JP2010175653A - Curable resin film and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin film, not much increasing surface glossiness in curing and having enough low glossiness to be used in an optical member or the like, a method of manufacturing the curable resin film, a light scattering film, a light shielding film and a lens unit including the light shielding film. <P>SOLUTION: In this curable resin film, the surface shape is formed by a plurality of protrusions and recesses, and the surface glossiness is lowered by the surface shape. In the curable resin film, the surface shape is formed by two types of relatively macro and micro protruded and recessed shapes at least different in size on at least one of the surfaces, and the plurality of macro protruded and recessed shapes and the plurality of micro protruded and recessed shapes get mixed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a cured resin film, a production method thereof, and an application thereof. More specifically, it is particularly suitable for optical applications, optical device applications, display device applications, etc., and can also be used as mechanical parts, electrical / electronic parts, etc. The present invention relates to a cured resin film useful as a light-shielding film further imparted with a light-shielding property, a production method thereof, and a light-scattering film, a light-shielding film, and a lens unit as its use.

A resin film having a plurality of minute surface irregularities has a light scattering property due to the irregular shape and can reduce glossiness, and it is considered to be used in various optical members using such characteristics. ing. For example, since the light-shielding property of the light-shielding film can be enhanced by light scattering, in recent years, new uses such as a light-shielding film attached to a lens unit as an optical member are expected.
The light-shielding film is used for suppressing the generation and expansion of optical noise in the lens unit in a camera module of a digital camera or a mobile phone camera.
By the way, in the optical member, the digital camera module is mounted on the mobile phone, and the miniaturization has been rapidly progressing in recent years, and the optical member has been required to be further reduced in size, thickness, and weight. Value conversion is progressing rapidly. Along with this, the light-shielding film used in digital camera modules, etc., and lens units with lenses, etc. are similarly required to be smaller, thinner and lighter, and not only that, but also cost reduction is required. Yes.

In such high functionality and high added value, in order to further reduce the cost in the manufacturing process, it is considered to assemble optical / electronic members such as digital camera modules and lens units by the reflow process. Yes. The reflow process (also called the solder reflow process) is not a conventional soldering process, but is a process in which soldering is performed by applying heat to the entire member after assembling the member. Thus, the manufacturing cost can be further reduced. In this case, an optical member such as a light-shielding film having a plurality of minute surface irregularities having excellent heat resistance and reflow resistance (withstanding reflowable specifications) is required.

As a resin film having a plurality of minute surface irregularities in the prior art, for example, a film manufactured by the following method is disclosed. That is, a method of sandblasting a polyester film mixed with carbon black (see, for example, Patent Document 1), an organic filler (matting agent) is bound to the surface of the base black film with a binder resin, and irregularities based on fine particles are formed. A method of forming (for example, see Patent Document 2), a method in which organic fillers and black fine particles are bound to the surface of the transparent substrate film with a binder resin to form irregularities based on the fine particles and blackening (for example, Patent Document 3). See).

However, in these technologies, for example, when they are to be used in the field of optical members, they are not sufficient to realize the high functionality and high added value that are currently being developed, and the light shielding property. It has not been achieved to form a film or the like with a material having high heat resistance that can withstand reflowable specifications. Furthermore, there has been room for improvement in order to be able to fully exhibit the effect of the unevenness. In addition to light-shielding films, various types of resin films with uneven surfaces are used for mechanical parts, electrical / electronic parts, etc. These films also have high basic performance such as heat resistance. In addition, there has been a demand for a material that can sufficiently exhibit the effect of unevenness.
In the field of optical members such as lens units, glass lenses are becoming resinous, and plastic lenses such as PMMA / PC and polycycloolefin are being used instead of inorganic glass. There is a need for a plastic lens with excellent heat resistance that can withstand reflowable specifications, but in connection with this, the heat resistance of various members such as a light-shielding film having a plurality of minute surface irregularities may be improved. If possible, a reflow process can be performed on the camera module and the like, and the optical member can be reduced in size, thickness, and weight. It can be expected that this will further promote the glass lens resinization.

JP-A-1-12503 JP 2003-147275 A JP 2003-266580 A

As described above, a resin film having a plurality of minute surface irregularities has light scattering properties, can reduce glossiness, and can be used for various applications. Among them, those that have basic performance such as heat resistance and can withstand reflowable specifications are required to be smaller, thinner, and lighter, and light scattering that is rapidly progressing in high functionality and high added value. It can be suitably used as an optical member such as a light-shielding film and a light-shielding film further imparted with a light-shielding property.
First, in order to obtain a resin film having such light scattering properties, the present inventors are effective to have a plurality of minute uneven shapes on the surface of the resin film. It has been found that it is effective to use a cured resin film formed from a curable resin composition as one having a basic performance such as the above and withstanding the reflowable specification.
Next, in order to form a plurality of minute uneven shapes controlled on the surface, for example, it is preferable to prepare a cured resin film using a mold having a surface uneven shape by a transfer method. From the transferability of the mold, it has been found that the formation of surface irregularities is preferably performed before the curable resin composition is completely cured.

However, it has been found that there is a problem peculiar to a curable resin that the glossiness is increased by heat curing and the light shielding property is lowered. This is considered to be due to a decrease in surface unevenness during heat curing, that is, due to a decrease in surface unevenness effect due to curing. The fact that the glossiness is increased and the surface unevenness effect is caused by the effect of heat curing is proved by the examples described later, so that the surface unevenness forming treatment is performed before complete curing. For example, any method is considered to be affected by heat-curing and increase glossiness.
In addition, when performing post-processing after curing, that is, when forming surface irregularities after complete curing, it is difficult to form surface irregularities so as to reduce the glossiness, for example, processing by sandblasting after complete curing In terms of means, it can be said that it is substantially impossible to obtain a cured resin film having a sufficiently reduced gloss. In the light-scattering film, performance such as a surface glossiness of 20 or less and 10 or less is required, but depending on such means, it is difficult to make the surface glossiness 20 or less and 10 or less. It's impossible. Further, such means is not advantageous in terms of industrial productivity and performance in optical members.
The present invention has been made in view of the above-mentioned present situation, has an optical performance, etc. that has basic performance such as heat resistance, can withstand reflowable specifications, and can sufficiently exhibit the effects of unevenness. It is an object of the present invention to provide a useful cured resin film, a production method thereof, and a light scattering film, a light shielding film, and a lens unit as its use.

The inventors of the present invention have made various studies on resin films having a plurality of minute surface irregularities, and the surface irregularities formed before curing are cured by making macro irregularities and micro irregularities coexist. It has been found that the decrease in the surface unevenness effect due to the above can be suppressed, the above-mentioned problems can be solved brilliantly, and the present invention has been achieved. Furthermore, as a result, it has been found that a cured resin film having a low glossiness, which is not found in the prior art, can be obtained.
Furthermore, in a cured resin film that specifies the height and average interval range of each of the macro uneven shape and the micro uneven shape, and a light shielding film that includes a light shielding layer in which a black material is dispersed and contained in an organic resin, a specific periodicity ( Resin layer (light-shielding layer) having a concavo-convex structure having a period A) and a fine concavo-convex structure (a concavo-convex structure having a period a smaller than the period A) formed on the surface of the concavo-convex structure on the surface (interface). Are preferable) and a preferable form such as a production method is found.

That is, the present invention is a cured resin film having a surface shape constituted by a plurality of concave and convex shapes, the surface gloss of which is lowered by the surface shape, and the cured resin film is at least one surface of the surface Furthermore, a cured resin film having a surface shape constituted by at least two types of uneven shapes of macro and micro, which are different in size, and a mixture of the plurality of macro uneven shapes and the plurality of micro uneven shapes. It is.
The present invention is also a method for producing the cured resin film, wherein the production method forms a concavo-convex shape forming step on the surface of the curable resin film composed of the curable resin composition by transfer. And a step of curing the curable resin film, and a method for producing a cured resin film in which a plurality of macro uneven shapes and a plurality of micro uneven shapes are formed by the uneven shape forming step.
This invention is also a light-scattering film provided with the said cured resin film.
The present invention is further a light-shielding film comprising the light-scattering film, wherein the light-shielding film is a light-shielding film having a transmittance of less than 1% for light having a wavelength of 550 nm.
The present invention is a lens unit including the light-shielding film and a lens, and the lens unit is also a lens unit that is a lens unit for an image sensor.
The present invention is described in detail below.

The cured resin film of the present invention has a surface shape constituted by a plurality of uneven shapes, and the surface glossiness is lowered by the surface shape.
The plurality of concavo-convex shapes only need to be constituted by a plurality of concavo-convex shapes that are optically sufficient to lower the surface glossiness, and the concavo-convex shapes on the cured resin film depending on the use / purpose of the member used. The density in which the concavo-convex shape is formed, the interval between the concavo-convex shapes and the uniformity thereof, the shape and size of the concavo-convex shape itself, the uniformity thereof, and the like may be set as appropriate.
Moreover, although the said uneven | corrugated shape is normally comprised by the some recessed part (it is also called a trough part) and a convex part (it is also called a peak part), a several minute hole is formed in the surface of a cured resin film. It may be configured only by the concave portion or the main portion of the concave portion as provided, and only by the convex portion or mainly by the convex portion such as providing a plurality of minute protrusions on the surface of the cured resin film. It may be configured. As described above, various uneven shapes can be considered in various forms, but in general, they are set in consideration of being suitable for industrial production and capable of effectively reducing the surface glossiness. become. These preferable forms will be described later.
Strictly speaking, even if any flat film is measured with a surface roughness meter or the like to increase the measurement accuracy, it can be said that there is an extremely minute uneven shape, but in the present invention, by a plurality of uneven shapes. To have a configured surface shape, it is necessary to be able to evaluate that the surface glossiness is lowered by the surface shape. For example, when used for a light diffusing film in an optical member, it is preferable to adopt a form in which it is evaluated that the glossiness is lowered so as to have a low glossiness as described later.

As the form of the concave and convex pair of concave and convex shapes, a form in which the concave part and the convex part are adjacent to each other (FIG. 1-1), and a form in which the concave part and the convex part are separated (see FIG. 1-2), the form (FIG. 1-3) etc. with which the convex part exists in a recessed part are mentioned. These sectional views are schematically and conceptually shown in FIGS.
In addition, as the form of the plurality of concave and convex shapes, (1) a concave portion and a convex portion are adjacent to each other and are continuously arranged, and the concave portion and the convex portion are linear. Forms that are shaped like corrugated plates (FIGS. 2-1), (2) Concavities and convexities are adjacent to each other, are continuously arranged, and are concentrically shaped. Forms in which donuts having different sizes are arranged in order (FIG. 2-2), (3) The concave and convex portions are not adjacent to each other and are not continuously arranged, and are in the shape of a sea island. The form (FIGS. 2-3) etc. are mentioned. These perspective views are schematically and conceptually shown in FIGS.
The plurality of concave and convex shapes may or may not have a plurality of concave portions and / or convex portions with orientation. The above forms (1) and (2) are examples of forms having an orientation, and the form in which the concave and convex parts (3) are scattered without regularity is an orientation. It is an example of the form which does not have. Even in the case of the above (3), the concave portions and the convex portions are alternately present in a grid pattern, for example, or the concave portions and the convex portions are linearly arranged, and the straight lines are alternately arranged. Such a form having regularity is also exemplified. In addition to this, a form in which a plurality of grooves in the vertical direction and the horizontal direction are provided on the film surface, which is so-called embossed, can be mentioned.

The cured resin film has at least one surface of which the surface shape is constituted by at least two types of uneven shapes of macro and micro that are different in size, and the plurality of macro uneven shapes and the plurality of micro uneven shapes, Are mixed.
The said surface shape should just be formed in at least one surface of the both sides of a cured resin film, and may be formed only in one surface, or may be formed in both surfaces.
Further, at least one surface of the cured resin film has a group of relatively large uneven shapes, and a group of uneven shapes relatively smaller than the group of uneven shapes exists on the film surface. In the present invention, a group of relatively large uneven shapes is referred to as a plurality of macro uneven shapes, and a group of relatively small uneven shapes is referred to as a plurality of micro uneven shapes. These uneven shapes may have different sizes in the cross-sectional direction (vertical direction) with respect to the film surface, and may have different sizes in the direction along the film surface (horizontal direction). Preferably, the vertical size is relatively macro and micro. In this case, it is normal that the horizontal size is relatively macro and micro. However, what is important in the present invention is the difference in the vertical size that is considered to have a large optical effect. is there.
The uneven shape in each group may or may not have the same size, and it is difficult to precisely align the size on the order of micrometers, but it is industrially large. It is preferable that it is a form which is evaluated that it is complete. The combination of the concavo-convex shape may be a form that can be evaluated that the concave part and the convex part have the same size (for example, a form in which the depth of the concave part and the height of the convex part are substantially the same). The form which cannot be evaluated that a part is the same magnitude | size (For example, the form from which the depth of a recessed part and the height of a convex part differ) may be sufficient. As one embodiment of the present invention, there are a plurality of relatively large uneven shapes, and in the group of these uneven shapes, the size of each uneven shape is strictly different, but relatively There are a plurality of macro concavo-convex shapes having a large vertical size, and apart from that, there are a plurality of relatively small concavo-convex shapes, and the size of each concavo-convex shape in a group of these concavo-convex shapes is strictly A form that can be said to be a plurality of macro uneven shapes that are different but relatively small in the vertical direction is mentioned.
In addition, when it is comprised only by several recessed parts, or several recessed parts as a main body, there may be a form with several recessed parts evaluated that it is a different size apart from that. In addition, there may be a form having a plurality of convex portions that are evaluated to have different sizes. In addition, in the case where the plurality of protrusions are mainly used or the plurality of protrusions are mainly configured, there may be a form having a plurality of protrusions that are evaluated to have different sizes. In addition, there may be a form in which there are a plurality of recesses that are evaluated to have different sizes.

In the present invention, the plurality of macro uneven shapes and the plurality of micro uneven shapes are mixed. As a form to be mixed, on the film surface, (1) a form in which a plurality of micro uneven shapes are present in the unevenness in a plurality of macro uneven shapes, that is, a plurality of micro uneven shapes are present in a region having a plurality of macro uneven shapes. Form that exists, (2) Form in which a plurality of micro concavo-convex shapes exist separately from the concavo-convex in a plurality of macro concavo-convex shapes, that is, a plurality of micro concavo-convex shapes in a region other than a region in which a plurality of macro concavo-convex shapes exist (3) A form in which these forms (1) and (2) are combined.
Among these, if a plurality of macro uneven shapes and a plurality of micro uneven shapes are located at too far away positions, the effect of mixing a plurality of macro uneven shapes and a plurality of micro uneven shapes is considered to be low, The form (1) is preferable, and in the form (2), it is evaluated that the plurality of macro uneven shapes and the plurality of micro uneven shapes are close to each other and the effects of the present invention are sufficiently exhibited. It is preferable to make it.
The form (1) will be described with reference to FIGS. 3-1 to 6 which are schematically and conceptually shown in cross-sectional views. In FIG. 3, all the solid line parts represent the cross-sectional shape on the film surface. In FIG. 3A, the micro uneven shape is present in the macro uneven shape indicated by the dotted line, and in FIG. 3-2, the micro uneven shape is present in the macro uneven shape indicated by the dotted line. In this case, it can be said that a micro uneven shape or a micro convex shape exists on the macro uneven shape indicated by the dotted line. Also in FIG. 3C, the micro uneven shape is present in the macro uneven shape indicated by the dotted line, but in this case, the micro uneven shape is present below the macro uneven shape indicated by the dotted line or is microscopic. It can be said that there is a concave shape. FIGS. 3-1 to 3 are cases where uneven shapes are continuously present, while FIGS. 3-4 to 6 are cases where micro uneven shapes are scattered rather than continuously.

As a configuration of the present invention, a configuration requirement in which any one of the following (1) to (5) is added to the above configuration requirement, or a combination of two or more or all of them is added. It is preferable to do.
(1) The height of the concavo-convex shape of the macro concavo-convex shape is 10 μm or more.
(2) The height of the concavo-convex shape of the micro concavo-convex shape is less than 10 μm.
(3) The average distance between adjacent macro uneven | corrugated shapes is 10-300 micrometers represented by the average space | interval of uneven | corrugated shape.
(4) The surface shape is a form in which the micro uneven shape is present on the surface of the macro uneven shape.
(5) The surface shape is a form in which the distance between adjacent micro uneven shapes is shorter than the distance between adjacent macro uneven shapes.
The above (1) and (2) are preferably (1) and (2). Thus, the macro uneven shape and the micro uneven shape can be clearly distinguished.
Next, the preferable structure which added the combination of 2 or more of said (1)-(5) is demonstrated.
As a preferable embodiment of the present invention, the macro uneven shape has a height of 10 μm or more, and the average distance between adjacent macro uneven shapes is 10 to 300 μm expressed by the average interval of the uneven shapes, As for the said micro uneven | corrugated shape, the height of an uneven | corrugated shape is less than 10 micrometers, and the said surface shape has the form where a micro uneven | corrugated shape exists in the surface of a macro uneven | corrugated shape.
Thus, in this invention, it is preferable that the height of a macro uneven | corrugated shape is 10 micrometers or more, and the height of a micro uneven | corrugated shape is less than 10 micrometers. The height of the concavo-convex shape is lower in the cross-sectional direction (vertical direction) with respect to the film surface, and the upper one is higher. It is expressed by the height difference from (the highest peak in the mountain).
On the film surface of the present invention, there is usually a group of relatively large concavo-convex shapes and a group of relatively small concavo-convex shapes having different individual sizes in the order of micrometers. The height of the concavo-convex shape is determined by a measuring method capable of measuring the concavo-convex shape of the surface. A method for determining the height of the uneven shape will be described in detail later.
The height of the concavo-convex shape can be expressed by a height difference between the film surface and the lowest point of the concave portion only when the concave portion or the concave portion is the main component. When constituted mainly, it can be expressed by a difference in height between the film surface and the highest point of the convex portion.

In addition, the average distance between adjacent macro concavo-convex shapes is usually represented by the average interval between the concavo-convex shapes because it is difficult to determine the distance from one concavo-convex shape to another adjacent concavo-convex shape. . When a plurality of macro uneven shapes are continuously present, it can be represented by the value of Sm in the measurement method defined in Japanese Industrial Standard (JIS) B0601-1994. This represents an average interval between a plurality of macro uneven shapes, that is, an average of some distances from end to end of a set of macro uneven shapes in the horizontal direction of the film surface. In this invention, it is preferable that the average space | interval of the said macro uneven | corrugated shape is 10-300 micrometers. With respect to this as well, a method for determining the average interval of the concavo-convex shape will be described in detail later.
In addition, the average interval of the above-described macro unevenness shape can be represented by the average distance from the end of the recess in the horizontal direction of the film surface when the recess is formed mainly by the recess or only the recess. Or in the case where the convex portion is mainly used, the average distance from the end of the concave portion to the end in the horizontal direction of the film surface can be represented.
In addition, the concave and convex portions are not adjacent to each other, and the concave and convex portions are separated from each other, as in the form of sea islands that are not continuously arranged. In the existing state, based on the result of observing the uneven shape state with a microscope or the like, the distance from the lowest point of the concave portion in the horizontal direction of the film surface to the lowest point of the adjacent concave portion or the highest point of the convex portion It is possible to determine the average interval of the macro uneven shape by measuring and averaging several times.

The surface shape in the preferable form of the present invention is such that the micro uneven shape is present on the surface of the macro uneven shape. This is a form in which a plurality of micro uneven shapes are present in the unevenness in the plurality of macro uneven shapes described above, that is, a form in which a plurality of micro uneven shapes are present in a region where a plurality of macro uneven shapes are present, as shown in FIG. It is a form as shown by -1-6.
According to the preferred embodiment of the present invention, the difference in size of the concavo-convex shape between the group of macro concavo-convex shapes and the group of micro concavo-convex shapes becomes more sufficient, and the plurality of macro concavo-convex shapes are closely connected. Since the macro uneven shape and the micro uneven shape are closely related to each other, the gloss reduction effect due to the presence of the macro uneven shape and the micro uneven shape, and The effect of suppressing gloss increase by mixing these becomes remarkable.
As described above, the result is obtained by specifying the size (height) and average interval of the macro uneven shape, the size (height) of the micro uneven shape, and the positional relationship where the macro uneven shape and the micro uneven shape exist. In particular, the height and average interval between the macro uneven shape and the micro uneven shape are specified, and it is specified that the macro uneven shape and the micro uneven shape are closely related to each other on the film surface. Become. In such a form, a concavo-convex structure having a specific periodicity (period A) and a fine concavo-convex structure formed on the surface of the concavo-convex structure (a concavo-convex structure having a period a smaller than the period A) are formed on the film surface. It can be said that it is a form to have.

In a preferred embodiment of the present invention, the macro uneven shape has a height of 10 μm or more, and the average distance between adjacent macro uneven shapes is 10 to 300 μm expressed by the average interval of the uneven shapes. The micro concavo-convex shape has a height of the concavo-convex shape of less than 10 μm, and the surface shape includes a form in which the distance between adjacent micro concavo-convex shapes is shorter than the distance between adjacent macro concavo-convex shapes.
Also in the surface shape in the preferable form of the present invention, for example, when there are a plurality of micro uneven shapes in a region where a plurality of macro uneven shapes exist, a plurality of micro uneven shapes exist in a region where one macro uneven shape exists. Therefore, it is specified that the macro uneven shape and the micro uneven shape are closely mixed with each other on the film surface. Such a form can also be said to be one of the forms having a concavo-convex structure having a specific periodicity and a fine concavo-convex structure formed on the surface of the concavo-convex structure on the film surface.
In the cured resin film of the present invention, the above-described micro uneven shape is present on the surface of the macro uneven shape, and the form in which the distance between adjacent micro uneven shapes is shorter than the distance between adjacent macro uneven shapes It is preferable that these are combined.

A preferred form of the height of the macro unevenness is 10 μm or more, more preferably 15 μm or more, still more preferably 20 μm or more, and particularly preferably 25 μm or more. On the other hand, regarding the upper limit of the height of the macro uneven shape, it is preferably 300 μm or less. More preferably, it is 200 micrometers or less, More preferably, it is 150 micrometers or less, Most preferably, it is 100 micrometers or less. Thus, as the height of the macro uneven shape increases, deterioration of the uneven shape due to the heat of the cured resin film tends to be suppressed (excellent heat-resistant shape stability), and as a result, an increase in glossiness due to heat is also suppressed. Although there is a tendency, if the height exceeds 300 μm, there is a possibility that the effect of reducing the glossiness due to having the micro uneven shape may not be sufficient, while if it is less than 10 μm, the macro uneven shape and the micro uneven shape coexist. There is a possibility that the effect of the present invention by making it not sufficient. Moreover, although the preferable form of the average distance between the said adjacent macro uneven | corrugated shape is 10-300 micrometers expressed with the average space | interval of uneven | corrugated shape, regarding the preferable form of the minimum in the various forms mentioned above, it is 20 micrometers or more. It may be 30 μm or more, or 40 μm or more. On the other hand, regarding the preferable form of the upper limit, More preferably, it is 250 micrometers or less, More preferably, it is 200 micrometers or less, Most preferably, it is 150 micrometers or less. Thus, when the average distance between adjacent macro uneven shapes is larger than 300 μm, the effect of coexisting micro uneven shapes in the curing process for producing a cured resin film (effect of suppressing an increase in glossiness due to curing) is obtained. In some cases, the light scattering effect may not be sufficiently exhibited, or the light scattering effect in which the macro uneven shape and the micro uneven shape coexist may not be sufficiently exhibited. On the other hand, when the thickness is less than 10 μm, the light scattering effect based on the micro uneven shape may not be sufficiently exhibited even when the micro uneven shape exists on the surface of the macro uneven shape.

Although the preferable form of the height of the micro uneven shape is less than 10 μm, the lower limit of the height of the micro uneven shape is preferably 0.1 μm or more. More preferably, it is 0.5 μm or more, more preferably 1 μm or more, and particularly preferably 2 μm or more. Thus, it can be said that the higher the height of the micro concavo-convex shape, the greater the influence on the optical properties such as light diffusibility, and the better. On the other hand, when the macro uneven shape mixed with the micro uneven shape is 10 μm or more and is in the vicinity of 10 μm, it becomes difficult to distinguish from the macro uneven shape, and the effect of providing the macro unevenness and the micro unevenness May not be fully exhibited. Therefore, in such a case, the preferred form of the upper limit of the height of the micro uneven shape is more preferably 9.5 μm or less, still more preferably 9.0 μm or less, and particularly preferably 8 μm or less. .5 μm or less.
Moreover, it is preferable that the preferable form of the average distance between the said adjacent micro uneven | corrugated shape is 0.1-10 micrometers expressed with the average space | interval of an uneven | corrugated shape. The preferred form of the lower limit may be 0.3 μm or more, 0.5 μm or more, or 1.0 μm or more. On the other hand, the preferred form of the upper limit is more preferably 9.0 μm or less, still more preferably 7.0 μm or less, and particularly preferably 5.0 μm or less. Thus, even if the average distance between adjacent micro uneven shapes is less than 0.1 μm or more than 10 μm, the light scattering performance may not be sufficiently exhibited.

Furthermore, as a preferable form of the present invention, the surface shape is a form in which a plurality of macro uneven shapes have orientation or a sea-island shape without orientation, and the micro uneven shape exists on the surface of the macro uneven shape. The form which consists of is mentioned. The orientation of the micro uneven shape is not particularly limited and is preferably present on one surface.
In such a form, since a plurality of micro uneven shapes are present on the surface of a plurality of macro uneven shapes, a plurality of macro uneven shapes have a form of orientation or a shape of a sea island without orientation. In any case, the macro uneven shape and the micro uneven shape are closely mixed with each other on the film surface. The size (height) and the average interval between the plurality of macro uneven shapes and the plurality of micro uneven shapes are preferably specified as described above.
As proved by the examples and comparative examples described later, a certain degree of gloss is usually obtained even in a form in which only a plurality of macro uneven shapes are present or in a form in which only a plurality of micro uneven shapes are present. Even if it has a lowering effect, it cannot be desired to suppress the gloss increase after curing.
When mixed as in the preferred embodiment of the present invention described above, the form in which the micro uneven shape is present on the surface of the macro uneven shape or the distance between adjacent micro uneven shapes is shorter than the distance between adjacent macro uneven shapes. If it is a form, the gloss increase inhibitory effect after hardening can be expressed notably.
In the cured resin film of the present invention, various preferred forms as described above can be considered, but the important thing is that the macro uneven shape and the micro uneven shape are closely related to the film surface and cured. This is to enhance the effect of suppressing the subsequent gloss increase. What is necessary is just to design a film surface shape in consideration of each shape of the macro unevenness | corrugation shape of a film surface, and a micro unevenness | corrugation shape, and those relevance (positional relationship) so that such an effect can be expected.

Next, a method for determining the height of the concavo-convex shape, the average interval, and the like will be described in detail with reference to FIGS. 4 and 5.
Regarding the height of the above-mentioned macro unevenness, the profile obtained by applying a smoothing process to smooth the height on the film surface in order to reduce the influence of extremely fine unevenness (including micro unevenness) and noise. Is measured by the same measurement method as Ry of Japanese Industrial Standards (JIS) B0601-1994, and it is preferable to obtain a value obtained by averaging the number of measurement points as 3. The smoothing process means smoothing the waveform of the profile graph by averaging the shape data when there is noise in the measurement data. The conditions for the smoothing treatment are described in catalog name “Color 3D Laser Microscope VK-9700 / VK-8700 Shape Analysis Application VK-H1A1 Reference Manual”, KEYENCE Inc., p. The method described in 7-15, 7-22 may be used.
This will be described in detail with reference to FIG. FIG. 4 is a model cross-sectional view of the concavo-convex shape on the film surface, where the X axis is a line drawn in the horizontal direction with respect to the film surface, and the Y axis is a line drawn in the direction perpendicular to the film surface. Yes, this Y axis represents the height direction. In this figure, the line along the concavo-convex shape is called the roughness curve f, and the line drawn along the film surface at the average value of the height on the Y axis of the roughness curve f at the reference length (l). This is called the average line m, which is the X axis.

In FIG. 4, the curve f is uneven in the negative direction of the Y axis in the direction of increasing the value of the X axis (rightward toward FIG. 4) from one point on the X axis (this point is A). Create a trough (concave) part, intersect the X axis (the point on the X axis that intersects this X axis is B), and create a concavo-convex peak (convex) part in the positive direction of the Y axis. (A point on the X axis that intersects this X axis is designated as C). A pair of a trough portion in the negative direction of the Y axis and a crest portion in the positive direction on the curve f is a combination of one concave and convex portion. Here, a combination of one concavo-convex shape of the macro concavo-convex shape is shown, but for a small concavo-convex shape between AB and BC, the height of the macro concavo-convex shape and the average distance described later are determined. Then, it shall not be considered. The explanations in FIG. 4 described above also apply to FIG.
In FIG. 4, the height Ry is obtained by extracting only the reference length (l) from the roughness curve f in the direction of the average line m, and the interval between the peak line and the valley bottom line of the extracted part is orthogonal to the average line. Measured in the direction, this value is expressed in micrometers (μm).

About the average distance between the said adjacent macro uneven | corrugated shape, it is preferable to represent with Sm of the average space | interval (JIS B0601-1994) of an uneven shape. The value of Sm is preferably in the range as described above. This will be described in detail with reference to FIG. FIG. 5 is a model cross-sectional view of an uneven shape on the film surface similar to FIG. Here, in order to reduce the influence of fine unevenness and the influence of noise, it is obtained from a cross-sectional view obtained by analyzing a profile obtained by performing a smoothing process such as height smoothing.
In FIG. 5, the average interval (Sm) of the concavo-convex shape is extracted by a reference length (l) from the roughness curve f in the direction of the average line m, and in this extracted portion, one trough and one adjacent to it The length of the average line m corresponding to the peak (referred to as the interval between the irregularities) is obtained, and the arithmetic average value of the intervals between the numerous irregularities is represented. In Japanese Industrial Standard (JIS) B0601-1994, the above (Sm) is expressed in millimeters (mm), but in the present invention, it is determined in units of micrometers (μm). The trough and the peak constitute one uneven combination. Said Sm is calculated | required by a following formula.

In the formula, Smi represents the interval between the projections and depressions, and represents an integer from i = 1. n represents the number of unevenness intervals within the reference length.

Regarding the height of the micro uneven shape, it is preferable to measure the height of the fine uneven shape present in the macro unevenness from the roughness curve f from the graph, and to set the range from the lower limit value to the upper limit value as the height. .
The average distance between the adjacent micro uneven shapes is preferably represented by Sm of the average interval of the uneven shapes (JIS B0601-1994).
However, in the case of the micro concavo-convex shape, the calculation is performed in the same manner as described above without performing the smoothing process of height smoothing in both the height and the average distance. In other words, it is preferable that the above-described smoothing process eliminates the uneven shape having a height of less than 10 μm. The profile obtained by performing the smoothing process in this way is analyzed to obtain the macro uneven shape. The height and average distance are obtained, and the profile obtained without performing the smoothing process is analyzed to obtain the height and average distance of the micro uneven shape.
In addition, in the formation of the film surface, when the macro uneven shape and the micro uneven shape are separately provided and these are mixed, the height of the micro uneven shape and the average distance are the film surface provided only with the micro uneven shape. Can be measured.
Further, the height and average distance of the concavo-convex shape may be obtained as described above. For convenience, when a mold for imparting the concavo-convex shape described later is used when forming the film surface, the mold is used. You may express by the height of the uneven | corrugated shape in this unevenness, and an average distance.

As the concavo-convex shape, it is preferable that the concavo-convex is formed without containing fine particles other than black fine particles in the cured resin film. When the irregularities are formed by containing fine particles, the fine particles are usually white or light-colored fine particles, so that the fine particles existing in the vicinity of the surface of the cured resin film serve as a light transmission path. When making a cured resin film excellent in heat resistance, the heat resistance is also required for the fine particles used. However, when white (or light-colored) fine particles having high heat resistance such as spherical silica and silicone resin particles are used, it may be an inhibiting factor for blackening in order to obtain excellent light shielding properties. Furthermore, in order to obtain sufficient light-shielding properties, it is necessary to add a large amount of black fine particles, which is disadvantageous for the formation of uniform unevenness on the surface. Further, when forming irregularities using fine particles, particles having a uniform particle size distribution are necessary for forming uniform irregularities, which may be expensive.
The cured resin film preferably has a concavo-convex structure on the surface opposite to the surface having the surface shape. By having the concavo-convex structure on the opposite surface, the above-described effects are sufficiently exhibited.

The cured resin contained in the cured resin film of the present invention contains a curable resin cured product. By including the above cured resin, preferably by including it mainly, a cured resin film having excellent heat resistance can be obtained at low cost. Moreover, it can have reflow resistance. As such a cured resin, when the cured resin film contains a black material, it is preferable that the cured resin film is excellent in compatibility with the black material and is uniformly dispersed in the cured resin. The cured resin film of the present invention may contain other components as long as the cured resin is essential, and the curable resin raw material before curing and, if necessary, other components and The composition containing is called a curable resin composition. In the present specification, the curable resin cured product is a cured or semi-cured curable resin. For example, a form having a cross-linked structure formed by cross-linking the curable resin is also a preferred form. one of.

Unlike the curable resin which comprises a cured resin film, the curable resin raw material in the said curable resin composition is a precursor or a monomer. For example, when the curable resin raw material is an epoxy resin that is a curable resin, the following forms are exemplified. When curable resin which comprises the said cured resin film is a cationic cured epoxy resin, a polyfunctional epoxy compound is mentioned as a curable resin raw material. In addition, when the curable resin composition contains a curing agent such as an acid anhydride, a polyvalent amine, or a polyhydric phenol in addition to a curable resin raw material such as a polyfunctional epoxy compound, these curing agents are also cured. It is a basic resin material. In addition, it is a preferable form as curable resin composition that the curable resin composition contains a cationic curing catalyst.

Examples of the curable resin include a resin curable by ultraviolet irradiation (ultraviolet curable resin), a resin curable by heating (thermosetting resin), a resin curable by electron beam irradiation (electron beam curable resin), and light. Any resin that cures upon irradiation of (a photocurable resin) may be used. The molecular weight before curing of such a curable resin is not particularly limited, and a resin having a high molecular weight to an oligomer can be used. As a form of the curable resin raw material containing a curable resin, for example, (1) a form made of a liquid or solid curable resin, (2) a liquid or solid curable resin, and lower than the curable resin, A form containing a molecular weight curable compound or a solvent (non-curable), and (3) a liquid or solid non-curable resin, and a curable compound having a lower molecular weight than the non-curable resin The form etc. are mentioned. Examples of the form containing (3) a liquid or solid non-curable resin and a curable compound having a lower molecular weight than the non-curable resin include an oligomer component of an acrylic resin such as PMMA, a (meth) acrylate monomer, and the like. The form to contain can be mentioned.

As the curable resin, for example, a compound having at least one epoxy group, a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, and the like can be suitably used. It can also be used as a mixture of the above. Among these, it is preferable to have at least one epoxy group. By having at least one epoxy group, heat resistance comparable to that of inorganic glass is exhibited, and excellent properties such as excellent molding and workability can be exhibited. A compound having at least one epoxy group, a polyhydric phenol compound, and a compound having a polymerizable unsaturated bond that can be suitably used as the curable resin used in the present invention will be described in detail later.
The epoxy group is an organic group having an oxirane ring, and an organic group having an oxirane ring such as a glycidyl group includes an epoxy group. Therefore, the compound having an epoxy group includes a compound having a glycidyl group. It is also a preferred embodiment that the compound having at least one epoxy group is a compound having at least one glycidyl group. Furthermore, it may have a plurality of epoxy groups, and in addition to the glycidyl group, an epoxy group different from the epoxy group possessed by the glycidyl group may coexist.
Moreover, as a curable resin, an epoxy resin raw material, a poly (amide) imide resin raw material, etc. can be used suitably. Epoxy resin is preferable because it is a heat-resistant resin having a high Tg, and optical characteristics, in particular, low transmittance wavelength dependency. Poly (amide) imide resin is a heat-resistant resin having a Tg of 150 ° C. or higher. It is preferable from a certain point. In addition, Tg of curable resin hardened | cured material, such as an epoxy resin and poly (amide) imide resin, means Tg in hardened | cured material after hardening. The Tg of the cured curable resin after curing the curable resin is not particularly limited, but is preferably 100 ° C. or higher from the viewpoint of heat resistance. More preferably, it is 120 degreeC or more, More preferably, it is 150 degreeC or more.
The poly (amide) imide resin will be described later in detail.
In the present invention, poly (amide) imide resins preferable as the cured resin for the cured resin film include those that do not melt even when heated at a temperature of 400 ° C. or lower, and those that can melt. In the poly (amide) imide resin in the present specification, the former (one that does not melt even when heated at a temperature of 400 ° C. or lower) is referred to as a cured curable resin. In the description of the poly (amide) imide resin, the former material (which does not melt even when heated at a temperature of 400 ° C. or lower) is obtained when speaking of the raw material of the curable resin or the curable resin cured product. Means raw material for.

The cured resin film preferably has a glossiness of 20 or less. When the glossiness of the cured resin film exceeds 20, light shielding is not sufficient and, for example, when used as a lens unit, it may cause malfunction as noise. More preferably, it is 10 or less, More preferably, it is 5 or less. The glossiness is measured at a measurement angle (θ) of 60 degrees using a gloss meter VG-2000 manufactured by Nippon Denshoku Industries Co., Ltd.

The cured resin film of the present invention preferably contains a black material. The black material imparts light shielding properties to the cured resin film of the present invention, and various black materials can be used. As content of the black material in the said cured resin film, it is preferable that it is 1-50 mass% in a total of 100 mass% of a black material and cured resin. If it is less than 1% by mass, the light-shielding property may not be sufficient, and if it exceeds 50% by mass, the viscosity of the curable resin composition is too high to handle and the film may break after film formation. There is. More preferably, it is 3-40 mass%, More preferably, it is 5-30 mass%.
The black material is preferably present by being dispersed or dissolved in the curable resin composition. When it does not exist in a dispersed or dissolved state, the cured resin film is not uniformly black, and there is a possibility that a sufficiently excellent light shielding property may not be exhibited. That is, the cured resin film of the present invention is preferably obtained using a curable resin composition obtained by dispersing or dissolving a black material in a curable resin material (resin binder).

Examples of the black material include carbon black fine particles such as carbon black and graphite; inorganic black fine particles such as metal oxide black fine particles such as titanium black; black organic fine particles such as aniline black (organic black fine particles); etc. Black fine particles, anthraquinone, indigoid, diazo black organic dye, and the like can be suitably used. The inorganic black fine particles (inorganic black material) include magnetite, cuprous oxide (cuprous oxide), composite oxide black fine particles containing copper and chromium as main metal components, copper, other than the above titanium black, copper Complex oxide black fine particles containing copper and iron as main metal components, composite oxide black fine particles containing copper, iron and manganese as main metal components, and complex oxide black fine particles containing cobalt, chromium and iron as main metal components Etc. is also one of the preferred forms.
Among the black materials, a fine particle black material (black fine particles) is preferable, and various black fine particles can be used. Among the black fine particles, carbon black fine particles and inorganic black fine particles are preferable in terms of excellent heat resistance. A carbon-based material such as a carbon-based fine particle is preferable in terms of excellent light-shielding performance in the visible light region, and can be imparted with a uniform black color to the cured resin film by being ultrafine and having excellent dispersibility in the cured resin. Carbon black is more preferable. In addition to excellent heat resistance, carbon black is preferable because it has a high degree of black and is inexpensive.

The black fine particles preferably have a primary particle diameter of 1 μm or less. More preferably, it is 0.1 μm or less. Moreover, the particle | grains by which secondary aggregation was suppressed are preferable. Furthermore, when the black fine particles are dispersed in the cured resin, it is preferable that the black fine particles have a particle size of 1 μm or less. The particle diameter of the black fine particles when dispersed in the cured resin is more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. When the black fine particles are dispersed in the cured resin, the hue (black) becomes uniform when the black fine particles are dispersed with a fine particle diameter. In addition, when the treatment for forming irregularities on the surface of the cured resin film is performed, if the particle size of the black fine particles is dispersed at 1 μm or less, there is no generation of defects due to the coarse particles of the black fine particles, and the workability is improved. Excellent.
The primary particle diameter can be measured by a transmission electron microscope image.
The black fine particles may exist in such a way that the primary particles exist independently without secondary aggregation or association, or the primary particles form a structure in which the primary particles aggregate in one, two, or three dimensions. The said primary particle diameter means the magnitude | size of a primary particle in any case. For example, when the black fine particles are carbon black, the particle diameter in the case where the primary particles are almost spherical or granular (has a contour due to microcrystals and is more difficult to be divided).
The size of the primary particles can usually be measured by a transmission electron microscope image, and the number average value (average primary particle diameter) is more preferably in the above range. In determining the average primary particle size, it is preferable to measure the size of 20 or more primary particles and determine the average of the measured values.
Further, when it is difficult to measure the size of the primary particles from the transmission electron microscope image, B.I. E. T. T. The specific surface area diameter calculated by the following formula using the specific surface area value measured by the method can be substituted as the average primary particle diameter.
Specific surface area diameter (μm) = 6 / (ρ × S)
(In the formula, ρ represents the true specific gravity. S represents the specific surface area (m ² / g).)
The particle size of the black fine particles when dispersed in the resin composition can be measured by using a dynamic light scattering type particle size distribution measuring device such as LB-500 (manufactured by Horiba Seisakusho). In the present invention, a volume-based arithmetic average value is adopted.

When the black fine particles are carbon black, dibutyl phthalate oil absorption can be used as a dispersibility index. The oil absorption is preferably 300 ml / 100 g or less. Thus, a cured resin film in which the black fine particles contain carbon black having an oil absorption of 300 ml / 100 g or less is also a preferred embodiment of the present invention. When the oil absorption exceeds 300 ml / 100 g, the dispersibility of the carbon black is deteriorated, the hue (black) is not sufficiently uniform, coarse particles of the carbon black are formed, and a process for forming irregularities on the surface is performed. There is a possibility that the processability at the time may not be sufficiently excellent. The oil absorption is more preferably 250 ml / 100 g or less, and still more preferably 200 ml / 100 g or less. The oil absorption amount indicates the characteristics of the carbon black itself (of the powdered carbon black), and indicates the characteristics of the carbon black before being dispersed in the cured resin or the like. Further, the oil absorption amount increases when the carbon black is aggregated and decreases when the carbon black is dispersed. As the carbon black is more dispersed, the uniformity in the cured resin film is improved. Therefore, it is preferable that the oil absorption is smaller. Thus, the cured resin film preferably has a form in which black fine particles are dispersed. That is, the cured resin film of the present invention is preferably obtained using a curable resin composition in which black fine particles are dispersed and contained in a curable resin material (resin binder) as a raw material. Moreover, it does not specifically limit as a containing form of the black material in a cured resin film. For example, the black resin etc. which are mentioned later are contained in the cured resin film as particles (black material-containing particles) dispersed and contained in other components such as a resin. Moreover, it does not specifically limit as preferable resin which comprises black material containing particle | grains, The resin mentioned later is mentioned as a preferable cured resin which comprises a cured resin film. Furthermore, as a specific aspect, the black material-containing particles are preferably black material-containing particles containing a cured resin having the same or equivalent refractive index as that of the cured resin contained in the cured resin film.

The means (method) for dispersing or dissolving the black material (preferably black fine particles) in the resin binder (curable resin raw material) is not particularly limited, and various methods can be suitably used. For example, when the resin binder is soluble in a solvent, a method in which a black material is mixed and dispersed or dissolved in a resin binder solution in which a curable resin material is dissolved in a solvent, and the resin binder is dissolved in a dispersion in which the black material is dispersed. Various methods such as a method of mixing, dispersing and dissolving a black material in a dispersion in which a resin binder is dispersed in fine particles, a method of melting and kneading a mixture of a resin binder and black particles, and the like. And can be appropriately selected and used according to the cured resin. Among these, a method in which the curable resin raw material is solvent-soluble and a black material is mixed and dispersed or dissolved in a resin binder solution in which the curable resin raw material is dissolved in a solvent is preferable. When the curable resin material is solvent-soluble, it is easy to uniformly disperse or dissolve the black material in a mixture (for example, curable resin material solution) composed of the curable resin material and the solvent. A curable resin composition uniformly dispersed or dissolved is obtained, and as a result, an excellent light-shielding curable resin film in which the black material is uniformly distributed can be obtained. Thus, a cured resin film comprising a cured resin in which the curable resin raw material is solvent-soluble is also a preferred embodiment of the present invention.

The solvent is appropriately selected according to the type of resin, but ketones such as methyl ethyl ketone (2-butanone), methyl isobutyl ketone (4-methyl-2-pentanone), cyclohexanone, etc .; PGMEA (2-acetoxy-1- Methoxypropane), glycol derivatives such as ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol ethyl ether acetate (ether compounds, ester compounds, ether ester compounds, etc.); amides such as N, N-dimethylacetamide Esters such as ethyl acetate, propyl acetate and butyl acetate; pyrrolidones such as N-methyl-2-pyrrolidone (more specifically, 1-methyl-2-pyrrolidone); aromatic carbonization such as toluene and xylene; Hydrogen; cyclohex Emissions, aliphatic hydrocarbons such as heptane; ethers such as diethyl ether and Djibouti ether and the like.
More preferably, the solvent is methyl ethyl ketone (2-butanone), methyl isobutyl ketone (4-methyl-2-pentanone), cyclohexanone, PGMEA (2-acetoxy-1-methoxypropane), N, N-dimethylacetamide, Examples include ethyl acetate and 1-methyl-2-pyrrolidone (NMP).
Further, the curable resin raw material is a precursor polymer such as polyamic acid which is a poly (amide) imide resin raw material, or an aromatic diamine compound and an aromatic tetracarboxylic dianhydride which are raw materials of the precursor polymer. , 1-methyl-2-pyrrolidone, N, N′-dimethylacetamide, aromatic hydrocarbons, and mixtures thereof are more preferred. When the curable resin raw material is a polyfunctional epoxy compound that is a raw material of an epoxy resin, or a polyfunctional epoxy compound and a curing agent, ketones, aromatic hydrocarbons, glycol derivatives, or these More preferably, it is a mixture.

As the solvent-soluble curable resin raw material, among the curable resin raw materials described above, an epoxy compound and a poly (amide) imide resin precursor polymer which are various solvent-soluble epoxy resin raw materials are preferable.
The solvent-soluble epoxy compound is, for example, a cation curing of a polyfunctional epoxy compound in the presence of a cation curing catalyst, or a curing of a polyfunctional epoxy compound using a curing agent such as an acid anhydride or a polyvalent amine. Therefore, a cured product (epoxy resin cured product) can be obtained. In any case, as a preferred embodiment, a light-shielding resin composition obtained by dispersing or dissolving a black material in the precursor polymer of the poly (amide) imide resin or an epoxy compound solution (cationic curing catalyst or curing agent). A light-shielding film is obtained by applying, drying, and heating (poly (amide) imidization and curing).
As the usage-amount of the said solvent, 150 weight part or more is preferable with respect to 100 weight part of organic resin raw materials, and 1900 weight part or less is preferable. More preferably, it is 200 parts by weight or more and 1400 parts by weight or less.

Since the cured resin film of this invention consists of the structure mentioned above, since it becomes a film which suppresses regular reflection of light, is excellent in light scattering property, and has low glossiness, it can be used suitably for a light scattering film. Such a light-scattering film including the cured resin film is also one aspect of the present invention. When the light scattering film contains, for example, a) a white pigment such as barium sulfate or titanium oxide, b) a carbon-based black fine particle such as carbon black or graphite; Inorganic black fine particles such as metal oxide black fine particles such as titanium black; Black fine organic particles such as aniline black (organic black fine particles); Black fine particles such as anthraquinone, indigoid and diazo black organic dyes When it contains a black material, it is useful as a light-shielding film. C) When it is transparent or semi-transparent, it is useful as a light-diffusing film having both diffusibility of transmitted light and scattering of reflected light.
Moreover, the light-shielding film can have a transmittance of less than 1% for light having a wavelength of 550 nm by using the light-scattering film of the present invention. Thus, the light-shielding film which consists of the said light-scattering film, Comprising: As for this light-shielding film, the light-shielding film whose transmittance | permeability with respect to the light of wavelength 550nm is less than 1% is also one of this invention.
The said transmittance | permeability is a value obtained by measuring the transmittance | permeability in 380-780 nm using the ultraviolet visible spectrophotometer needle | hook (Shimadzu UV-3100 (made by Shimadzu Corporation)).

Next, although the light-shielding film will be described, the same configuration can be applied to the above-described light-scattering film, which is an upper conceptual application of the light-shielding film.
Although the said light-shielding film will not be specifically limited if it is provided with the cured resin film of this invention, The other component may be contained as needed. In the case where the cured resin film is a thin film that does not have sufficient strength, it is preferable to include a base material in order to obtain sufficient strength. Thus, as a light-shielding film, (1) the form which is a laminated film consisting of a base material and a cured resin film (one side), (2) the form which is a laminated film consisting of a base material and a cured resin film (both sides), (3) The form which is a cured resin film single layer is suitable. The schematic diagram of these forms is shown in FIG. 6A shows the form of (1), (b) shows the form of (2), and (c-1) and (c-2) show the form of (3). In addition, you may set suitably the layer which has another function in the said light-shielding film.
In the forms of (1) and (2), since the strength of the light-shielding film can be obtained by the base material, the cured resin film can be thinned. By thinning the cured resin film, it is easy to control the film thickness when applying the curable resin composition, and when drying, the solvent contained in the composition can be removed by evaporation in a short time. It has an advantage that a cured resin film in which the generation of defects in the film that causes a decrease in light shielding performance such as generation of bubbles accompanying evaporation is suppressed can be easily obtained.
In the form of the laminated film comprising the base material and the cured resin film of (1) and (2), the thickness of the cured resin film is preferably 5 μm or more. More preferably, it is 10 μm or more. Moreover, as an upper limit of the thickness of a cured resin film, it is preferable that it is 80 micrometers or less, More preferably, it is 50 micrometers or less, More preferably, it is 30 micrometers or less. Moreover, as a particularly preferable range, it is 10-30 micrometers.
In the form in which the light-shielding film of (3) is composed of a single layer of cured resin film, the thickness of the cured resin film depends on the cured resin of the cured resin film, but it is easy to perform post-processing of the film and has excellent mechanical strength. From the viewpoint, it is preferably 20 μm or more, more preferably 30 μm or more. Although the upper limit of the thickness of the cured resin film depends on the material of the cured resin film, it is preferably 200 μm or less, more preferably 200 μm or less in view of sufficient light shielding performance and application to a lens unit that is highly demanded of thinning. 100 μm or less. A particularly preferable range is 30 to 80 μm.
The light-shielding film may further have a layer other than the cured resin film and the substrate. Although the thickness of a light-shielding film changes also with the form of a light-shielding film, and the application to apply, it is preferable that it is 1-1000 micrometers. More preferably, it is 10-200 micrometers as thickness of the said cured resin film, More preferably, it is 20-100 micrometers. Here, the thickness of the cured resin film is a thickness obtained by measuring the cured resin film with a micrometer. By setting the thickness of the cured resin film to 1 to 1000 μm, the light-shielding film of the present invention becomes thin. For example, when the light-shielding film is used as an optical member, the optical path can be shortened. Thereby, this optical member (for example, camera module etc.) can be thinned.

When the said light-shielding film has layers other than a cured resin film and a base material, the surface shape comprised by the several uneven | corrugated shape of this invention is the surface in which the said layer (layers other than a cured resin film) is formed. Is preferably formed on the opposite surface of the cured resin film. More preferably, both surfaces of the light-shielding film have the surface shape.

In the above light-shielding film, the arrangement of the cured resin film and the substrate in the case of having a substrate is not particularly limited, and any of the incident light surfaces is not particularly limited because the effects of the present invention are exhibited, but the reflection is not limited. For prevention, a mode in which the cured resin film is disposed on the incident light surface is preferable.
The shape of the light-shielding film can be appropriately selected according to the application. When the lens is attached to a lens unit, it can be effectively transmitted and light other than the optical path by sticking it to the heel that fixes the lens. Reflection can be suppressed, and optical noise can be reduced. That is, in the lens unit, as schematically shown in FIG. 7, it is preferable that a light-shielding film (in particular, a cured resin film) is attached to a bag for fixing the lens. That is, the positional relationship between the lens and the cured resin film in the lens unit is preferably that schematically shown in FIG. 8 when viewed as a cross-sectional view of the lens unit. Therefore, it is preferable that the cured resin film of the light-shielding film has a planar shape (ring shape) as schematically shown in FIG. 9 when viewed from the lens unit incident light side. The center of the ring may be a cavity, a transparent film that transmits visible light, or a lens. Preferably, the center of the ring is a cavity.

The light-shielding film preferably has a single layer structure. That is, the form comprised only with a cured resin film is suitable. By adopting such a form, the thickness of the light-shielding film can be reduced, and when used for optical applications (lens units), the optical path can be shortened, and the lens unit can be reduced in size and thickness. it can. A schematic diagram of a light-shielding film having a single-layer structure is shown in FIG. FIG. 6C-1 shows a form in which the unevenness is formed on one side, and FIG. 6C-2 shows a form in which the unevenness is formed on both sides.

When the light-shielding film has a substrate (FIGS. 6a and b), the light-shielding film can have sufficient strength. As a material which comprises the said base material, any of an organic material, an inorganic material, an organic-inorganic composite material, and a metal material may be sufficient, and these may use 1 type, or 2 or more types. The above organic materials (for example, thermoplastic resin compositions and curable resin compositions) are easy to handle, the inorganic materials (for example, glass) are excellent in thermal expansion coefficient, and the organic / inorganic composite material has the characteristics of both. It is suitable from the point of providing. Any of these materials can be suitably used, but a material having reflow resistance is preferable.

The material of the substrate constituting the light-shielding film is preferably a material having reflow resistance. Specifically, (1) a fluorinated aromatic polymer, (2) a polycyclic aromatic polymer, ( It is preferable to include at least one selected from the group consisting of 3) poly (amide) imide resin, (4) fluorine-containing polymer compound, (5) glass film, and (6) polyetherketone resin. Thus, the light-shielding film is at least one selected from the group consisting of a fluorinated aromatic polymer, a polycyclic aromatic polymer, a poly (amide) imide resin, a fluorine-containing polymer compound, a glass film, and a polyether ketone resin. A light-shielding film comprising one material is also a preferred embodiment of the present invention.

As the substrate, any of the materials described above can be suitably used. As the material for the substrate, two or more kinds may be mixed or laminated. Among them, when two or more kinds are laminated to form a substrate having a multilayer structure, a plurality of characteristics of the material to be used are exhibited, and the substrate can be suitably used. For example, in applications such as camera modules where the light-shielding film needs to be thinned to less than 100 μm, there is a problem that when an inorganic material such as glass is thinned (for example, 30 μm to 100 μm), the organic material and / or Alternatively, by laminating with the organic / inorganic composite material, when the light shielding layer is further laminated on the base material, the base material is not deformed or cracked, and the base material is suitable as an optical member. More preferred is a form in which an organic resin is formed on one or both sides of a glass thin film, and particularly preferred is a form in which an organic resin is formed on both sides. Further, from the viewpoint of preventing cracking, an organic substance may be laminated after the light shielding layer is formed.

The thickness of the substrate can be appropriately selected according to the thickness of the light-shielding film. For example, when glass is used as the substrate, the thickness of the glass is preferably 30 to 500 μm, more preferably The thickness exceeds 100 μm. In the case of using a resin, for example, poly (amide) imide, kapton and the like can preferably use a sheet having a thickness of about 100 μm, but a film having a thickness of less than 100 μm is preferable.

It is preferable that the material in this invention has heat resistance, and it is preferable that a cured resin film or a base material has such a characteristic. When the cured resin film has a substrate as described above, it is preferable that both the cured resin film and the substrate have heat resistance.
As the heat resistance temperature of the cured resin film (especially light-shielding film) and the heat resistance temperature of the substrate, the 10% decomposition temperature is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and further preferably 300 ° C. or higher. 350 ° C. or higher is most preferable. Tg is preferably 80 ° C. or higher, more preferably 150 ° C. or higher, further preferably 200 ° C. or higher, and most preferably 250 ° C. or higher. By using such a substrate having reflow resistance and a cured resin film (particularly a light-shielding film), it can be suitably applied to automatic mounting of a light-shielding film or the like.

In this specification, “having heat resistance” means having high resistance to heat. For example, in materials such as organic resins, Tg is high and decomposition temperature is high (preferably 10% decomposition). It is preferable to satisfy at least one of a high temperature), a cured resin film, a light-scattering film, particularly a light-shielding film, a use using the film (for example, a lens unit), and a substrate used in these, It is preferable to satisfy at least one of excellent shape retention, low dimensional change rate, and high decomposition temperature (preferably high 10% decomposition temperature). “Having reflow resistance” means that it has sufficient resistance to the temperature used in the reflow process, and as in the case of having heat resistance, for example, in materials such as organic resins, Tg is It is preferable to satisfy at least one of high and high decomposition temperature (preferably high 10% decomposition temperature). In cured resin film, light scattering film, light-shielding film, substrate, lens unit, etc. It is preferable to satisfy at least one of excellent shape retention and high decomposition temperature (preferably high 10% decomposition temperature). As preferable requirements for Tg, decomposition temperature, shape retention, and the like, it is preferable to satisfy the preferable requirements for the above-described characteristics.

Next, the manufacturing method of the cured resin film of this invention is demonstrated.
The method for producing a cured resin film of the present invention is a method for producing the cured resin film, wherein the production method comprises a continuous concavo-convex shape on the surface of a curable resin film formed from a curable resin composition by transfer. And a step of curing the curable resin film, and a plurality of macro uneven shapes and a plurality of micro uneven shapes are formed by the uneven shape forming step.
By using such a manufacturing method, as described above, the surface shape is constituted by the two types of uneven shapes of macro and micro, and the plurality of macro uneven shapes and the plurality of micro uneven shapes are mixed. A surface shape can be formed, and the shape, size, height, average distance, and the like of the unevenness can be appropriately set. Furthermore, the mat | matte property based on uniform and fine uneven | corrugated shape can be provided to the surface, being excellent in flatness. The concavo-convex shape forming step is not particularly limited as long as the concavo-convex shape on the surface of the cured resin film is formed by transfer. Alternatively, the concavo-convex shape may be formed by transferring the curable resin composition formed into a film, and the means, the order of steps, etc. are not particularly limited. Below, an uneven | corrugated shape formation process is explained in full detail.

The uneven shape forming step is a step of forming a plurality of macro uneven shapes and a plurality of micro uneven shapes on the surface of the curable resin film composed of the curable resin composition. As a method for forming such a surface shape, there is a transfer layer (a concavo-convex layer, a substrate for concavo-convex transfer, a transfer material) for forming a surface shape composed of a macro concavo-convex shape and a micro concavo-convex shape. The surface shape may be formed by a single transfer, or the formation of the micro uneven shape and the formation of the macro uneven shape may be performed separately. When the formation of the micro uneven shape and the formation of the macro uneven shape are performed separately, the means, the order of the steps, etc. are not particularly limited, but the transfer layer for forming the micro uneven shape After the concavo-convex shape forming step using, the concavo-convex shape forming step using the transfer layer for forming the macro concavo-convex shape is preferably performed. This makes it easy to form a micro uneven shape, and it is easy to set the form such as the size, height, and depth of the micro uneven shape.

In forming the surface shape, it is preferable to form a concavo-convex shape on the surface using a transfer layer having a concavo-convex shape to be formed on the surface of the cured resin film. In this case, it is preferable to form irregularities by bringing the curable resin composition into contact with the transfer layer. At this time, the curable resin composition that is not solidified or cured, or has not been solidified or cured is brought into contact with the transfer layer, and dried, solidified, and cured as necessary to form irregularities. Is preferred.
As described above, the curable resin composition only needs to contain a curable resin raw material, and in a preferable form containing a black material, the black material is uniformly dispersed or dissolved in the curable resin composition. It is preferable. In this case, the black material is dispersed or dissolved in a solution in which the curable resin raw material (heat-resistant resin binder raw material) is finely dispersed or dissolved (for example, black fine particles are uniformly dispersed in a fine particle size), and curable. It is preferable to prepare a resin composition and form a cured resin film by a coating method. If it does in this way, homogeneous blackness can be obtained as a light-shielding film, and the outstanding light-shielding property will be exhibited.

In the curable resin composition, the content of the black material is preferably the same as described above. That is, it is preferable that it is 1-50 mass% in 100 mass% of total (solid content) of black material and curable resin, More preferably, it is 1-40 mass%, More preferably, it is 1-30. % By mass. Moreover, it is also preferable that it is 3-40 mass%, More preferably, it is 5-30 mass%.
In the curable resin composition, the solid content (total of the black fine particles and the curable resin raw material) is preferably 5 to 40% by mass in 100% by mass of the curable resin composition. If it is less than 5% by mass, there are many solvents, and it takes time to dry the film, and film thickness characteristics may be deteriorated due to aggregation, etc. If it exceeds 40% by mass, the viscosity is too high to be coated. It may not be possible to More preferably, it is 10-35 mass%, More preferably, it is 15-30 mass%.

In the method for producing the cured resin film, when the curable resin composition is applied to form a resin film, the concavo-convex shape forming step is performed simultaneously with and / or continuously with the step of applying the curable resin composition. It is preferable to do it. By carrying out in this way, it is possible to make the surface uneven by a one-step process that is simultaneous or continuous with the coating process, so that the manufacturing process can be simplified or omitted, the manufacturing time can be shortened, and the manufacturing can be performed at low cost. There are advantages. When the concavo-convex shape forming step is performed at the same time as the coating step, the time during which the step of applying the curable resin composition is performed and the time during which the concavo-convex shape forming step is performed overlap at least partially. It is preferable. For example, when the step of applying the curable resin composition and the step of forming the concavo-convex shape are performed at once (the concavo-convex is formed simultaneously with the application), or the step of applying the curable resin composition This is the case where the concavo-convex shape forming step is performed on the already applied curable resin composition before the process is completed. When the concavo-convex shape forming step is performed continuously with the coating step, the coating step and the concavo-convex shape forming step are performed in a substantially continuous step. In this case, it is preferable to perform the concavo-convex shape forming step immediately after the coating step is completed, but a certain amount of time may be allowed between the time when the coating step is completed and the time when the concavo-convex shape forming step starts. . For example, between the time when the coating process is completed and the time when the concavo-convex shape forming process is started, there may be a time for leaving, or there may be a time for drying the applied curable resin composition. Good. That is, when the concavo-convex shape forming step is performed continuously with the coating step, the step of leaving between the coating step and the concavo-convex shape forming step until the next step is performed and the applied curable resin composition It is preferable not to interpose a process other than the process of drying the liquid.

As the concavo-convex shape forming step, it is preferable to form a concavo-convex shape by bringing the curable resin composition into contact with the transfer layer, and a specific method is appropriately selected according to the composition and characteristics of the curable resin composition. do it. For example, after applying a curable resin composition to a transfer layer (for example, a surface uneven substrate), drying, solidifying, or curing or reacting (for example, reacting polyamic acid to poly (amide) imide). And forming a concavo-convex shape (this is also referred to as transfer method 1 or substrate template transfer method). In this case, usually, after forming the concavo-convex shape, the molded curable resin composition is peeled off from the transfer layer. As the transfer layer, any one of frosted glass and matte film (surface unevenness PET or the like) is preferable. In addition, the curable resin composition is formed into a film in advance, and the film is chemically or compositionally intermediate, or semi-dried, semi-cured, or unreacted / semi-reactive, and then the film. And a method of forming irregularities by bringing the formed film into contact with the transfer layer (this is also referred to as transfer method 2). In this case, the transfer layer is preferably any one of frosted glass, mat film (surface irregular PET, etc.), and mat roll.
That is, a method of forming irregularities by bringing a curable resin composition previously formed into a film into contact with the transfer layer as in transfer method 2 is also one of preferable transfers.

In the transfer method 1, the concavo-convex shape is formed before or during the course of drying / solidifying, curing, or reacting the curable resin composition.
In any of the transfer methods 1 and 2, a liquid composition can be suitably used. That is, the concavo-convex shape forming step includes a step of forming a film made of the curable resin composition on the transfer layer so as to be performed by the transfer method 1, or the curable resin composition is performed by the transfer method 2. It is preferable to form a film from a curable resin composition that is a liquid composition by including a step of forming a film made of a product and bringing the film-shaped film into contact with the transfer layer One of the forms.
As the film forming method in forming the uneven shape in the transfer method 1 and forming the film to be transferred in the transfer method 2, the solvent casting method, spin coating method, bar coater method, roll coater method, gravure coater method, knife A conventionally known coating method such as a coating method may be employed.

In the above transfer method 2, the curable resin composition is formed in a film shape in advance, and the film is chemically or compositionally intermediate, or semi-dried, semi-cured, or unreacted / half-reacted Then, the film-like shape is brought into contact with the transfer layer to form a concavo-convex shape. Therefore, a drying / solidifying or curing step is not necessarily required in the process of forming the uneven shape. Moreover, in the transfer method 2, after forming an uneven | corrugated shape, you may dry, solidify, or harden | cure, and you may dry, solidify, or harden | cure, forming an uneven | corrugated shape. From the viewpoint of more following the uneven shape of the transfer layer, it is preferable to dry, solidify or cure while forming the uneven shape. In the transfer method 2, the curable resin composition is semi-dried and semi-cured beforehand if the curable resin composition provided to the transfer method 2 is in contact with the transfer layer so that an uneven shape can be formed. Say what you want.

In the transfer method 2, when semi-drying and semi-curing in advance, the curable resin composition may be applied on the above-described base material and semi-drying and semi-curing. Further, when a mat roll is used as the transfer layer, it is possible to continuously give an uneven shape to the surface.

As the concavo-convex shape forming step, a mode in which the transfer method 1 and the transfer method 2 are used in combination (also referred to as a transfer method 3) is also preferable. By combining the transfer method 1 and the transfer method 2, the transfer method 1 and the transfer method 2 can form irregularities on different surfaces of the film, respectively, so that both surfaces of the cured resin film can be irregularized.

In the transfer method 3 described above, when the transfer methods 1 and 2 are continuously performed, a mode in which the other transfer is performed immediately after performing one transfer is preferable, but the other transfer is performed after performing one transfer. There may be a certain amount of time until it is performed. Such a time interval can be appropriately selected depending on the material used and the like, and when making unevenness continuously on both surfaces of the cured resin film, the time interval in the production method that is usually used is preferably used. Can do.
When the transfer methods 1 and 2 are continuously performed, a mode in which the transfer method 2 is performed after the transfer method 1 is performed is preferable. For example, the transfer method 1 forms an unevenness on one surface of the cured resin film and the curable resin composition is semi-dried, semi-cured, or has been dried, solidified, or cured, and then transferred. By Method 2, an uneven shape can be formed on the other surface. When a cured resin film is obtained by such a method, a cured resin film having a small dimensional change rate and excellent heat resistance can be obtained as compared with the case obtained by performing only the transfer method 1. Thus, the form in which the uneven shape forming step is based on the transfer method 3 is also a preferred form of the present invention.

The transfer methods 1 to 3 can be used by appropriately selecting one or two or more according to the curable resin composition, the cured resin film to be produced, and the like. Among these, the formation of a stable uneven shape (less shake), the formation of a uniform and fine uneven shape, the excellent size and shape controllability of the uneven shape, and the ability to impart matting properties while being excellent in flatness And the method of 3 is preferable.
In the transfer methods 1 to 3, the base material and / or the transfer layer (unevenness layer) may be integrated with the curable resin composition in the uneven shape forming step. The layer may be laminated with a cured resin film, and the substrate and / or the transfer layer may be removed. Usually, the transfer layer is removed (peeled), and the substrate is removed as necessary. In the above transfer method 1 or 3, when the substrate is removed, a cured resin film having a single layer of cured resin and having a concavo-convex shape on the surface is obtained. Thus, it is possible to realize the formed uneven shape forming film.
As the above-mentioned base material, the above-mentioned base material can be suitably used. However, when the base material is removed, it is preferable that the base material is excellent in releasability in order to separate from the cured resin film after forming the uneven shape. In addition, the curable resin composition is applied to a smooth substrate, and the semi-dried to dry, semi-solidified to solidified, semi-cured to cured, or peeled off from the precursor in a curable resin film state, It is also preferable to form a concavo-convex shape by the transfer method 2.

As the material for the transfer layer (transfer material), frosted glass; matte films (matte treated polymer films) such as matte treated PET films (matpet film), matte treated PP films, and matte PC films are suitable. It can be preferably used in the above-mentioned transfer methods 1 to 3, particularly 1 and 3.
The form of the transfer layer is not particularly limited as long as the surface uneven shape is formed on the surface. For example, the transfer layer may be flat (for example, ground glass, resin or metal), film (for example, Various forms such as a mat film) and a roll (for example, a mat roll) can be used. In particular, in the above transfer method 2, it is preferable to use a mat roll shape, and it is possible to transfer the uneven shape of the roll surface in roll coating, which enables continuous production and keeps manufacturing costs low. it can. The shape of the concavo-convex shape of the transfer layer is preferably the same as the concavo-convex shape of the cured resin film described above, that is, the concavo-convex shape of the cured resin film described above is expressed.
Although the cured resin film is suitably produced by the production method of the present invention described above, the cured resin film obtained by the production method is also one of the preferred embodiments of the present invention.

An example of the preferable form in the manufacturing method of the cured resin film of this invention is demonstrated with reference to figures. As the transfer, the transfer method 3 is preferably used, and as the transfer layer, a mat film and a mat roll are preferably used. Such a configuration is schematically shown in FIG. As a result, it is easy to make both sides uneven. A curable resin composition is applied to the transfer layer 11, and an uneven shape is formed on the surface in contact with the transfer layer 11 while being semi-dried or semi-cured. At this time, pressure is applied with a roll 9 as necessary. Subsequently, the semi-dried and semi-cured state is obtained, and then the curable resin composition is brought into contact with the mat roll type transfer layer 10 to form an uneven shape on the other surface, the transfer layer 11 is peeled off, and the uneven shape is formed on both surfaces. A cured resin film having a single layer structure can be obtained continuously.
The cured resin film of the present invention has a macro uneven shape and a micro uneven shape mixed on at least one surface of the surface, but the macro uneven shape and the micro uneven shape are mixed. The surface can be obtained by employing the transfer layer and transfer methods 1 to 3 described above.
For example, a) a method of forming in one step (simultaneously) using a transfer layer having a macro uneven shape and a micro uneven shape, and b) a micro using a transfer layer (micro transfer layer) capable of providing a micro uneven shape. After forming the concavo-convex shape, a method of forming the macro concavo-convex shape with a transfer layer (macro transfer layer) capable of imparting the macro concavo-convex shape, c) After forming the macro concavo-convex shape using the macro transfer layer, A method of forming a micro uneven shape is exemplified. A) and b) are preferable in that the transfer accuracy of the macro uneven shape and the micro uneven shape is excellent.
As the transfer layer in the above a) to c), the above-mentioned various transfer layers can be adopted.
Specific preferred forms in the above b) are: b-1) a form in which the transfer method 1 is performed and then a transfer method 2; b-2) a process in which the transfer method 2 is performed, and then a transfer method 2 is further performed. Form is preferred.
In the above b-1), after the curable resin composition is applied to the microtransfer layer to form a micro uneven shape, and the micro transfer layer is peeled off (transfer method 1), the micro unevenness of the obtained curable resin film is obtained. In this method, the macro unevenness is further transferred by the transfer method 2 using a macro transfer layer on the shape forming surface. As the microtransfer layer in this case, a film-like transfer layer (mat film) is preferable. As the macro transfer layer, a flat transfer layer and a roll transfer layer (mat roll) are preferable, but a roll transfer layer (mat roll) is more preferable in terms of excellent continuous productivity.
In addition, the above b-2), after forming a micro uneven shape using a micro transfer layer to the curable resin film composed of the curable resin composition (transfer method 2), This is a method of forming a macro uneven shape using a macro transfer layer (transfer method 2). Both the micro transfer layer and the macro transfer layer are preferably a flat transfer layer and a roll transfer layer, but a roll transfer layer (mat roll) is more preferable for the same reason as described above.
As a specific preferable form in c) above, in the specific preferable form in the above b), the micro concave / convex shape formation is changed to the macro uneven shape formation, and the macro uneven shape formation is changed to the micro uneven shape formation, and the order is reversed. It is.

Hereinafter, the curable resin composition for forming the curable resin film of the present invention and the curable resin composition that is a raw material for forming the curable resin constituting the curable resin film (the curable resin raw material before curing and other components) Will be described in more detail. As described above, in the cured resin film of the present invention, the cured resin included as an essential component is a cured curable resin, and specifically, the above-described cured resin can be suitably used. As the curable resin for forming the curable resin cured product, a compound having at least one epoxy group, a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, a poly (amide) imide resin, and the like are preferable. . These compounds are further described below.

When the cured resin contained in the cured resin film of the present invention is a cured resin such as an epoxy resin or a poly (amide) imide resin, a corresponding curable resin is used as the curable resin material. be able to.
A compound having at least one epoxy group that can be suitably used as a curable resin material contained in the curable resin film of the present invention will be described. The compound having at least one epoxy group is preferably a polyfunctional epoxy compound having two or more epoxy groups in the molecule.
As the compound having at least one epoxy group, the following compounds are suitable. Epibis type glycidyl ether type epoxy resin obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and epihalohydrin, and these bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc. High molecular weight epibis type glycidyl ether type epoxy resin obtained by further addition reaction with other bisphenols; phenols such as phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol And formaldehyde, acetoaldehyde, propionaldehyde, benzaldehyde, hydroxybenzaldehyde Obtained by condensation reaction of polyhydric phenols obtained by condensation reaction of hydride, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc. with epihalohydrin. Novolak aralkyl type glycidyl ether type epoxy resin; aromatic crystalline epoxy resin obtained by condensation reaction of tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol and the like with epihalohydrin, and the above bisphenols and tetramethyl Aromatic crystalline epoxy tree obtained by addition reaction of biphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc. High molecular weight polymers of the above; alicyclic glycols hydrogenated aromatic skeletons such as bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, PEG600, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, PPG, glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and its multimer, pentaerythritol and its multimer, glucose, fructose, lactose Aliphatic glycidyl ether type epoxide obtained by condensation reaction of mono / polysaccharides such as maltose and epihalohydrin (3,4-epoxycyclohexane) epoxy resin having an epoxycyclohexane skeleton such as methyl 3 ′, 4′-epoxycyclohexyl carboxylate; condensation of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin A glycidyl ester type epoxy resin obtained by reaction; a tertiary amine-containing glycidyl ether type epoxy resin solid at room temperature obtained by a condensation reaction of hindatoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin. Among them, the aliphatic glycidyl ether type epoxy resin and the epoxy resin having an epoxycyclohexane skeleton are more preferably used for the purpose of suppressing the appearance deterioration during light irradiation.

The compound having at least one epoxy group is also preferably a compound having flexibility. By including a compound having flexibility, for example, handling properties are excellent in processes such as processing and molding. By using a compound having flexibility, it is particularly suitable, for example, when it is formed into a film shape or the like. As the compound having at least one flexible epoxy group, specifically, a compound having an oxyalkylene skeleton represented by — [— (CH ₂ ) _n —O—] _m — (n is 2 or more) , M is an integer greater than or equal to 1. Preferably, n is 2-12, m is an integer of 1-1000, More preferably, n is 3-6, m is an integer of 1-20.) Polymer epoxy resin (for example, hydrogenated bisphenol type epoxy resin (manufactured by Japan Epoxy Resin, YL-7170, epoxy equivalent 1000, solid hydrogenated epoxy resin); epoxy resin whose oxyalkylene skeleton is oxybutylene (Japan epoxy resin) YL-7217, epoxy equivalent 437, liquid epoxy resin (10 ° C. or higher), YED-216D manufactured by Japan Epoxy Resin); Resin (for example, YE-8100BX, YX6954BX, etc., manufactured by Japan Epoxy Resin Co., Ltd.); Alicyclic solid epoxy resin (EHPE-3150, manufactured by Daicel Industries, Ltd.); Cycloaliphatic liquid epoxy resin (Delcel Industries, Celoxide 2081) Among these, more preferred are compounds containing an epoxy group at the terminal, side chain, main chain skeleton, etc. Thus, a compound having at least one epoxy group has flexibility. This is one of the preferred embodiments of the present invention.

In the present invention, a curable resin containing a non-curable component such as a thermoplastic resin and a low molecular weight curable compound can also be used. Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, acrylonitrile / styrene copolymer (AS resin), ABS resin made of acrylonitrile / butadiene / styrene, vinyl chloride resin, (meth) acrylic resin, polyamide resin, and acetal resin. , Polycarbonate resin, polyphenylene oxide, polyester, poly (amide) imide and the like. As the curable compound, a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, a poly (amide) imide resin, and a compound having at least one epoxy group may be appropriately selected and used. That's fine.

When the curable resin raw material has at least one epoxy group as the curable resin composition of the present invention, the cured resin may be obtained by cation curing using a heat latent cation generator. preferable. That is, the curable resin raw material has at least one epoxy group, and the curable resin composition is a cation curable resin composition in which the thermal latent cation generator is essential. This is one of the preferred forms.

Examples of the heat latent cation generator include the following general formula (1):
_{^{(R 1 b R 2 c R}} 3 d R 4 e Z) + m (MXn) -m (1)
(In the formula, Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N and halogen elements. R ¹ , R ² , R ³ and R ⁴ is the same or different and represents an organic group, b, c, d and e are 0 or a positive number, and the sum of b, c, d and e is equal to the valence of Z. Cation (R ^{1 _{.M b R 2 c R 3 d}} R 4 e Z) + m are representative of the onium salt, represents a metal or metalloid which is the central atom of a halide complex (metalloid), B, P, as, Al, Ca, It is at least one selected from the group consisting of In, Ti, Zn, Sc, V, Cr, Mn, and Co. X represents a halogen element, and m is the net charge of the halide complex ion. Is the number of halogen elements in the halide complex ion.) It is preferable that it is represented by these.

Specific examples of the anion (MXn) ^-m of the general formula (1) include tetrafluoroborate (BF ⁴⁻ ), hexafluorophosphate (PF ⁶⁻ ), hexafluoroantimonate (SbF ⁶⁻ ), hexafluoro arsenates ^{(AsF 6-),} hexachloroantimonate (SbCl ^6-), and the like.
Further general formula MXn (OH) ^- anions may be used which is represented by. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzenesulfone. An acid ion etc. are mentioned.

Specific products of the above-mentioned heat-latent cation generator include diazonium salt types: AMERICURE series (American Can), ULTRASET series (Adeka), WPAG series (Wako Pure Chemical Industries), iodonium salt type : UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone-Poulenc), WPI series (manufactured by Wako Pure Chemical Industries), sulfonium salt type : CYRACURE series (manufactured by Union Carbide), UVI series (manufactured by General Electric), FC series (manufactured by 3M), CD series (manufactured by Satomer), optomer SP series, optomer CP series (ADEKA) Etsu Chemical Co., Ltd.), San-Aid SI series (Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), CPI series (manufactured by San-Apro Ltd.), and the like. These are all trade names.

Examples of the curing agent other than the thermal latent cation generator include acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, and methylnadic acid; Various phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, terpene phenol resin; various phenols and various such as hydroxybenzaldehyde, crotonaldehyde, glyoxal Various phenol resins such as a polyhydric phenol resin obtained by a condensation reaction with aldehydes; one or more of BF ₃ complexes, sulfonium salts, imidazoles and the like can be used.

In the curing of the curable resin composition containing the compound having at least one epoxy group, a curing accelerator can be used. For example, triphenylphosphine, tributylhexadecylphosphonium bromide, tributylphosphine, tris ( One or more organic phosphorus compounds such as dimethoxyphenyl) phosphine are suitable.
As said hardening temperature, 70-200 degreeC is preferable. More preferably, it is 80-150 degreeC. The curing time is preferably 30 seconds to 1 hour. More preferably, it is 1 to 3 minutes.

Examples of the cured resin suitably used for the cured resin film of the present invention include poly (amide) imide resins, and specifically include thermosetting poly (amide) imide resin cured products. As long as these have an imide ring, the compound as a raw material is not limited, but when used for the cured resin film of the present invention, from the viewpoint of production productivity, cost, heat resistance, A thermosetting poly (amide) imide resin is preferable, and an aromatic thermosetting poly (amide) imide resin is more preferable.
The poly (amide) imide resin means a polyimide resin in a narrow sense (resin including an imide bond and not including an amide bond) and a polyamideimide resin (resin including an amide bond and an imide bond). There are two types of such poly (amide) imide resins, thermosetting resins and thermoplastic resins. In the present invention, thermosetting poly (amide) imide resins are preferred, and more preferably aromatic It is a group thermosetting poly (amide) imide resin.
The poly (amide) imide resin is a raw material of a poly (amide) imide resin obtained by a reaction between a polyvalent carboxylic acid compound and a polyvalent amine compound and / or a polyvalent isocyanate compound (hereinafter also referred to as a precursor polymer). Can be obtained by imidization reaction, but the form in which the curable resin composition contains such a precursor polymer is one of the preferred forms of the present invention. More preferably, the precursor polymer has an aromatic ring.

In the precursor polymer, the polyvalent carboxylic acid compound is a compound having two or more carboxyl groups or carboxyl group-derived groups in the molecule, and includes anhydrides thereof. The carboxyl group-derived group is a group represented by COX, and X is a halogen element or a group represented by OR ⁴ (R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group).
As the polyvalent carboxylic acid compound, a tetracarboxylic acid compound (including its anhydride) and a tricarboxylic acid compound (including its anhydride) are suitable. These may be reacted with alcohols such as methanol and ethanol to form ester compounds.

As the tetracarboxylic acid compound, the following aromatic tetracarboxylic dianhydrides are suitable.
Pyromellitic dianhydride (PMDA), 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3'4'-biphenyltetracarboxylic dianhydride, 3,3', 4 4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride ,Screw( , 4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane dianhydride (BPADA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, oxydiphthalic anhydride (ODPA), bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfoxide dianhydride, thiodiphthalic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 9,9-bis (3 , 4-dicarboxyphenyl) fluorene dianhydride and 9,9-bis [4- (3,4'-dicarboxyphenoxy) phenyl] fluorene dianhydride.

Among these, pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Anhydride (BTDA), 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane dianhydride (BPADA), oxydiphthalic anhydride (ODPA), 2,3,3 ′, 4-biphenyltetra Carboxylic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) propane dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, bis (3,4-di Carboxyphenyl) ether dianhydride, ethylenetetracarboxylic dianhydride and the like are preferred.

As the tricarboxylic acid compound (including tricarboxylic acid monoanhydride), those containing an aliphatic cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring are suitable. For example, a phenyl group, a biphenyl group, a terphenyl group, Three carboxyl groups or derivatives thereof are bonded to groups such as naphthalene group, perylene group, diphenyl ether group, diphenylsulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoropropane group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. And the like. Among these, those containing an aromatic ring are preferable, and trimellitic acid, hydrogenated trimellitic acid, and anhydrides and derivatives thereof are more preferable.

The polyvalent amine compound is a compound having two or more amino groups in the molecule, and particularly preferably a compound having two amino groups in the molecule (diamine compound). As the diamine compound, an aromatic diamine containing an aromatic ring between two amino groups, an aliphatic diamine composed of an aliphatic group between two amino groups, and a structural unit containing a siloxane bond between two amino groups Siloxane diamine etc. which have can be used.

Specific examples of the aromatic diamine include paraphenylenediamine (PPD), metaphenylenediamine (MPDA), 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4′-diaminobiphenyl, 3, 3'-dimethyl-4,4'-biphenyl, 3,3'-dimethoxy-4,4'-biphenyl, 2,2-bis (trifluoromethyl) -4, 4'-diaminobiphenyl, 4,4'- Bis (3-aminophenoxy) biphenyl, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane (MDA), 2,2-bis- (4-aminophenyl) propane, 3,3′-diaminodiphenylsulfone (33DDS), 4,4'-diaminodiphenylsulfone (44DDS), 3,3'-diaminodiphenyl sulfide, 4,4 ' Diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether (34 ODA), 4,4′-diaminodiphenyl ether (ODA), 1,5-diaminonaphthalene, 4,4′-diaminodiphenyldiethylsilane 4,4′-diaminodiphenylsilane, 4,4′-diaminodiphenylethylphosphine oxide,

1,3-bis (3-aminophenoxy) benzene (133APB), 1,3-bis (4-aminophenoxy) benzene (134APB), 1,4-bis (4-aminophenoxy) benzene, bis [4- ( 3-aminophenoxy) phenyl] sulfone (BAPSM), bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), 2,2-bis (3-aminophenyl) 1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) 1,1,1,3,3,3- Hexafluoropropane and 9,9-bis (4-aminophenyl) fluorene, 3,3'-dichlorobenzidine, 1,5-diaminonaphthalene, 3,3'-dimethyl- 4,4'-biphenyldiamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylpropane, 2,4-bis (β-amino-t-butyl) toluene Bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ-aminophenyl) benzene, bis-p- (1,1-dimethyl-5-amino-pentyl) benzene, Examples include 1-isopropyl-2,4-m-phenylenediamine, m-xylylenediamine, and p-xylylenediamine.

Among these, paraphenylenediamine (PPD), metaphenylenediamine (MPDA), 4,4′-diaminodiphenylmethane (MDA), 3,3′-diaminodiphenylsulfone (33DDS), 4,4′-diaminodiphenylsulfone ( 44DDS), 3,4'-diaminodiphenyl ether (34ODA), 4,4'-diaminodiphenyl ether (ODA), 1,3-bis (3-aminophenoxy) benzene (133APB), 1,3-bis (4-amino) Phenoxy) benzene (134APB), bis [4- (3-aminophenoxy) phenyl] sulfone (BAPSM), bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS), 2,2-bis [4- ( 4-aminophenoxy) phenyl] propane (BAPP) and the like Is preferred.

Examples of the aliphatic diamine include di (p-aminocyclohexyl) methane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminopropyltetramethylene, and 3-methylheptamethylenediamine. 4,4-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis-3-aminopropoxyethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhepta Methylenediamine, 5-methylnonamethylenediamine, 2,17-diaminoeicosadecane, 1,4-diaminocyclohexane, 1,10-diamino-1,10-dimethyldecane, 1,12-diaminooctadecane, piperazine, _{2 N (CH 2) 3 O} (CH 2) 2 OCH 2 NH 2, H 2 N (CH 2) 3 S (CH 2) 3 NH 2, H 2 N (CH 2) 3 N (CH 2) 2 ( CH ₂ ) ₃ NH _{2 and the} like.

Examples of the siloxane diamine include polydimethylsiloxane diamine (silicone oil X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500), X- 22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200), KF-8010 (amine equivalent 415) (above, manufactured by Shin-Etsu Chemical Co., Ltd.)) and the like.

The polyvalent isocyanate compound is a compound having two or more isocyanate groups in the molecule, and particularly preferably a compound (diisocyanate compound) having two isocyanate groups in the molecule.
Examples of the diisocyanate compound include methylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4′-bis ( 3-Tolylene) diisocyanate, 3,3′-dichloro-4,4′-diisocyanate biphenyl, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate and the like. .

In the reaction of the polyvalent carboxylic acid compound with the polyvalent amine compound and / or the polyvalent isocyanate compound, the ratio of these components may be appropriately set by adjusting the molecular weight recommended for the precursor polymer or the like. For example, when the total amount of the carboxyl group and the derivative group thereof is 1 mol, it is preferable that the total molar amount of the amino group and the isocyanate group is 0.7 to 1.5 mol. When the amount is more than 1.5 mol, unreacted polyvalent amine compound or polyvalent isocyanate compound tends to remain, and there is a possibility that the film forming property may not be sufficient. When the amount is less than 0.7 mol, gelation occurs. In this case, the film forming property may not be sufficient. More preferably, the total molar amount of amino group and isocyanate group is 0.9 to 1.3 mol.

The above reaction may be carried out by a usual method. For example, the reaction temperature is preferably 80 to 210 ° C. This makes it possible to shorten the reaction time and sufficiently suppress gelation. More preferably, it is 100-190 degreeC, More preferably, it is 120-180 degreeC. The reaction time is preferably 30 minutes to 15 hours, more preferably 1 to 10 hours.

The above reaction may also be performed in the presence of an organic solvent or a catalyst as necessary.
The organic solvent is preferably an organic polar solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2 -Imidazolidinone, N-methylcaprolactam, hexamethylphosphoric triamide, 1,2-dimethoxyethane, diglyme and triglyme. Among these, N, N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP) are preferable. These solvents can be used alone or as a mixture, or can be used by mixing with other solvents such as aromatic hydrocarbons such as toluene and xylene.
Examples of the catalyst include tertiary amines, alkali metals, alkaline earth metals, metals such as tin, zinc, titanium, and cobalt, or metalloid compounds.

As said precursor polymer (raw material of poly (amide) imide resin), following formula (2);

(In the formula, R ⁵ is the same or different and represents a trivalent or tetravalent organic group having at least 2 or more carbon atoms. R ⁶ is the same or different and contains at least 2 or more carbon atoms. X is the same or different and represents a halogen element or a group represented by OR ^7. R ⁷ is the same or different and is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or a phenyl group, wherein r is a number from 1 to 2, and n is the number of repeating units, and is an integer from 1 to 1000). Is preferred.

In the above formula (2), R ⁵ preferably contains an aliphatic cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring from the viewpoint of heat resistance. More preferably, R ⁵ is an aliphatic cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring, and is a trivalent or tetravalent group having 4 to 30 carbon atoms. Specifically, for example, phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenylsulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoropropane group, cyclobutyl group, cyclopentyl group, cyclohexane Although a hexyl group etc. are mentioned, it does not specifically limit and various organic groups can be used.

R ⁶ preferably contains an aliphatic cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring from the viewpoint of heat resistance. More preferably, R ⁶ is an aliphatic cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring and is a divalent group having 6 to 30 carbon atoms. Specifically, for example, phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenyl sulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoropropane group, diphenylmethane group, dicyclohexylmethane group, etc. However, it is not particularly limited, and various organic groups can be used.

Further, the COX group represents a carboxyl group or a derivative group thereof. X is the same or different and represents a halogen element or a group represented by OR ⁷ , and R ⁷ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. As a halogen element, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.

In the general formula (2), n represents the number of repeating structural units represented by the general formula (2) in the precursor polymer, and is an integer of 1 to 1000. Preferably, it is 2 or more, and if the viscosity becomes too high, the compatibility with the black material may not be sufficient, so that it is preferably 500 or less.

In the precursor polymer containing the structural unit (2), the content of the structural unit (2) is preferably 30 to 100% by mass with respect to 100% by mass of the polymer. More preferably, it is 50-100 mass%.

In the above general formula (2), as a precursor polymer mainly composed of the structural unit (2) where r = 2, for example, a polyamic acid (polyimide precursor) synthesized from tetracarboxylic dianhydride and diamine Polymer). Moreover, as a precursor polymer which has the structural unit (2) which is r = 1 as a main component, for example, a polyvalent carboxylic acid compound containing a tricarboxylic acid compound, a polyvalent amine compound and / or a polyvalent isocyanate compound A polyamideimide precursor polymer obtained by the reaction is preferable.

The compound having a polymerizable unsaturated bond, which is one of the preferred forms of the curable resin raw material of the present invention, will be described in detail.
The compound having a polymerizable unsaturated bond may be any compound having a polymerizable unsaturated bond, but one or more selected from the group consisting of a (meth) acryloyl group, a vinyl group, a fumarate group, and a maleimide group. It is preferable that it is a compound which has these groups. That is, it is preferably at least one compound selected from the group consisting of a compound having a (meth) acryloyl group, a compound having a vinyl group, a compound having a fumarate group, and a compound having a maleimide group. In the present invention, the (meth) acryloyl group means an acryloyl group and a methacryloyl group, and when it has an acryloyl group, it has a vinyl group in the acryloyl group. Does not have an acryloyl group and a vinyl group, but has an acryloyl group. The fumarate group means a group having a fumarate structure, that is, a group having a fumarate ester structure.

When the curable resin raw material of this invention contains a polyhydric phenol compound, it can be set as hardened | cured material by thermosetting using a hardening | curing agent. Examples of the curing agent include a compound having at least two epoxy groups. As the compound having at least two epoxy groups, an epoxy resin having an average of two or more epoxy groups in one molecule is preferable. Epibis type glycidyl ether type epoxy resin obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S and epihalohydrin; such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, etc. Phenols and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene dimethyl ether, dichloroparaxyl A novolak-aralkyl-type glycidyl ether-type epoxy resin obtained by further condensing a polyhydric phenol obtained by the condensation reaction of benzene with an epihalohydrin; tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and an epihalohydrin Glycidyl ester type epoxy resin obtained by condensation reaction; Glycidyl ether type epoxy resin obtained by condensation reaction of hydrogenated bisphenol or glycol and epihalohydrin; Amine-containing glycidyl ether type obtained by condensation reaction of hindatoin or cyanuric acid and epihalohydrin Epoxy resins; aromatic polycyclic epoxy resins such as biphenyl type epoxy resins and naphthalene type epoxy resins are suitable. Moreover, the compound which has an epoxy group in a molecule | numerator by addition reaction with these epoxy resins, polybasic acids, and / or bisphenols may be sufficient. These can use 1 type (s) or 2 or more types.

The blending mass ratio of the polyhydric phenol compound and the epoxy resin curing agent (polyhydric phenol compound / epoxy resin curing agent) is preferably 30/70 or more, and 70/30 or less. It is preferable that If it is less than 30/70, the mechanical properties and the like of the cured product formed may be reduced, and if it exceeds 70/30, the flame retardancy may be insufficient. More preferably, it is 35/65 or more and 65/35 or less. A curing accelerator may be used for the curing. Examples of the curing accelerator include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; 2,4,6-tris (dimethylaminomethyl). ) Amines such as phenol, benzylmethylamine, DBU (1,8-diazabicyclo [5.4.0] -7-undecene), DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea) An organic phosphorus compound such as tributylphosphine, triphenylphosphine, and tris (dimethoxyphenyl) phosphine is preferable.

The curable resin composition of the present invention preferably contains a surface conditioner in addition to the curable resin raw material described above. The surface conditioning agent can be suitably used for improving the uniformity of the light-shielding layer film, specifically, for eliminating holes or eliminating skin. As the surface conditioner, a compound having a high surface tension reducing ability is preferable because it has a high effect of eliminating holes. Further, a compound having a high polarity is preferable in terms of a high effect of eliminating the yuzu skin. As the surface conditioner, for example, a silicon-based surface conditioner (silicon-based additive) is preferable. As the silicon-based surface conditioning agent, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, manufactured by BYK Japan BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK- 349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, and the like. Among these, from the viewpoint of high polarity, BYK-306, BYK-310, BYK-333, BYK-370, BYK-375 and the like are preferable. From the viewpoint of high surface tension reducing ability, BYK-306, BYK-307, BYK-330, BYK-333, BYK-370, BYK-377, BYK-341, BYK-375 and the like are preferable. Moreover, BYK-306, BYK-333, and BYK-375 are particularly preferable because of their high polarity and high surface tension reducing ability. These are all trade names.

The curable resin composition of the present invention includes a curing accelerator, a reactive diluent, a saturated compound having no unsaturated bond, a pigment, and a dye in addition to the above-described curable resin raw material, black material, surface conditioner, and the like. , Antioxidants, UV absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic and organic fillers, coupling agents Adhesion improver, heat stabilizer, antibacterial / antifungal agent, flame retardant, matting agent, antifoaming agent, leveling agent, wetting / dispersing agent, anti-settling agent, thickener / anti-sagging agent, color separation An inhibitor, an emulsifier, an anti-slip / scratch agent, an anti-skinning agent, a drying agent, an antifouling agent, an antistatic agent, a conductive agent (electrostatic aid), and the like may be contained.

The present invention is also a lens unit including the light-shielding film and a lens, and the lens unit is a lens unit that is a lens unit for an image sensor. The lens unit of the present invention is useful for optical applications and optical device applications, and can also be used as display device applications, mechanical components, electrical / electronic components, and the like.
In the lens unit, the light-shielding film is a film having a light-shielding layer that suppresses generation and expansion of optical noise inside the lens unit and removes the generated optical noise in the camera module. As the light-shielding film in the lens unit, the above-described light-shielding film is preferable. That is, it is preferable that the resin contained as an essential component in the light-shielding film is as described above. When the resin is as described above, the light-shielding film has reflow resistance and is suitably used for a lens unit having reflow resistance. Other suitable examples and preferred forms of the light-shielding film are as described above. In addition, although the said lens unit will be equipped with a light-shielding film and a lens, these numbers should just be equipped with one or more respectively, and the number with which it mounts according to the use etc. of a lens unit. Can be set as appropriate, and a plurality of may be provided. In the present specification, the “lens unit having reflow resistance” is a lens unit that is excellent in at least the shape retention of the light-shielding film. As a preferred form, as with the shape-retaining property of the light-shielding film described above, when heated at 200 ° C. for 1 minute, the change rate of each length (dimensional change rate) is 10% or less, more preferably 260 ° C. When heated for 2 minutes, the change rate of each length (dimensional change rate) is 10% or less. Under any condition, the dimensional change rate is more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1% or less.

In the lens unit, the lens may be any material that can transmit and transmit a wavelength in the visible light region, and may be any one of an organic material, an inorganic material, and an organic / inorganic composite material. Two or more kinds may be used. The organic material (for example, thermoplastic resin composition, curable resin composition) is excellent in processability, and the inorganic material (for example, glass) is excellent in transparency / thermal expansion coefficient, for example, an organic / inorganic composite material (for example, The organic-inorganic composite resin composition) having both characteristics is suitable. A lens made of any material can be suitably used, but a material having reflow resistance (heat resistant material) is preferable.
Thus, the form in which the light-shielding film and the lens constituting the lens unit have reflow resistance is one of the preferred forms of the present invention. Since both the light-shielding film and the lens have sufficient heat resistance, automatic mounting becomes possible, the mounting cost is sufficiently reduced, and it can be suitably used for optical applications such as a camera module. As described above, the light-shielding film of the present invention is suitable for an imaging lens unit used for a camera module, and particularly suitable for an imaging lens unit used for a camera module subjected to a solder reflow process. That is, the lens unit is preferably an imaging lens unit used for a camera module, and particularly preferably an imaging lens unit used for a camera module subjected to a solder reflow process.

As a preferable specific example of an organic material as the material of the lens, a curable resin composition containing a compound (raw material) mainly composed of a compound having at least one epoxy group is cured from the viewpoint of excellent colorless transparency and heat resistance. Cured resin cured product such as a material obtained by curing a curable resin composition containing a compound having a polymerizable unsaturated bond as a main resin (raw material); a phenol resin as a main resin (raw material) Tg of a material obtained by curing a curable resin composition, a material obtained by curing using a silicone resin as a main resin (raw material), a thermoplastic resin comprising a silicone resin, a polycycloolefin resin, a polycarbonate resin, etc. is 150 ° C. The above thermoplastic resin. Curing means conventionally known curing such as curing by heat or curing by irradiation with active energy rays, and the curable resin composition further includes the above main compound, a curing catalyst for accelerating curing, and curing. A conventionally known material such as an accelerator or a curing agent is used in combination. In the above, “main” means 70% by mass or more based on the total amount of the resin (raw material).
Particularly preferred as the material is a material obtained by curing a curable resin composition containing an epoxy group-containing compound as a main resin (raw material). About the epoxy group containing compound and the compound which has a polymerizable unsaturated bond, the aspect regarding the same kind compound in the curable resin composition for cured resin films can be applied.
The organic material component of the organic / inorganic composite material is preferably the preferred organic material.

The lens is preferably obtained by curing a curable resin composition. By using a curable resin composition, it is possible to perform complicated processing that cannot be performed with an inorganic material (for example, glass) at low cost, and a lens having heat resistance that cannot be achieved when a thermoplastic resin composition is used. In the processing (molding) and mounting on the lens unit, there is an advantage that it is suitable for an industrial production process and can be performed efficiently. The lens is preferably obtained by curing a curable resin composition, but the curable resin composition preferably includes a compound having at least one epoxy group as an organic resin component. The curable resin composition may be an organic-inorganic composite resin composition having an inorganic component.
In the present invention, as described above, the lens is preferably obtained by curing a curable resin composition. Thus, a lens unit comprising the light-shielding film of the present invention and a lens, the lens unit having reflow resistance, and the lens is obtained by curing a curable resin composition. A lens unit that is also one of the preferred embodiments of the present invention. Among these, a lens obtained by cationically curing a curable resin composition containing an epoxy group-containing compound as a main resin material and containing a cationic curing catalyst such as a thermosetting curing agent is preferable.

As the compound having at least one epoxy group, the compounds described in the epoxy group-containing compound described later as an example of the cured resin contained in the cured resin film can be suitably used. Among them, epibis type glycidyl ether type epoxy resin; novolak aralkyl type glycidyl ether type epoxy resin; aromatic crystalline epoxy resin; aliphatic glycidyl ether type epoxy resin; epoxy resin having epoxy cyclohexane skeleton; glycidyl ester type epoxy Resin; Tertiary amine-containing glycidyl ether type epoxy resin and the like are preferable. Moreover, what contains non-hardening components, such as a thermoplastic resin, and a low molecular weight curable compound can also be used as curable resin. As a use form of the curable resin composition (thermosetting epoxy resin composition) used for the lens, a form described as a cured resin film to be described later can be suitably used, and in particular, a thermal latent curing agent is used. Form is preferred. In addition, since curable resin composition is used for a lens use, it is preferable that black fine particles are not included.

The organic-inorganic composite resin composition preferably contains an organic resin and inorganic fine particles or organopolysiloxane. Organic resins having a high Abbe number are those having an Abbe number of 45 or more, forms that are curable resins, forms that essentially contain an alicyclic epoxy compound, and those having a molecular weight of 700 or more. Form is preferred. The inorganic fine particles have a form obtained by a wet method, a form having an average particle diameter of 400 nm or less, and a pH of 3.4 to 11 at 25 ° C. when dispersed in a solution. Form is preferred. As an organic inorganic composite resin composition, the form in which an unsaturated bond is 10 mass% or less and the form containing a flexible component are preferable.

The lens preferably has a thickness of less than 1 mm. When the thickness of the lens (the maximum thickness of the region where the image is projected) is less than 1 mm, the optical path length can be shortened and the lens unit can be further reduced, combined with the use of the light-shielding film. The thickness of the lens is more preferably less than 800 μm, and still more preferably less than 500 μm.
The Abbe number of the lens is not particularly limited. For example, when the Abbe number is 45 or more, the wavelength dispersion of light is reduced, the resolution is increased, and the optical characteristics can be improved. If it is less than 45, for example, bleeding may be observed, sufficient optical characteristics may not be exhibited, and a material suitable for the lens unit may not be obtained. The Abbe number is more preferably 50 or more, still more preferably 55 or more, particularly preferably 58 or more, and most preferably 60 or more.

The lens constituting the lens unit is a single lens whose optical properties (Abbe number, refractive index, etc.) and lens shape (concave, convex, curvature, etc.) are controlled according to the target resolution, or Used in combination. The number of lenses used may be one, or two or more. In the case of a single lens, it is preferable to use a lens having a high Abbe number in that the wavelength dispersion of light is reduced, the resolution is increased, and the optical characteristics are excellent. The combination is arbitrary, and various combinations can be applied. For example, it is preferable to use a combination of a lens having a high Abbe number and a lens having a low Abbe number.

The lens unit is not particularly limited as long as it includes a light-shielding film and a lens, but an embodiment having other members such as an infrared cut filter, a sea moss sensor, a barrel, and an adhesive is preferable. The adhesive is used to fix a member such as a lens or a light shielding film to the unit.
The arrangement of each component of the lens unit is not particularly limited as long as the characteristics as the lens unit are exhibited. However, as described above, the light-shielding film is attached to the edge where the light-shielding layer fixes the lens. It is preferable that it is arrangement | positioning. The positional relationship between the light-shielding film and the lens includes a form in which the lens is on the incident light side and a form in which the light-shielding film is on the incident light side, but absorbs reflected light from the lens surface. It is preferable that two light-shielding films are arranged on the incident light side from the lens.
As the shape of the light-shielding film, as described above, the light-shielding layer is preferably in the shape of a ring and the center of the ring is preferably a cavity. By setting it as such arrangement | positioning and shape, the light-shielding function can fully be exhibited. Specifically, as schematically shown in FIG. 11 (b), when the central portion is a transparent film, the optical path length is increased by having the light-shielding film. On the other hand, if the central portion is hollow, the optical path length does not increase as schematically shown in FIG. Since the lens unit is required to be downsized, it is preferable that the lens unit has a light-shielding layer in a ring shape and a hollow center. In the case of a light-shielding film, if a light-shielding film is provided between the lens and the seamos sensor, the optical path length can be shortened by reducing the thickness of the light-shielding film located between the lens and the seamos sensor. The lens unit can be made smaller and the thickness of the unit can be made thinner.

In the lens unit, the arrangement of the light-shielding film and the lens is arranged in the order of the light-shielding film, one or more lenses, and the Cimos sensor along the traveling direction of the incident light as shown in FIG. Form is preferred. When there are two or more lenses, a form in which a light-shielding film is provided on each lens is more preferable. Thus, if a plurality of light-shielding films are used, unnecessary light can be sufficiently blocked. The light shielding film may be disposed between the lenses. In addition, when using other functional layers, such as the infrared cut filter mentioned later, it is preferable to provide in the form where those effects are fully exhibited. In FIG. 7, the infrared cut filter is disposed at a position closest to the sea moss sensor. The infrared cut filter may be disposed so as to be positioned on the incident light surface of the lens unit.

The size of the lens unit of the present invention is preferably small because it can be suitably used for various applications. The thickness of the lens unit is preferably 50 mm or less. By setting it as such thickness, it can use suitably for various optical members, such as a camera module. More preferably, it is 30 mm or less as a thickness of a lens unit, More preferably, it is 10 mm or less.

When a light-shielding film having a transparent film at the center is used, the length of the lens unit can be made smaller as the light-shielding film located between the lens and the sea moss sensor is thinner. Specifically, the camera module has a light-shielding film, a lens, and a seamos sensor. 7 and 11 schematically show an example of the camera module. Note that these figures refer to materials from the Electronic Journal 81st Technical Seminar (Electronic Journal 81st Technical Seminar). When the light-shielding film is arranged on the camera module as shown in FIG. 11B, the focal length is extended, so that the back focus is extended and the module is enlarged. As shown in FIG. 11B, when the light-shielding film is positioned between the incident light surface and the lens and the Simoth sensor, the thickness of the light-shielding film is t and the refractive index n is about 1.5, the back focus Is extended by about t / 3, and the module becomes large. However, the light-shielding film can be made thin, the focal length can be shortened, and the module can be made small. Thereby, for example, the optical path length of an optical size of 1/10 inch is preferably 120% or less in the case of no light-shielding film. More preferably, it is 110% or less, More preferably, it is 105% or less.

The present invention consists of the above-described configuration, and there is little increase in surface glossiness upon curing, and a cured resin film having a sufficiently low glossiness for use in an optical member, a method for producing the cured resin film, a light scattering film, A light-shielding film and a lens unit including the light-shielding film, and the lens unit is suitably used for various applications such as an optical device application, a display device application, a mechanical component, and an electric / electronic component. .

1-1 shows one of the uneven | corrugated shaped cross-sectional diagrams with which the convex part and recessed part of the cured resin film of this invention adjoin. 1-2 shows one of the cross-sectional schematic diagrams of the uneven | corrugated shape in which the convex part and recessed part of the cured resin film of this invention exist in isolation. 1-3 shows one of the cross-sectional schematic diagrams of the uneven | corrugated shape in which the convex part exists in the recessed part of the cured resin film of this invention. FIG. 2-1 shows one of the schematic views of the surface shape in the form in which the concave portions and the convex portions of the cured resin film of the present invention are arranged in parallel lines. FIG. 2-2 shows one of the schematic views of the surface shape in a form in which the concave portions and the convex portions of the cured resin film of the present invention are arranged concentrically. FIG. 2-3 shows one of the schematic views of the surface shape of the sea-island shape in which the uneven shape of the cured resin film of the present invention has no orientation. FIG. 3-1 is a schematic cross-sectional view of a surface shape of a form in which micro unevenness formed by a combination of protrusions and recesses continuously exists on the surface of the macro unevenness of the cured resin film of the present invention. Indicates one. 3-2 shows one of the cross-sectional schematic diagrams of the surface shape of the form in which the micro uneven | corrugated shape formed only by the convex part exists continuously on the macro uneven | corrugated shaped surface of the cured resin film of this invention. 3-3 shows one of the cross-sectional schematic diagrams of the surface shape of the form where the micro uneven | corrugated shape formed only by the recessed part exists continuously on the macro uneven | corrugated shaped surface of the cured resin film of this invention. FIGS. 3-4 shows one of the cross-sectional schematic diagrams of the surface shape of the form with the micro uneven | corrugated shape formed from the combination of a convex part and a recessed part on the macro uneven | corrugated surface of the cured resin film of this invention. 3-5 shows one of the cross-sectional schematic diagrams of the surface shape of the form in which the micro uneven | corrugated shape formed only by the convex part on the surface of the macro uneven | corrugated shape of the cured resin film of this invention is dotted. 3-6 shows one of the cross-sectional schematic diagrams of the surface shape of the form in which the micro uneven | corrugated shape formed only by the recessed part was scattered on the surface of the macro uneven | corrugated shape of the cured resin film of this invention. FIG. 4 shows one of the schematic cross-sectional views of the cured resin film in the case of obtaining the height (Ry) of the cured resin film of the present invention. FIG. 5 shows one of the schematic cross-sectional views of the cured resin film in the case of obtaining the average interval (Sm) of the uneven shape of the cured resin film of the present invention. FIG. 6 is a schematic cross-sectional view showing one preferred form of the cured resin film of the present invention. FIG. 7 is a schematic cross-sectional view showing the configuration of a camera module which is one of the preferred embodiments of the lens unit of the present invention. FIG. 8 is a schematic cross-sectional view showing the relationship between the light-shielding film and the lens in the lens unit of the present invention. FIG. 9 is a schematic plan view showing one preferred form of the light-shielding film in the lens unit of the present invention. FIG. 10 is a schematic view showing an example of a preferred embodiment in the method for producing a cured resin film of the present invention. FIG. 11 is a schematic diagram showing the extension of back focus depending on the presence or absence of a light-shielding film.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

Method for evaluating physical properties of cured resin film (Evaluation of surface irregularities)
The surface shape of the transfer surface of the obtained film (transfer film and transfer cured film) was observed with a microscope image using a laser microscope (Color 3D laser microscope (VK-9700) manufactured by KEYENCE) and Japanese Industrial Standard (JIS). ) Evaluation was made by measuring the line roughness according to B0601-1994. The measurement conditions of the line roughness are as follows.
The period and height, which are indicators of macro unevenness, are analyzed by analyzing the profile obtained by smoothing the height to reduce the effects of fine unevenness and noise. Asked. That is, the distance between the apex of the convex portions of the large mountain shapes (semi-circular shapes) and the apexes of the convex portions is set as a cycle, and the height is the same as Ry of Japanese Industrial Standard (JIS) B0601-1994. In addition, a measured numerical value is a value averaged with the number of measurement points being 3.

The measurement conditions of the line roughness are as follows.
Objective lens: 20x Zoom: 1.0x Measurement pitch: RPD
Measurement mode: Surface shape measurement area: Surface measurement quality: Ultra-high definition analysis software: VK-9700 / VK-8700 Shape analysis application VK-H1A1
Analysis surface (image) tilt correction: quadratic surface correction (automatic)
Analysis length (reference length l: 500 μm
Analysis line tilt correction: straight line (automatic)
Height smoothing: Simple average, coefficient ± 12, all areas (correction area)

(Glossiness measurement)
Regarding the obtained films (transfer film and transfer cured film), the glossiness of the transfer-treated surface was measured.
The glossiness was determined by measuring the glossiness at a measurement angle (θ) of 60 ° using a gloss meter (VG-2000) manufactured by Nippon Denshoku Industries Co., Ltd.

(Solid content of film)
The solid content in the curable resin film to be transferred was determined as follows. That is, using a film piece as a sample, TG-DTA (manufactured by BRUKER AXS, TG-DTA 2000SA) was used to measure the weight loss from room temperature to 350 degrees at a heating rate of 10 degrees / minute. Was the solvent content, and the remainder was the solid content.

(Heat resistance test)
The produced cured resin film was cut into the following sizes and used as test pieces.
Test piece: 50 mm × 10 mm size film The test piece was subjected to a heat test under the following test conditions, and the dimensional change in the length direction of the test piece before and after the test was measured and evaluated.
Test conditions: Heat treatment at 260 ° C. for 2 minutes (Test pieces are put into a hot air dryer heated and maintained at 260 ° C. and taken out after 2 minutes)
When the rate of dimensional change in the length direction was less than 3%, rank A was ranked 3% or more.

(Visible light transmittance)
The transmittance | permeability in 380-780 nm was measured using the ultraviolet visible spectrophotometer needle | hook (Shimadzu UV-3100 (made by Shimadzu Corporation)).

Example 1, Comparative Examples 1-2
Preparation of coating liquid (curable resin composition) Curable resin composition in which carbon black is dispersed in a polyamic acid solution. S. Weights shown in Table 1 using poly (amide) imide varnish Pyre-ML RC5083 manufactured by T Company, Graft Carbon Black Solution Epotone LY (carbon black concentration 7.8%) manufactured by Nippon Shokubai Co., Ltd., BYK-306 manufactured by Big Chemie Japan Co., Ltd. % Curable resin composition (1) was obtained by mixing in a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirrer and pressure filtration with a 300 mesh made of SUS. . The mixing conditions and pressure filtration conditions are shown below.
(Mixing conditions)
Stirring blade: 2-stage paddle mixing time: 60 minutes stirring, under nitrogen atmosphere (pressure filtration)
Pressure filter used: ADVANTEC, KST-293-10-JA

Example 1
<Preparation of curable resin film (1)>
The curable resin composition (1) was applied to a matte pet film (brand: PSG, thickness 100 μm) manufactured by Teijin DuPont, dried at 140 ° C. for 5.6 minutes, and then peeled to be curable. A resin film (1) was obtained.
The curable resin film (1) has a solid content of 67%, a thickness of 61 μm, and a width of 25 cm. The mat pet film contact surface has a glossiness of 2 to 3, and the opposite surface has a high gloss. It was a toned film. The coating conditions are shown below.
Coating method: Slot die Coating width: 26cm
Drying furnace temperature: 140 ° C. Drying time: 5.6 minutes

<Preparation of transfer film (1)>
The curable resin film (1) was subjected to a surface unevenness process by a transfer process using a mat roll as a transfer material to prepare a transfer film (1).
Specifically, the transfer process of pressing the heated mat roll under pressure was performed twice on the high gloss (glossy) surface of the curable resin film (1) using an electric heating embossing machine. That is, in the one-day transfer process, the transfer using the mat roll (A) is performed, and further, the transfer process is performed by the mat roll (B) on the mat roll (A) transfer surface of the obtained film. A transfer film (1) was produced.
The surface unevenness shape of each mat roll is shown below.
The conditions for the transfer treatment are as follows: the mat roll temperature is 90 ° C. for both the first and second times, the linear pressure on the mat roll and the receiving resin roll (smooth surface) is 185 N / mm, and the film supply speed is 2 m / min. It is.
As a result of observing the mat roll-treated surface with a laser microscope, the transfer film (1) was confirmed to have corrugated macro unevenness and micro unevenness formed on one surface.

(Surface morphology of the transfer material used)
Surface form of mat roll (A): Micro unevenness (Sm = 4.6 μm, Ry = 23 μm) is formed on the entire surface.
Surface form of mat roll (B): It consists of repeated wave shapes. The cross-sectional shape in the direction perpendicular to the rotation direction of the roll is a repetitive structure of waves having a wavelength of 100 μm and an amplitude of 30 μm, and the wave convex portions (or concave portions) are arranged in parallel in the roll rotation direction.

<Preparation of transfer cured film (1)>
The transfer film (1) was baked in an inert oven under the following conditions to obtain a transfer cured film (1) having a thickness of about 50 μm. The firing conditions were 200 ° C. and 20 minutes, 250 ° C. and 10 minutes, and 300 ° C. and 10 minutes.
It was observed with a laser microscope that the transfer surface of the obtained transfer cured film (1) had macro unevenness and micro unevenness, similar to the transfer film (1).
Regarding the transfer cured film (1) and the transfer film (1), the glossiness and the surface unevenness shape were evaluated. The evaluation results are shown in Table 2.

Moreover, the heat resistance test result of the transfer cured film (1) was rank A, and the visible light transmittance was 0.1% or less at 380 to 780 nm at each wavelength. Further, the transfer cured film (1) had a glossiness of 18 and remained unchanged even after the heat resistance test.

Comparative Example 1
In Example 1, the curable resin film (c1) was produced in the same manner as the curable resin film (1). The solid content concentration was 67%, the thickness was 61 μm, the width was 25 cm, the matte pet film contact surface had a glossiness of 2-3, and the opposite surface was a glossy film with high glossiness.
In the production of the transfer film in Example 1, the curable resin film was similarly obtained except that only the transfer process using the mat roll (B) was performed without performing the transfer process using the mat roll (A). A transfer film (c1) was produced from (c1), and further heat-treated in the same manner as in the production conditions of the transfer cured film in Example 1, thereby producing a transfer cured film (c1).
The evaluation results are shown in Table 2.
In addition, regarding the transfer cured film (c1), the data relating to the surface unevenness shape is not shown in Table 1, but the transfer surfaces of the transfer film (c1) and the transfer cured film (c1) are both macroscopic unevenness. It was confirmed by a laser microscope that there was no micro unevenness.

Comparative Example 2
In Example 1, the curable resin film (c2) was produced in the same manner as the curable resin film (1). The solid content concentration was 67%, the thickness was 61 μm, the width was 25 cm, the matte pet film contact surface had a glossiness of 2-3, and the opposite surface was a glossy film with high glossiness.
In the production of the transfer film in Example 1, the curable resin film (c2) was similarly obtained except that the transfer process using the mat roll (A) was performed and the transfer process using the mat roll (B) was not performed. ) To prepare a transfer film (c2), and further, the transfer cured film (c2) was produced by heat treatment in the same manner as the production conditions of the transfer cured film in Example 1.
The evaluation results are shown in Table 2.
In addition, regarding the transfer cured film (c2), the data relating to the surface unevenness shape is not shown in Table 1, but the transfer surface of the transfer film (c2) and the transfer cured film (c2) are both micro unevenness. It was confirmed by a laser microscope that the material had no macro unevenness.
When measuring the macro uneven shape of Example 1, height smoothing was performed for evaluation. Regarding the evaluation of the micro uneven shape, it was measured from the surface shape measured without smoothing the height.

The surface shape of the cured resin film of Example 1 is composed of relatively macro and micro uneven shapes that are different in size, and a plurality of macro uneven shapes and a plurality of micro uneven shapes are mixed. On the other hand, Comparative Example 1 is configured only by macro unevenness, and Comparative Example 2 is configured only by micro unevenness. When comparing Example 1 with Comparative Examples 1 and 2, in Example 1, the glossiness before curing is 4 and the glossiness after curing is 18, so that the glossiness increases only by 16. As a result, a cured resin film having a low glossiness is obtained. On the other hand, in Comparative Example 1, the glossiness before curing is 4, and the glossiness after curing is 35. Therefore, the glossiness is increased by 31. Also in Comparative Example 2, the glossiness before curing is 8 and the glossiness after curing is 29, so the glossiness is increased by 21. In this way, depending on only the macro unevenness or only the micro unevenness, it is considered that the surface unevenness is deteriorated by heat curing, and due to this, the glossiness is increased and the light shielding property is inevitably decreased. It was. It can be said from the above experimental results that the effect of the surface unevenness effect is caused by heat curing. In the said Example, it is shown that a gloss increase can be suppressed only by mixing a some macro uneven | corrugated shape and a some micro uneven | corrugated shape. At least, as long as the surface unevenness forming treatment is performed before complete curing, it is considered that any method is affected by heat curing, and the glossiness is increased. It is possible to sufficiently maintain the effect of gloss reduction caused by the uneven shape.
In the above embodiment, the concave and convex portions are adjacent to each other and are continuously arranged, and the concave and convex portions are linear, conceptually like a tin roof or corrugated plate shape. Are used as macro uneven shapes, but the mechanism of action by which various uneven shapes exhibit light scattering properties is the same, and therefore the present invention can be applied to various forms disclosed in this specification. It can be said that advantageous effects can be exhibited.

1: Cured resin film 2: Base material 3: Light-shielding film 4: Lens 5: Infrared cut filter 6: Barrel 7: Sensor lens 8: Edge 9: Roll 10: Mat roll type transfer layer 11: Transfer layer f: Coarse Curve m: Average line

Claims (9)

A cured resin film having a surface shape constituted by a plurality of uneven shapes, and having a reduced surface glossiness due to the surface shape,
In the cured resin film, at least one surface of the surface is composed of at least two types of uneven shapes of macro and micro that are different in size, and the plurality of macro uneven shapes and the plurality of micro uneven shapes A cured resin film characterized by comprising a mixture of the above. The macro concavo-convex shape has a concavo-convex shape height of 10 μm or more, and an average distance between adjacent macro concavo-convex shapes is 10 to 300 μm expressed by an average interval of the concavo-convex shape,
The micro concavo-convex shape has a concavo-convex height of less than 10 μm,
The cured resin film according to claim 1, wherein the surface shape is such that a micro uneven shape exists on a surface of a macro uneven shape. The macro concavo-convex shape has a concavo-convex shape height of 10 μm or more, and an average distance between adjacent macro concavo-convex shapes is 10 to 300 μm expressed by an average interval of the concavo-convex shape,
The micro concavo-convex shape has a concavo-convex height of less than 10 μm,
The cured resin film according to claim 1, wherein the surface shape has a distance between adjacent micro uneven shapes shorter than a distance between adjacent macro uneven shapes. The surface shape is a shape of a plurality of macro uneven shapes having an orientation or a sea-island shape having no orientation, and the micro uneven shapes are present on the surface of the macro uneven shape. The cured resin film in any one of 1-3. The said cured resin film contains a black material, The cured resin film in any one of Claims 1-4 characterized by the above-mentioned. A method for producing a cured resin film according to any one of claims 1 to 5,
The manufacturing method includes an uneven shape forming step of forming a continuous uneven shape on the surface of a curable resin film composed of a curable resin composition by transfer, and a step of curing the curable resin film, A method for producing a cured resin film, comprising forming a plurality of macro uneven shapes and a plurality of micro uneven shapes by an uneven shape forming step. A light-scattering film comprising the cured resin film according to claim 1. A light-shielding film comprising the light-scattering film according to claim 7,
The light-shielding film has a transmittance of less than 1% for light having a wavelength of 550 nm. A lens unit comprising the light-shielding film according to claim 8 and a lens,
The lens unit is a lens unit for an image sensor.

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