JP2019014046A - Acrylic resin film, production method of acrylic resin film, coating method, production method of laminate and laminate - Google Patents

Abstract

To provide an acrylic resin film having a controlled surface property, a production method of the acrylic resin film, a coating method for the acrylic resin film, a production method for a laminate comprising the acrylic resin film, and a laminate comprising the acrylic resin film.SOLUTION: An acrylic resin film 10 has controlled surface properties with respect to fine structure, surface roughness and the like of a surface of the film 10 caused by rubber elastic particles 12. For example, a surface of the film 10 has an average Rd of a controlled depth of a recess 10c from a reference plane X and an average Rh of a controlled height from the reference plane X of a projection 10d.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an acrylic resin film obtained from an acrylic resin composition in which rubber elastic particles are blended with an acrylic resin, a method for producing an acrylic resin film, a coating method, a method for producing a laminate, and a laminate. About.

  Acrylic resin films have excellent transparency and moisture permeability, and have been used in a wide range of fields in recent years, such as the optical film field and the decorative film field. On the other hand, an acrylic resin film mainly composed of an acrylic resin has drawbacks such as low strength and toughness, and poor film moldability and transportability.

  In order to eliminate such drawbacks, an acrylic resin film is manufactured using an acrylic resin composition containing fine particles such as rubber elastic particles (see Patent Document 1). In this case, strength and toughness are imparted to the acrylic resin while maintaining the excellent physical properties unique to the acrylic resin, and film moldability and transportability are improved.

  As a method for producing an acrylic resin film from such an acrylic resin composition containing fine particles such as rubber elastic particles, in addition to the solvent casting method, it is melt-extruded in that it is excellent in productivity, work environment, etc. The method is preferably used.

International Publication No. 2012/060082

  However, in acrylic resin films containing rubber elastic particles as fine particles, depending on the manufacturing conditions, characteristics such as film transparency may deteriorate, or film sticking may occur in the form of a film roll, resulting in unevenness on the film surface. A sticking defect may occur. Further, when a coating layer is provided by applying a coating liquid on the film surface, it may be difficult to form a coating layer free from voids or streaks, or it may be difficult to form a laminate having good visibility.

In order to solve the above-mentioned problems, the present inventors have intensively studied, and when producing an acrylic resin film containing rubber elastic particles as fine particles, fine particles on the film surface caused by the rubber elastic particles are produced. The inventors have found that the above problems can be solved by controlling the surface properties such as a simple structure and surface roughness, and have completed the present invention.
The present invention provides an acrylic resin film in which the above-described problems are solved, a method for producing the acrylic resin film, a method for coating the acrylic resin film, and a laminate including the acrylic resin film. It aims at providing the method and the laminated body containing the said acrylic resin film.

  The present inventors have made extensive studies to solve the above problems. As a result, in the acrylic resin film, the acrylic resin film in which the above problems are solved by controlling the surface properties such as the fine structure and surface roughness on the film surface caused by the rubber elastic particles. As a result, the present invention was completed.

  According to the present invention, the acrylic resin film in which the above-mentioned problems are solved by controlling the surface properties of the film surface, the method for producing the acrylic resin film, and the coating method on the acrylic resin film And the manufacturing method of the laminated body containing the said acrylic resin film, and the laminated body containing the said acrylic resin film can be provided.

It is a side view which shows typically the structure of an acrylic resin film. It is sectional drawing which shows the structure of an acrylic resin film typically. It is a top view which shows typically the structure of an acrylic resin film. It is a partial expanded sectional view which shows typically the structure of an acrylic resin film provided with a hard-coat layer. It is a figure which shows typically a part of structure of the manufacturing apparatus of an acrylic resin film. It is a figure which illustrates typically the uneven | corrugated state of the film-form melt surface immediately after melt extrusion. It is a figure which illustrates typically the behavior of formation of the unevenness in the film-like melt taken up with glass transition temperature Tg at the time of film formation. It is a figure which illustrates typically the behavior of formation of unevenness in the film-like melt taken up at Tg + 140 ° C at the time of film formation. It is a figure which illustrates typically the behavior of formation of the unevenness in the film-like melt taken up at Tg + 180 ° C at the time of film formation. It is a side view which shows typically the structure of the laminated body which consists of the single-sided smooth film which has a rough surface and a smooth surface, and the coating layer formed on the rough surface. The method for measuring the external haze H _{i 1} and H _{h 1} of the smooth surface is a diagram schematically illustrating. The method for measuring the external haze H _{i 2} and H _{h 2} of the roughened surface is a diagram schematically illustrating. It is a figure which shows typically a part of structure of the manufacturing apparatus of an acrylic resin film provided with a temperature control apparatus. It is a figure which shows typically an example of the manufacturing apparatus of an acrylic resin film. It is a figure which shows the height curve about the film cross section containing an unevenness | corrugation acquired by AFM observation of the surface of the acrylic resin film of Example 1-2. It is a figure which shows the height curve about the film cross section containing an unevenness | corrugation acquired by AFM observation of the surface of the acrylic resin film of Comparative Example 1-1. It is a figure which shows the height curve about the film cross section containing an unevenness | corrugation acquired by AFM observation of the surface of the acrylic resin film of Comparative Example 1-3. It is a figure which shows the AFM observation image of the surface of the acrylic resin film of Example 1-2.

Hereinafter, an acrylic resin film, a manufacturing method of the acrylic resin film, and the like will be described in the order of the first embodiment, the second embodiment, and the third embodiment.
Hereinafter, the acrylic resin film may be simply referred to as “film”.

<< First Embodiment >>
<Acrylic resin film>
Hereinafter, the acrylic resin film according to the first embodiment will be described in detail with reference to the drawings. FIG. 1 is a side view schematically showing the structure of a film. FIG. 2 is a cross-sectional view schematically showing the structure of the film. FIG. 3 is a top view schematically showing the structure of the film. FIG. 4 is a cross-sectional view schematically showing the structure of a film provided with a hard coat layer. 1 to 4, the rubber elastic body particles show only particles exposed from the film surface, and FIGS. 2 to 4 show only a part of the film surface.

As shown in FIGS. 1 to 3, the film 10 is made of an acrylic resin composition including an acrylic resin 11 constituting a matrix portion and rubber elastic particles 12 dispersed in the matrix portion. When the film 10 is observed from the thickness direction of the film 10, on the surface 10a and the surface 10b of the film 10, an annular concave portion 10c and a convex portion 10d positioned inside the ring formed by the concave portion 10c are observed. The The recess 10c is recessed in the thickness direction of the film 10 on the surface 10a and the surface 10b. The convex part 10d protrudes in the thickness direction of the film 10 on the surface 10a and the surface 10b.
Typically, the convex portion 10 d is mainly composed of a rubber elastic body particle 12 protruding from the surface 10 a and the surface 10 b, and the concave portion 10 c is formed in an annular shape so as to surround the rubber elastic body particle 12.
1 to 4, the rubber elastic particles 12 are illustrated as being exposed from the surface 10a and the surface 10b, but the acrylic resin 11 and the rubber elastic particles 12 have good compatibility. The protruding portion of the rubber elastic particle 12 may be covered with an extremely thin acrylic resin 11 layer. In FIG. 3, the recesses 10 c are all formed in an annular shape, but the shape of the recesses 10 c is not necessarily annular, and may be formed in a shape in which the ring is interrupted, for example, a C shape. Good. In this case, the location where the ring is interrupted is not limited to one location. As long as the shape of the concave portion 10c can be recognized as being generally annular, the ring may be interrupted at two or three locations.

  As described above, in the film 10 having the fine structure including the concave portion 10c and the convex portion 10d on the surface 10a or the surface 10b of the film 10, and the surface property is controlled, the coating layer is formed on the surface 10a or the surface 10b. When the coating liquid for coating is applied, the coating liquid easily penetrates into the recess 10c, and the coating property is good. Moreover, when forming a coat layer in the surface 10a or the surface 10b of the film 10 using a coating liquid, an anchor effect arises because a coat layer enters into the recessed part 10c. For this reason, the adhesiveness between the coat layer and the film 10 is high. As a result, for example, as shown in FIG. 4, in the laminate 13, when the coating layer 14 is formed on the film 10 using the coating liquid, the adhesion between the surface 10 a and the coating layer 14 is strong. , Air entrainment (void) and coating streaks are less likely to occur, and excellent visibility.

Hereinafter, the concave portion 10c and the convex portion 10d will be described in detail.
As shown in FIG. 2, when a surface parallel to the surface direction of the film 10 on the surface of the film 10 is used as the reference surface X, the average depth Rd of the recesses 10 c from the reference surface X (hereinafter simply referred to as “ Rd ”) is from 1.0 nm to 50 nm, preferably from 3 nm to 30 nm, more preferably from 5 nm to 20 nm. When Rd is within the above range, when the coating solution is applied to the surface 10a or the surface 10b of the film 10, the coating solution easily penetrates into the concave portion 10c, and the film 10 is excellent in coating property. In addition, when the coating liquid is applied to the surface 10a or the surface 10b of the film 10 to form a coating, and the coating layer 14 is formed from the formed coating, it is caused by the presence of the concave portion 10c and the convex portion 10d. Then, the coat layer 14 adheres well to the film 10. As a result, in the film 10 (laminated body 13) having the coating layer 14 formed using the coating liquid, air entrainment is suppressed and the occurrence of coating stripes is also suppressed, so that the visibility is excellent.

  Moreover, when the surface parallel to the surface direction of the film 10 on the surface of the film 10 is used as the reference plane X, the average height Rh (hereinafter, simply referred to as “Rh”) of the convex portion 10d from the reference plane X. Is from 0.1 nm to 100 nm, preferably from 10 nm to 90 nm, and more preferably from 20 nm to 80 nm. When Rh is within the above range, the coatability is good. As a result, in the film 10 (laminated body 13) having the coating layer 14 formed using the coating liquid, air entrainment is suppressed and the occurrence of coating stripes is also suppressed, so that the visibility is excellent.

  The haze of the film 10 is preferably less than 2%, more preferably 1.5% or less. ΔRa (hereinafter simply referred to as “ΔRa”), which is the absolute value of the difference between the arithmetic average roughness Ra of the surface 10a which is one surface of the film 10 and the surface 10b which is the other surface, is 0.01 nm or more. It is preferably less than 5.0 nm, more preferably 0.5 nm or more and less than 4.5 nm. When ΔRa is in the above range, the film 10 is less whitened and has good optical characteristics.

The average interval Sm between adjacent convex portions 10d on the surface of the film 10 is preferably 0.01 μm or more and 5 μm or less, and more preferably 0.05 μm or more and 4.5 μm or less. As shown in FIG. 3, the average interval Sm can be obtained as a number average value of the measured intervals by measuring the intervals Sm1, Sm2, Sm3,...
When the average interval Sm of the convex portions 10d is in the above range, a coating liquid is applied to the surface 10a or the surface 10b of the film 10 to form a coating, and when the coating layer 14 is formed from the formed coating, The adhesion between the film 10 and the coat layer 14 is good. As a result, in the film 10 (laminated body 13) having the coating layer 14 formed using the coating liquid, air entrainment is suppressed, the occurrence of coating stripes is also suppressed, and the visibility is excellent.

The number of convex portions 10d per surface area of 1 μm ^{2 of the} film 10 is preferably 0.1 or more and 5 or less, and more preferably 0.3 or more and 3.0 or less. As described above, when the number of the convex portions 10d is within the above range, the coating property of the film 10 is good, and the film 10 of the coating layer 14 is formed when the coating layer 14 is formed on the surface of the film 10 by coating. Good adhesion to As a result, in the film 10 (laminated body 13) having the coating layer 14 formed using the coating liquid, air entrainment is suppressed, the occurrence of coating stripes is also suppressed, and the visibility is excellent.

  Note that Rd, Rh, ΔR, and Sm of the film 10 are average values of the values measured in accordance with JIS B 0601-1994 with respect to particles existing in a visual field size of 5 μm × 5 μm by an atomic force microscope.

  In the film 10, the volume average particle diameter of the rubber elastic body particles 12 is preferably 100 nm or more and 300 nm or less, and more preferably 120 nm or more and 280 nm or less from the viewpoint of the above-described coating properties and visibility.

  The thickness of the acrylic resin film is preferably 5 μm or more and 300 μm or less, and more preferably 20 μm or more and 280 μm or less from the viewpoint of the above-described coating properties and visibility.

Here, in the film 10, it is preferable that the coat layer 14 is formed on the surface 10 a and / or the surface 10 b, but it is generally sufficient that the coat layer 14 is formed on one surface of the film 10.
The film 10 may have the recessed part 10c and the convex part 10d which satisfy | fill the conditions mentioned above in both the surface 10a and the surface 10b. However, for the above reason, for example, when the coating layer 14 is formed only on one surface 10a, only one surface 10a may have the concave portion 10c and the convex portion 10d that satisfy the above-described conditions. .

<Method for producing acrylic resin film>
FIG. 5 is a diagram schematically showing a part of the configuration of an acrylic resin film manufacturing apparatus.
As shown in FIG. 5, the acrylic resin film manufacturing method according to the first embodiment is obtained by extruding an acrylic resin composition containing an acrylic resin and rubber elastic body particles from a die 5 to form a film-like melt. And melt extrusion to 10 ′, and sandwich molding in which the film-like melt 10 ′ is sandwiched between the cast roll 6 and the touch roll 7 to form a film. In melt extrusion, when the glass transition temperature of the acrylic resin composition is Tg, the temperature of the acrylic resin composition at the exit of the die 5 is Tg + 130 ° C. or higher and Tg + 150 ° C. or lower. In the sandwich molding, the line speed, which is the speed in the flow direction of the film-like melt 10 ', is preferably 5 m / min to 50 m / min, more preferably 10 m / min to 30 m / min, and more preferably 13 m / min. 18 m / min or less is more preferable.

  The glass transition temperature Tg of the acrylic resin composition is calculated by the following measuring method. Using a differential scanning calorimeter (DSC) SSC-5200 manufactured by Seiko Instruments Inc., the sample (acrylic resin composition) was once heated up to 200 ° C. at a rate of 25 ° C./min, then held for 10 minutes, and 25 ° C. / Through preliminary adjustment to lower the temperature to 50 ° C. at a rate of minutes, measure while heating up to 200 ° C. at a rate of temperature increase of 10 ° C./min, and determine the integral value from the obtained DSC curve (DDSC), The glass transition temperature is obtained from the maximum point.

  Thus, by setting the temperature of the acrylic resin composition at the exit of the die 5 and the line speed at the time of sandwich molding to the above range, the Rd and Rh of the film 10 can be easily controlled to the above range. This is because the elastic modulus is different between the acrylic resin and the rubber elastic particles as described later. The line speed is preferably higher in consideration of productivity. However, from the viewpoints of control of Rd and Rh of the film 10 described above, various physical properties (haze and phase difference), risk of breakage, and performance base, 13 m / min. It is preferably 18 m / min or less.

If the temperature of the acrylic resin composition at the outlet of the die 5 is too low, Rd tends to be excessive and Rh tends to be excessively small. In this case, ΔRa tends to increase.
If the temperature of the acrylic resin composition at the outlet of the die 5 is too high, Rd tends to be too small and Rh tends to be too large. Also in this case, ΔRa tends to increase.

  If the line speed of the film-like melt 10 'is too slow, Rd tends to be excessive and Rh tends to be excessive. On the other hand, if the line speed of the film-like melt 10 ′ is too high, Rd becomes excessive, the concave portions 10 c and the convex portions 10 d that excessively increase Rh are likely to be formed, and ΔRa tends to increase.

  The temperature of the acrylic resin composition may be adjusted by the heating temperature at the die 5 and can also be adjusted by the discharge amount at the outlet of the die 5 and the lip clearance.

  Hereinafter, the behavior in which the concave portion 10c or the convex portion 10d is formed in the film-like melt 10 'will be described with reference to FIGS. 6-9, only the part close | similar to the surface of film-like melt 10 'is shown in figure, and only the rubber elastic body particle | grains 12 close to the surface of film-like melt 10' are shown in figure. Further, in FIGS. 7 to 9, the force F <b> 2 and the force F <b> 3 indicated by thin arrows in the drawings are shown only toward some rubber elastic body particles 12. In addition, it cannot be overemphasized that the force similar to force F2 and force F3 is applied also about the other rubber elastic body particle | grains 12 in which the thin arrow is not described in FIGS.

  As shown in FIG. 6, in the film-like melt 10 ′ immediately after melt extrusion, the rubber elastic body particles 12 are present in a state surrounded by the acrylic resin 11. For this reason, the rubber elastic body particles 12 slightly protrude in the state covered with the acrylic resin 11 on the surface of the film-like melt 10 ′ immediately after melt extrusion.

  As shown in FIG. 7, when the melt-extruded acrylic resin composition (film-like melt 10 ′) is taken up by the cast roll 6 and the touch roll 7 at Tg, the acrylic resin 11 and the rubber elastic body Both particles 12 receive a tension F1 in the direction of the thick arrow in the figure. At this time, due to the fact that the acrylic resin 11 is hardly softened, a force F2 that causes the surface of the film-like melt 10 'to be depressed around the rubber elastic particles 12 is in the direction of the thin arrow in the figure. As a result, a large recess in which the rubber elastic particles 12 are present at the bottom is formed. As a result, the rubber elastic body particles 12 do not protrude from the plane portion that is the reference plane X, and the film 10 having an excessive Rd is formed.

  As shown in FIG. 8, when the acrylic resin composition (film-like melt 10 ′) is taken up by the cast roll 6 and the touch roll 7 at Tg + 140 ° C., it receives a tension F <b> 1 in the direction of the thick arrow in the figure. At this time, since the acrylic resin 11 is slightly softened, the force F3 for pushing up the rubber elastic body particles 12 existing at the center of the recess is shown in the figure while the formation of the recess as shown in FIG. 7 proceeds. It works in the direction of the thin arrow and protrudes from the surface 10a in a state where the rubber elastic body particles 12 are covered with a very thin layer of the acrylic resin 11 at the center of the recess. Thereby, the recessed part 10c and the convex part 10d whose Rd and Rh are each in the desired range are formed.

  On the other hand, as shown in FIG. 9, when the acrylic resin composition (film-like melt 10 ′) is taken up by the cast roll 6 and the touch roll 7 at Tg + 180 ° C., the tension F1 in the thick arrow direction in the figure is When it receives, due to the fact that the acrylic resin 11 is considerably softened, the force F3 that pushes up the rubber elastic body particles 12 works strongly in the direction of the arrow in the figure, and Rh becomes excessive.

  Thus, by controlling the temperature of the acrylic resin composition at the exit of the die 5 and the line speed at the time of sandwich molding within the above range, the protruding ratio of the rubber elastic body particles 12 exposed on the surface 10a is controlled. Rd and Rh can be controlled within the above range.

<Laminate>
Hereinafter, the laminated body using the film which concerns on 1st Embodiment is demonstrated.
As shown in FIG. 4, the laminate 13 includes a coat layer 14 on the surface 10 a of the film 10 described above in contact with the surface 10 a. According to the laminate 13, as described above, the adhesion between the surface 10 a and the coat layer 14 is high, so that there is no coating streak or air entrainment and excellent visibility.

Although it does not specifically limit as the coating layer 14, A hard-coat layer, a high refractive index layer, a low refractive index layer, an antistatic layer etc. are mentioned preferably.
The material of the coat layer 14 is not particularly limited. For example, in the case of a hard coat layer, a material obtained by coating and curing an acrylic resin, a urethane resin, a silicone resin, or the like can be appropriately used. .

  The thickness of the coat layer 14 is not particularly limited. From the viewpoint that the coatability when forming the laminate 13 is good and the visibility of the laminate 13 is good, the thickness of the coat layer 14 is preferably 1 μm or more and 10 μm or less, and more preferably 1 μm or more and 8 μm or less. It is preferably 1 μm or more and 5 μm or less.

<Method for producing laminate>
The manufacturing method of the laminated body 13 includes the coating which forms a coating film by applying a coating liquid on the surface 10a of the film 10 described above, and the formation of a coating layer which forms a coating layer from the coating film. According to the manufacturing method of this laminated body, since Rd and Rh of the surface 10a of the film 10 are controlled by the said range, it is excellent in the coating property of the film 10. FIG. In addition, according to the method for manufacturing the laminate, since the adhesion between the surface 10a and the coating layer 14 formed using the coating liquid is high, the coating can be applied even when the coating layer is formed. There is no streak or air entrainment, and a laminate 13 (film with a coat layer) excellent in visibility can be obtained.
Here, various methods can be widely applied as the method for forming the coat layer, and examples thereof include natural drying, drying by heat, thermal curing by heat, and photocuring by electromagnetic waves such as ultraviolet rays. .

<Coating method>
In the coating method, a coating solution is applied to the surface 10a or the surface 10b which is at least one surface of the film 10 described above.

  According to this coating method, for example, since Rd and Rh of the surface 10a of the film 10 are controlled within the above range, the coating property is excellent as described above. Moreover, since it is excellent in the adhesiveness of the surface 10a and a coating liquid, even when the coating layer 14 is formed using a coating liquid, there is no coating streak and air entrainment, and the laminated body 13 is visible. Excellent.

Here, various coating methods can be widely applied to the coating liquid coating, for example, slot die coating method, roll coating method, bar coating method, spin coating method, blade coating method and the like. .
The coating liquid may be a coating liquid for forming the coat layer 14 on the surface of the film 10 like a coating liquid for forming a hard coat layer. For example, a hydrophilic agent or a water repellent agent may be used. Thus, the coating liquid which does not form a coating layer on the surface of the film 10 may be sufficient as a result of coating.

According to the first embodiment of the present invention described above,
(1-1) An acrylic resin film comprising an acrylic resin composition containing an acrylic resin and rubber elastic particles,
When the acrylic resin film is observed from the thickness direction of the acrylic resin film, on the surface of the acrylic resin film, an annular concave portion and a convex portion located inside the ring formed by the concave portion are observed,
The recess is recessed in the thickness direction of the acrylic resin film on the surface,
The protrusion protrudes in the thickness direction of the acrylic resin film on the surface,
When a surface parallel to the surface direction of the acrylic resin film on the surface is used as a reference surface, the average depth Rd from the reference surface of the recess is 1.0 nm or more and 50 nm or less, and from the reference surface of the protrusion An acrylic resin film having an average height Rh of 0.1 nm or more and 100 nm or less,
(1-2) haze is less than 2%,
The acrylic resin film according to (1-1), wherein ΔRa, which is an absolute value of a difference in arithmetic average roughness Ra between one surface and the other surface of the acrylic resin film, is 0.01 nm or more and less than 5.0 nm,
(1-3) The acrylic resin film according to (1-1) or (1-2), wherein an average interval Sm between adjacent convex portions is 0.01 μm or more and 5 μm or less.
(1-4) The acrylic resin film according to any one of (1-1) to (1-3), wherein the number of convex portions per surface area of 1 μm ^{2 of the} film is 0.1 or more and 5 or less. ,
(1-5) The volume average particle diameter of the rubber elastic particles is 100 nm or more and 300 nm or less,
The acrylic resin composition includes 5% by mass or more and 20% by mass or less of rubber elastic particles with respect to the mass of the acrylic resin,
The acrylic resin film according to any one of (1-1) to (1-4), wherein the acrylic resin film has a thickness of 5 μm or more and 300 μm or less,
(1-6) A method for producing an acrylic resin film using an acrylic resin composition comprising an acrylic resin and rubber elastic particles,
Melt extrusion to extrude an acrylic resin composition from a die to form a film-like melt;
Sandwiching a film-like melt into a film sandwiched between a cast roll and a touch roll, and
In melt extrusion, when the glass transition temperature of the acrylic resin composition is Tg, the temperature of the acrylic resin composition at the exit of the die is Tg + 130 ° C. or higher and Tg + 150 ° C. or lower,
In the sandwich molding, a method for producing an acrylic resin film, wherein the line speed, which is the speed in the flow direction of the film-like melt, is 13 m / min or more and 18 m / min or less,
(1-7) A coating method for coating a coating liquid on at least one surface of the acrylic resin film according to any one of (1-1) to (1-5),
(1-8) The coating method according to (1-7), wherein the coating liquid is a coating liquid for forming a hard coat layer,
(1-9) Coating that forms a film by applying a coating liquid on at least one surface of the acrylic resin film according to any one of (1-1) to (1-5);
Forming a coat layer from the coating; forming a coat layer;
A method for producing a laminate,
(1-10) The method for producing a laminate according to (1-9), wherein the coat layer is a hard coat layer,
(1-11) A laminate including a coat layer in contact with the surface on at least one surface of the acrylic resin film according to any one of (1-1) to (1-5), and
(1-12) The laminate according to (1-11), wherein the coat layer is a hard coat layer,
Is provided.

  As described above, the acrylic resin film according to the first embodiment, the method for producing the acrylic resin film, the method for coating the acrylic resin film, the method for producing a laminate including the acrylic resin film, And according to the laminate including the acrylic resin film, the surface property is controlled by the fine structure of the film surface, so that the coating property is particularly good and the coating liquid is applied to the surface. Even if the coat layer is formed, the visibility is good.

<< Second Embodiment >>
<Acrylic resin film>
The acrylic resin film according to the second embodiment is a film made of an acrylic resin composition including an acrylic resin and rubber elastic particles. When the surface with the smaller arithmetic average roughness is the first surface and the surface with the larger arithmetic average roughness is the second surface, the arithmetic average roughness Ra1 of the first surface and the second surface The sum of the arithmetic average roughness Ra2 and the absolute value of the difference between Ra1 and Ra2 are set within a predetermined range.

When winding up a film to make a product in the form of a film roll, the first surface and the second surface are in contact with each other in the film roll. As a result of the study by the present inventors, the arithmetic average between both surfaces due to the sum of the protruding amount of the rubber elastic body particles on the first surface and the protruding amount of the rubber elastic body particles on the second surface It was found that when the sum of roughness is large, the first surface and the second surface are slippery and sticking defects are less likely to occur.
Furthermore, it was found that when the difference between the arithmetic average roughness of the first surface and the arithmetic average roughness of the second surface is small, it is easy to obtain a film having excellent transparency. This is probably because there are small differences in the incident state, transmitted state, scattered state, etc. of the light beam on both sides of the film.

In such a film, the sum of Ra1 and Ra2 is 6.5 nm or more and 8.9 nm or less, and preferably 6.9 nm or more and 8.5 nm or less.
In the film in which the total value of Ra1 and Ra2 is within the above range, the rubber elastic particles protrude moderately on the first surface and the second surface to such an extent that the transparency of the film is not impaired, and the film serves as a roll. Even in this case, the slipperiness between the first surface and the second surface is good. For this reason, in such a film, there are few sticking defects and transparency is favorable.

  In such a film, the value of Ra2-Ra1 is 1.0 nm or less, more preferably 0.9 nm or less, and more preferably 0.5 μm or less. If the value of Ra2-Ra1 is 1.0 nm or less, even if the sum of the protruding amount of the rubber elastic body particles on the first surface and the protruding amount of the rubber elastic body particles on the second surface is large, the transparency Can form a good film.

  The haze of such a film is 1.0% or less and preferably 0.8% or less from the viewpoint of obtaining good transparency. Here, haze is a value measured in accordance with JIS K 7105.

In such a film, the static friction coefficient between the first surface and the second surface is preferably 2.0 or less, more preferably 1.5 or less, and particularly preferably 1.2 or less. When the static friction coefficient between the 1st surface and the 2nd surface is 2.0 or less, since slip nature of film both sides is good and film sticking is suppressed in a film roll form, it is preferred.
Here, the static friction coefficient is such that the first and second surfaces of the acrylic resin film are brought into contact with each other, the load is 500 g, the contact area is 60 mm × 60 mm, the measurement speed is 2000 mm / min, the temperature is 23 ° C. ± 2 ° C., and the humidity is 50% ±. It is a coefficient of static friction measured under the condition of 5%.

  The thickness of the film is not particularly limited. As a general tendency, the thinner the acrylic resin film is, the greater the adverse effect of sticking defects on various film properties such as optical properties. However, when the film satisfies the above-mentioned predetermined requirements, even if it is an extremely thin acrylic resin film having a thickness of 30 μm to 100 μm, preferably 35 μm to 70 μm, more preferably 40 μm to 60 μm, sticking defects may occur. Remarkably suppressed.

<Method for producing acrylic resin film>
As shown in FIG. 5, the method for producing the acrylic resin film 10 according to the second embodiment includes melt extrusion and film melting by extruding the acrylic resin composition from the die 5 to form a film melt 10 ′. This includes sandwiching molding in which the object 10 ′ is sandwiched between the cast roll 6 and the touch roll 7 to be molded into the film 10. The flexibility of the surface of the cast roll 6 is lower than the flexibility of the surface of the touch roll 7, as will be described later.

And the arithmetic average roughness of the 1st surface which is the surface where the arithmetic average roughness of the film 10 is smaller is Ra1, and the arithmetic average roughness of the second surface which is the surface where the arithmetic average roughness of the film 10 is larger When Ra is Ra2, the value of the difference between Ra1 and Ra2 (Ra2-Ra1) is set to 1.0 nm or less by sandwich molding.
The film, cast roll, and touch roll in the first embodiment may be different in surface shape from the film, cast roll, and touch roll in the second embodiment, but the basic properties are the same. For convenience, description will be made with reference to the same drawings.

The cast roll 6 has a function of supporting the film-like melt 10 ′ discharged from the die 5 on the surface and cooling the film-like melt 10 ′. The cast roll 6 also has a function of forming a film 10 on the smooth film 10 by sandwiching the film-like melt 10 ′ together with the touch roll 7 while applying pressure. The surface of the cast roll 6 is usually made of a hard material such as metal.
The touch roll 7 has a function of forming a film 10 on the smooth film 10 by sandwiching the film-like melt 10 ′ together with the cast roll 6 while applying pressure. In the touch roll 7, the surface of the roll made of an elastic body such as rubber is usually covered with a metal film.

Thus, the flexibility of the surface of the cast roll 6 is often lower than the flexibility of the surface of the touch roll 7. Moreover, the time when the film-like melt 10 ′ is in contact with the cast roll 6 is often longer than the time when the film-like melt 10 ′ is in contact with the touch roll 7.
Under such conditions, when the film-like melt 10 ′ is sandwiched and formed by the cast roll 6 and the touch roll 7, the surface roughness of the cast roll 6 and the touch roll 7 is the same or close. The amount of protrusion of the rubber elastic body particles 12 on the surface in contact with the 10 cast rolls 6 tends to be smaller than the amount of protrusion of the rubber elastic body particles 12 on the surface in contact with the touch roll 7 of the film 10.
Hereinafter, the surface of the film 10 that contacts the cast roll 6 is also referred to as a “cast roll surface”. The surface of the film 10 that contacts the touch roll 7 is also referred to as “touch roll surface”.

As described above, when the difference between the arithmetic average roughness of the cast roll surface and the arithmetic average roughness of the touch roll surface is small, it is easy to obtain a film having excellent transparency.
Therefore, the difference between the arithmetic average roughness of the cast roll surface of the film 10 and the arithmetic average roughness of the touch roll surface, that is, the difference between the arithmetic average roughness of the first surface and the arithmetic average roughness of the second surface, of Ra2-Ra1 By performing sandwich molding such that the value is 1.0 nm or less, the film 10 having good transparency is formed. If the value of Ra2-Ra1 is 1.0 nm or less, even if the sum of the protruding amount of the rubber elastic body particles 12 on the cast roll surface and the protruding amount of the rubber elastic body particles 12 on the touch roll surface is large, The film 10 with good transparency can be formed. The value of Ra2-Ra1 is preferably 0.7 μm or less, and more preferably 0.5 μm or less.

A method for adjusting at least one of Ra1 and Ra2 and adjusting the value of Ra2-Ra1 within a predetermined range is not particularly limited. As a preferable example of such a method, a method of increasing or decreasing the surface roughness of the cast roll 6 and / or the touch roll 7, specifically, the arithmetic average roughness Ra or the maximum height Ry is preferable. Ra1 or Ra2 also increases or decreases according to the increase or decrease of the arithmetic average roughness Ra or the maximum height Ry of the surface of the cast roll 6. Similarly, Ra1 or Ra2 is increased or decreased according to the increase or decrease of the arithmetic average roughness Ra or the maximum height Ry of the surface of the touch roll 7.
In general, the smoother the surface of the cast roll 6 and / or touch roll 7, the easier the rubber elastic particles are embedded in the film 10 on both surfaces of the film 10 during sandwich molding.

Moreover, as mentioned above, when winding the film 10 and making it into the product of a film roll form, in a film roll, a cast roll surface and a touch roll surface contact.
When the sum of arithmetic average roughness is large between the cast roll surface and the touch roll surface of the film 10, the cast roll surface and the touch roll surface are slippery, and sticking defects are less likely to occur.
Therefore, Ra1 and Ra2, which is the sum of the arithmetic average roughness of the cast roll surface of the film 10 and the arithmetic average roughness of the touch roll surface, that is, the sum of the arithmetic average roughness of the first surface and the arithmetic average roughness of the second surface, It is preferable to perform sandwich molding so that the sum of the above is 6.5 nm or more and 8.9 nm or less. The total of Ra1 and Ra2 is more preferably 6.9 nm or more and 8.5 nm or less.
When the total value of Ra1 and Ra2 is within the above range, the rubber elastic body particles 12 are appropriately projected on the cast roll surface and the touch roll surface so as not to impair the transparency of the acrylic resin film. Even when the resin film is used as a roll, the slipperiness between the cast roll surface and the touch roll surface is good. For this reason, an acrylic resin film with few sticking defects and excellent transparency can be produced.

  The total value of Ra1 and Ra2 can be prepared by adjusting at least one of Ra1 and Ra2, similarly to the value of Ra2-Ra1.

  Here, arithmetic average roughness Ra2 and Ra1 of the film 10 are measured based on JIS B 0601-1994 by an atomic force microscope. The maximum height Ry and the arithmetic average roughness Ra of the surface of the cast roll 6 or the touch roll 7 are measured based on JIS B 0601-1994 by a surface roughness measuring machine.

  In order to set the value of Ra2-Ra1 to 1.0 nm or less, the maximum height Ry of the surface of the cast roll 6 is preferably 0.15 μm or more and 0.40 μm or less, and preferably 0.16 μm or more and 0.30 μm or less. More preferably, it is 0.16 μm or more and 0.26 μm or less.

  Moreover, in order to make the value of Ra2-Ra1 1.0 nm or less, the arithmetic average roughness Ra of the surface of the cast roll 6 is preferably 0.015 μm or more and 0.040 μm or less, and 0.018 μm or more and 0.035 μm or less. Is more preferable, and 0.020 μm or more and 0.030 μm or less is particularly preferable.

  In order to set the value of Ra2-Ra1 to 1.0 nm or less, the maximum height Ry of the surface of the touch roll 7 is preferably 0.10 μm or less, more preferably 0.02 μm or more and 0.08 μm or less. Particularly preferred is 0.04 μm or more and 0.06 μm or less.

  Moreover, in order to make the above-mentioned Ra2-Ra1 value 1.0 nm or less, the arithmetic average roughness Ra of the surface of the touch roll 7 is preferably 0.010 μm or less, more preferably 0.003 μm or more and 0.009 μm or less. It is preferably 0.005 μm or more and 0.008 μm or less.

The surface temperature of the cast roll 6 and the touch roll 7 is preferably Tg−70 ° C. or higher and Tg or lower, more preferably Tg−60 ° C. or higher and Tg−10 ° C. or lower, with the glass transition temperature of the acrylic resin composition as Tg. -50 degreeC or more and Tg-20 degrees C or less are especially preferable.
When the surface temperature of the cast roll 6 and the touch roll 7 is Tg or less, the film-like melt 10 ′ is sandwiched between the cast roll 6 and the touch roll 7 and at the same time, is solidified well. As a result, it is easy to control the surface roughness of the film 10 within a preferable range.
On the other hand, when the surface temperature of the cast roll 6 and the touch roll 7 is Tg−70 ° C. or higher, the film 10 adheres to the cast roll 6 when the film 10 is conveyed from the cast roll 6 to the downstream cooling roll. It is also preferable from the viewpoint of suppressing film surface defects (peeling patterns) at the time of peeling.

In the method for producing an acrylic resin film, the value of Ra2-Ra1 described above may be adjusted to 1.0 nm or less by lowering the surface temperature of the cast roll 6 below the surface temperature of the touch roll 7. As described above, the protruding amount of the rubber elastic body particles 12 on the cast roll surface of the film 10 tends to be smaller than the protruding amount of the rubber elastic body particles 12 on the touch roll surface of the film 10.
However, when the temperature of the surface of the cast roll 6 is lower than the temperature of the surface of the touch roll 7, the surface on the cast roll 6 side of the film-like melt 10 ′ becomes the touch roll in the sandwich molding of the film-like melt 10 ′. Harder than the 7 side surface. For this reason, the rubber elastic body particles 12 on the cast roll surface are not easily buried. As a result, the protruding amount of the elastic rubber particles 12 is made uniform between the cast roll surface and the touch roll surface.

Further, in the method for producing an acrylic resin film, the temperature of the surface on the cast roll 6 side of the film-like melt 10 ′ is lower than the temperature of the surface on the touch roll 7 side of the film-like melt 10 ′. You may adjust the value of Ra2-Ra1 of 1.0 nm or less.
For the same reason as when the temperature of the surface of the cast roll 6 is lower than the temperature of the surface of the touch roll 7, the amount of protrusion of the rubber elastic body particles 12 is made uniform between the cast roll surface and the touch roll surface.
The temperature of the cast roll surface of the film-like melt 10 'and the temperature of the touch roll surface can be controlled, for example, at the outlet of the die 5, by the temperature of the heating means, the cooling means, etc. You may carry out by installing the adjustment apparatuses 23 and 24. FIG.

According to the second embodiment of the present invention described above,
(2-1) A method for producing an acrylic resin film using an acrylic resin composition comprising an acrylic resin and rubber elastic particles,
Including melt extrusion to form a film-like melt by extruding an acrylic resin composition from a die, and sandwich-molding for sandwiching the film-like melt between a cast roll and a touch roll to form a film,
The flexibility of the surface of the cast roll is lower than the flexibility of the surface of the touch roll,
When the arithmetic average roughness of the surface with the smaller arithmetic average roughness of the acrylic resin film is Ra1, and the arithmetic average roughness of the surface with the larger arithmetic average roughness of the acrylic resin film is Ra2, A method for producing an acrylic resin film, wherein the value of Ra2-Ra1 is 1.0 nm or less by the sandwich molding,
(2-2) The method for producing an acrylic resin film according to (2-1), wherein the sum of Ra1 and Ra2 is 6.5 nm or more and 8.9 nm or less,
(2-3) The maximum height Ry of the surface of the cast roll is 0.15 μm or more and 0.40 μm or less, and the maximum height Ry of the surface of the touch roll is 0.10 μm or less, (2-1) or ( The manufacturing method of the acrylic resin film as described in 2-2),
(2-4) The arithmetic average roughness Ra of the surface of the cast roll is 0.020 μm or more and 0.040 μm or less, and the arithmetic average roughness Ra of the surface of the touch roll is 0.010 μm or less, (2-1) Or the manufacturing method of the acrylic resin film as described in (2-2),
(2-5) The temperature of the surface in contact with the cast roll in the film-like melt is lower than the temperature of the surface in contact with the touch roll, according to any one of (2-1) to (2-4). Manufacturing method of acrylic resin film,
(2-6) A manufacturing apparatus for manufacturing a film using an acrylic resin composition containing an acrylic resin and rubber elastic particles,
It is equipped with an extruder, a die, a cast roll, and a touch roll, and the flexibility of the surface of the cast roll is lower than the flexibility of the surface of the touch roll,
The acrylic resin film manufacturing apparatus, wherein the maximum height Ry of the surface of the cast roll is 0.15 μm or more and 0.40 μm or less, and the maximum height Ry of the surface of the touch roll is 0.10 μm or less,
(2-7) A production apparatus for producing a film using an acrylic resin composition containing an acrylic resin and rubber elastic particles,
It is equipped with an extruder, a die, a cast roll, and a touch roll, and the flexibility of the surface of the cast roll is lower than the flexibility of the surface of the touch roll,
An apparatus for producing an acrylic resin film, wherein the arithmetic average roughness Ra of the surface of the cast roll is 0.015 μm or more and 0.040 μm or less, and the arithmetic average roughness Ra of the surface of the touch roll is 0.010 μm or less,
(2-8) An acrylic resin film comprising an acrylic resin composition containing an acrylic resin and rubber elastic particles,
When the surface having the smaller arithmetic average roughness of the acrylic resin film is the first surface and the surface having the larger arithmetic average roughness is the second surface, the arithmetic average roughness Ra1 of the first surface, The sum of the arithmetic average roughness Ra2 of the two surfaces is 6.5 nm or more and 8.9 nm or less,
The value of Ra2-Ra1 is 1.0 nm or less,
An acrylic resin film having an haze of an acrylic resin film of 1.0 or less,
(2-9) The acrylic resin film according to (2-8), wherein the static friction coefficient between the first surface and the second surface is 2.0 or less,
(2-10) The acrylic resin composition contains 5% by weight or more and 20% by weight or less of rubber elastic particles with respect to the weight of the acrylic resin composition,
The volume average particle diameter of the rubber elastic particles is 80 nm or more and 450 nm or less, the acrylic resin film according to (2-8) or (2-9), and (2-11) the thickness is 100 μm or less. The acrylic resin film according to any one of (2-8) to (2-10),
Is provided.

  As described above, according to the acrylic resin film manufacturing method and the acrylic resin film according to the second embodiment, the surface properties such as the surface roughness of the film are controlled. And the suppression of sticking defects.

<< Third Embodiment >>
<Acrylic resin film>
The acrylic resin film according to the third embodiment is a film made of an acrylic resin composition including an acrylic resin and rubber elastic particles. And in a film, one surface is a smooth surface and the other surface is a rough surface. In FIG. 11, the structure of the laminated body which consists of the single-sided smooth film which has a smooth surface and a rough surface, and the coating layer formed on the rough surface is shown. Here, the smooth surface and the rough surface are not determined based on the absolute smoothness evaluation, but are determined based on a relative roughness difference between both surfaces.

As shown in FIG. 11, there are many cases where a laminate 21 is formed by laminating a coat layer such as a coat layer 22 on at least one surface of the film 20. Since the protruding rubber elastic particles 12 are embedded in the coat layer 22 on the surface on which the coat layer 22 is laminated, the transparency of the laminate 21 due to the unevenness of the surface of the film 20 based on the protrusion of the rubber elastic particles 12. The decline in sex is alleviated.
Thus, since the protrusion of the rubber elastic body particles 12 on the surface on which the coat layer 22 is laminated has little influence on the transparency of the laminate 21, the surface on which the coat layer 22 is laminated is attached in the form of a film roll. In order to suppress the occurrence of sticking defects, the amount of protrusion of the rubber elastic body particles 12 can be increased to impart lubricity to the film 20.
On the other hand, on the surface on which the coat layer 22 is not laminated, excessive protrusion of the rubber elastic body particles 12 adversely affects the transparency of the laminated body 21, so that the protrusion amount of the rubber elastic body particles 12 is preferably reduced.

Therefore, the film 20, and the external haze _{H i} 2 external haze _{H i} 1 and rough 20b of the smooth surface 20a is in the range shown below, respectively.
The external haze H _i 1 of the smooth surface 20a is not less than 0.1% and not more than 0.8%, preferably not less than 0.1% and not more than 0.6%. When the external haze H _i 1 of the smooth surface 20a is within such a range, the occurrence of sticking defects is easily suppressed, and the laminate 21 having excellent transparency can be easily obtained.
The external haze H _i 2 of the rough surface 20b is 0.6% or more and 1.5% or less, preferably 0.8% or more and 1.5% or less, more preferably more than 1.0% and 1.5% or less. . When the external haze H _i 2 of the rough surface 20b is within such a range, the occurrence of sticking defects is easily suppressed, and the laminate 21 having excellent transparency can be easily obtained.
The value of H _i 2 -H _i 1 is 0.3% or more. When the value of H _i 2 -H _i 1 is 0.3% or more, the laminate 20 is obtained by suppressing the sticking defect of the film 20 and laminating the coat layer 22 on at least the rough surface 20b of the film 20. In this case, it is easy to achieve both good transparency of the laminate 21.

Further, when the glass transition temperature of the acrylic resin composition is Tg, the external haze H _h 1 of the smooth surface 20a and the rough surface 20b measured after the film 20 was heat-treated at Tg−10 ° C. for 5 minutes. For the external haze H _h 2, the absolute value of the difference between H _h 1 and H _i 1 and the absolute value of the difference between H _h 2 and H _i 2 are both 0.2% or less.
That is, the transparency of the film 20 is not easily changed even when heated.

The film 20 is typically produced by making the surface temperatures of both surfaces of the film-like melt 20 ′ different as described above. In this case, the rubber elastic body particles 12 are buried in the surface of the film-like melt 20 ′ while the acrylic resin 11 is sufficiently softened. For this reason, in the above-described film 20, it is considered that the embedded state of the rubber elastic body particles 12 is hardly changed by the heat treatment.
On the other hand, for example, when a difference is caused in the degree of embedding of the rubber elastic body particles 12 on both surfaces of the film 20 only by making a difference between the surface temperatures of the cast roll 6 and the touch roll 7, a slightly hard acrylic Since the rubber elastic body particles 12 are forcibly buried in the resin 11, when the acrylic resin 11 is slightly softened by the heat treatment, the rubber elastic particles 12 are likely to float on the surface of the film 20 and the protrusion amount is likely to increase. It is.

Here, measurement methods of the external haze H _i 1 and H _h 1 of the smooth surface 20a and the external haze H _i 2 and H _h 2 of the rough surface 20b will be described. FIG. 11 is a diagram schematically illustrating a method for measuring the external haze H _i 1 and H _h 1 of a smooth surface. FIG. 12 is a diagram schematically illustrating a method of measuring the external haze H _i 2 and H _h 2 of the rough surface. In addition, in FIG.11 and FIG.12, a part of rubber elastic body particle | grains exposed on the film surface are shown in figure.

As shown in FIG. 11, in the film 20, the external haze H _i 1 and H _h 1 of the smooth surface 20 a are obtained by attaching a flat transparent glass 30 to the rough surface 20 b with pure water. The haze was measured in accordance with JIS K 7105 by irradiating a light beam from the light source 31 for haze measurement. A smooth surface based on the surface roughness of the smooth surface 20a and the scattering of light within the film 20 while canceling the influence of the rough surface 20b on haze by measuring the glass 30 attached to the rough surface 20b. The external haze value of 20a can be measured.

On the other hand, as shown in FIG. 12, in the film 20, the external haze H _i 2 and H _h 2 of the rough surface 20b are in a state where the flat transparent glass 30 is attached to the smooth surface 20a with pure water. The haze is measured in accordance with JIS K 7105 by irradiating light from a light source 31 for haze measurement toward the glass 30. Rough surface based on surface roughness of rough surface 20b and scattering of light rays in film 20 while canceling the influence on haze of smooth surface 20a by attaching glass 30 to smooth surface 20a The external haze value of 20b can be measured.

  The glass 30 is not particularly limited as long as it is a so-called cover glass that is thin and flat, colorless, and highly transparent. For example, a square cover glass (40 × 50 mm square, thickness tolerance of 0 by Matsunami Glass Industrial Co., Ltd.). .12 to 0.17 mm) or the like can be used.

In such a film 20, when the arithmetic average roughness of the smooth surface 20a is Ra1 and the arithmetic average roughness of the rough surface 20b is Ra2, the value of Ra2-Ra1 is preferably 5 nm or less. 5 nm or more and 3.5 nm or less are more preferable.
In the film 20 where the value of Ra2-Ra1 is 5 nm or less, it is easy to produce a laminate having excellent transparency while satisfactorily suppressing the occurrence of sticking defects.
Here, the arithmetic average roughness Ra1 of the smooth surface 20a of the film 20 and the arithmetic average roughness Ra2 of the rough surface 20b are measured based on JIS B 0601-1994.

<Method for producing acrylic resin film>
The method for producing an acrylic resin film according to the third embodiment includes a melt extrusion in which an acrylic resin composition is extruded from a die to form a film-like melt, and the surface of the roll by supporting the film-like melt with a roll. And forming a film by cooling it while moving it along.
And in any position in the section from the exit of the die to the roll, the surface temperature of one surface of the film-like melt is different from the surface temperature of the other surface by 10 ° C. or more and 30 ° C. or less.

In the melt extrusion, the acrylic resin composition is extruded from the die 5 to form a film-like melt 20 ′. By making the surface temperature of one surface of the film-like melt 20 ′ different from the surface temperature of the other surface, the protrusion amount of the rubber elastic body particles 12 on both surfaces of the film-like melt 20 ′ is made different. Can do. Specifically, in the film-like melt 20 ′, the rubber elastic particles 12 are likely to be buried on the surface having a high surface temperature due to the softness of the acrylic resin 11. On the surface having a lower surface temperature, the rubber elastic body particles 12 are less likely to be buried than the opposite surface due to the acrylic resin 11 being harder than the opposite surface.
As a result, in the film-like melt 20 ′, the rubber elastic body particles 12 are unlikely to protrude on a surface having a high temperature, and the rubber elastic body particles 12 are likely to protrude on a surface having a low temperature.

As described above, since the protrusion of the rubber elastic body particles 12 on the surface on which the coat layer 22 is laminated has little influence on the transparency of the laminate 21, the surface on which the coat layer 22 is laminated is in the form of a film roll. In order to suppress the occurrence of sticking defects, the amount of protrusion of the rubber elastic body particles 12 can be increased to impart lubricity to the film 20.
On the other hand, on the surface on which the coat layer 22 is not laminated, excessive protrusion of the rubber elastic body particles 12 adversely affects the transparency of the laminated body 21, so that the protrusion amount of the rubber elastic body particles 12 is preferably reduced.

  For this reason, in the section from the exit of the die 5 to the cast roll 6, the surface of the film-like melt 20 ′ where the coating layer such as the coating layer 22 is to be stacked is more than the surface where the coating layer 22 is not stacked. However, it is preferable to lower the surface temperature.

Specifically, immediately after the exit of the die 5, the surface temperature of one surface of the film-like melt 20 ′ and the surface temperature of the other surface are 10 ° C. or more and 30 ° C. or less, preferably 10 ° C. or more and 20 ° C. Different below.
Since the difference between the surface temperature of one surface of the film-like melt 20 ′ and the surface temperature of the other surface is 10 ° C. or more, the occurrence of sticking defects can be sufficiently suppressed on one surface of the film 20. The rubber elastic particles 12 can be easily protruded to the extent that the other surface does not have a significant adverse effect on the transparency of the laminate 21 produced using the film 20, and the occurrence of sticking defects is sufficient. The rubber elastic body particles 12 can be easily protruded to such an extent that they can be suppressed.
When the difference between the surface temperature of one surface of the film-like melt 20 ′ and the surface temperature of the other surface is 30 ° C. or less, it is easy to suppress thermal deterioration of the film-like melt 20 ′. When thermal deterioration occurs, streaks may appear on the surface of the film 20.

  In melt extrusion, when the glass transition temperature of the acrylic resin composition is Tg, the temperature of the molten acrylic resin composition supplied to the outlet of the die 5 is preferably Tg + 120 ° C. or higher. When the temperature of the molten acrylic resin composition is within this range, it is easy to adjust the protruding amount of the rubber elastic body particles 12 in the film-like melt 20 '.

The method for making the surface temperature of one surface of the film-like melt 20 ′ different from the surface temperature of the other surface is not particularly limited. As shown in FIG. 13, the temperatures of both surfaces of the film-like melt 20 ′ are respectively provided near the outlet (die lip) of the die 5, and the temperature adjusting device 23 as an auxiliary heating device and the temperature adjusting device 24. It is preferable to adjust by at least one of the following.
The temperature adjusting device 23 is a device that adjusts the film surface temperature on the side in contact with the cast roll 6. The temperature adjusting device 24 is a device that adjusts the film surface temperature on the side that does not come into contact with the cast roll 6.
The temperature adjusting device 23 and the temperature adjusting device 24 may be non-contact devices that adjust the temperature of the film-like melt 20 ′ immediately after being extruded from the outlet of the die 5. Examples of the non-contact type device include a heating device such as an infrared heater and a cooling device such as a pipe through which a refrigerant flows. In addition, in FIG. 13, although the example which installed the temperature control apparatus 23 and the temperature control apparatus 24 in the exit of the die | dye 5 is shown, only any one may be installed.

  Further, a temperature control device is installed near the intermediate point between the die 5 and the cast roll 6 or in the vicinity of the cast roll 6, so that the surface temperature of one surface of the film-like melt 20 ′ and the surface of the other surface The temperature may be different. As the temperature control device, a device similar to a non-contact type temperature control device that can be used at the outlet of the die 5 can be used.

  As described above, the method of making the surface temperature of one surface of the film-like melt 20 'different from the surface temperature of the other surface may be either heating or cooling. From the viewpoint of easily adjusting the protruding amount of the elastic rubber particles 12, it is preferable that the surface temperatures of both surfaces of the film-like melt 20 'are made different by heating.

Furthermore, in melt extrusion, the temperature of both ends of the film-like melt 20 ′ in the width direction of the film-like melt 20 ′ is the temperature of the central part of the film-like melt 20 ′ in the width direction of the film-like melt 20 ′. May be higher.
In this case, the amount of protrusion of the elastic rubber particles 12 is greater at the center of the film 20 obtained than at both ends of the film 20. Then, while the slipperiness is high at the central portion of the film 20, the slippage is unlikely to occur when the film 20 is conveyed by a roll because the slipperiness is low at both ends of the film 20.
In addition, even if the edge part and center part of film-like melt 20 'here are the edge part and center part in one surface of film-like melt 20', the edge part and center part in the other surface It may be. Since at least one surface of the film-like melt 20 ′ has a difference in temperature between the end portion and the central portion, it is easy to suppress a side slip when the film 20 is conveyed by a roll.

In film formation, the film-like melt 20 ′ is supported by a roll (for example, a cast roll 6) and cooled along with the surface of the roll to form a film 20.
In film formation, as shown in FIG. 13, the film-like melt 20 ′ may be sandwiched between the cast roll 6 and the touch roll 7 while being formed on the film 20 while being supported by the cast roll 6.
Thus, it is easier to adjust the protruding amount of the rubber elastic body particles 12 on both surfaces of the film 20 by forming the film by sandwiching it between the cast roll 6 and the touch roll 7.

When the film-like melt 20 ′ is sandwiched between the cast roll 6 and the touch roll 7 and formed into the film 20, there is a difference between the surface temperature of the cast roll 6 and the surface temperature of the touch roll 7. Also good. Depending on the surface temperatures of the cast roll 6 and the touch roll 7, it is possible to adjust the protruding amount of the rubber elastic body particles 12 on both surfaces of the film 20.
For example, the higher the surface temperature of the cast roll 6, the easier it is for the rubber elastic particles 12 to be buried on the surface of the film-like melt 20 ′ that comes into contact with the cast roll 6. The same applies to the touch roll 7.

In the film-like melt 20 ′, one surface temperature is set to be high for the purpose of easily embedding the rubber elastic particles 12, and the other surface temperature is set to be difficult for the rubber elastic particles 12 to be embedded. Set lower.
In consideration of this point, when there is a temperature difference between the surface of the cast roll 6 and the surface of the touch roll 7, the higher surface of the film-like melt 20 ′ is the cast roll 6 or the touch roll 7. It is preferable to contact the one having a higher surface temperature.

<Laminate>
Hereinafter, the laminated body using the film which concerns on 3rd Embodiment is demonstrated. As described above, the laminate 21 shown in FIG. 11 includes the acrylic resin film 20 and the coat layer 22. The coat layer 22 preferably covers at least the rough surface 20b of the acrylic resin film, and may cover both the rough surface 20b and the smooth surface 20a. Such a laminate 21 is capable of laminating the coat layer 22 without sticking defects because the occurrence of sticking defects is suppressed in the form of a roll before the coat layer 22 is coated. And as mentioned above, transparency is good.
The coat layer 22 can be formed in the same manner as the coat layer 14 described above.
7 (side view) does not show the recess 10c in the film 10 shown in FIG. 4 (cross-sectional view), but, like the film 10, the recess is formed around the rubber elastic particles 12. Needless to say, may be formed.

According to the third embodiment of the present invention described above,
(3-1) A method for producing an acrylic resin film using an acrylic resin composition comprising an acrylic resin and rubber elastic particles.
Melt extrusion to extrude an acrylic resin composition from a die to form a film-like melt;
A film-like melt is supported by a roll and cooled while moving along the surface of the roll to form a film, and
An acrylic resin film, wherein the surface temperature of one surface of the film-like melt is different from the surface temperature of the other surface by 10 ° C. or more and 30 ° C. or less at any position in the section from the die outlet to the roll. Production method,
(3-2) The method for producing an acrylic resin film according to (3-1), wherein the surface temperature of one surface of the film-like melt is made different from the surface temperature of the other surface immediately after the outlet of the die. ,
(3-3) In melt extrusion, when the glass transition temperature of the acrylic resin composition is Tg, the temperature of the molten acrylic resin composition supplied to the outlet of the die is Tg + 120 ° C. or higher. (3-1) or the method for producing an acrylic resin film according to (3-2),
(3-4) Temperature control is performed by a temperature control device provided in the vicinity of the die outlet, and the surface temperature of one surface of the film-like melt is made different from the surface temperature of the other surface. (3-1) A method for producing a thermoplastic resin film according to any one of-(3-3),
(3-5) Production of acrylic resin film according to any one of (3-1) to (3-4), wherein the surface of the film-like melt having the higher temperature is in contact with the roll in film formation. Method,
(3-6) The acrylic according to any one of (3-1) to (3-5), wherein in film formation, a film-like melt is sandwiched between a cast roll and a touch roll to form a film. -Based resin film manufacturing method,
(3-7) There is a difference between the temperature of the surface of the cast roll and the surface of the touch roll,
The method for producing an acrylic resin film according to (vi), wherein the higher surface of the film-like melt is in contact with the higher surface temperature of the cast roll and the touch roll,
(3-8) In melt extrusion, the temperature of both ends of the film-like melt in the width direction of the film-like melt is made higher than the temperature of the central portion of the film-like melt in the width direction of the film-like melt. (3-1) A method for producing an acrylic resin film according to any one of (3-7),
(3-9) An acrylic resin film comprising an acrylic resin composition containing an acrylic resin and rubber elastic particles,
One surface is a smooth surface, the other surface is a rough surface,
The external surface haze H _i 1 of the smooth surface is 0.1% or more and 0.8% or less,
The external haze H _i 2 of the rough surface is 0.6% or more and 1.5% or less,
The value of H _i 2 -H _i 1 is 0.3% or more,
When the glass transition temperature of the acrylic resin composition is Tg, the external haze H _h 1 of the smooth surface and the external surface of the rough surface were measured after the acrylic resin film was heat-treated at Tg−10 ° C. for 5 minutes. For haze H _h 2, the absolute value of the difference between H _h 1 and H _i 1 and the absolute value of the difference between H _h 2 and H _i 2 are both 0.2% or less,
Each of H _i 1 and H _h 1 is irradiated with light from a light source for haze measurement toward the glass in a state where a flat transparent glass is pasted on the rough surface, and in accordance with JIS K 7105. Measured haze,
Each of H _i 2 and H _h 2 is irradiated with light from a light source for haze measurement toward the glass in a state where a flat transparent glass is attached to a smooth surface, and conforms to JIS K 7105. An acrylic resin film having a measured haze,
(3-10) The acrylic according to (3-9), wherein the value of Ra2-Ra1 is 5 nm or less when the arithmetic average roughness of the smooth surface is Ra1 and the arithmetic average roughness of the rough surface is Ra2. Resin film, and
(3-11) A laminate including the acrylic resin film according to (3-9) or (3-10) and a coating layer, wherein the coating layer covers a rough surface of the acrylic resin film. The laminate,
Is provided.

  As described above, according to the acrylic resin film manufacturing method, the acrylic resin film, and the laminate including the acrylic resin film according to the third embodiment, surface properties such as the surface roughness of the film surface are obtained. Since it is controlled, the laminated body which can suppress especially generation | occurrence | production of a sticking defect and is excellent in transparency can be given.

  Each structure about 1st Embodiment, 2nd Embodiment, and 3rd Embodiment demonstrated above can mutually be applied between each embodiment in the range which does not inhibit the solution of the desired subject.

  Hereinafter, an acrylic resin film manufacturing apparatus and an acrylic resin composition, which are common in the first embodiment, the second embodiment, and the third embodiment, will be described.

≪Acrylic resin film manufacturing equipment≫
Hereinafter, the manufacturing apparatus of the films 10 and 20 which concerns on 1st thru | or 3rd embodiment is a manufacturing apparatus which manufactures a film using the acrylic resin composition containing acrylic resin and rubber elastic-body particle | grains.
The acrylic resin film manufacturing apparatus essentially includes an extruder, a die, a cast roll, and a touch roll. In addition to these essential components, the acrylic resin film manufacturing apparatus may have various configurations that have been conventionally applied to acrylic resin film manufacturing apparatuses.

FIG. 14 is a diagram schematically illustrating a preferred example of an acrylic resin film manufacturing apparatus. The acrylic resin film manufacturing apparatus shown in FIG. 14 includes an extruder 2, a die 5, a cast roll 6, and a touch roll 7 as essential components, and as an optional component, an extruder hopper 1 and The gear pump 3, the filter device 4, and the cooling roll 8 are provided.
In FIG. 14, the extruder hopper 1 with temperature control function, the extruder 2, the gear pump 3, the filter device 4, the die 5, the cast roll 6, the touch roll 7, and the cooling roll 8 are arranged in this order. It is arranged.

  The acrylic resin composition containing the acrylic resin and the rubber elastic body particles is supplied to the extruder 2 after being adjusted to a predetermined resin temperature in the extruder hopper 1 having a temperature adjusting function. The acrylic resin composition is brought into a molten state by heating and kneading in the extruder 2. Next, the melted acrylic resin composition is measured by the gear pump 3 and then filtered by the filter device 4 including the filter 4a. The molten acrylic resin composition after filtration is supplied to the die 5 and discharged as a film-like melt 10 '. Subsequently, the film-like melt 10 ′ is sandwiched between the cast roll 6 and the touch roll 7, and the surface is smoothed. Is done. The obtained film 10 is conveyed while being cooled by a plurality of cooling rolls 8, taken up by a winder 9, and obtained in the form of a film roll. The cooling rolls 8 after the cast roll 6 can be arbitrarily installed between one and a plurality of cooling rolls 8 so that the film is sufficiently cooled and solidified according to the film conveyance speed.

  The extruder 2 is not particularly limited, and various conventionally known extruders can be used. For example, single screw extruder, same direction meshing type twin screw extruder, same direction non-meshing type twin screw extruder, different direction meshing type twin screw extruder, different direction non-meshing type twin screw extruder, multi screw extruder, etc. Various types of extruders can be used. Among them, the single screw extruder is preferable because the resin staying portion in the extruder is small and the thermal deterioration of the acrylic resin composition during extrusion is easily suppressed and the equipment cost is low. Moreover, it is preferable to use the extruder which has a vent mechanism in order to remove the residual volatile matter in an acrylic resin composition, and the heat generation thing in the extruder 2. FIG. The size (caliber) of the extruder 2 is selected according to the desired discharge amount.

  As a screw used in a single screw extruder, a general full-flight configuration with a compression ratio of 2 or more and 3 or less for an extruder with or without a vent can be used, but no unmelted material remains. A special kneading mechanism (mixing element) may be provided.

The residence time of the acrylic resin composition in the extruder 2 is preferably within 10 minutes, more preferably within 5 minutes, and particularly preferably 2 from the viewpoint of preventing resin thermal deterioration due to an increase in residence time. Within minutes.
Although the residence time depends on the type of the extruder 2 and the extrusion conditions, it can be shortened by adjusting the material supply amount, L / D, screw rotation speed, screw groove depth, and the like. is there.

  The molten acrylic resin composition obtained by the extruder 2 is then supplied to the die 5. The supply of the molten acrylic resin composition is preferably performed using a gear pump 3 as shown in FIG. By using the gear pump 3, fluctuations in the discharge amount in the extruder 2 are absorbed, the quantitativeness of the supply is remarkably improved, and the stability of the film thickness with time is improved.

  The molten acrylic resin composition quantitatively supplied from the gear pump 3 or the molten acrylic resin composition directly supplied from the extruder 2 is supplied to the die 5 through, for example, a tubular flow path, and the die outlet. Is discharged into a film. As shown in FIG. 14, it is preferable to provide a filter device 4 in the flow path from the gear pump 3 to the die 5 or in the flow path from the extruder 2 to the die 5 when the gear pump 3 or the like is not interposed. Thereby, the foreign material contained in the acrylic resin composition as a raw material and the foreign material generated by the extruder 2 and the gear pump 3 are trapped, and the occurrence of foreign material defects in the film 10 can be easily reduced. As the filter 4a of the filter device 4, a leaf disk filter, a screen mesh, a pleated filter, or the like can be used.

As the die 5, those having various structures can be used. The die 5 is preferably a T die, and for example, a general coat hanger die can be used. Furthermore, a die that can adjust the gap in the width direction arbitrary part of the lip by pushing a bolt or the like is preferable as the width direction thickness adjusting mechanism.
Furthermore, a thermally actuated bolt or the like that can measure the thickness of the film 10 online and can automatically adjust a portion having a deviation from an arbitrary thickness profile can be used. It is preferable to automatically adjust the thickness profile using a thermally actuated bolt or the like because a change with time can be accurately performed without intervention of a human hand.

  The residence time of the molten acrylic resin composition taken from the extruder 2 to the discharge from the outlet of the die 5 is preferably 15 minutes or less, more preferably 10 minutes or less. From the viewpoint of suppressing thermal degradation of the acrylic resin composition, the shorter the residence time of the molten acrylic resin composition, the better.

  The configuration of the acrylic resin film manufacturing apparatus described above is not limited to the configuration shown in FIG. For example, if necessary, the acrylic resin film manufacturing apparatus further includes a device for knurling the end of the film, a device for laminating the protective film, and slitting both ends of the film to cut the desired product width. You may provide the apparatus and the apparatus which extends | stretches a film.

≪Acrylic resin composition≫
Hereinafter, the acrylic resin composition which is the material of the acrylic resin film will be described. Hereinafter, the acrylic resin composition to be described is used as a raw material for the acrylic resin film in the above-described method for producing an acrylic resin film.

The acrylic resin composition has rubber elastic particles and an acrylic resin.
The volume average particle size of the rubber elastic particles is preferably from 80 nm to 450 nm, more preferably from 100 nm to 350 nm, and particularly preferably from 200 nm to 300 nm. When the volume average particle diameter of the rubber elastic particles is 80 nm or more, it is easy to obtain a film having a sufficiently high strength using the acrylic resin composition. When the volume average particle diameter of the rubber elastic particles is 450 nm or less, it is easy to obtain a film having excellent transparency. The volume average particle diameter can be measured by a dynamic scattering method, for example, by using MICROTRAC UPA150 (manufactured by Nikkiso Co., Ltd.).

  The content of the elastic rubber particles in the acrylic resin composition is preferably 5% by weight or more and 20% by weight or less, and more preferably 8% by weight or more and 18% by weight or less based on the weight of the acrylic resin composition. When the blending amount of the rubber elastic particles with respect to the weight of the acrylic resin is 5% by weight or more, it is easy to obtain a film having excellent strength. In this case, it is easy to obtain a film having a desired surface property by projecting rubber elastic particles to a desired degree on the film surface. When the blending amount of the rubber elastic particles with respect to the weight of the acrylic resin is 20% by weight or less, it is easy to obtain a film having excellent transparency.

[Acrylic resin]
The acrylic resin is a material constituting the matrix portion of the film, and is preferably used in terms of excellent optical properties, heat resistance, moldability, and the like.

The acrylic resin is not particularly limited, but a methacrylic resin having methyl methacrylate as a monomer component can be used. The methacrylic resin contains a structural unit derived from methyl methacrylate in an amount of 30% to 100% by weight, preferably 50% to 100% by weight, and a structural unit derived from a monomer copolymerizable with methyl methacrylate. 0 to 70% by weight, preferably 0 to 50% by weight. When the content of the structural unit derived from methyl methacrylate is 30% by weight or more, good optical characteristics, appearance, weather resistance, and heat resistance specific to the acrylic resin can be obtained.
In the case of using a methacrylic resin having methyl methacrylate as a monomer component, the glass transition temperature Tg of the methacrylic resin can be set according to the conditions and applications. The glass transition temperature Tg is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, further preferably 115 ° C. or higher, and most preferably 120 ° C. or higher.

Moreover, as a heat resistant acrylic resin, for example,
1) an acrylic resin in which an N-substituted maleimide compound is copolymerized as a copolymerization component;
2) Glutaric anhydride acrylic resin,
3) an acrylic resin having a lactone ring structure,
4) Glutarimide acrylic resin,
5) an acrylic resin containing a hydroxyl group and / or a carboxyl group,
6) Aromatic vinyl-containing acrylic polymer obtained by polymerizing aromatic vinyl monomer and other monomer copolymerizable therewith (for example, styrene monomer and other monomer copolymerizable therewith) Styrene-containing acrylic polymer obtained by polymerizing the body),
7) A hydrogenated aromatic vinyl-containing acrylic polymer (for example, a styrene monomer and other monomers copolymerizable therewith) obtained by partially or entirely hydrogenating the aromatic ring of 6) above. A partially hydrogenated styrene-containing acrylic polymer obtained by partial hydrogenation of an aromatic ring of a styrene-containing acrylic polymer obtained by polymerization), and 8) an acrylic polymer containing a cyclic acid anhydride repeating unit ,
Can be mentioned.

  In particular, from the viewpoint of heat resistance and optical properties, an acrylic polymer composed of 97% by weight to 100% by weight of methyl methacrylate and 0% by weight to 3% by weight of methyl acrylate, and 4) glutarimide acrylic Resins can be used more preferably.

[Rubber elastic particles]
The resin constituting the rubber elastic body particles is not particularly limited. Examples of the resin include a polymer having a glass transition temperature Tg of less than 20 ° C., and specifically, for example, a butadiene-based crosslinked polymer, a (meth) acrylic crosslinked polymer, and an organosiloxane-based crosslinked polymer. And rubbery polymers such as Of these, a (meth) acrylic crosslinked polymer (hereinafter sometimes simply referred to as “acrylic rubbery polymer”) is particularly preferred in terms of the weather resistance and transparency of the film.

  Examples of the acrylic rubber-like polymer include ABS resin rubber and ASA resin rubber. From the viewpoint of transparency and the like, an acrylic graft copolymer including the following acrylic ester rubber polymer (hereinafter sometimes simply referred to as “acrylic graft copolymer”) can be preferably used. . The acrylic graft copolymer can be obtained by polymerizing at least one monomer mixture of a methacrylic acid ester as a main component in the presence of an acrylic ester rubbery polymer.

  The acrylic ester rubbery polymer is a rubbery polymer mainly composed of an acrylic ester. Specifically, a monomer mixture (100% by weight) comprising 50% by weight or more and 100% by weight or less of an acrylate ester and 0% by weight or more and 50% by weight or less of another vinyl monomer that can be copolymerized, and It is obtained by polymerizing 0.05 to 10 parts by weight (based on 100 parts by weight of the monomer mixture) of a polyfunctional monomer having 2 or more non-conjugated reactive double bonds per molecule. An acrylic ester rubbery polymer is preferred. All the monomers may be mixed and used, or may be used in two or more stages by changing the monomer composition.

  When the acrylic ester is an ester of acrylic acid and an alcohol represented by R—OH (R is a hydrocarbon group), the number of carbon atoms of the hydrocarbon group as R is 1 from the viewpoint of polymerizability and cost. It is preferably 12 or less. Examples of such an acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, benzyl acrylate, cyclohexyl acrylate, and acrylic acid 2 -Ethylhexyl, n-octyl acrylate, etc. are mentioned. Two or more of these acrylic esters may be used in combination.

  As other vinyl monomers that can be copolymerized, (meth) acrylic acid esters are particularly preferred from the viewpoint of weather resistance and transparency. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methacrylate n -Butyl, 2-butyl methacrylate, isobutyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, and the like. Aromatic vinyls and derivatives thereof, and vinyl cyanides are also preferable, and examples thereof include styrene, methylstyrene, acrylonitrile, methacrylonitrile and the like. Other examples include unsubstituted and / or substituted maleic anhydrides, (meth) acrylamides, vinyl esters, vinylidene halides, (meth) acrylic acid and salts thereof, and (hydroxyalkyl) acrylic esters.

  The polyfunctional monomer may be a commonly used one. Examples of polyfunctional monomers include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinyl benzene, ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol diester. Methacrylate, trimethylol propane trimethacrylate, tetramethylol methane tetramethacrylate, dipropylene glycol dimethacrylate and acrylates thereof can be used. Two or more of these polyfunctional monomers may be used in combination.

  Polymerization of a monomer mixture mainly composed of a methacrylic acid ester into an acrylic ester rubbery polymer, that is, the monomers used for graft copolymerization include the above-mentioned methacrylic acid esters, acrylic acid esters, and the like. Can be used similarly, and methacrylic acid ester and acrylic acid ester are preferably used. Methyl methacrylate, methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferred from the viewpoint of suppressing compatibility with acrylic resins from the viewpoint of suppressing methylation of zipper depolymerization.

  The acrylic graft copolymer can be produced by a general emulsion polymerization method. Specifically, a method of continuously polymerizing an acrylate monomer using an emulsifier in the presence of a water-soluble polymerization initiator can be exemplified.

  In the emulsion polymerization method, a usual polymerization initiator can be used. For example, inorganic peroxides such as potassium persulfate and sodium persulfate, organic peroxides such as cumene hydroperoxide and benzoyl peroxide, and oil-soluble initiators such as azobisisobutyronitrile are also used. These may be used alone or in combination of two or more. These initiators are used as normal redox polymerization initiators in combination with reducing agents such as sodium sulfite, sodium thiosulfate, sodium formaldehyde, sulfoxylate, ascorbic acid, ferrous sulfate and disodium ethylenediaminetetraacetate complex. May be used.

  A chain transfer agent may be used in combination with the polymerization initiator. Examples of the chain transfer agent include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol, carbon tetrachloride and the like. These may be used alone or in combination of two or more.

  There is no particular limitation on the emulsifier used in the emulsion polymerization method, and any emulsifier for ordinary emulsion polymerization can be used. For example, sulfate ester surfactants such as sodium alkyl sulfate, sulfonate surfactants such as sodium alkylbenzene sulfonate, sodium alkyl sulfonate, sodium dioctyl sulfosuccinate, sodium alkyl phosphate, polyoxyethylene alkyl ether Anionic surfactants such as phosphate surfactants such as sodium phosphate ester are listed. The sodium salt may be other alkali metal salt such as potassium salt or ammonium salt. These emulsifiers may be used alone or in combination of two or more. Further, nonionic surfactants represented by polyoxyalkylenes or alkyl-substituted or aryl-substituted terminal hydroxyl groups may be used or partially used together. Among these, from the viewpoint of polymerization reaction stability and particle system controllability, sulfonate surfactants or phosphate surfactants are preferable, and among them, dioctyl sulfosuccinate or polyoxyethylene alkyl ether phosphate Ester salts can be used more preferably.

  In addition, you may add antioxidant, a ultraviolet absorber, a ultraviolet stabilizer, etc. for improving the stability with respect to a heat | fever or light to the acrylic resin composition containing a rubber elastic body particle. These additives may be used alone or in combination of two or more.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.
Hereinafter, Example 1-1 to Example 1-3 are tests related to the first embodiment, and Comparative Example 1-1 to Comparative Example 1-3 are for comparison with these Examples. It is a test. Example 2-1 to Example 2-2 are tests related to the second embodiment, and Comparative Example 2-1 to Comparative Example 2-5 are tests for comparison with these Examples. is there. Examples 3-1 to 3-6 are tests related to the above-described third embodiment, and Comparative Examples 3-1 to 3-6 are tests for comparison with these Examples. is there.

<Example 1-1 to Example 1-3 and Comparative Example 1-1 to Comparative Example 1-3>
Various settings are made for the temperature of the film-like melt at the die exit and the line speed from the die exit to the touch roll and cast roll, and evaluation of the film surface shape (Rd, Rh, ΔRa), coating properties and visibility An example performed using the following method will be described.

[Example 1-1]
(Production Example 1: Preparation of rubber elastic particles (acrylic graft copolymer))
The following substances were charged into an 8 L polymerization apparatus equipped with a stirrer.
Deionized water 180 parts by weight Polyoxyethylene lauryl ether phosphoric acid (emulsifier) 0.031 parts by weight Boric acid 0.4725 parts by weight Sodium carbonate 0.04725 parts by weight Sodium hydroxide 0.0098 parts by weight Nitrogen gas is sufficient in the polymerization machine Then, the internal temperature was set to 80 ° C., and 0.027 parts by weight of potassium persulfate as a polymerization initiator was added in the form of a 2% by weight aqueous solution. Next, 27 parts by weight of the monomer mixture (93.2% by weight of methyl methacrylate, 6% by weight of butyl acrylate, 0.8% by weight of styrene), 0.135 parts by weight of allyl methacrylate which is a polyfunctional monomer Then, 0.3 part by weight of n-octyl mercaptan as a chain transfer agent and 0.0934 part by weight of polyoxyethylene lauryl ether phosphoric acid as an emulsifier were continuously added over 81 minutes. Polymerization (I) was obtained by continuing superposition | polymerization for 60 minutes.

  Thereafter, 0.0267 part by weight of sodium hydroxide was added to the polymer (I) in the form of a 2% by weight aqueous solution, and 0.08 part by weight of potassium persulfate was added in the form of a 2% by weight aqueous solution. Subsequently, a monomer mixture (82% by weight of butyl acrylate, 18% by weight of styrene), 0.75 parts by weight of allyl methacrylate, and 0.2328 parts by weight of polyoxyethylene lauryl ether phosphoric acid are continuously added over 150 minutes. did. After completion of the addition, 0.015 part by weight of potassium persulfate as an initiator was added in the form of a 2% aqueous solution, and polymerization was continued for 120 minutes to obtain a polymer (II).

Thereafter, 0.023 part by weight of potassium persulfate was added to the polymer (II) in the form of a 2% by weight aqueous solution. Next, 15 parts by weight of a monomer mixture (methyl methacrylate 95% by weight, butyl acrylate 5% by weight) was continuously added over 45 minutes, and polymerization was continued for another 30 minutes.
Next, 8 parts by weight of the monomer mixture (methyl methacrylate 52% by weight, butyl acrylate 48% by weight) was continuously added over 25 minutes, and the polymerization was continued for 60 minutes, whereby the multistage polymerization graft copolymerization was performed. A combined latex was obtained.
The obtained latex was salted out and coagulated with magnesium sulfate, washed with water, and dried to obtain a white powdered multistage polymerization acrylic graft polymer. The average particle diameter of the obtained acrylic graft copolymer was 221 nm.

(Production Example 2: Preparation of acrylic resin composition)
The rubber elastic particles (acrylic graft copolymer) obtained in Production Example 1 and the acrylic resin (Mw: 105,000) having a polymethyl methacrylate structural unit of 100% in a weight ratio of 15:85 And mixed. Subsequently, this mixture was melt-extruded in a φ58 mm vented twin-screw extruder, the resin coming out as a strand from a die provided at the exit of the extruder was cooled in a water tank, and the acrylic system pelletized with a pelletizer A resin composition was obtained. The obtained acrylic resin composition had a glass transition temperature Tg of 120 ° C.

(Film production equipment)
In order from the upstream side, φ90 mm vent type single screw extruder and gear pump, T die, maximum height Ry = 0.260 μm, cast roll with arithmetic average roughness Ra = 0.030 μm, maximum height Ry = 0.050 μm, A film manufacturing apparatus in which touch rolls having an arithmetic average roughness Ra = 0.007 μm were arranged was used.

  Using the acrylic resin composition obtained in Production Example 2 and the film production apparatus described above, melt extrusion was performed with the temperature of the film-like melt at the die exit being 250 ° C. (Tg + 130 ° C.) (see FIG. 8). ). The film melt is sandwiched using a touch roll and a cast roll having a surface temperature of 95 ° C. to obtain an acrylic resin film in the form of a film roll having a thickness of 80 μm, a width of 1500 mm, and a length of 1000 m. did. The line speed from the die exit to the touch roll and cast roll was 13 m / min.

(Coat layer formation)
A coating liquid for forming a hard coat layer (urethane acrylate resin (UV hard coat agent for molding processed film) / solvent methyl ethyl ketone / solid component 30% by mass) is applied to an acrylic resin film obtained with a film manufacturing apparatus. Was applied with a thickness of 1 μm. And it dried at 80 degreeC for 3 minute (s), and irradiated the ultraviolet-ray with the integrated light quantity 300-400mJ / cm < ² >, the hard-coat layer was formed, and the laminated body (film with a hard-coat layer) was acquired.

[Example 1-2]
Except for changing the temperature of the film-like melt at the die exit to 260 ° C. (Tg + 140 ° C.) and changing the line speed to 15 m / min, the laminate ( Film with a hard coat layer) was obtained.

[Example 1-3]
Except for changing the temperature of the film-like melt at the die exit to 270 ° C. (Tg + 150 ° C.) and changing the line speed to 18 m / min, the laminate ( Film with a hard coat layer) was obtained.

[Comparative Example 1-1]
The temperature of the film-like melt at the die exit was changed to 200 ° C. (Tg + 80 ° C.), and melt extrusion was performed (see FIG. 7). And the laminated body (film with a hard-coat layer) was acquired by the method similar to Example 1-1 except changing a line speed to 13 m / min.

[Comparative Example 1-2]
A laminate (film with a hard coat layer) was obtained in the same manner as in Example 1-1 except that the line speed was changed to 30 m / min.

[Comparative Example 1-3]
The temperature of the film-like melt at the die exit was changed to 300 ° C. (Tg + 180 ° C.), and melt extrusion was performed (see FIG. 9). And the laminated body (film with a hard-coat layer) was acquired by the method similar to Example 1-1 except changing a line speed to 15 m / min.

[Results of Example 1-1 to Example 1-3 and Comparative Example 1-1 to Comparative Example 1-3]
The surface shape of the acrylic resin film obtained in Example 1-1 to Example 1-3 and Comparative Example 1-1 to Comparative Example 1-3 was measured according to the following method.

In FIG. 15, the height curve about the film cross section containing an unevenness | corrugation acquired by AFM observation of the surface of the acrylic resin film obtained in Example 1-2 is shown.
In FIG. 16, the height curve about the film cross section containing the unevenness | corrugation acquired by AFM observation of the surface of the acrylic resin film obtained in Comparative Example 1-1 is shown.
In FIG. 17, the height curve about the film cross section containing an unevenness | corrugation acquired by AFM observation of the surface of the acrylic resin film obtained by Comparative Example 1-3 is shown.
FIG. 18 shows an AFM observation image of the surface of the acrylic resin film obtained in Example 1-2.

  Moreover, the laminated body (film with a hard-coat layer) acquired in Example 1-1 to Example 1-3 and Comparative Example 1-1 to Comparative Example 1-3 was evaluated according to the following criteria. These evaluation results are shown in Table 1.

(Surface shape)
Using an atomic force microscope (AFM, NanoCute SII (manufactured by Hitachi High-Tech Science)), the surface shape of the film (Rd, Rh, ΔRa) is compliant with JIS B 0601-1994 at a visual field size of 5 μm × 5 μm. It was measured.

(Coating property)
The presence or absence of voids (bubbles having a size of less than 0.3 mm) and line-shaped coating streaks appearing in the coating direction of the coating liquid were observed.
The presence or absence of a line-shaped coating streak was determined by whether or not the streak was observed under an illuminance of 1000 Lux.
The evaluation criteria for coatability are as follows.
A: Neither void nor coating stripe was observed.
B: Either void or coating streak was observed.
C: Both voids and coating streaks were observed.

(Visibility)
The presence or absence of occurrence of interference fringes (hard coat layer thickness unevenness of ± 0.3 μm or more) and whitening (haze of 1% or more) was observed. The thickness unevenness was observed with an atomic force microscope in the same manner as the surface shape. The haze of the film was measured according to JIS K 7136 (ISO 14782) using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement conditions were a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 5%.
The evaluation criteria for visibility are as follows.
A: Neither interference paper nor whitening was observed.
B: Either interference fringes or whitening was observed.
C: Both interference papers and whitening were observed.

  According to FIGS. 15 and 18, in the acrylic resin film obtained in Example 1-2, when the acrylic resin film is observed from the thickness direction of the acrylic resin film, the surface of the acrylic resin film is observed. A fine structure consisting of an annular recess and a protrusion located inside the ring formed by the recess is observed. The recess is recessed in the thickness direction of the acrylic resin film on the surface, and the protrusion is on the surface. It can be seen that it protrudes in the thickness direction of the acrylic resin film.

  Further, as can be seen from Table 1, the temperature of the film-like melt (acrylic resin composition) at the exit of the die is Tg + 130 ° C. or more and Tg + 150 ° C. or less, and the line speed is 13 m / min or more and 18 m / min in the sandwich molding. In Examples 1-1 to 1-3, which are less than or equal to minutes, an acrylic resin film in which Rd is 1.0 nm or more and 50 nm or less and Rh is 0.1 nm or more and 100 nm or less is obtained. I was able to. About the acrylic resin film obtained in Example 1-1-Example 1-3, it was confirmed that the laminated body (film with a hard-coat layer) excellent in coating property and excellent in visibility can be formed.

  On the other hand, according to Table 1 and FIGS. 16 to 17, Comparative Example 1-1 to Comparative Example 1-3 in which the temperature of the acrylic resin composition is too low, too high, or the line speed is too high. Then, an acrylic resin film in which Rd and Rh are in the desired range was not obtained. About the acrylic resin film obtained by Comparative Example 1-1-Comparative Example 1-3, the applicability | paintability of the coating liquid to an acrylic resin film is also bad, and the visibility of a laminated body (film with a hard-coat layer). Also not good.

<Example 2-1 to Example 2-2 and Comparative Example 2-1 to Comparative Example 2-5>
Various kinds of surface roughness (maximum height Ry, arithmetic average roughness Ra) of the touch roll and cast roll are set, and the following methods are used to evaluate the film for surface roughness, static friction coefficient, sticking, and transparency. An example performed using this method will be described.

[Example 2-1 to Example 2-2 and Comparative Example 2-1 to Comparative Example 2-5]
About a cast roll and a touch roll, except having used what has maximum height Ry shown in Table 2, and arithmetic mean roughness Ra, it is inserted and formed into a film-like melt like Example 1-1, thickness An acrylic resin film in the form of a film roll having a thickness of 80 μm, a width of 1500 mm, and a length of 1000 m was obtained. In Comparative Example 2-5, no touch roll was installed.

[Results of Example 2-1 to Example 2-2 and Comparative Example 2-1 to Comparative Example 2-5]
Surface roughness (Ry, Ra) of cast roll and touch roll used in Example 2-1 to Example 2-2 and Comparative Example 2-1 to Comparative Example 2-5, cast roll surface of film and touch of film The surface roughness (Ra1, Ra2) of the roll surface was measured according to the following method. Moreover, about the film obtained in Example 2-1 to Example 2-2 and Comparative Example 2-1 to Comparative Example 2-5, the static friction coefficient, the sticking defect, and the transparency were evaluated according to the following criteria. These measurement results and evaluation results are shown in Table 2.

(Surface roughness)
The surface roughness (arithmetic mean roughness Ra1, Ra2) of the cast roll surface of the film and the touch roll surface of the film is 5 μm in field size using an atomic force microscope (manufactured by Hitachi High-Tech Science Co., Ltd., NanoCute SII). × 5 μm, measured according to JIS B 0601-1994.
The surface roughness (maximum height Ry, arithmetic average roughness Ra) of the cast roll and the touch roll is JIS B 0601 using a surface roughness / contour shape measuring machine (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom 130A). -Measured according to 1994.

(Static friction coefficient)
A film cut from a film roll was used as a sample. Using a surface property measuring machine (manufactured by Shinto Kagaku Co., Ltd., 14DR), the cast roll surface and the touch roll surface of the sample film were brought into contact with each other, and the static friction coefficient was measured. The measurement conditions were a load of 500 g, a contact area of 60 mm × 60 mm, a measurement speed of 2000 mm / min, a temperature of 23 ° C. ± 2 ° C., and a humidity of 50% ± 5%.

(Sticking defect)
A film cut from a film roll was placed on a black plate, and the entire width of the film was visually observed under a light source having an illuminance of 4000 lux. Film sticking defects were evaluated according to the following criteria.
A: Uneven defects are not visually recognized on the film surface B: Uneven defects are visually recognized on the film surface

(transparency)
The haze of the film piece cut from the film roll was measured according to JIS K 7136 (ISO 14782) using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement conditions were a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 5%. Film transparency was evaluated according to the following criteria.
A: Haze less than 1.0% B: Haze 1.0% or more

As can be seen from the results in Table 2, the surface roughness of the cast roll surface and the touch roll surface of the film is adjusted by adjusting the surface roughness (maximum height Ry, arithmetic average roughness Ra) of the cast roll and the touch roll. (Ra1, Ra2) can be adjusted.
In particular, the acrylic resin films of Example 2-1 and Example 2-2 manufactured under conditions that can reduce the value of Ra2-Ra1 to 1.0 nm or less suppress the occurrence of sticking defects, and are transparent. Was good.
From Comparative Example 2-1 and Comparative Example 2-2, the acrylic resin film produced under the conditions where the value of Ra2-Ra1 exceeds 1.0 nm and the value of Ra1 + Ra2 is less than 6.5 nm is stuck. It can be seen that it is difficult to suppress the occurrence of defects.
From the comparative example 2-3 and the comparative example 2-4, the value of Ra2-Ra1 exceeds 1.0 nm and the acrylic resin film manufactured under the high condition of Ra1 + Ra2 value exceeding 8.9 nm is transparent. It turns out that is easy to be damaged.
Even if an acrylic resin film is produced under the condition that the value of Ra2-Ra1 can be 1.0 nm or less from Comparative Example 2-5, the film is excellent in transparency when sandwiched molding is not performed on the film-like melt. It is difficult to obtain.

<Example 3-1 to Example 3-6 and Comparative Example 3-1 to Comparative Example 3-6>
A heating device, which is a temperature control device, is installed at the die outlet, and various settings are made for the temperature of the heating device and the temperature of the touch roll and cast roll, and evaluation of the film with respect to haze, surface roughness, transparency, and sticking An example performed using the following method will be described.

[Example 3-1]
A cast roll side heating device that heats the surface of the film-like melt that contacts the cast roll and a touch roll side heating device that heats the surface that contacts the touch roll are installed at the exit of the T-die (FIG. 13). reference).
In Example 3-1, the cast roll surface in contact with the cast roll in the film was a smooth surface, and the touch roll surface in contact with the touch roll was a rough surface.

  Using the film production apparatus described above, the acrylic resin composition obtained in Production Example 2 was supplied to a die at 250 ° C. and melt-extruded, and the temperature of the cast roll surface of the film-like melt was measured by a cast roll side heating device. Was warmed to 270 ° C. And, using a cast roll having a surface temperature of 95 ° C. and a touch roll having a surface temperature of 85 ° C., a thickness of 80 μm, as in Example 1-1, except that film formation was performed by sandwiching the film-like melt. An acrylic resin film in the form of a film roll having a width of 1500 mm and a length of 1000 m was obtained.

[Example 3-2 and Example 3-3]
An acrylic resin film in the form of a film roll was obtained in the same manner as in Example 3-1, except that the temperature condition of the film-like melt was changed to the conditions described in Table 3.

[Example 3-4 and Example 3-6]
Except for changing the temperature condition of the film-like melt to the conditions shown in Table 3 and changing the surface temperature of the touch roll to the temperature shown in Table 3, Example 3-1 and Similarly, an acrylic resin film in the form of a film roll was obtained.
In Example 3-6, the cast roll surface was a rough surface, and the touch roll surface was a smooth surface.

[Example 3-5]
An acrylic resin film in the form of a film roll was obtained in the same manner as in Example 3-1, except that a film manufacturing apparatus (noted as “open” in Table 3) without a touch roll was used.

[Comparative Example 3-1]
Similar to Example 3-1, except that the temperature condition of the film-like melt is changed to the conditions shown in Table 4 and the surface temperature of the touch roll is changed to the temperature shown in Table 4. An acrylic resin film in the form of a film roll was obtained.

[Comparative Example 3-2]
Changing the temperature of the acrylic resin composition supplied to the die to the temperature shown in Table 4, changing the temperature condition of the film-like melt to the conditions shown in Table 4, and the surface temperature of the touch roll Acrylic resin film in the form of a film roll was obtained in the same manner as in Example 3-1, except that the temperature was changed to the temperature described in Table 4.

[Comparative Example 3-3]
Example 3 in which a film manufacturing apparatus (noted as “open” in Table 4) without a touch roll was used, the temperature condition of the film-like melt was changed to the conditions described in Table 4, and As in -1, an acrylic resin film in the form of a film roll was obtained.

[Comparative Example 3-4 and Comparative Example 3-5]
An acrylic resin film in the form of a film roll was obtained in the same manner as in Example 3-1, except that the temperature condition of the film-like melt was changed to the conditions described in Table 4.

[Comparative Example 3-6]
Changing the temperature of the acrylic resin composition supplied to the die to the temperature shown in Table 4, changing the temperature condition of the film-like melt to the conditions shown in Table 4, a cast roll and a touch roll An acrylic resin film in the form of a film roll was obtained in the same manner as in Example 3-1, except that the surface temperature was changed to the temperature shown in Table 4.

[Results of Example 3-1 to Example 3-6 and Comparative Example 3-1 to Comparative Example 3-6]
About the film obtained in Example 3-1 to Example 3-6 and Example 3-1 to Example 3-6, haze (total haze, smooth surface external haze, rough surface external haze) was performed according to the following method. And the surface roughness was measured.
Moreover, about the film obtained in Example 3-1 to Example 3-6 and Example 3-1 to Example 3-6, transparency and sticking defect were evaluated according to the following criteria. These evaluation results are shown in Tables 3 and 4.

(Total haze measurement)
Using the film piece cut from the film roll as a measurement sample, the total haze of the film was measured with a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K 7105. The measurement conditions were a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 5%.

(Measurement of external haze H _i 1 and H _h 1 on a smooth surface)
The external haze H _i 1 of the smooth surface of the film after manufacture and the external haze H _h 1 of the smooth surface of the heat-treated film are formed on the rough surface of the film piece cut from the film roll, as shown in FIG. With the glass attached, measurement was performed by irradiating the glass with a light beam for haze measurement. Other measurement conditions are the same as for all haze measurements.
Incidentally, the sample for measurement of H _{h 1} is a smooth surface external haze of the film after heat treatment, a film 110 ° C. to (Tg-10 ℃), obtained by heat treatment for 5 minutes.

(Rough external haze H _i 2 and H _h 2 measurement)
The outer haze H _i 2 of the rough surface of the film after manufacture and the outer haze H _h 2 of the rough surface of the heat-treated film are formed on the smooth surface of the film piece cut from the film roll, as shown in FIG. With the glass attached, measurement was performed by irradiating the glass with a light beam for haze measurement. Other measurement conditions are the same as for all haze measurements.
Incidentally, the sample for measurement of H _{h 2} is a rough external haze of the film after heat treatment, a film 110 ° C. to (Tg-10 ℃), obtained by heat treatment for 5 minutes.

(Surface roughness)
Using an atomic force microscope (NanoCute SII, manufactured by Hitachi High-Tech Science Co., Ltd.), the arithmetic average roughness Ra1 of the smooth surface of the film and the arithmetic average roughness Ra2 of the rough surface were respectively calculated as the arithmetic average at a visual field size of 5 μm × 5 μm. The roughness was measured according to JIS B 0601-1994.

(Film transparency)
Film transparency was evaluated according to the following criteria. The external haze H _{i 1} of the smooth surface used as an evaluation criterion is the haze assuming the transparency of the laminate coat layer is provided on the rough surface of the film.
A: The external haze H _i 1 of the smooth surface is 0.5% or less.
B: The external haze H _i 1 of the smooth surface is more than 0.5% and 0.9 or less.
C: The external haze H _i 1 of the smooth surface is more than 0.9.

(Film sticking defects)
A film cut from a film roll was placed on a black plate, the entire width of the film was visually observed by changing to a light source having an illuminance of 4000 lux, and the film sticking defect was evaluated according to the following criteria according to the presence or absence of irregularities.
A: Concavity and convexity defects are not visually recognized when three months have elapsed in the form of a film roll. B: Concavity and convexity defects were not visually recognized when one month has elapsed in the form of a film roll, but concavity and convexity defects were visually recognized when two months had elapsed.
C: Immediately after the film roll was formed, the irregular defect was not visually recognized, but the irregular defect was visually recognized when one month had passed.
D: Imperfect defects were visually recognized immediately after the film roll was formed.

As can be seen from the results in Table 3, the films of Example 3-1 to Example 3-6 manufactured by varying the surface temperature of the cast roll surface of the film-like melt and the surface temperature of the touch roll surface were: Assuming that a coating layer is provided on the rough surface, the smooth surface external haze H _i 1 is low and the transparency evaluation result is good (Evaluation A and B), and the occurrence of sticking defects is also suppressed (Evaluation A to A). C) The change in external haze after heating was also small.
On the other hand, as can be seen from the results in Table 4, Comparative Example 3-1 to Comparative Example 3-6 were manufactured in which the surface temperature of the cast roll surface of the film-like melt and the surface temperature of the touch roll surface were the same. The film satisfies all of good transparency evaluation (A and B), suppression of sticking defects (evaluation A to C), and small external change after heating (0.2% or less). I couldn't.

5 T-die 6 Cast roll 7 Touch roll 10 Film 10a Cast roll surface 10b Touch roll surface 10c Recess 10d Protrusion 11 Acrylic resin 12 Rubber elastic particle 13 Laminate 14 Coat layer 20 Single-side smooth film 20a Smooth surface 20b Rough surface 21 Laminate 22 Coat layer 23 Temperature controller 24 Temperature controller

Claims (12)

An acrylic resin film comprising an acrylic resin composition comprising an acrylic resin and rubber elastic particles,
When the acrylic resin film is observed from the thickness direction of the acrylic resin film, on the surface of the acrylic resin film, an annular concave portion and a convex portion located inside the ring formed by the concave portion are provided. Observed,
The recess is recessed in the thickness direction of the acrylic resin film on the surface,
The convex portion protrudes in the thickness direction of the acrylic resin film on the surface,
When a surface parallel to the surface direction of the acrylic resin film on the surface is used as a reference surface, an average Rd of the depth from the reference surface of the concave portion is 1.0 nm or more and 50 nm or less, and the convexity The acrylic resin film whose average Rh of the height from the said reference plane of a part is 0.1 nm or more and 100 nm or less. Haze is less than 2%,
2. The acrylic resin film according to claim 1, wherein ΔRa, which is an absolute value of a difference in arithmetic average roughness Ra between one surface and the other surface of the acrylic resin film, is 0.01 nm or more and less than 5.0 nm.   The acrylic resin film of Claim 1 or 2 whose average space | interval Sm of the said convex part which adjoins is 0.01 micrometer or more and 5 micrometers or less. The number of the convex portions of the surface area of 1 [mu] m ² per film is 5 or less 0.1 or more, the acrylic resin film according to claim 1. The volume average particle size of the rubber elastic particles is 100 nm or more and 300 nm or less,
The acrylic resin composition includes 5% by mass or more and 20% by mass or less of the rubber elastic body particles with respect to the mass of the acrylic resin,
The acrylic resin film in any one of Claims 1-4 whose thickness of the said acrylic resin film is 5 micrometers or more and 300 micrometers or less. A method for producing an acrylic resin film using an acrylic resin composition comprising an acrylic resin and rubber elastic particles,
Melt extrusion to form a film-like melt by extruding the acrylic resin composition from a die; and
Sandwiching the film-like melt into a film sandwiched between a cast roll and a touch roll, and
In the melt extrusion, when the glass transition temperature of the acrylic resin composition is Tg, the temperature of the acrylic resin composition at the exit of the die is Tg + 130 ° C. or higher and Tg + 150 ° C. or lower,
In the sandwich molding, a method for producing an acrylic resin film, wherein a line speed that is a speed in a flow direction of the film-like melt is 13 m / min or more and 18 m / min or less.   The coating method of applying a coating liquid to the at least one surface of the acrylic resin film in any one of Claims 1-5.   The coating method according to claim 7, wherein the coating solution is a coating solution for forming a hard coat layer. Coating at least one surface of the acrylic resin film according to any one of claims 1 to 5 to form a film by applying a coating liquid;
Forming a coat layer from the coating, forming a coat layer;
The manufacturing method of a laminated body containing this.   The manufacturing method of the laminated body of Claim 9 whose said coating layer is a hard-coat layer.   A laminate comprising a coating layer in contact with the surface on at least one surface of the acrylic resin film according to claim 1.   The laminate according to claim 11, wherein the coat layer is a hard coat layer.