present invention will be specifically described below.
(Resin composition constituting the reflection sheet)
In the method for producing a reflective sheet of the present invention, a polypropylene resin (A) and a hole forming material (B) that is incompatible with the polypropylene resin (A) are used as the resin constituting the reflective sheet.
<Polypropylene resin (A)>
The polypropylene resin (A) is a polypropylene resin such as a homopolymer of propylene or a copolymer with a monomer such as ethylene that can be copolymerized with propylene. The polypropylene resin (A) is preferably a polypropylene resin having a melt flow rate of 0.1 to 10 g / min measured at a temperature of 230 ° C. and a load of 21.2 N by the method of JIS K7210. The melt flow rate is 0. From the viewpoint of discoloration due to the load of the extruder and the heat of the resin composition when the polypropylene resin is melt-molded. It is preferable that it is lg / min or more, and it is preferable that it is 10 g / min or less from a viewpoint of the viscosity and moldability of resin. From the viewpoint of tension and stretchability during resin stretching, the proportion of the polypropylene resin (A) in the entire resin composition is preferably 50% by volume or more. On the other hand, in order to obtain a reflective sheet having a high average total reflectance of 95% or more by stretching a sheet obtained by extruding the resin composition to form holes in the sheet, a polypropylene resin (A ) Is preferably less than 90% by volume, more preferably less than 80% by volume. The average total reflectivity here refers to an average value in both directions when the total reflectivity when light having a wavelength of 550 nm is incident from each of the MD direction and the TD direction of the sheet is measured.

<Pole forming material (B)>
As the hole forming material (B), an inorganic material powder or resin incompatible with polypropylene resin can be used.
As the inorganic material powder, the average particle diameter is preferably 0.01 to 20 μm, more preferably 0.01 to 10 μm, still more preferably 0.1 to 5 μm, calcium carbonate, barium sulfate, magnesium oxide, magnesium sulfate, carbonic acid. Examples include magnesium, talc, titanium dioxide, alumina, and silica. Two or more kinds of these inorganic material powders may be used in combination, and by using two or more kinds of inorganic material powders having different refractive indexes in combination, higher reflectance and opacity can be imparted. In the present invention, calcium carbonate, barium sulfate, and titanium dioxide are preferable from the viewpoint of reflection performance, moldability, and cost.

  Examples of the resin include polyethylene resins, polystyrene resins, polymethyl methacrylate resins, polycarbonate resins, polymethylpentene resins, polycycloolefin resins such as polynorbornene resins, polyester resins, and polyamide resins. Among these resins, a resin having a higher elastic modulus at a temperature at which the polypropylene resin can be stretched is more preferable than the polypropylene resin. For example, a polycycloolefin resin such as a polycarbonate resin, a polymethylpentene resin, or a polynorbornene resin, or a polyester resin. And polyamide resin. Of these resins, at least one kind of resin is preferably used by being melt mixed with a polypropylene resin, and most preferably a polycarbonate resin.

The volume ratio of the polypropylene resin (A) to the hole forming material (B) is 50% by volume or more and less than 90% by volume for the polypropylene resin (A), and 10% by volume or more and less than 50% by volume for the hole forming material (B). More preferably, the polypropylene resin is 50 volume% or more and less than 80 volume%, and the pore-forming material (B) is 20 volume% or more and less than 50 volume%. The pore-forming material (B) is preferably less than 50% by volume of the entire resin composition from the viewpoint of reducing the stretching tension. Further, from the viewpoint of increasing the number of holes and the hole volume of the sheet to obtain a high average total reflectance of 95% or more, the hole forming material (B) is preferably 10% by volume or more of the entire resin composition, more preferably. The volume ratio between the polypropylene resin and the pore-forming material, which is 20% by volume or more, is calculated from the density of the basic characteristics of each material. For example, the density of the polypropylene resin 0.89~0.91g / cm ^3, the density of calcium carbonate 2.72~2.95g / cm ^3, the density of barium sulphate 4.50 g / cm ^3, the density of the polycarbonate resin Is 1.2 g / cm ³ and can be easily converted from these values.

  Usually, biaxially stretched polypropylene undergoes large thermal shrinkage when the temperature is raised to the vicinity of the stretching temperature. The present invention actively utilizes this heat shrinkability to produce a reflective sheet having high reflection performance, thermal dimensional stability, and heat formability. Therefore, the finally obtained sheet must have excellent thermal dimensional stability and heat formability. A biaxially stretched molded article containing a hole forming material that is incompatible with the polypropylene resin as in the present invention has excellent thermal dimensional stability and thermal formability after being subjected to the heat shrink treatment of the present invention. The reason is considered that after the hole forming material has been subjected to the heat treatment of the present invention, a great effect is exhibited in maintaining its thermal dimensional stability. The effect of this thermal dimensional stability is preferably a resin in which the hole forming material is a resin, and the elastic modulus is higher than the elastic modulus of the polypropylene resin at a temperature at which the polypropylene can be stretched. When the hole forming material is a resin, the composition sheet is stretched at a temperature at which the polypropylene resin can be stretched to cleave the interface between the hole forming material and the polypropylene resin phase, thereby forming holes in the sheet. In addition, when the elastic modulus of the resin is larger than the elastic modulus of the polypropylene resin at the stretching temperature, the deformation amount due to the stretching force of the resin phase is smaller than the deformation amount of the polypropylene resin phase, so that the resin phase and the polypropylene resin phase The interface is more easily cleaved. A more preferable pore forming material is polycarbonate resin.

  The polycarbonate resin which is a preferable example as the pore-forming material (B) can be used alone or in combination from aromatic polycarbonate, linear polycarbonate and branched polycarbonate. The polycarbonate resin is preferably a polycarbonate resin having a melt flow rate of 0.1 to 50 g / lOmin measured by a method of JISK7210 at a temperature of 300 ° C. and a load of 11.8 N. From the viewpoint of making the mixing with the polypropylene resin uniform, the melt flow rate of the polycarbonate resin is preferably 0.1 g / lOmin or more, and from the viewpoint of easily forming pores during stretching, the melt flow rate is 50g / l0min or less. Is preferred.

  An example of the resin (B) other than the polycarbonate resin is a polyamide resin. The polyamide resin can be used alone or in combination among polyamide 66, polyamide 6, polyamide 610, polyamide 612, polyamide 11, polyamide 12, aromatic polyamide and the like. The polyamide resin is preferably a polyamide resin having a melting point of 300 or less from the viewpoint of dispersibility when extruded by an extruder.

In the present invention, a polystyrene resin can be used in addition to the polypropylene resin (A) and the hole forming material (B). As the polystyrene resin, a polystyrene resin having a melt flow rate of 0.1 to 20 g / lOmin measured at a temperature of 200 ° C. and a load of 49 N by the method of JISK7210 is preferable. By adding 5% by volume or less of polystyrene resin to the entire resin composition, the rotational torque of the extruder for melting and mixing the entire resin composition can be reduced without significantly impairing the transparency of the entire resin composition. The effect of making the process and equipment for manufacturing the reflective sheet simpler, such as reducing the tension when the sheet is stretched to generate holes in the sheet, is provided. From the viewpoint of sufficiently obtaining the effect of reducing the rotational torque of the extruder and reducing the stretching tension of the sheet, and from the viewpoint of obtaining an optically uniform sheet, the ratio of the polystyrene resin to the entire resin composition is 5% by volume or less. Is preferred.
In the present invention, a resin composition in which a polypropylene resin (A) and a resin (B) are mixed with a polystyrene resin as necessary is used. For the resin composition, an ultraviolet absorber, a light stabilizer, A heat stabilizer, a nucleating agent, an antistatic agent or the like may be added.

  For example, the reflective sheet of the present invention melts and mixes 50% by volume or more and less than 90% by volume of polypropylene resin (A) and 10% by volume or more and less than 50% by volume of resin (B) into the sea of polypropylene resin. A resin composition having a so-called sea-island structure in which the islands of the resin (B) are dispersed is obtained by extruding into a sheet and then stretching.

  When resin is used as the hole forming material and the pellets of the polypropylene resin (A) and the hole forming material (B) are melted and extruded using an extruder such as a twin screw extruder, the hole forming material (B) When passing through a gap between the cylinder and the screw of the extruder or between the screws inside the extruder, the shear force generated by the rotation of the screw causes a number of resin pellets of about several millimeters in size. It is finely divided into a dispersed phase having a size of about μm. By appropriately setting the shape of the screw of the extruder, the cylinder temperature, the number of rotations of the screw, and the like, the average value and distribution of the size at which the resin (B) is divided can be adjusted.

(Physical properties of reflective sheet)
The reflection sheet obtained by the production method of the present invention has a structure having a large number of minute holes therein, and the hole structure has a basis weight of 100 to 500 g / m ² and a density of 0.3 to 0.75 g / It is characterized by being cm ³ . When the basis weight is less than 100 g / m ² , the strength is not sufficient and a high reflectance cannot be obtained. ^{On the other hand} , if it exceeds 500 g / m ² , the thickness is increased in order to obtain sufficient reflection performance, the productivity is poor, and molding is difficult. Preferably it is 150-400 g / m < ² >, More preferably, it is 200-350 g / m < ² >. If the density is less than 0.3 g / cm ³ , the strength is not sufficient, and it is difficult to form a structure having a large number of minute holes, so that a high reflectance cannot be obtained. ^{On the other hand} , if it exceeds 0.75 g / cm ³ , it is difficult to produce a structure having a large number of minute holes, so that a high reflectance cannot be obtained. Preferably 0.35~0.70g / cm ^3, more preferably 0.40~0.60g / cm ^3.

Furthermore, the reflective sheet obtained by the production method of the present invention is characterized by its thermal shrinkage rate. The sheet obtained by the usual biaxial stretching method depends on the stretching method, but when stretched in the vicinity of the stretching temperature after stretching, either the machine direction (MD direction) or the transverse direction (TD direction) or the machine direction The heat shrinks greatly in both directions.
In contrast, the reflective sheet of the present invention has a thermal shrinkage rate at 150 ° C./30 minutes of 15% or less in both MD and TD directions. The shrinkage rate is preferably 12% or less, and more preferably 10% or less.
The present inventors suppress the heat shrinkage rate in both directions of the sheet to the specified value or less, thereby allowing the reflectance of the reflective sheet to be compared with a reflective sheet having the same basis weight and density obtained by a normal method. And 0.5 to 5% higher. In the technical field of reflective sheets, this degree of improvement in reflectivity is a very significant characteristic difference in practice.

  Moreover, the sheet | seat obtained with the manufacturing method of this invention has the characteristic that it is excellent in thermal dimensional stability. For example, in the direct type backlight system, the reflection sheet is used by being disposed directly under a light source lamp composed of a plurality of cold cathode ray tubes. In this case, heat from the light source is applied to the reflection sheet. Usually, a polypropylene-based biaxially stretched sheet depends on the type of the sheet, but if it exceeds 100 ° C., there is a risk of causing a dimensional change. Therefore, a reflective sheet with little dimensional change even at high temperatures is desired, and the characteristic that the sheet obtained by the production method of the present invention has excellent thermal dimensional stability is preferable as the characteristic of the reflective sheet.

Furthermore, the sheet | seat obtained with the manufacturing method of this invention has the characteristic that it is excellent in heat formability.
In the direct type backlight system, a cold cathode ray tube is currently used as a backlight light source, but there is a prediction that it will be replaced with a light emitting diode (LED) system in the near future. In this case, in order to further improve the reflection efficiency, it is said that a reflective sheet having a formability that can be formed into a concave shape according to the shape of a large number of LEDs arranged like a grid is desirable. The concave molding is usually performed by compression molding or vacuum molding after heating the sheet to a temperature higher than the heat deformation temperature. However, when a polypropylene biaxially stretched sheet is heated to a temperature equal to or higher than the heat distortion temperature, it usually has a large heat shrinkage and is difficult to be molded into a desired shape.
On the other hand, the sheet obtained by the production method of the present invention has a small thermal shrinkage due to reheating due to the effect of thermal dimensional stability developed by performing a relaxation heat treatment near the heat distortion temperature. It can meet the demand for formability.

(Molding method)
In the present invention, the raw material resin composition melt-mixed by an extruder is preferably extruded into a sheet form from a die attached to the tip of the extruder. In order to stabilize the amount of the extruded resin composition, A gear pump may be used between them. In the present invention, a sheet forming die such as a T die or a fish tail die is used. The die may be a single-layer die or a laminated die. When a laminated die is used, the ratio of the hole forming material (B) incompatible with the polypropylene resin (A) and the polypropylene resin may be changed between the center layer and the surface layer. The addition ratio of polystyrene resin can be changed.
For example, by increasing the ratio of the hole forming material (B) in the center layer and decreasing the ratio of the hole forming material (B) in the surface layer, it is easy to obtain a sheet with high sheet reflectivity that is easy to stretch. Become. Also, by adding a polystyrene resin to the surface layer, it is possible to easily obtain a sheet having good stretchability and high reflectance.
When resin is used as the hole forming material, by appropriately adjusting the temperature of the die, the resin (B) is expanded in the flow direction inside the sheet extruded from the die, and the resin (B ) Can be made to have a sea-island structure dispersed with elongated islands.

(Biaxial stretching method)
In the present invention, preferably, the sheet extruded from the die is cooled and solidified by a cooling roller or the like, and then stretched by a stretching machine. In the stretching step, it is preferable to perform stretching at as low a temperature as possible in order to generate holes in the sheet. When stretching is performed at a high temperature, it tends to be less likely to generate pores inside the sheet than when stretching at a low temperature. Therefore, it is preferable to make the stretching ratio larger than when stretching at a low temperature.
In the present invention, it is preferable to set the operating conditions of the extruder and die so that the temperature of the extruded resin is in the range of 200 ° C to 300 ° C, and the extruded resin is cooled to be in the range of 20 ° C to 150 ° C. It is preferable to set the temperature and speed of the roller. By stretching the sheet, the interface between the polypropylene resin (A) and the hole forming material (B) inside the sheet is cleaved to generate holes in the sheet, and at the same time, the sheet thickness is reduced to a desired thickness. Can do.

In the present invention, a normal biaxial stretching method can be adopted. That is, longitudinal / horizontal sequential biaxial stretching, lateral / longitudinal sequential biaxial stretching, simultaneous biaxial stretching, and after these biaxial stretching, re-stretching can be performed in either or both of the longitudinal and lateral directions. Preferably, it is the most versatile longitudinal and transverse sequential biaxial stretching.
Stretching includes a longitudinal stretching process in which a sheet is passed between a plurality of rollers with different speeds and the sheet is stretched in the flow direction, and a transverse stretching process in which the sheet is stretched in the width direction of the sheet using a clip tenter or the like. Or it can carry out in combination. Alternatively, the flow direction and the width direction can be simultaneously stretched using a simultaneous biaxial stretching machine such as a pantograph stretching machine.
The stretching ratio of the biaxial stretching is 1.5 times or more in each of the MD direction and the TD direction, and the area stretching ratio is from 3 times to 50 times. Preferably, MD and TD are each 2 times or more and the area magnification is 4 times or more and 30 times or less.

(Method of relaxation heat treatment)
In the present invention, the molded composition sheet is biaxially stretched to form holes, and then heat shrinkage of 10% or more in both the longitudinal direction and the transverse direction, or in either the longitudinal direction or the transverse direction. Do. The heat shrinkage is preferably 15% or more, and more preferably 20% or more.
In order to cause the sheet after biaxial stretching to undergo the above heat shrinkage, for example, a relaxation heat treatment method as shown in the following (1) to (4) may be performed.

(1) Heat shrink in an oven at an appropriate temperature without constraining the edge of the sheet. The temperature at this time is 130-170 degreeC. The temperature and time in this case are set according to the type of resin composition, composition ratio, and molding conditions (particularly stretching conditions). The effect is small when the processing temperature is low. On the other hand, if the treatment temperature is too high, the polypropylene resin is greatly shrunk or softened and melted, so that the reflectance is lowered. Therefore, it is preferably 140 to 160 ° C., more preferably 145 to 155 ° C., and the treatment time varies depending on the treatment temperature, but is 5 sec to 1 hr. If the treatment time is short, the effect is small, and if it is too long, the reflectance is lowered or industrially disadvantageous, and preferably 10 sec to 10 min.
(2) The sheet end portion is constrained and contracted while being constrained under specific conditions until an appropriate contraction ratio is obtained. This method is preferable in that a uniform product can be obtained due to the flatness of the sheet after the heat treatment. The conditions are the same as in (1) above. In this case, the restraining direction of the sheet may be only the vertical direction, only the horizontal direction, or both vertical and horizontal. In the restraint in the longitudinal direction, using a roll longitudinal stretching machine composed of a low speed roll and a high speed roll, the high speed roll can be made slower than the low speed roll, contrary to stretching. Further, in the restraint in the lateral direction, a tenter transverse stretching machine can be used to shrink between the tenter clips as the tenter travels. Furthermore, in both vertical and horizontal restraints, the tenter type simultaneous biaxial stretching machine can be used to simultaneously shrink the vertical and horizontal directions as the tenter runs.
The relaxation heat treatment may be performed after biaxial stretching and once cooled to a certain temperature, or may be continuously performed without cooling. The cooling temperature in the case of cooling is not particularly limited, but it is effective to select it within the range of room temperature to the crystallization temperature of PP. As a method of continuously performing as it is without cooling, it is possible to shrink between the tenter clips together with the tenter running using a heat treatment zone after the transverse stretching using a tenter transverse stretching machine.
(3) In combination with the biaxial stretching method, the transverse constraint relaxation heat treatment is continuously performed in the same tenter after the longitudinal and transverse sequential biaxial stretching. This method is a preferred method. When cooling before the relaxation heat treatment, a cooling zone can be provided in the tenter between the stretching zone and the relaxation heat treatment zone.
(4) Biaxial stretching is a longitudinal and lateral sequential biaxial stretching method, and the relationship between the MD and TD stretch ratios is MD ≦ TD, and after transverse stretching, the transverse stretching ratio at a temperature near the transverse stretching temperature. A relaxation heat treatment is performed in which the thermal shrinkage is 10% or more, preferably 15% or more, more preferably 20% or more in the transverse direction. For example, after stretching 3 times in the vertical direction and 4 to 5 times in the horizontal direction, a relaxation heat treatment of 10% or more is performed in the horizontal direction.

<Evaluation method>
First, the physical property items to be evaluated for the reflective sheet and the evaluation method will be described.
(1) Thickness The thickness of the reflective sheet was measured using a thickness meter manufactured by Peacock.
(2) Total light reflectivity / average total reflectivity The total light reflectivity of the reflective sheet was determined by using a spectrophotometer UV-3150 manufactured by Shimadzu Corporation and an integrating sphere sample stand. The relative reflectance with the reflectance of (Spectralon) made as 100% was measured in the wavelength range of 400 nm to 700 nm. The average total reflectivity was measured for light having a wavelength of 550 nm when incident from each of the MD direction and TD direction of the sheet, and the average value of both was taken as the average total reflectivity.
(3) Basis weight A sheet was cut into a 50 mm square and determined by measuring its weight.
(4) Density A sheet was cut into a 50 mm square, and the average value of the weight, the central part, and the thickness of a total of five points of each side was obtained, and the density was calculated.
(5) Thermal contraction rate The sheet was cut into a 150 mm square, placed in a heating oven, heated under predetermined conditions, taken out, and determined from dimensional changes before and after heating.

[Example 1]
A raw material resin obtained by mixing 62% by volume (55% by weight) of polypropylene resin (Prime Polymer Co., Ltd. E-105GM) and 38% by volume (45% by weight) of polycarbonate resin (Asahi Kasei Co., Ltd. Wanderlight PC110) has a cylinder diameter of 25 mm. Using a co-rotating twin screw extruder with a cylinder-to-bore ratio of 48, melted under the operating conditions of a cylinder temperature of 250 ° C. and a screw rotation speed of 100 rpm, and through a gear pump adjusted to a temperature of 250 ° C. The sheet was extruded from a sheet die having a lip width of 400 mm and a clearance of 1.7 m. The extruded molten resin was taken up by a pair of pinch rollers set at 80 ° C., and the resin was cooled and solidified while pulling the molten resin in the extrusion direction to prepare a sheet having a thickness of 1.5 mm.
The obtained sheet was stretched 3 times in the extrusion direction (longitudinal direction) at a temperature of 155 ° C. using a roll longitudinal stretching machine, and then 4 times in the width direction (transverse direction) at a temperature of 155 ° C. using tenter transverse stretching. Stretched to obtain a white sheet. When the total reflectance of this white sheet was measured, the average total reflectance of light having a wavelength of 550 nm was 96.5%. The basis weight and density of this sheet are 220 g / m ² and 0.48 g / cm ³ , respectively, the thickness is 460 μm, the thermal shrinkage at 150 ° C./30 minutes is 8% in the MD direction, and 28 in the TD direction. %Met.
This white sheet is cut into A4 size, each end is not constrained, and it is placed in an oven set at 5 ° C. intervals as shown in Table 1 for 10 minutes in a temperature range of 130 ° C. to 170 ° C. for relaxation heat treatment. It was. The heat treatment time at 165 ° C. was 3 minutes. For each sheet, the contraction rate contracted by this relaxation heat treatment, the total reflectance of light having a wavelength of 550 nm of the reflection sheet obtained by this heat treatment (average value of MD direction incidence and TD direction incidence: average total reflectance), basis weight The amount, density, and thermal shrinkage in each direction of MD and TD at 150 ° C./30 minutes were measured, and the results are shown in Table 1. It can be seen that the reflectance of the sheet of the present invention obtained by performing the relaxation heat treatment is improved by 0.6 to 2.3% as compared with that before the heat treatment.

[Comparative Example 1]
In Example 1, the tenter transverse stretch ratio was increased to 3 times, and the film was stretched in the transverse direction. Then, a 5% normal relaxation heat treatment was subsequently performed in the width direction to obtain a biaxially stretched white sheet. The average total reflectance of the white sheet was 96.8%. The basis weight and density of this sheet are 260 g / m ² and 0.53 g / cm ³ , respectively, the thickness is 490 μm, the thermal shrinkage at 150 ° C./30 minutes is 10% in the MD direction, and 22 in the TD direction. %Met. It can be seen that even if the sheet has a basis weight and density substantially equal to those in Example 1, the reflectance is 2% lower if the thermal shrinkage at 150 ° C./30 minutes is outside the range of the present invention.

[Example 2]
In Example 1, after stretching by 4 times with a tenter transverse stretching machine, in the heat treatment zone in the rear part of the tenter, the interval between the clips was set so that the tenter exit rate was tripled, that is, contracted by 25% in the lateral direction. The film was set so as to be subjected to relaxation heat treatment and then stretched laterally. The stretching temperature and heat treatment temperature were both 155 ° C. The average total reflectance at a wavelength of 550 nm of the obtained sheet was 99.0%. Moreover, the basis weight and density of this sheet are 250 g / m ² and 0.50 g / cm ³ , respectively, the thickness is 500 μm, and the thermal shrinkage rate at 150 ° C./30 minutes is 10.5% in the MD direction, TD direction. It was 7%.

[Example 3]
In Example 2, the tenter transverse stretch was set to 5 times, and similarly, in the heat treatment zone in the rear part of the tenter, the space between the clips was set so that the tenter exit doubled was 4 times, that is, contracted by 20% in the transverse direction. The film was set so as to be subjected to relaxation heat treatment and then stretched laterally. The stretching temperature and heat treatment temperature were both 155 ° C. The average total reflectance of the obtained sheet at a wavelength of 550 nm was 98.8%. The basis weight and density of this sheet are 225 g / m ² and 0.48 g / cm ³ , respectively, the thickness is 470 μm, the thermal shrinkage at 150 ° C./30 minutes is 9% in the MD direction, and 10 in the TD direction. %Met. It can be seen that the reflectance is improved by 2.3% with respect to the sheet before relaxation heat treatment of Example 1 having the same basis weight and density.

[Example 4]
A raw material resin in which 77% by volume (40% by weight) of polypropylene resin (Prime Polymer Co., Ltd. E-105GM) and 23% by volume (60% by weight) of barium sulfate having an average particle diameter of 0.8 μm were mixed was used as a cylinder with a cylinder diameter of 25 mm. Using a co-rotating twin screw extruder with a caliber ratio of 48, the temperature of the lip was adjusted through a gear pump that was melted under the operating conditions of a cylinder temperature of 250 ° C. and a screw speed of 100 rpm and the temperature adjusted to 250 ° C. The sheet was extruded from a sheet die having a width of 400 mm and a clearance of 1.7 m. The extruded molten resin was taken up by a pair of pinch rollers set at 80 ° C., and the resin was cooled and solidified while pulling the molten resin in the extrusion direction to prepare a sheet having a thickness of 1.5 mm.
After the obtained sheet was stretched 4.5 times in the extrusion direction (longitudinal direction) and 4.5 times in the width direction (transverse direction) at a temperature of 155 ° C. using a batch type biaxial stretching machine, Subsequently, the magnification in each direction was shrunk to 3.5 times, and relaxation heat treatment was performed at the same temperature to finally obtain a white sheet stretched by 3.5 × 3.5 times. This white sheet has an average total reflectance of 98.3% of light having a wavelength of 550 nm, a basis weight of 445 g / m ² and a density of 1.32 g / cm ³ , a thickness of 340 μm, and 150 ° C./30 minutes. The thermal shrinkage rates in the MD and TD directions were 12% and 11%, respectively. It can be seen that the reflectance of the sheet of the present invention subjected to the relaxation heat treatment is improved by 1.5%.

[Comparative Example 2]
Using the batch type biaxial stretching machine, the extruded sheet obtained in Example 4 was 3.5 times in the extrusion direction (longitudinal direction) and 3.5 times in the width direction (transverse direction) at a temperature of 155 ° C. The film was stretched in the transverse direction and then subjected to a relaxation heat treatment that is normally carried out by 5% in the width direction in the tenter to obtain a white sheet. When the total reflectance of this white sheet was measured, the average total reflectance of light having a wavelength of 550 nm was 96.8%. The basis weight and density of this sheet are 440 g / m ² and 1.35 g / cm ³ , respectively, the thickness is 325 μm, the thermal shrinkage at 150 ° C./30 minutes is 35% in the MD direction, and 32 in the TD direction. %Met.

[Example 5]
The sheets obtained in Example 2 and Comparative Example 1 were cut into 200 mm squares and set on a vacuum forming mold having nine recesses shown in FIG. The mold is provided with a suction port in the lower part of the mold for vacuum forming, and the aa ′ section and the bb ′ section are the same. After setting the sheet on the mold for 12 seconds, it was transferred to an oven at 150 ° C., and after 10 seconds, the vacuum valve was opened to perform vacuum forming. After 15 seconds, the mold was taken out from the oven, the molded product was quenched with an air gun, and then the molded product was taken out from the mold. From the sheet of Example 2, a uniform molded product almost in the shape of the mold was obtained. On the other hand, in the sheet of Comparative Example 1, since the shrinkage in the horizontal direction was large, wrinkles were partially generated and obvious deformation due to the shrinkage in the horizontal direction was observed, and a uniform molded product could not be obtained.

  Since the reflective sheet obtained by the production method of the present invention exhibits high reflectance, it can be suitably used as a backlight of a liquid crystal display device.

It is a figure which shows the shape and structure of the reflective sheet molded product of this invention produced in Example 5. FIG.

Claims (10)

  Biaxially stretching a composition sheet containing 50% by volume or more and less than 90% by volume of the polypropylene resin (A) and 10% by volume or more and less than 50% by volume of the pore forming material (B) incompatible with the polypropylene resin. A method for producing a reflective sheet, wherein after forming the holes, heat shrinkage of 10% or more is performed in both the longitudinal direction and the transverse direction, or in either the longitudinal direction or the transverse direction.   The method for producing a reflective sheet according to claim 1, wherein after the formation of the holes, thermal shrinkage of 20% or more is performed in both the vertical direction and the horizontal direction, or in either the vertical direction or the horizontal direction. .   The method for producing a reflective sheet according to claim 1, wherein the hole forming material (B) is an inorganic material.   The method for producing a reflective sheet according to any one of claims 1 to 3, comprising at least one selected from the group consisting of calcium carbonate, barium sulfate and titanium dioxide as the hole forming material (B).   The reflection material according to claim 1 or 2, wherein the pore-forming material (B) is a resin, and the elastic modulus of the resin is higher than that of the polypropylene resin (A) at a temperature at which the polypropylene resin (A) can be stretched. Sheet manufacturing method.   The method for producing a reflective sheet according to claim 1, wherein a polycarbonate resin is included as a resin incompatible with the polypropylene resin.   The stretching ratio of biaxial stretching is 1.5 times or more in each of the MD direction and the TD direction, and the area stretching ratio is from 3 times to 50 times. Manufacturing method of the reflective sheet.   The method for producing a reflective sheet according to claim 7, wherein the stretching ratio of biaxial stretching is 2 times or more in each of the MD direction and the TD direction, and the area stretching ratio is from 4 times to 30 times.   Biaxial stretching is a longitudinal and transverse sequential biaxial stretching method, and the relationship between MD and TD stretching ratios is MD ≦ TD. After transverse stretching, the transverse stretching ratio is 10 in the transverse direction at a temperature near the transverse stretching temperature. The manufacturing method of the reflective sheet in any one of Claims 1-8 characterized by performing the relaxation heat processing which performs heat shrink of more than%.   The method for producing a reflective sheet according to claim 9, wherein after the transverse stretching, a relaxation heat treatment is performed to perform thermal shrinkage of 20% or more in the transverse direction with respect to the transverse stretching ratio at a temperature in the vicinity of the transverse stretching temperature.

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