JP2011191693A - Light selective transmission filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a light selective transmission filter, with which crack, layer peeling, break, warpage etc. do not take place, and with which a light selective transmission filter exhibiting excellent light selective transmission and having a uniform cutting plane is obtained with ease and with high productivity; and to provide the light selective transmission filter obtained with the production method, a support film of the light selective transmission filter, and a lens unit. <P>SOLUTION: The method for producing the light selective transmission filter having at least a substrate and a light selective transmission layer includes a step of cutting out the light selective transmission filter from a laminated film having the light selective transmission layer on at least one face of the substrate with a laser, wherein the substrate is a resin film composed of a resin layer formed of a predetermined organic material, or a glass film having the resin layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a light selective transmission filter and a manufacturing method thereof. More specifically, the present invention relates to a method for producing a light selective transmission filter used for applications such as optical members, mechanical parts, electrical / electronic parts, automobile parts, and the like, and a light selective transmission filter obtained from such a production method.

The light selective transmission filter is a filter that selectively reduces (blocks) the transmittance of light having a specific wavelength, and generally has a structure having at least a base material and a light selective transmission layer. Such a light selective transmission filter is useful for applications such as optical members / equipment, mechanical parts, electrical / electronic parts, automobile parts, etc., and is particularly preferably used as an optical member. Specifically, for example, in a camera module, a filter that blocks (cuts) infrared rays (particularly wavelength> 800 nm) that becomes optical noise is used. As such an infrared cut filter, an infrared shielding glass in which an inorganic layer such as a metal is vapor-deposited on a glass substrate to form an inorganic multilayer film, and the refractive index of each wavelength is controlled, is usually used. It is manufactured by cutting out a desired shape by a dicing cut method.

In recent years, in the field of optical members / equipment and the like, for example, camera modules are mounted on mobile phones, and the miniaturization of the optical members / equipment and the like is further demanded. Along with this, it is also desired to reduce the size and weight of a light selective transmission filter used in a camera module or the like, or a lens unit having a lens or the like. Therefore, a light selective transmission filter that is sufficiently thin and excellent in various physical properties such as heat resistance has been developed (see Patent Document 1). This Patent Document 1 exemplifies laser cutting, punching, and dicing cut as methods for cutting out the light selective transmission filter. If the base material is an organic material, the base material can be cut off regardless of the cutting method used. No cracks occur, it can be applied to shapes such as circles and polygons, and among these methods, the punching method is preferred.

JP 2008-181121 A (pages 2, 3, 12 etc.)

As described above, there are various cutting methods for producing a light selective transmission filter having at least a base material and a light selective transmission layer, and a dicing cut method is usually employed. However, the dicing cut method is a technique of cutting with a straight line and can be formed into a shape consisting of only a straight part such as a quadrangle, but a shape having a curved part (non-linear part) such as a circle or an ellipse (unshaped) It cannot be molded into. In addition, forming into an irregular shape, that is, an irregularly shaped shape is possible by a punching method or a laser cutting method, but in a light selective transmission filter having a structure composed of only a light selective transmission layer and a glass base material using glass as a base material, Even if these methods are used, the substrate and the light selective transmission layer are broken and cannot be applied. However, as shown in Patent Document 1, it is possible to use a resin as a substrate. However, in the punching method described in Patent Document 1, since the die and the Thomson blade are pressed against the object to be cut and cut, the diameter is small even when the resin is used as a base material. In addition, when trying to obtain a complicated shape including a curved portion, a high pressure is applied to a small area, and cracking may occur. Therefore, even if the light selective transmission filter has a small irregular shape with a smaller diameter and includes a curved portion, it can be obtained more easily and with high productivity without causing cracks, cracks, delamination, etc. There is a need for microfabrication techniques that can be used.

By the way, when a lens unit including a light selective transmission filter and a lens is attached to an optical device such as a mobile phone, the shapes of the lens and the light selective transmission filter are conventionally different. That is, in the existing lens unit, the shape of the light selective transmission filter (light selective transmission layer / glass substrate) is a quadrangle processed by the dicing cut method, while the lens has a curved portion such as a circle or an ellipse. Since the shape having the shape is normal, the adhesion work between the lens and the light selective transmission filter is difficult due to the difference in shape. In particular, a small optical device / member is a very complicated operation, and there are problems in terms of handling, workability, and productivity.

The present invention has been made in view of the above-mentioned present situation, without causing cracks or delamination, cracks, warpage, etc., a light selective transmission filter with a uniform cut surface and capable of exhibiting excellent light selective transmission, An object of the present invention is to provide a method for producing a light selective transmission filter that can be obtained easily and with high productivity, a light selective transmission filter obtained by the production method, a light selective transmission filter support film, and a lens unit. It is.

While the inventors of the present invention have studied various methods for producing a light selective transmission filter having at least a base material and a light selective transmission layer, a resin film composed of a resin layer or a glass film having a resin layer is used as the base material. Focusing on improving the strength and flexibility of the base material, it is possible to obtain a light selective transmission filter with a uniform cut surface only when a specific material is used as the organic material for forming the resin layer. I found it. And when it is set as the manufacturing method including the process of cutting out a light selective transmission filter with a laser from a laminated film which has a light selective transmission layer in at least one side of such a substrate, generation of a crack, delamination, a crack, warpage, etc. It has been found that a light selective transmission filter having a shape in which cuts are suppressed and the cut surfaces are aligned (aligned) can be obtained more easily, simply and with high productivity.

According to such a manufacturing method, even if the light selective transmission filter has a small irregular shape and includes a curved line, cracks and delamination do not occur, and light selective transmission can be achieved. Since it can be easily obtained in a state where it can be fully demonstrated, this manufacturing method is an excellent technology that can be further adapted to the needs of downsizing, weight reduction, thinning, etc. in recent optical fields, etc., and light selection We have found that handling, workability, and productivity can be further improved when handling permeation filters. In addition, the light selective transmission filter obtained by such a manufacturing method and the lens unit provided with the light selective transmission filter can be suitably used particularly for a camera module for a mobile phone or a digital camera. It has also been found that a light selective transmission filter support film having a plurality of light selective transmission filters obtained by the production method of the present invention on a body film is suitable for transfer and storage of the light selective transmission filter, and the above-mentioned problems are observed. Thus, the present invention has been achieved.

That is, the present invention is a method for producing a light selective transmission filter having at least a base material and a light selective transmission layer, the manufacturing method comprising a laminated film having a light selective transmission layer on at least one surface of the base material. Cutting the light selective transmission filter with a laser, wherein the substrate is at least selected from a fluorinated aromatic polymer, a polycyclic aromatic polymer, a poly (amide) imide resin, a fluorine-containing polymer compound, and a curable resin. It is the manufacturing method of the light selective transmission filter which is a resin film which consists of a resin layer formed from 1 type of organic material, or a glass film which has this resin layer.
The present invention is also a light selective transmission filter obtained by the above production method.
The present invention is also a light selective transmission filter support film having a plurality of the above light selective transmission filters on a support film.
The present invention is also a lens unit including the light selective transmission filter.
The present invention is described in detail below.

<Method for producing light selective transmission filter>
The method for producing a light selective transmission filter of the present invention includes a step of cutting out the light selective transmission filter with a laser from a laminated film having a light selective transmission layer on at least one surface of the substrate (also referred to as “cutout step”). Further, it may further include one or more other steps. Preferably, at least a light selective transmission layer is laminated (formed) on one side or both sides of the substrate to obtain a laminated film (also referred to as “lamination step”), and a step of cutting out a specific shape from the laminated film with a laser (cutout) Step).

The laminated film may have at least a base material and a light selective transmission layer, and may have a light selective transmission layer on one side or both sides of the base material. (A functional material layer other than the above) may be further provided, and the other layer may be laminated between the base material and the light selective transmission layer. Moreover, these base materials and layers may each have a single layer structure or a multilayer structure.
The details of the base material and the functional material layer such as the light selective transmission layer will be described later.

The thickness of the laminated film may be set as appropriate depending on the use of the obtained light selective transmission filter, but is 200 μm or less from the viewpoint of realizing further reduction in size and weight in the use of the light selective transmission filter. Preferably it is. More preferably, it is less than 200 μm. In particular, 180 μm or less, 150 μm or less, 120 μm or less, 100 μm or less, 90 μm or less, 75 μm or less, or 50 μm or less is preferable (the smaller the value, the more preferable). Moreover, it is preferable that it is 1 micrometer or more from the viewpoint of the handleability of a laminated film, workability | operativity, etc., More preferably, it is 5 micrometers or more.

[Lamination process]
In the above laminating step, the light selective transmission layer is laminated on the base material (or other layer) (formation method) by, for example, direct light on one or both sides of the base material (or other layer) by a vapor phase method. Method for forming a selective transmission layer; Method for bonding a light selective transmission layer obtained by a vapor phase method onto a substrate (or other layer) with an adhesive; Material for forming a light selective transmission layer (for example, an inorganic material) Etc.) is preferably applied to a substrate (or other layer) and dried to form a film. As the vapor phase method, a CVD method (chemical vapor deposition method), a vacuum vapor deposition method, a sputtering method or the like is preferable, and a vacuum vapor deposition method is more preferable.

Among the above laminating methods (formation methods), a method in which a light selective transmission layer is directly formed on one side or both sides of a base material (or other layer) by a vapor phase method is preferable. Specifically, for example, a base material (or other layer) is installed in a vapor deposition apparatus or the like, and a light selective transmission layer is formed on the base material (or other layer) (one side or both sides) by vapor deposition. And adhere. From the economical viewpoint, it is preferable that the area of the light selective transmission layer on the base material is large (the area of the base material and the light selective transmission layer is close) because a large number of light selective transmission filters can be cut out. Further, from the viewpoint of achieving uniform light selective transmission, it is preferable that the area of the light selective transmission layer on the substrate is smaller because unevenness in the film thickness and smoothness of the light selective transmission layer does not occur. The size of the substrate and the area and shape of the light selective transmission layer formed thereon are preferably set as appropriate from the above viewpoint.

In the above-described lamination step, when the light selective transmission layer is laminated on the substrate (or other layer), the light selective transmission layer is disposed around the light selective transmission layer lamination portion (also referred to as a light selective transmission layer forming portion). It is preferable to have an edge that is not laminated (also referred to as a light selective transmission layer non-forming portion). For example, when the light selective transmission layer is laminated to the edge of the base material and no edge is provided, the light selective transmission layer laminated on the edge of the base material may be peeled off during or after the lamination. Moreover, also when producing the hole etc. for fixing to a base material, a light selective transmission layer may peel from the circumference | surroundings of a hole. This is because the light selective transmission layer is laminated on the side surface other than the upper surface (smooth surface) of the base material, such as the edge of the base material or the periphery of the hole, so that the adhesion is not sufficient, and the peeling starts. There is a possibility. By forming the light selective transmission layer non-forming portion along the edge or hole of the base material, peeling of the light selective transmission layer can be more sufficiently suppressed. In this way, light is applied to one surface or both surfaces of the base material (or other layer) so that the laminating step has a non-formation portion (edge) of the light selective transmission layer on the surface of the base material (or other layer). A form in which the permselective layer is laminated is also one suitable form. In this case, in the laminated film obtained by the laminating step, an edge where the light selective transmission layer is not laminated is formed around the light selective transmission layer lamination portion.
In order to provide the light selective transmission layer non-forming portion, it is preferable to use a material that prevents adhesion of the light selective transmission layer such as a screen or a vapor deposition tape. That is, it is preferable to laminate the light selective transmission layer after shielding the periphery of the light selective transmission layer lamination portion with a screen and / or a vapor deposition tape.

In the laminating step, the temperature at which the light selective transmission layer is formed (laminated) is preferably set to 250 ° C. or lower, for example. Thereby, for example, when a base material having reflow resistance is used, the influence on the base material can be further reduced. More preferably, it is 200 degrees C or less, More preferably, it is 170 degrees C or less. Moreover, it is suitable that it is 50 degreeC or more.

In the laminating step, when the laminated film further has another functional material layer in addition to the light selective transmission layer, these layers are provided between the base material and the light selective transmission layer according to the use and function. May be laminated (formed) on the light selective transmission layer or the base material, or may be laminated on the outermost layer of the base material and the light selective transmission layer. The lamination can be performed in the same manner as the above-described lamination of the light selective transmission layer.

[Cutting step]
In the cutout step, the laminated film is irradiated with laser light to cut out a desired shape (laser cut). Usually, when obtaining a light selective transmission filter, a punching method or a dicing cut method is adopted. However, in the punching method, a die or a Thomson blade is pressed against an object to be cut and cut, for example, a diameter. A small irregular shape that is smaller and includes a curved portion cannot be obtained more suitably, and a shape including a curved portion cannot be obtained by the dicing cut method. On the other hand, if the laser cutting method of the present invention is employed, even a unique minute irregular shape that is difficult to cut out can be obtained more easily and simply. In addition, unlike the punching and dicing cutting methods, the laser cut method can be molded (cut out) in a non-contact manner, so that the light selective transmission filter is not broken by pressure, and the laser cutting device is set. Since it is possible to easily change the desired shape (size change, etc.) simply by the change, there is no need to produce / use an expensive mold necessary for the punching method, and the cost is excellent. Furthermore, the laser cutting method is less prone to cracking and cracking than the punching method, and the number of light selective transmission filters that can be cut out (molded) from a single laminated film is very excellent in productivity. ing.

As the laser used in the laser cutting method, for example, a carbon dioxide (CO ₂ ) laser, a UV yag laser, or the like is preferable. Among these, a carbon dioxide laser is preferable. In addition, the laser beam diameter may be set as appropriate from the viewpoints of laser performance, productivity of the light selective transmission filter, and the like, for example, 20 to 100 μm for a carbon dioxide laser and 10 to 80 μm for a UV yag laser. Is preferred.

In the cutout process, it is preferable that the light selective transmission filter is cut out from one laminated film to be used in the cutout process, and the number of cutouts is plural. As described above, since the number of light selective transmission filters that can be cut out from a single laminated film is large when the laser cutting method is adopted in the cutting step, the light selective transmission of the present invention can be performed with higher productivity if the number of times of cutting is set to a plurality of times. It becomes possible to obtain a filter.

In the above cutting process, the resin may be scattered from the cut surface at the time of laser cutting (laser cutting), so that the substrate and the light selective transmission layer are protected in order to further protect the product from contamination. It is preferable to form (cut out) in a state further having a protective film (protective layer). That is, the laminated film preferably has a protective layer in addition to the base material and the light selective transmission layer. This makes it possible to protect the substrate and the light selective transmission layer from dirt, etc., for example, not only when cutting out, but also when transporting or storing the light selective transmission filter in some cases. Is preferred. Thus, the form in which the laminated film and the light selective transmission filter further have a protective layer is also a preferred form of the present invention.

The protective layer is preferably located on the uppermost layer (outermost layer) on one or both sides of the laminated film and the light selective transmission filter. For example, in the case of a laminated film composed of a base material and a light selective transmission layer, for example, (i) when the light selective transmission layer is provided on both surfaces of the base material, it is formed on at least one or both of the light selective transmission layers. Form having a protective layer, (ii) In the case of having a light selective transmission layer on one surface of the substrate, the upper layer of the light selective transmission layer and / or the upper layer of the base on the side not having the light selective transmission layer Examples include a form having a protective layer. The light selective transmission filter obtained using the laminated film of such a form is obtained by first forming a light selective transmission layer on one or both sides of the substrate in the above production method, and further laminating a protective layer on one or both sides thereof. Then, it is preferable to obtain by performing a cutting step.
In addition, when providing a protective layer in this way, it is suitable to perform the process of peeling a protective layer after the said cutting-out process as needed.

Next, the base material and the functional material layer constituting the laminated film and the light selective transmission filter will be further described.
〔Base material〕
The substrate is a resin film made of a resin layer formed from a specific organic material, or a glass film having the resin layer. That is, at least the resin layer is included, but this makes it possible to sufficiently suppress chipping and cracking of the obtained light selective transmission filter and to be useful for various applications. Usually, when a substrate made of an inorganic material alone such as glass is used, strength and flexibility may not be sufficient, but by including at least a resin layer, strength and Because flexibility is improved, breakage, cracking, deformation, etc. can be prevented in the post-process etc. to carry out multilayering and functionality addition during transportation, molding or incorporation into equipment, A light selective transmission filter excellent in workability can be obtained. In the present invention, a laser cutting step (laser cut) is performed. In this case, since the cut portion is heated, when a base material made of an inorganic material alone such as glass is used, a light selective transmission filter is used depending on the temperature difference. There is also a risk of cracks. However, the occurrence of cracks can be sufficiently prevented by using a substrate including at least a resin layer.
It is also preferred that the substrate is a transparent substrate.

By using a resin film composed of a resin layer or a glass film having a resin layer as the base material, various uses in terms of processability, moldability, flexibility, economy, strength (hardness to crack), etc. Thus, a light selective transmission filter useful for the above can be obtained. For example, when the substrate is a resin film made of a resin layer, complicated processing that cannot be performed with an inorganic material such as glass can be performed at low cost.
The resin layer is a layer formed of one kind or two or more kinds of organic materials, but a mixture (single layer structure) formed using one kind of organic material as a material (preferably a mixture of two or more kinds (preferably , A mixture that maintains transparency) may be formed as a material, or may be a form in which two or more kinds are laminated (multilayer structure). In addition, when setting it as a mixture, you may mix and make an organic material liquid.

The resin film comprising the resin layer can be obtained by forming an organic material by, for example, a solvent casting method, a melt molding method, or the like. Moreover, the glass film which has a resin layer means the form which has a resin layer on the one surface or both surfaces of a glass film, for example, apply | coating 1 type, or 2 or more types of organic material to both surfaces or one side of a glass film Or it can obtain by casting.

The resin layer contained in the base material is a layer formed of one or more organic materials, and the organic material includes (1) a fluorinated aromatic polymer, (2) a polycyclic aromatic polymer, At least one selected from the group consisting of (3) poly (amide) imide resin, (4) fluorine-containing polymer compound and (5) curable resin is suitable. That is, the resin layer is suitably formed from at least one organic material selected from these groups. By using these organic materials, strength and flexibility can be improved, heat resistance and reflow resistance are excellent, and a light selective transmission filter having a cut surface without cracks or chipping of the light selective transmission layer is obtained. It becomes possible. If the cut surfaces are not aligned, the light selective transmission layer may be peeled off from the base material at the cutting part, that is, around the laser light irradiation part, and the base material may be exposed, so that the light selective transmission can be sufficiently exerted. Disappear. Even when a substrate having a resin layer is used and laser cutting is performed, if the resin layer is formed from an organic material other than the organic materials described above, the cut surfaces may be aligned. Although it is difficult and sufficient light selective transmission cannot be exhibited, in the present invention, by using the above-mentioned specific organic material, it is possible to obtain a light selective transmission filter that has a uniform cut surface and can exhibit excellent light selective transmission. Has been realized.

(1) Fluorinated aromatic polymer As the fluorinated aromatic polymer, an aromatic ring having at least one fluorine group and an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. And a polymer composed of a repeating unit containing at least one selected bond. Specifically, for example, polyimide having a fluorine atom, polyether, polyetherimide, polyetherketone, polyethersulfone , Polyamide ether, polyamide, polyether nitrile, polyester and the like. Among these, it is preferable that it is a polymer which has as an essential part the repeating unit containing the aromatic ring which has an at least 1 or more fluorine group, and an ether bond, and the following general formula (1-1) or (1- A polyether ketone having a fluorine atom containing the repeating unit represented by 2) is more preferred. Among these, fluorinated polyether ketone (FPEK) is particularly preferable.
In addition, the repeating unit represented by the general formula (1-1) or (1-2) may be the same or different, and may be in any form such as a block shape or a random shape.

In the general formula (1-1), R ¹ represents a divalent organic chain having an aromatic ring having ¹ to 150 carbon atoms. Z represents a divalent chain or a direct bond. x and y are integers of 0 or more, satisfy x + y = 1 to 8, and represent the number of fluorine atoms that are the same or different and are bonded to the aromatic ring. n ¹ represents a degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.
In the general formula (1-2), R ² may have a substituent, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkylamino group having 1 to 12 carbon atoms. Represents an alkylthio group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an arylthio group having 6 to 20 carbon atoms. R ³ represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. z is the number of fluorine atoms bonded to the aromatic ring and is 1 or 2. n ¹ represents a degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.

In the general formula (1-1), x + y is preferably in the range of 2 to 8, and more preferably in the range of 4 to 8. Further, the position at which the ether structure moiety (—O—R ¹ —O—) is bonded to the aromatic ring is preferably para to Z.

In the general formulas (1-1) and (1-2), R ¹ and R ³ are divalent organic chains. For example, any one represented by the following structural formula group (2): Or it is preferable that it is the organic chain of the combination.

In the structural formula group (2), Y ^{1 to} Y ⁴ are the same or different and each represents a hydrogen group or a substituent, and the substituent is a halogen atom or an alkyl group which may have a substituent. Represents an alkoxy group, an alkylamino group, an alkylthio group, an aryl group, an aryloxy group, an arylamino group or an arylthio group.
More preferable specific examples of R ¹ and R ³ include organic chains represented by the following structural formula group (3).

In the general formula (1-1), Z represents a divalent chain or a direct bond. For example, the divalent chain is preferably a chain represented by the following structural formula group (4) (structural formulas (4-1) to (4-13)).

In the structural formula group (4), X is a divalent organic chain having 1 to 50 carbon atoms. Examples thereof include the organic chain represented by the structural formula group (3) described above, and among them, diphenyl ether. A chain, a bisphenol A chain, a bisphenol F chain, and a fluorene chain are preferred.

In R ² in the general formula (1-2), examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, An isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 2-ethylhexyl group and the like are preferable.
As the alkoxy group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group , Dodecyloxy group, furfuryloxy group, allyloxy group and the like are preferable.
As the alkylamino group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, propylamino group, n-butylamino group, sec-butylamino group, tert-butylamino group and the like are preferable.
As the alkylthio group, methylthio group, ethylthio group, propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, iso-propylthio group and the like are preferable.

As the aryl group, phenyl group, benzyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, A biphenylyl group, a benzhydryl group, a trityl group, a pyrenyl group, and the like are preferable.
Examples of the aryloxy group include groups derived from a phenoxy group, a benzyloxy group, hydroxybenzoic acid and esters thereof (for example, methyl ester, ethyl ester, methoxyethyl ester, ethoxyethyl ester, furfuryl ester, and phenyl ester). A naphthoxy group, o-, m- or p-methylphenoxy group, o-, m- or p-phenylphenoxy group, phenylethynylphenoxy group, a group derived from cresotinic acid and esters thereof, and the like are preferable.
The arylamino group includes an anilino group, o-, m- or p-toluidino group, 1,2- or 1,3-xylidino group, o-, m- or p-methoxyanilino group, anthranilic acid and its Groups derived from esters are preferred.
The arylthio group is preferably a phenylthio group, a phenylmethanethio group, an o-, m- or p-tolylthio group, a group derived from thiosalicylic acid and esters thereof, and the like.
Of these, R ² is preferably an alkoxy group, aryloxy group, arylthio group or arylamino group which may have a substituent. However, R ² may or may not contain a double bond or a triple bond.

Examples of the substituent for R ² in the general formula (1-2) include an alkyl group having 1 to 12 carbon atoms as described above; a halogen atom such as fluorine, chlorine, bromine and iodine; a cyano group, a nitro group, and a carboxy group. An ester group or the like is preferred. Moreover, hydrogen of these substituents may or may not be halogenated. Among these, preferably, a halogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, and a carboxy ester, which may or may not be halogenated. It is a group.

(2) Polycyclic aromatic polymer As the polycyclic aromatic polymer, at least two aromatic rings are selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond. It is linked from one type of bond. For example, a compound having a monomer unit having two or more linked aromatic rings such as a naphthalene ring and a fluorene ring as the main skeleton is preferable. Specifically, polyester (polyethylene naphthalate) having naphthalenedicarboxylic acid as the main acid component and ethylene glycol as the main glycol component is preferable.

As such a polyethylene naphthalate, a homopolymer of polyethylene-2,6-naphthalenedicarboxylate is suitable. For example, a part of the 2,6-naphthalenedicarboxylic acid component (less than 30 mol%) is converted to 2 , 7-, 1,5-, 1,7-Other naphthalenedicarboxylic acid isomers or terephthalic acid or isophthalic acid; diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, etc. Aromatic dicarboxylic acids; Alicyclic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid; Aliphatic dicarboxylic acids such as adipic acid, sebacic acid and azelaic acid; p-β-hydroxyethoxybenzoic acid, ε-oxy Other bifunctional cals such as oxyacids such as caproic acid It may be replaced with boronic acid.

As the polyethylene naphthalate, a part of the ethylene glycol component may be, for example, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, 1,1-cyclohexanedimethanol, 1, Substitution with one or more other polyfunctional compounds such as 4-cyclohexanedimethanol, 2,2-bis (4'-β-hydroxyethoxyphenyl) propane, bis (4'-β-hydroxyethoxyphenyl) sulfonic acid The copolymer may be copolymerized in a range of less than 30 mol%.

A more preferable compound as the polycyclic aromatic polymer is, for example, the following formula (5):

(Wherein n ² represents the number of repetitions and is an integer of ² to 10000), for example, polyethylene naphthalate (PEN) represented by Teijin DuPont Films Theonex Q83 (thickness) 25 μm or 75 μm, melting point 269 ° C.).

(3) Poly (amide) imide resin The above poly (amide) imide resin is a narrowly defined polyimide resin (resin containing an imide bond and not containing an amide bond) and a polyamideimide resin (an amide bond and an imide bond). Any of the resins).
The poly (amide) imide resin is obtained by imidizing a raw material of a poly (amide) imide resin obtained by reacting a polyvalent carboxylic acid compound with a polyvalent amine compound and / or a polyvalent isocyanate compound. Can do.
The poly (amide) imide resin also preferably has transparency. In order to improve transparency, it is preferable that there are few aromatic rings. Among them, it is more preferable to have a structure in which the aromatic ring is replaced with an alicyclic ring or a fatty chain. More preferably, the weight of the aromatic ring in the total weight of 100% is 65% or less, more preferably 45% or less, and particularly preferably 30% or less.

Although it will not specifically limit if it is a compound which has an imide bond as said poly (amide) imide resin, For example, following formula (6):

(Wherein n ³ is an integer of 0 to 4, p ³ is 0 or 1, and n ³ + p ³ is an integer of 1 to 5). preferable. Specifically, Neoprim L-3430 (thickness 50 μm or 100 μm) manufactured by Mitsubishi Gas Chemical Company may be mentioned.

(4) Fluorine-containing polymer compound As the above-mentioned fluorine-containing polymer compound, fluorine-containing alicyclic diamine or fluorine-containing aromatic diamine containing at least two cyclohexyl rings and two fluoroalkyl groups in one molecule, A fluorine-containing polymer compound used in at least a part of the monomer is preferable. Specifically, for example, the following formulas (8-1) to (8-4):

(In the formula, R ⁴ represents at least one divalent group selected from the group consisting of linear, branched, alicyclic, aromatic and heterocyclic rings, partially containing fluorine, oxygen or nitrogen. Or a fluorine-containing polymer compound having a fluorine-containing alicyclic polyamide structure or a fluorine-containing aromatic polyamide structure containing a repeating unit represented by the following formulas (9-1) to (9-4):

(In the formula, R ⁵ represents at least one tetravalent group selected from the group consisting of linear, branched, alicyclic, aromatic and heterocyclic rings, partially containing fluorine, oxygen or nitrogen. R ⁶ is hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, and may partially contain fluorine, oxygen, nitrogen, an unsaturated bond, or a cyclic structure. ) -Containing fluorine-containing alicyclic polyamic acid, fluorine-containing aromatic polyamic acid, or fluorine-containing polymer compound which is an ester thereof; the following formulas (10-1) to (10-4) ):

(In the formula, R ⁵ represents at least one tetravalent group selected from the group consisting of linear, branched, alicyclic, aromatic and heterocyclic rings, partially containing fluorine, oxygen or nitrogen. And a fluorine-containing polymer compound which is a fluorine-containing alicyclic polyimide or fluorine-containing aromatic polyimide containing a repeating unit represented by
In the above formula (10-3), R ^{5 in} the formula is more preferably a form represented by the following formula (11).

A more preferable compound as the fluorine-containing polymer compound is, for example, the following formula (12):

4,4′-hexafluoropropylidenebisphthalic dianhydride (6FPA) represented by the following reaction with 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (TFBD) A fluorinated polyimide resin (F-PI) (film thickness 50 μm) obtained by obtaining a polymer solution and then heating is exemplified.

As the fluorine-containing polymer compound, those containing tetrafluoroethylene are also suitable. In particular, from the viewpoint of transparency, a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer is preferable. Specifically, a Neoflon TM film PFA (50 μm) manufactured by Daikin or a Naflon PFA sheet (T / # 9000-PFA) and the like, and Neoflon TM film PFA (50 μm) manufactured by Daikin is particularly suitable.

(5) Curable resin As said curable resin, an epoxy resin, an acrylic resin, etc. are suitable.
The said epoxy resin is a hardened | cured material of the curable composition containing the compound (epoxy compound) which has an epoxy group. Examples of the form of the cured product include a form obtained by curing the epoxy compound with light and / or heat in the presence of a cationic curing catalyst, a form of a cured product obtained by reacting the epoxy compound with an additional curing agent, and the like. In the latter case, a conventionally known curing accelerator can be used in combination for accelerating the curing reaction. Examples of the additional curing agent include acid anhydrides, polyhydric phenol compounds, and polyvalent amines. Among them, acid anhydrides are preferable.

As said epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, a hydrogenated epoxy compound etc. are suitable, For example, Osaka Gas Chemical Co., Ltd. fluorene epoxy (Oncoat EX-1); Bisphenol A type epoxy resin (Epicoat 828EL) manufactured by Japan Epoxy Resin; Hydrogenated bisphenol A type epoxy resin (Epicoat YX8000) manufactured by Japan Epoxy Resin; Alicyclic liquid epoxy resin (Celoxide 2021) manufactured by Daicel Industries, Ltd. Can be preferably used.
In addition, in this specification, an epoxy group includes an oxirane ring that is a three-membered ether, and includes a glycidyl group (including a glycidyl ether group and a glycidyl ester group) in addition to a narrowly defined epoxy group. Means.

In the epoxy resin, it is preferable that the curable composition before curing includes a flexible component (flexible component). By including a flexible component, it is possible to obtain a resin composition having a sense of unity, such as not cracking, not losing shape, being easily peeled off, and having flexibility when being removed from molding or from a substrate or mold.
The flexible component may be a compound different from the epoxy compound, or at least one of the epoxy compounds may be a flexible component.

Specifically, the flexible component is a compound having an oxyalkylene skeleton represented by — [— (CH ₂ ) _n —O—] _m — (n is 2 or more, and m is an integer of 1 or more. Preferably, n is 2 to 12, m is an integer of 1 to 1000, and more preferably, n is 3 to 6 and m is an integer of 1 to 20.), for example, (I) An epoxy compound containing an oxybutylene group (YED-216D manufactured by Japan Epoxy Resin; YL-7217 manufactured by Japan Epoxy Resin, epoxy equivalent 437, liquid epoxy compound (10 ° C. or higher)) is preferable. Other suitable flexible components include (II) polymer epoxy compounds (for example, hydrogenated bisphenol (manufactured by Japan Epoxy Resin, YX-8040, epoxy equivalent 1000, solid hydrogenated epoxy compound)); III) Alicyclic solid epoxy compound (EHPE-3150 manufactured by Daicel Industries, Ltd.); (IV) Compound containing epoxy group such as alicyclic liquid epoxy compound (Daicel Industry, Celoxide 2081); (V) Liquid nitrile rubber Liquid rubber such as polybutadiene, polymer rubber such as polybutadiene, and fine particle rubber having a particle size of 100 nm or less are preferable. Among these, more preferred are compounds containing a curable functional group in the terminal side chain or main chain skeleton. The “curable functional group” refers to a functional group that cures with heat or light, such as an epoxy group (a group that cures an organic resin).

The acrylic resin is a cured product of a curable composition containing a compound having a (meth) acryloyl group ((meth) acryloyl group-containing compound).

Regarding the base material, a glass film having a resin layer is a form having a layer (resin layer) formed of one or more organic materials on one or both surfaces of the glass film. Good. As described above, organic materials used in such a form include (1) fluorinated aromatic polymer, (2) polycyclic aromatic polymer, (3) poly (amide) imide resin, and (4) At least one selected from the group consisting of fluorine polymer compounds and (5) curable resins is suitable. Among these, a fluorinated aromatic polymer, an epoxy resin, and a composite resin of a fluorinated aromatic polymer and an epoxy resin are preferable. As a result, the strength and flexibility can be further improved.

As the glass film, a film having a thickness of 150 μm or less is preferable from the viewpoint of excellent bending strength and the achievement of a thinner film. More preferably, it is 100 micrometers or less, More preferably, it is 50 micrometers or less. Moreover, the glass film should just be a form which has a silica as a main component, and if transparency can be ensured with 80% (irradiation light wavelength 500nm), the ratio of the other component, a kind, etc. will not be limited. The glass film is preferably a glass cord (D263, 30 μm) manufactured by SCHOTT.

A preferred form of the glass film having the resin layer is a form having a resin layer on both surfaces of the glass film. Among them, as an organic material for forming the resin layer, a fluorinated aromatic polymer, an epoxy resin, or a fluorinated product is used. It is preferable to use a composite resin of an aromatic polymer and an epoxy resin.
In addition, from the viewpoint of preventing cracking and the like, a resin layer may be laminated after placing another layer on the glass film.

The base material is also preferably heat resistant, which makes it even more useful in various fields. In particular, it is preferable that the organic material forming the resin layer has heat resistance. Having heat resistance means, for example, that the 10% decomposition temperature is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, more preferably 300 ° C. or higher, particularly preferably 350 ° C. or higher, as the heat resistant temperature of the substrate. is there. Moreover, it is preferable that the glass transition temperature (Tg) of a base material is 80 degreeC or more, More preferably, it is 150 degreeC or more, More preferably, it is 200 degreeC or more, Most preferably, it is 250 degreeC or more.
In the present invention, since the light selective transmission filter is obtained by using the laser cut method, it is more preferable to use a base material having high heat resistance, thereby suppressing the deformation of the base material at the time of laser cutting more sufficiently. In addition, the occurrence of cracking and peeling of the inorganic layer can be more sufficiently prevented.

The above-mentioned base material is also suitable for those having reflow resistance, so that even if the thickness of the light selective transmission filter is thin, it can be made more excellent in heat resistance, so it is more suitable for various applications such as optical applications. Can be used. For example, since the heat resistance when mounting the light selective transmission filter can be made more sufficient, automatic mounting is possible, mounting costs are further reduced, and it is preferably used for reflowable camera modules, etc. Can do. Moreover, when forming a light selective transmission layer on a base material by vapor deposition, the heat resistance by vapor deposition is required, but also from this point, a base material having reflow resistance is preferable. Thus, the form in which the substrate is a reflow resistant functional film is also one of the preferred forms of the present invention.

Here, having reflow resistance means having a characteristic capable of withstanding the heating in the soldering process. For example, the reflow resistant functional film is a reflowable specification film that is promising as the next generation specification of a camera module. It is.
Specifically, the substrate having reflow resistance is preferably one that retains its shape at 250 ° C. · 3 min or 200 ° C. · 5 hr. More preferably, the shape is maintained at 250 ° C. · 3 min and 200 ° C. · 5 hr. More preferably, the shape is held at 260 ° C. · 3 min or 200 ° C. · 5 hr, and particularly preferably the shape is held at 260 ° C. · 3 min and 200 ° C. · 5 hr. If there is no reflow resistance, the film dissolves and cannot keep its shape when the light selective transmission layer is formed on the base material by the vapor phase method, and it cannot be deposited, or the shape changes during the reflow process. It may become impossible to implement. In the present invention, having reflow resistance means that the change in shape and dimensions before and after applying heat is 20% or less of the original shape and dimensions. The change in shape and dimensions is preferably 5% or less, and more preferably 1% or less.
Note that holding the shape at 250 ° C. for 3 minutes indicates that the reflow resistance at the time of mounting is sufficient, and holding the shape at 200 ° C. for 5 hours means that the inorganic layer is formed on the substrate. It shows that the reflow resistance at the time of vapor deposition for laminating etc. is sufficient. In addition, when the shape is maintained at 260 ° C. for 3 minutes, it indicates that the reflow resistance during mounting is further improved.

The base material is also preferably a heat-treated base material, particularly preferably a heat-treated resin film (resin film made of a resin layer). That is, the laminated film and the light selective transmission filter preferably include a heat-treated resin film. Since the heat-treated resin film has better heat resistance, it is possible to obtain a light selective transmission filter that is less likely to be deformed by heat. The heat treatment is to perform a hot press, a hot roll, a stretching treatment or the like. For example, the light selective transmission filter may be heated when used in various applications. For example, in an optical application such as a lens unit, it is usually mounted (mounted) by soldering. When a heat-treated resin film is used as a base material, it is preferable that thermal deformation during mounting is more sufficiently suppressed and no curling occurs. In other words, such a light selective transmission filter can further solve the problem of thermal deformation by forming a light selective transmission layer or the like on the heat-treated resin film. In addition, the heat treatment can further improve the mechanical strength, heat resistance, adhesion, and the like of the resin film.

As a condition for the heat treatment, it is preferable that the treatment temperature is a temperature in the vicinity of Tg of the organic material forming the resin film. More preferably, the temperature is Tg or higher. Moreover, as a temperature range of process temperature, the temperature range which is Tg vicinity or more and Tg vicinity +150 degrees C or less is preferable. More preferably, the temperature range is Tg or more and around Tg + 150 ° C. or less. “Near Tg” means a temperature within a range of 15 ° C. with respect to the glass transition temperature.

From the viewpoint that the base material is more excellent in adhesion with an adjacent layer (light selective transmission layer or the like), among the forms described above (resin film made of resin layer or glass film having a resin layer), (1 ) A fluorinated aromatic polymer, (2) a polycyclic aromatic polymer, (3) a poly (amide) imide resin, and (5) at least one organic material selected from the group consisting of curable resins. A resin film made of a resin layer is suitable. When such a resin film is used as the substrate, for example, when a light selective transmission layer is formed by vapor deposition, it is possible to obtain a vapor deposition film that is more excellent in the adhesion between the deposited light selective transmission layer and the substrate. it can.

The thickness of the substrate is preferably, for example, 200 μm or less. Thereby, the light selective transmission filter can be more preferably applied to a field where downsizing and thinning are required. More preferably, it is 150 micrometers or less, More preferably, it is 100 micrometers or less.

[Functional material layer]
The functional material layer is a layer formed from a functional material, and can be appropriately selected depending on the function imparted to the light selective transmission filter. For example, in addition to the light selective transmission layer essential in the present invention, a protective layer, a layer having toughness, a buffer layer (intermediate layer, relaxation layer) that absorbs stress applied to the light selective transmission filter, a reinforcing layer, a hydrophilic layer , A water repellent layer, an antireflection layer, a retardation layer, a refractive index adjusting layer, an adhesive layer, a conductive layer, an insulating layer, an optical compensation layer, and the like. Further, when another functional material layer is formed in addition to the light selective transmission layer, a layer having a thermal expansion coefficient intermediate between the base material and the light selective transmission layer may be further laminated.

The light selective transmission filter preferably has a structure having functional material layers on both sides thereof. For example, it is preferable to have a structure in which functional material layers are laminated on both sides of a substrate. By forming a functional material layer in which both surfaces of the light selective transmission filter are laminated with a functional material, a light selective transmission filter having a more fulfilling function can be obtained. In addition, when functional materials are laminated by vapor deposition, it is preferable to vapor-deposit materials on both surfaces, but in this case, curling during vapor deposition and / or mounting can be further suppressed, and light more suitable for various applications. It can be a selective transmission filter.

Different functional material layers may be laminated on both surfaces of the substrate, or functional material layers having the same function may be laminated. Among these, (1) a mode in which both sides are light selective transmission layers, (2) a mode in which one side is a light selective transmission layer and the other is an antireflection layer, and (3) one side is a light selective transmission layer and the other is preferred. Is an antireflection layer / light selective transmission layer. Among these, the form (1) is preferable, and the form in which the light selective transmission filter and the laminated film have the light selective transmission layers on both surfaces of the base material is also one of the preferable forms of the present invention. is there. Thereby, generation | occurrence | production of curvature, a crack, etc. of the light selective transmission filter obtained can be suppressed more fully. If necessary, another functional material layer may be provided between the base material and the light selective transmission layer.
The functional material layer is preferably laminated in a form in which each function can be exhibited most. In the present invention, the transmittance of a desired wavelength can be reduced by appropriately selecting the light selective transmission layer. For example, in the case of reducing infrared light, the light selective transmission layer is an infrared cut layer among the forms (1) to (3).

-Light selective transmission layer-
The light selective transmission layer is a functional material layer having the ability to selectively reduce (block) the light transmittance, that is, the light selective transmission, but in particular, it is an inorganic layer that is hardly deteriorated by laser. Is preferred. Further, an (organic) dispersion film in which an organic dye is dispersed in an inorganic binder or an organic binder can also be used as the light selective transmission layer.
The said inorganic layer means the layer formed from an inorganic material, and becomes a light selective transmission filter which is excellent in heat resistance etc. by having such an inorganic layer. The inorganic material contains an inorganic component, and the inorganic component may be appropriately selected according to the function / function expected of the inorganic layer, the use of the light selective transmission filter, and the like.
Examples of the inorganic component include metals (including alloys and intermetallic compounds), metal oxides, metal fluorides, metal carbides, metal nitrides, metal chalcogenides (metal sulfides, metal selenides, metal tellurides). Etc. are preferably exemplified. Among these, metals, metal oxides, and metal fluorides are preferable because they can be easily formed on a substrate suitable for the present invention by a vapor-phase film forming method described later.

Preferred examples of the metal include chrome, gold, silver, copper, indium, magnesium, aluminum, and calcium.
Preferred examples of the metal oxide include silica, titania, alumina, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, titanium oxide, and iron oxide. , Tin oxide, cerium oxide, MgIn ₂ O ₄ , MgIn ₂ O _{4 and} other single oxides and complex oxides; tin-doped indium oxide (ITO), fluorine-doped indium oxide, phosphorus-doped tin oxide, aluminum-doped zinc oxide, indium-doped Examples thereof include solid solution metal oxides formed by dissolving different elements in a single oxide or composite oxide such as zinc oxide.
Preferred examples of the metal fluoride include lithium fluoride, lanthanum fluoride, magnesium fluoride, and aluminum hexafluoride sodium.

The inorganic layer may have a single layer structure or a multilayer structure (multilayer film), and the inorganic component constituting each layer may be a single composition or a composition in which two or more inorganic components are mixed. It may be.
As the form of the layer constituting the inorganic layer, the form of the thin film substantially composed of only the inorganic component described above (form 1), the form in which fine particles composed of the inorganic component are dispersed in the inorganic binder (form 2), the inorganic component The form (form 3) etc. which the microparticles | fine-particles which consist of disperse | distribute to the organic binder are illustrated.
In the inorganic layer, the higher the proportion of the inorganic component, the more preferable the effect in the present invention is. For example, the content of the inorganic component in each layer constituting the inorganic layer is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 95% with respect to 100% by mass of the inorganic material forming the layer. It is more than mass%, and it is particularly preferable that it consists essentially of an inorganic component. Moreover, the form of the thin film which consists only of an active ingredient substantially from the point which is excellent in the optical performance and durability in optical uses, such as a light selective transmission filter so that it may be shown later, is preferable.
The inorganic layer of Form 1 is preferably formed by a vapor deposition method, as will be described later. Moreover, the inorganic layer of the said form 2 and form 3 is normally formed by the apply | coating method.

The inorganic layer preferably has a multilayer structure, more preferably a multilayer deposited film, from the viewpoint of sufficiently reducing desired light. By adopting a multilayer structure, the transmittance of the wavelength to be selectively reduced can be easily reduced to 10% or less in the entire wavelength region. In other words, a sharp light selective transmission filter having a high transmittance in the wavelength region desired to be transmitted and a low transmittance in the wavelength region desired to be reduced can be obtained. More specifically, when the light selective transmission filter is an infrared cut filter that reduces infrared light having a wavelength of 780 nm to 10 μm, the transmittance suddenly changes at 780 nm. For example, light having a transmittance of less than 780 nm is transmitted with a transmittance of 70% or more, and the transmittance is sharply changed so that it is transmitted with a transmittance of 10% or less at 780 nm or more. There is an advantage that infrared light can be selectively removed from light reaching the sensor.
The inorganic layer is preferably a crystalline film rather than an amorphous film. A particularly preferable form of the inorganic layer is a multilayer deposited film composed of a crystalline inorganic layer.

A more preferable form of the inorganic layer is an inorganic multilayer film capable of controlling the refractive index of each wavelength; a transparent conductive film having a function of reflecting light of a desired wavelength; a dispersion film having a function of absorbing light of a desired wavelength, etc. It is. Among these, as the transparent conductive film, a transparent conductive film as a film that reflects infrared rays, such as indium-tin oxide (ITO), is preferable. Moreover, as an infrared-absorbing dispersion film, a film in which inorganic particles such as ITO (preferably inorganic nanoparticles) are dispersed in an inorganic or organic binder is preferable. Among these preferable forms, an inorganic multilayer film, a transparent conductive film, a film in which inorganic nanoparticles are dispersed in an inorganic binder, and the like are preferable because they are superior in heat resistance. Among these, an inorganic multilayer film is preferable.

In the light selective transmission filter having the inorganic multilayer film as a light selective transmission layer, a low refractive index material and a high refractive index material are formed on a base material or other functional material layer by a vacuum deposition method or a sputtering method. Are alternately laminated to form a light selective transmission layer, which selectively reflects light of the wavelength to be reduced (for example, infrared region or ultraviolet region), and the phase of incident light and reflected light is half wavelength. By deviating, the light transmittance is selectively reduced. That is, the light selective transmission layer is particularly preferably a refractive index control multilayer film in which a low refractive index material and a high refractive index material are alternately laminated. Specifically, a dielectric multilayer film (for example, an infrared reflective film, an ultraviolet reflective film) in which dielectric layers A and dielectric layers B having a refractive index higher than that of the dielectric layer A are alternately stacked. Or, an ultraviolet / infrared reflective film) is preferable. By having such a dielectric multilayer film on at least one surface of a base material (preferably a transparent base material), a light selective transmission filter having an excellent ability to selectively reflect light of a desired wavelength can be obtained. it can. Among them, a multilayer film having a structure in which about 15 to 60 layers (1 to 7 μm) of a low-refractive index material and a high-refractive index material are stacked on the surface of the substrate on which incident light is incident (multilayer deposition layer, multilayer deposition film, It is particularly preferable that it is also referred to as a dielectric multilayer film. As described above, a mode in which the light selective transmission filter has a light selective transmission layer made of a dielectric multilayer film is also a preferred embodiment of the present invention.

As the material constituting the dielectric layer A, a material having a refractive index of 1.6 or less can be generally used, and a material having a refractive index range of 1.2 to 1.6 is preferably selected. For example, silica, alumina, lanthanum fluoride, magnesium fluoride, sodium hexafluoride sodium and the like are suitable.
As the material constituting the dielectric layer B, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of 1.7 to 2.5 is preferably selected. For example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, etc., and these as the main components, containing a small amount of titanium oxide, tin oxide, cerium oxide, etc. What was made to do etc. is suitable.

The method for laminating the dielectric layer A and the dielectric layer B is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, CVD, sputtering, vacuum evaporation Thus, a dielectric multilayer film can be formed by alternately laminating the dielectric layers A and B. By such a method, a dielectric multilayer film can be suitably formed, but in order to reduce the possibility of the light selective transmission filter being deformed and curled or cracked by vapor deposition, the following method is used. Can be used. Specifically, a vapor-deposited layer is formed on a temporary substrate such as glass that has been subjected to a release treatment, and the vapor-deposited layer is transferred to a true substrate that is a substrate of a light selective transmission filter to form a multilayer film. A multilayer film transfer method is preferred. In this case, it is preferable to form an adhesive layer on the true base material used as the base material of the light selective transmission filter. When the substrate is a resin film made of a resin layer or a glass film having a resin layer, the organic material forming the resin layer is in an uncured or semi-cured state (substrate), A method of curing the substrate after vapor deposition is preferred. When such a method is used, the base material becomes fluid during cooling after multi-layer deposition and becomes a liquid state, so that the difference in thermal expansion coefficient between the organic material and the dielectric layer does not become a problem. Deformation (curl) of the light selective transmission filter can be more sufficiently suppressed.

The thicknesses of the dielectric layer A and the dielectric layer B are usually 0.1λ to 0.5λ of the wavelength λ (nm) of light to be blocked. When the thickness is out of the above range, the product (n × d) of the refractive index (n) and the film thickness (d) is significantly different from the optical film thickness calculated by λ / 4, and the optical characteristics of reflection and refraction are different. This may break the relationship, and control to block / transmit specific wavelengths may not be possible.

When the dielectric multilayer film has the dielectric multilayer film only on one surface of the base material (preferably a transparent base material), the number of the dielectric multilayer films is usually in the range of 10 to 80 layers, preferably 15 to 60 layers. Range. On the other hand, when the dielectric layer film is provided on both surfaces of a base material (preferably a transparent base material), the number of laminated layers of the dielectric layers is usually in the range of 10 to 80 layers as the whole number of laminated layers on both sides of the substrate. , Preferably in the range of 15-60 layers.

In the light selective transmission filter, the function of cutting light of a desired wavelength is preferably exhibited by a form having a light selective transmission layer (preferably a multilayer light selective transmission layer) as described above. It may be exhibited by other forms. For example, in an infrared cut filter that reduces infrared transmittance, (i) a form in which a thin film made of a metal oxide that transmits visible light and shields near infrared rays is formed on the surface of the substrate; (ii) infrared absorption A form in which a coating film having a function (for example, containing an infrared absorbing dye) is formed, and (iii) a form in which a material (raw material) having a function of cutting infrared rays is used as a base material are suitable. The same applies to the case where other wavelengths are selectively reduced. By using such a configuration, the number of multilayer films (multilayer deposition layers) can be reduced or omitted, and a light selective transmission filter. The film thickness can be reduced. For example, in the form (i), a thin film having a single layer structure can be formed. Therefore, the optical path can be shortened, and it can be useful in an optical member such as a camera module. When an organic material is used as the constituent material of the base material, curling of the base material when forming the multilayer film can be suppressed, and the cost can be reduced.
The thin film made of the metal oxide in the form (i) and the coating film containing an inorganic component in the form (ii) also correspond to the light selective transmission layer (inorganic layer) in the light selective transmission filter. obtain.

The above (i) a thin film made of a metal oxide that transmits visible light and shields near infrared rays is formed on the substrate surface as a red film made of indium oxide, tin oxide, zinc oxide, tungsten oxide, or the like. A thin film having at least one of external reflection and absorption functions is preferred. In particular, a tetravalent metal element such as Sn or Ti or an In ₂ O ₃ based oxide formed by dissolving 0.1 to 20 atomic% (/ indium) of fluorine; pentavalent such as Sb and P SnO ₂ -based oxide formed by solid solution of metal element or fluorine at a ratio of 0.1 to 20 atomic% (/ tin); trivalent metal element such as B, Al, In or tetravalent metal element or fluorine is 0 ZnO-based oxide formed as a solid solution at a rate of 1 to 20 atomic% (/ zinc); tungsten oxide based on WO ₃ ; complex oxide containing In and Zn as metal components (In-Zn based, In A method of forming a thin film made of a metal oxide that transmits visible light and shields near infrared rays, such as Mg-based, In-Sn-based, and Sn-Zn-based, is preferable. Such a thin film is preferably formed by sputtering, vacuum deposition, or the like.

As the form for forming the coating film having the infrared absorption function (ii), a method of forming a coating film containing ultrafine particles made of the oxide and an infrared absorbing pigment such as metal phthalocyanine is preferable. . As such a coating film, a method of forming a paint having ultrafine particles and infrared absorbing dyes and using an organic binder or an inorganic binder as a binder is preferable.
(Iii) As a form using a material (raw material) having a function of cutting infrared rays in the base material, the oxide or pigment is kneaded into the organic material forming the resin layer contained in the base material, and is in the form of a film A method of forming (molding) into a suitable shape is suitable.

The light selective transmission layer preferably has a thickness of 50 μm or less from the viewpoint of further improving the bending strength and further reducing warpage, and further realizing a thin film. More preferably, it is 30 micrometers or less, More preferably, it is 10 micrometers or less. Moreover, 1 nm or more is preferable, More preferably, it is 3 nm or more.

-Protective layer-
It is preferable that the laminated film and the light selective transmission filter further have a protective layer (also referred to as “protective film”) as described above. This makes it possible to protect the substrate and the light selective transmission layer from dirt, etc., for example, not only when cutting out, but also when transporting or storing the light selective transmission filter in some cases. Is preferred.

In consideration of releasability from the light selective transmission filter after cutting, it is preferable that the protective layer be in a slightly sticky state with the layer (substrate) on which the protective layer is laminated (formed) or the substrate. . If the adhesiveness with the layer on which the protective layer is laminated is too high, it becomes difficult to peel off the protective layer from the light selective transmission filter after cutting, which may improve the workability in applications that do not require a protective layer. It may not be possible.
Moreover, when providing the said protective layer on both surfaces of a light selective transmission layer, in order to improve workability | operativity further, it is suitable that the adhesiveness of these protective layers differs. A particularly preferred form is a form in which the laminated film (and the light selective transmission filter) has protective layers on both sides thereof, and the adhesiveness of the two protective layers is different. Thereby, the workability at the time of handling the laminated film (and the light selective transmission filter) is further improved.

The protective layer is preferably a resin film formed from one or more organic materials. Examples of the organic material include polyester resin films such as polyethylene terephthalate (PET), Examples thereof include polyolefin resin films such as polyethylene and polypropylene. Of these, polyester resin films and polyolefin resin films are preferable, and PET resin films and polyethylene resin films are more preferable. In addition, polyethylene-based resin film has insufficient laser processability compared to PET-based resin film, and may be carbonized depending on the intensity of laser irradiation. In view of the above, a PET resin film is more preferable. For these reasons, it is preferable not to provide the polyethylene resin film on the laser beam side. However, the polyethylene resin film may be provided on the laser beam side by appropriately adjusting the strength and the like.

The resin film used as the protective layer (protective film) is also preferably a resin film that does not damage the laminate in the step of removing the glue from the protective film, generating contaminants, attaching or peeling off. Preferably, it is a slightly tacky protective film. In addition, it is preferable that at least a surface to be brought into contact with a layer to be protected such as a base material or a light selective transmission layer is subjected to a fine adhesion treatment. The adhesive strength is preferably 1.2 N / cm or less, more preferably 0.5 N / cm or less, still more preferably 0.3 N / cm or less, and most preferably 0.1 N / cm or less. Further, if the adhesive strength is too low, the adhesive strength is preferably 0.0001 N / cm or more, and more preferably 0.001 N / cm or more because there is a risk of peeling off during processing or transportation.
When providing the said protective film on both surfaces, it is preferable that an upper protective film (laser beam side) is low adhesion rather than a lower protective film. The adhesive strength of the upper protective film is preferably 0.2 N / cm or less, more preferably 0.1 N / cm or less, and most preferably 0.05 N / cm or less.
In addition, preferable examples of the protective film having slight adhesiveness in the present invention include Panaprotect manufactured by Panac, and PET75-H2120 manufactured by Niei Engineering Co., Ltd.

[Especially preferred form of manufacturing method of light selective transmission filter]
A particularly preferred embodiment of the production method of the present invention will be described with reference to the drawings.
1 to 3, the protective film a is laminated on the laser beam side of the film b composed of the base material and the light selective transmission layer, and the protective film c (and d) is laminated on the opposite side of the film b from the laser beam side. It is a conceptual diagram which shows the preferable example of the method of irradiating the laminated | multilayer film which consisted of the shape which cut | disconnected a laser beam, and cutting out specific shape. A light selective transmission filter can be obtained more suitably by the technique shown in these drawings. The film b may be in a form having a light selective transmission layer on one surface of the substrate, may be in a form having a light selective transmission layer on both surfaces of the base material, It may have a functional material layer.

FIG. 1 shows an example in which a polyethylene terephthalate (PET) resin film is used as the protective film a and a polyethylene resin film is used as the protective film c. Since it is hard to cut | disconnect with a laser beam compared with this, if the laser beam g is irradiated in this state, the part e which consists of the protective film a and the film b can be cut out. In addition, when using as a product, the protective film a is peeled off from the film b as necessary.

FIG. 2 shows an example in which a PET-based resin film is used as the protective film a, and a thicker PET-based resin film than that used as the protective film a is used as the protective film c. By adjusting the strength, the portion e consisting of a part of the protective film a, the film b and the protective film c can be cut out. In this case, the contact cross section of the film b on the protective film c side becomes smoother than the method of FIG. As the thick-film PET-based resin film used as the protective film c, for example, a film having a thickness of 50 μm or more is preferably used, and more preferably 75 μm or more. In addition, when using as a product, the protective films a and c are peeled off from the film b as necessary.

FIG. 3 shows an example in which a PET resin film is used as the protective film a, a PET resin film is used as the protective film c, and a polyethylene resin film is used as the protective film d. In this example, FIG. Similarly to the method shown, since the polyethylene-based resin film is less likely to be cut with laser light than the PET-based resin film, when irradiated with the laser light g in this state, a portion e composed of the protective film a, the film b, and the protective film c Can be cut out. In this example, it is not necessary to adjust the intensity of the laser beam g as compared with the method of FIG. 2, and the contact cross section on the protective film c side of the film b is smoother than that of the method of FIG. In addition, when used as a product, the protective films a and c are peeled off from the film b as necessary, but the adhesiveness and adhesiveness between the protective film c and the protective film d should be strengthened. Thus, the protective film c can be more easily peeled off from the film b.

Thus, the methods as shown in FIGS. 1 to 3 described above, that is, (1) The protective films a and c having different laser processability are respectively provided on both surfaces of the film b composed of at least the base material and the light selective transmission layer. After laminating, a method of cutting out a light selective transmission filter e comprising the film b and the protective film a having a high laser processability by irradiating laser light from the side having the protective film a having a high laser processability. 2) After laminating protective films a and c having different thicknesses on both surfaces of a film b composed of at least a base material and a light selective transmission layer, respectively, a laser beam is irradiated from the side having the protective film a having a small thickness, A method of cutting out a light selective transmission filter e comprising the film b, the protective film a having a small thickness, and a part of the protective film c having a large thickness; Protective films a and c are laminated on both sides of a film b composed of at least a base material and a light selective transmission layer, and more laser workability than the protective film c laminated on the opposite side of the laser irradiation side. After laminating an inferior protective film d on the protective film c, a method of irradiating a laser beam to cut out the light selective transmission filter e comprising the film b, the protective film a, and the protective film c Is also one of the preferred embodiments of the present invention.
“Laser workability” means ease of cutting by laser light irradiation. For example, a film having high laser workability among films having different laser workability is irradiated with the same laser light. The film that is easier to cut.

Also, as shown in FIG. 4, an adhesive sheet / film f is applied so as to cover e obtained by the methods of FIGS. 1 to 3, and more specifically, to cover a protective film a positioned on the upper layer of e. It is also suitable to do. Thereby, since the protective film a in contact with the pressure-sensitive adhesive sheet / film f can be more easily peeled off from the film b, for example, the film b can be removed from the pressure-sensitive adhesive sheet / film f and the protective film a when transporting and storing the light selective transmission filter. Since the protective film a is also peeled off by simply peeling off the adhesive sheet / film f in actual use, a higher quality product can be obtained with higher workability and productivity.

<Light selective transmission filter support film>
The present invention is also a light selective transmission filter support film having a plurality of light selective transmission filters obtained by the above production method on a support film. The support film is a film for supporting the light selective transmission filter. For example, the protective film used in the cutting process by laser cutting and the light selective transmission filter as shown in FIG. 4 described above were produced. Examples thereof include an adhesive sheet / film to be deposited later.
Such a light selective transmission filter support film is particularly advantageous for transport and storage of the light selective transmission filter.

The light selective transmission filter support film using the protective film as the support film can be obtained, for example, by performing the cutting out a plurality of times in the methods (2) and (3). That is, as such a light selective transmission filter support film, a protective film that has not been cut by laser irradiation (for example, the remainder of the protective film c in the method (2), and the protective film d in the method (3)). Examples include a form in which a plurality of light selective transmission filters e exist, and a form in which the protective film a located on the laser irradiation side is peeled from the light selective transmission filter e.

As the light selective transmission filter support film in the form of using an adhesive sheet / film as the support film, for example, the light selective transmission filter e obtained by the methods (1) to (3) on the table or the sheet h. Can be obtained by adhering (attaching) an adhesive sheet / film f on the upper surface thereof. In addition, by obtaining a film having a plurality of light selective transmission filters e on the protective film c / d by performing a plurality of times of cutting in the methods (2) and (3) above, It can also be obtained by adhering (attaching) the pressure-sensitive adhesive sheet / film f to the surface of the selectively transmissive filter e opposite to the adhesive surface with the protective film c / d. In this case, the light selective transmission filter support film in a form in which both sides are protected and supported by the film, that is, as the support film, specifically, the protective film used in the cutting process by laser cutting, and the adhesive sheet / film The light selective transmission filter support film of the form used is obtained.

<Light selective transmission filter>
The present invention is also a light selective transmission filter obtained by the above production method. Such a light selective transmission filter is capable of exhibiting excellent light selective transmission with a uniform cut surface without causing cracks, delamination, cracking, warping, etc., by the above manufacturing method. It is useful in various fields such as optical members / equipment, machine parts, electrical / electronic parts, automobile parts and the like.

The light selective transmission filter selectively reduces (blocks) light transmittance. Specifically, it is preferable to block a desired wavelength by reflection or absorption. The light to be reduced is not particularly limited as long as it is between 10 nm and 100 μm, and can be appropriately selected according to the application. The transmittance of the wavelength to be selectively reduced is preferably 10% or less of the total wavelength. More preferably, it is 5% or less, more preferably 3% or less, and most preferably substantially 0%. Further, the transmittance of the wavelength that transmits through the light selective transmission filter is preferably 70% or more of the total wavelength. More preferably, it is 75% or more, more preferably 80% or more, particularly preferably 85% or more, and most preferably 90% or more. With such a high transmittance, the intensity of light passing through the light selective transmission filter is more sufficiently secured. For example, optical applications such as a filter for blocking optical noise in a lens unit of a camera module or an imaging lens. It is possible to use it more suitably.

In the light selective transmission filter, it is also preferable that the transmittance of wavelengths other than the wavelength to be selectively reduced (that is, the wavelength that transmits the light selective transmission filter) is constant. In particular, when used for optical applications such as a filter for blocking optical noise in a camera module or a lens unit of an imaging lens, it is preferable that the transmittance of visible light 380 to 780 nm is constant in the entire wavelength range of visible light. . In the said use, it is especially preferable that it is constant with a wavelength of 400-600 nm among visible light. If the intensity of the transmitted light is constant without depending on the wavelength, the intensity of the light having a specific wavelength does not occur and the transmitted light is not colored. Therefore, the light transmitted through the light selective transmission filter is not colored and can be suitably used for the above application.

Specifically, the light selective transmission filter is a form that selectively reduces infrared transmittance (infrared cut filter); a form that selectively reduces ultraviolet transmittance (ultraviolet cut filter); A form (ultraviolet / infrared cut filter) or the like that selectively reduces both transmittances is preferable. In these forms, the function of cutting light of a desired wavelength (the function of selectively reducing the transmittance of the desired light) is exhibited by the form described above, but other than this function It is also suitable to have various functions.

[Infrared cut filter]
The infrared cut filter (also referred to as an infrared cut filter, IR cut filter, or IRCF) is a filter having a function of selectively reducing (blocking) infrared rays by absorption or reflection. Specifically, a filter having a function of selectively reducing light of any wavelength (range) among light having a wavelength of 780 nm to 10 μm that is an infrared region and transmitting other light. Good. The wavelength range to be selectively reduced is preferably 780 nm to 2.5 μm, 780 to 1000 nm, 800 nm to 1 μm, or 1 to 1.5 μm. A filter that selectively reduces at least one of the wavelengths in these ranges is also included in the preferred form of the infrared cut filter of the present invention. The range of the wavelength to be selectively reduced is more preferably 780 nm to 2.5 μm, which is the near infrared region.

The transmittance of the wavelength to be selectively reduced and the transmittance of the other wavelengths are preferably in the above-described range. Specifically, the infrared cut filter is preferably one that selectively reduces the infrared transmittance of 780 to 1000 nm to 10% or less, and the transmittance in other wavelength regions is preferably 70% or more. The preferable range of the transmittance is as described above. In addition, only the transmittance | permeability of a specific wavelength range may be high according to the use of a filter. For example, when the infrared cut filter is used as a camera module, it is preferable that the transmittance of infrared light is 5% or less and the transmittance of visible light (380 to 780 nm) is 75% or more. Preferably it is 80% or more. Moreover, it is preferable that the transmittance | permeability of the light of the wavelength range of 400-600 nm is 80% or more among visible light, More preferably, it is 85% or more. Furthermore, it is preferable that the transmittance | permeability of the wavelength range of 400-700 nm is 80% or more among visible light, More preferably, it is 85% or more.
A particularly preferable form of the infrared cut filter is an infrared cut filter having a light transmittance of 80% or more at a wavelength of 400 to 600 nm and a transmittance of 5% or less at 800 to 1000 nm. . A suitable range of these transmittances is as described above.

Examples of the form in which the infrared cut filter has various functions other than the function of reducing (blocking) infrared rays include, for example, forms having various functions other than infrared cut such as a function of shielding ultraviolet rays, toughness, strength, and the like. A form having a function of improving the physical properties of the infrared cut filter is suitable. Among these, the infrared cut filter has a function of shielding ultraviolet rays. (A) A thin film made of a metal oxide that transmits visible light and shields ultraviolet rays such as titanium oxide, zinc oxide, and cerium oxide. A method of forming on the surface of the substrate, (b) a coating film containing ultrafine particles of the oxide, a method of forming a coating film containing an organic ultraviolet absorber, and (c) a material having a function of shielding ultraviolet rays ( It is preferable to impart a function of shielding ultraviolet rays by a method using a raw material.

The method for forming a thin film in (a) and the method for forming a film in (b) are as follows: (i) a thin film made of a metal oxide that transmits visible light and shields near infrared rays is formed on the substrate surface. It is preferable to be the same as the thin film forming method and (ii) the thin film forming method in the form of forming a coating film having an infrared absorption function. As (c), when an organic material is used as a constituent material of the base material, a method of forming an organic material kneaded with the oxide or the pigment into a film is preferable. In addition, when an inorganic material (for example, glass) is used as a constituent material of the base material, an infrared absorbing glass obtained by dissolving a metal element such as Ag, Bi, Co, Fe, Ni, Ti, or Ce is used. It is preferable to use it.

[Ultraviolet cut filter]
The ultraviolet cut filter is a filter having a function of blocking ultraviolet rays. The wavelength range to be selectively reduced is preferably 350 nm or less. More preferably, it is 380 nm or less.
The transmittance of the wavelength to be selectively reduced and the transmittance of the other wavelengths are preferably in the above-described range. Specifically, the ultraviolet cut filter preferably has an ultraviolet transmittance of 350% or less of 10% or less, and more preferably an ultraviolet transmittance of a wavelength of 380 nm or less is 10% or less. Further, the transmittance in other wavelength regions is preferably 70% or more. In addition, the suitable range of these transmittance | permeability is as having mentioned above.

The ultraviolet cut filter has a function of reducing (blocking) ultraviolet rays, and is made of a material having an ultraviolet absorbing function such as titanium oxide, zinc oxide, cerium oxide, or iron oxide as the light selective transmission layer. It is preferable to use a thin film. Among them, one or more metal elements selected from the group consisting of Cu, Ag, Mn, Bi, Co, Fe, and Ni are dissolved in titanium oxide, zinc oxide, and cerium oxide at a ratio of 0.1 to 20 atomic%. It is preferable to use an oxide formed of

[UV / IR cut filter]
The ultraviolet / infrared cut filter is a filter having a function of blocking both ultraviolet rays and infrared rays. The range of wavelengths to be selectively reduced, the transmittance of the wavelength, and the transmittance of other wavelengths are preferably in the above-described ranges.
In the said ultraviolet and infrared cut filter, the transmittance | permeability of light other than infrared rays and an ultraviolet-ray is so preferable that it is high. Specifically, the visible light (380 nm to 780 nm) transmittance is preferably 70% or more, and a more preferable range is as described above. Further, from the viewpoint of preventing the light transmitted through the ultraviolet / infrared cut filter from being colored (not selectively absorbing specific visible light), it is preferable that the transmittance of visible light in each wavelength region is substantially constant. In particular, the light transmittance at each wavelength in the wavelength range of 400 to 600 nm is preferably 85% or more, and more preferably 90% or more. The function of the ultraviolet ray / infrared cut filter for blocking infrared rays is preferably to block infrared rays by reflection or absorption, and more preferably to mainly reflect infrared rays. Further, it is more preferable to block light having a wavelength of at least 800 to 1000 nm among infrared rays.

The ultraviolet / infrared cut filter can be particularly suitably used as a filter for blocking optical noise in an imaging lens. As a light selective transmission filter for the purpose of blocking optical noise in an imaging lens or the like, the light transmittance at each wavelength in the visible light region of 400 to 600 nm is preferably 85% or more. More preferably, it is 90% or more. Moreover, it is preferable that the transmittance | permeability of 350 nm or less ultraviolet rays of an ultraviolet region is less than 5%. In particular, the transmittance of ultraviolet rays of 380 nm or less is preferably less than 5%. The light selective transmission filter has a light transmittance at a wavelength of 400 to 600 nm of 85% or more, a transmittance at 800 to 1000 nm of 5% or less, and a light transmittance at a wavelength of 300 to 380 nm. Is particularly preferably an ultraviolet / infrared cut filter with 5% or less. In the infrared region, it is preferable to block light having a wavelength of 800 nm to 1 μm. Specifically, the transmittance at 800 nm to 1 μm is preferably 5% or less. More preferably, the transmittance at 800 nm to 1.5 μm is 5% or less, and further preferably the transmittance at 800 nm to 2.5 μm is 5% or less.

As a mode in which the ultraviolet / infrared cut filter has a function of reducing (blocking) ultraviolet rays and infrared rays, the light selective transmission layer preferably has a laminated structure of the dielectric layers (A) and (B) described above. In addition, for the oxide layer with infrared cut function such as indium oxide system, tin oxide system, zinc oxide system, tungsten oxide system, etc., and UV cut function such as titanium oxide system, zinc oxide system, cerium oxide system, iron oxide system etc. A form in which an excellent layer is laminated can also be preferably used.

The light selective transmission filter preferably has a thickness of 200 μm or less, more preferably less than 200 μm, from the viewpoint of further realizing a reduction in size and weight. In particular, 180 μm or less, 150 μm or less, 120 μm or less, 100 μm or less, 90 μm or less, 75 μm or less, or 50 μm or less is preferable (the smaller the value, the more preferable). Further, from the viewpoint of excellent reflow resistance, particularly heat resistance at a temperature of 260 ° C. or higher, the thickness is preferably 1 μm or more, and more preferably 5 μm or more.

Thus, when the thickness of the light selective transmission filter is sufficiently thin, the light selective transmission filter can be further reduced in size and weight, and can be more suitably used for various applications. In particular, it can be used more suitably for optical applications such as optical members. In optical applications, as with other optical members, the light selective transmission filter is also strongly required to be small and light. For example, by making the thickness 200 μm or less, a thinner film can be achieved. When used in a lens unit, it is possible to further reduce the height of the lens unit. In other words, when a thin-film light selective transmission filter is used as an optical member, the optical path can be shortened and the optical member can be made small.
This point will be described by taking as an example a camera module having a lens, a light selective transmission filter, and a seamos sensor. 5 and 6 schematically show an example of the camera module. These figures refer to materials from the Electronic Journal 81st Technical Seminar (Electronic Journal 81st Technical Seminar).

As shown in FIG. 5, the light selective transmission filter has a role of cutting light of a desired wavelength (in the camera module, light having a wavelength of 700 nm or more, for example), and preventing malfunction of the sea moss sensor. When a light selective transmission filter is inserted into the camera module, the focal length is extended, so that the back focus is extended and the module is enlarged. When the thickness of the light selective transmission filter is t and the refractive index n is about 1.5, as shown in FIG. 6, the back focus is extended by about t / 3 and the module is enlarged, but the light selective transmission filter is thinned. Thus, the focal length can be shortened and the module can be made smaller. Thereby, for example, the optical path length of an optical size of 1/10 inch is preferably 120% or less when there is no light selective transmission filter. More preferably, it is 110% or less, More preferably, it is 105% or less.

Preferred forms of the light selective transmission filter of the present invention include an infrared cut filter, an ultraviolet cut filter, and an ultraviolet / infrared cut filter. In the present invention, it is possible to suitably cope with an optical member / equipment that is particularly required to be reduced in size, weight, and thickness, and the handling property, workability, and productivity can be sufficiently improved. In addition to such effects, the performance required for these filters can be sufficiently exhibited. For example, when used as an infrared cut filter, in addition to the above effects, it has excellent infrared cut ability and is difficult to break, so it is not only useful as a heat ray cut filter attached to glass of automobiles or buildings, etc. In particular, it is useful for correcting the visibility of a solid-state imaging device such as a CCD or CMOS, such as a digital still camera or a mobile phone camera. When used as an ultraviolet cut filter, in addition to the above effects, it has an excellent ultraviolet cut ability and is difficult to break, so it is useful as an ultraviolet protection filter, for correcting visibility. When used as an ultraviolet / infrared cut filter, in addition to the above effects, it has excellent infrared and ultraviolet cut ability, is difficult to break, and is useful as a filter for blocking optical noise for imaging lenses.

In the present invention, by adopting the manufacturing method of the present invention described above, even if the light selective transmission filter has a small irregular shape and a curved shape, cracks and the like are generated. In addition, the light selective transmission filter can be easily obtained without deteriorating the characteristics (light selective transmission, etc.) of the light selective transmission filter. Therefore, for example, it is possible to realize a light selective transmission filter having an unusual shape that includes a curved portion and has a maximum diameter of 6 mm or less. If the maximum diameter is 6 mm or less, it is possible to more preferably cope with a small optical device such as a cellular phone in recent years, and the handling property, workability, and productivity can be exhibited more. The maximum diameter is preferably 5.5 mm or less, more preferably 5 mm or less, still more preferably 4.5 mm or less, particularly preferably 4 mm or less, and most preferably 3.5 mm or less. Further, the minimum diameter is not particularly limited, and for example, although it varies depending on the laser beam used in the above production method, it is preferably 12 μm or more, for example.
The “maximum diameter” as used herein refers to the longest diameter of the planar portion of the light selective transmission filter (ie, the portion that is not the side surface portion, the surface perpendicular to the stacking direction), and the “minimum diameter” is the shortest diameter. Respectively.
Further, “including a curved portion” means that the outer periphery of the plane portion of the light selective transmission filter is a shape having only a curved portion (also referred to as a non-linear portion) or a shape having a curved portion and a straight portion. means. For example, when the total length of the outer periphery of the planar portion of the light selective transmission filter is 100%, the total length of the curved portion is preferably 30% or more. More preferably, it is 50% or more. Specifically, for example, a circular shape or an elliptical shape is suitable.

<Lens unit>
The light selective transmission filter of the present invention is also useful as a material constituting the lens unit. Thus, a lens unit including the light selective transmission filter is also one aspect of the present invention. The lens unit means an element that includes one or two or more lenses and a lens barrel that supports and fixes these lenses and that has an opening necessary for the incidence and / or emission of light. The light selective transmission filter of the present invention is particularly useful as a material constituting a lens unit (hereinafter also referred to as a microlens unit) in which the maximum diameter of the opening in the lens unit or the optical path diameter in the unit is 6 mm or less. That is, a microlens unit including the light selective transmission filter and the lens is also a preferred embodiment of the present invention.

Here, the light selective transmission filter is not incorporated in a lens unit (preferably a microlens unit), and may be used by being arranged on the light incident side or the emission side of the lens unit. is there. For example, an image pickup device used in a mobile phone or a digital camera has a lens unit, but there is a mode in which a light selective transmission filter constitutes the lens unit. There are also forms. The light selective transmission filter of the present invention can be suitably employed in any form.

The above lens unit can be suitably applied to optical members / equipment that are particularly required to be small, light, thin, etc., and can be sufficiently improved in handling, workability, and productivity. In addition to exhibiting this effect, the optical path length is shortened, the lens unit can be made smaller, and the thickness of the unit can be reduced. Therefore, it can be suitably used in various applications such as a camera module. The length of the lens unit is preferably 120 or less, where 100 is the case where there is no light selective transmission filter. More preferably, it is 110 or less, More preferably, it is 105 or less.
In addition, when using the said light selective transmission filter for a lens unit, it is suitable to use the base material which has reflow resistance as a base material of a light selective transmission filter, and this can further improve heat resistance. . Among them, a resin film having reflow resistance is used as the base material.

In the lens unit, it is preferable that the lens has reflow resistance (reflow lens). In addition, the light selective transmission filter may be any of those described above, but it is particularly preferable that the filter has reflow resistance. Thus, the form in which the light selective transmission filter and the lens constituting the lens unit have reflow resistance is a particularly preferable form. Since both the light selective transmission filter and the lens have sufficient heat resistance, automatic mounting becomes possible, the mounting cost is sufficiently reduced, and it can be more suitably used for optical applications such as camera modules.

The lens preferably has an Abbe number of 45 or more. By setting the Abbe number to 45 or more, the dispersion of light is reduced, the resolution is increased, and the optical characteristics can be improved. If it is less than 45, for example, there is a risk of bleeding, and sufficient optical properties cannot be exhibited, and there is a possibility that the lens unit will not be a more suitable material. The Abbe number is more preferably 50 or more, and the lens unit preferably has one or more lenses having an Abbe number of 50 or more. The Abbe number is more preferably 55 or more, particularly preferably 58 or more, and most preferably 60 or more.

In the lens unit, the number of lenses may be one, or two or more. In the case of a single lens, the Abbe number of the lens is preferably 45 or more. When there are two or more lenses, it is sufficient that the Abbe number of at least one lens is 45 or more, and the other lenses may have an Abbe number of less than 45. In the case of combining a lens having an Abbe number of 45 or more and a lens having an Abbe number of less than 45, it is more preferable to combine a lens having an Abbe number of 50 or more and a lens having an Abbe number of 40 or less. By combining a lens having an Abbe number of 50 or more and a lens having an Abbe number of 40 or less, there is an advantage that the resolution is improved and the characteristics required for the lens unit are satisfied.

The lens preferably has a thickness of less than 1 mm. By making the thickness of the lens (the maximum thickness of the region where the image is captured) less than 1 mm, the optical path length can be shortened in combination with the use of a light selective transmission filter having a thickness of 200 μm or less (preferably less than 200 μm), The lens unit can be made smaller. The thickness of the lens is more preferably less than 800 μm, and further preferably less than 500 μm. It is more preferable to use a light selective transmission filter having a thickness of 100 μm or less.

The material constituting the lens is a heat-resistant material and preferably has reflow resistance. Specifically, any of an organic material, an inorganic material, and an organic-inorganic composite material may be used, and these may be used alone or in combination of two or more.
As the organic component in the organic material and the organic-inorganic composite material, an organic resin is preferable, and a thermoplastic resin excellent in heat resistance such as cyclopolyolefin and polycarbonate, or a curable resin cured material such as an epoxy resin and a silicone resin is more preferable. . Furthermore, a curable resin cured product is preferable in terms of excellent reflow resistance. That is, a more preferable form of the lens unit is a form in which the lens contains a cured thermosetting resin.
The organic component in the organic material or organic-inorganic composite material is also a form having an Abbe number of 45 or more, a form that is a thermosetting resin, a form containing an alicyclic epoxy compound as an essential component, or a molecular weight of 700 or more. The form which is a thing is preferable.
As the inorganic material, glass or the like is preferable.

The inorganic component in the organic-inorganic composite material is preferably inorganic fine particles or a metalloxane polymer.
The inorganic fine particles include metal oxide fine particles, a form obtained by a wet method, a form having an average particle size of 400 nm or less, and a pH at 25 ° C. of 3 when dispersed in a solution. The form which is 4-11 is preferable.
The metalloxane polymer is preferably an organosiloxane polymer. Examples of the organosiloxane polymer include a polysilsesquioxane having a cage structure or a ladder structure; a chain polysiloxane having a repeating basic unit such as a diphenylsiloxane unit, a dialkylsiloxane unit, or an alkylphenylsiloxane unit. It is done.

The lens unit includes the light selective transmission filter and two or more lenses, and the lens is a reflow resistant lens having a thickness of less than 1 mm, and has at least one lens having an Abbe number of 50 or more. preferable. 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. The thickness of the lens unit is more preferably 30 mm or less, and still more preferably 10 mm or less.

From the viewpoint of downsizing the lens unit, the distance between the sea moss sensor and the lens is also important. The distance between the sea moss sensor and the lens is the distance between the outermost surface of the lens and the sea moss sensor. When the light selective transmission filter is mounted on the side of the sea moss sensor, the light selective transmission filter and the sea moss sensor It becomes the distance.

In the lens unit, for example, it is preferable that the light selective transmission filter is disposed on the side of the moth sensor as shown in FIG. 5, but the light selective transmission filter may be disposed between the lenses. . In addition, from the point of sufficiently blocking the light of the desired wavelength, it is arranged in both the upper part and the lower part of the lens, that is, the light selective transmission filter, one or two, along the light traveling direction. A form in which the lens, the light selective transmission filter, and the sea moss sensor are arranged in this order is also suitable.
The lens unit may further include a configuration other than the above.

Since the method for producing a light selective transmission filter of the present invention has the above-described configuration, it can exhibit excellent light selective transmission with a uniform cut surface without causing cracks, delamination, cracks, warpage, or the like. A light selective transmission filter can be obtained easily and with high productivity. According to such a manufacturing method, even a light selective transmission filter having a unique minute irregular shape having a smaller diameter and including a curved portion can be easily obtained without causing cracks or delamination. . Moreover, the light selective transmission filter obtained by the production method of the present invention can be suitably applied to small members and equipment, and can improve its handling property, workability, and productivity. It is suitably used for various uses such as uses, mechanical parts, and electrical / electronic parts.

It is a conceptual diagram which shows the preferable example of the method of irradiating a laminated film which provided the protective film on both surfaces of the film b, and cutting out a specific shape. It is a conceptual diagram which shows the preferable example of the method of irradiating a laminated film which provided the protective film on both surfaces of the film b, and cutting out a specific shape. It is a conceptual diagram which shows the preferable example of the method of irradiating a laminated film which provided the protective film on both surfaces of the film b, and cutting out a specific shape. It is a conceptual diagram which shows the example which stuck the adhesive sheet / film f on the upper surface of the light selective transmission filter e obtained by the method shown in FIGS. It is a cross-sectional schematic diagram which shows the structure of a camera module. It is a schematic diagram which shows the expansion | extension of a back focus by the presence or absence of a light selective transmission filter.

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 “% by mass”.

1. Base material (1) Preparation of FPEK film <Synthesis of FPEK>
In a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirrer, 16.74 parts of BPDE (4,4′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether), 10.5 parts of HF (9,9-bis (4-hydroxyphenyl) fluorene), 4.34 parts of potassium carbonate, and 90 parts of DMAc (dimethylacetamide) were charged. The mixture was warmed to 80 ° C. and reacted for 8 hours. After completion of the reaction, the reaction solution was poured into a 1% aqueous acetic acid solution with vigorous stirring with a blender. The precipitated reaction product was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated aromatic polymer (FPEK (1)). The reaction formula is shown below. The fluorinated aromatic polymer is a fluorinated aromatic polymer containing a repeating unit obtained by the following reaction formula.

The polymer had a glass transition temperature (Tg) of 242 ° C., a number average molecular weight (Mn) of 70770, and a surface resistance value of 1.0 × 10 ¹⁸ Ω / cm ² or more.
<Formation of substrate>
A 50 μm film (hereinafter also referred to as FPEK film) was obtained by the solvent casting method, and this was used as the substrate (1). In addition, about the film forming, the solvent at the time of using the solvent cast method used the mixed solvent of ethyl acetate and toluene.

(2) Polyethylene naphthalate film (PEN film)
Teijin DuPont Films (Teonex Q83), thickness 75 μm, melting point 269 ° C. (PEN film) (base material (2)) was used.

(3) Polyimide film (3-1) Mitsubishi Gas Chemical Company, Neoprim L-3430 Thickness 50 μm (base material (3-1)) was used.
(3-2) Neoprim L-3430, manufactured by Mitsubishi Gas Chemical Company, Inc., having a thickness of 100 μm (base material (3-2)) was used.

(4) Epoxy resin <Synthesis of epoxy resin>
19 parts of polytetramethylene ether glycol diglycidyl ether (trade name: Epicoat YL7217, manufactured by Japan Epoxy Resin Co., Ltd.), 55 parts of bisphenol A type epoxy resin (trade name: Epicoat 828EL, manufactured by Japan Epoxy Resin Co., Ltd.), hydrogenated bisphenol A Type epoxy resin (trade name: Epicoat YX8000, manufactured by Japan Epoxy Resin Co., Ltd.) 22 parts, phosphorus hexafluoride arylsulfonium salt (trade name: UVI-6922, manufactured by The Dow Chemical Company) 4 parts Mixing was performed using a centrifugal mixing device (product name: Awatori Nertaro (registered trademark), manufactured by Shinky Corporation).
<Formation of substrate>
The epoxy resin composition was formed into a film with a thickness of 50 μm by a casting method, and then exposed at an illuminance of 10 mW / cm ² using an exposure machine (product name: MA-60F, manufactured by Mikasa) using a high-pressure mercury lamp as a light source. An epoxy resin film was obtained by performing photocuring by irradiating with ultraviolet rays at an exposure energy of 9 J / cm ^{2 for} a minute, and this was used as a substrate (4).

(5) Arton Film JSR Co., Ltd. Arton F thickness 190micrometer (base material (5)) was used.

(6) Glass film SCHOTT glass cord: D263, thickness 30 μm (base material (6)) was used.

(7) Preparation of FPEK / glass / FPEK film 1.57 g of fluorinated polyether ketone (FPEK) was added to 10.45 g of propylene glycol monomethyl ether acetate and stirred uniformly. Using a spin coating method, after forming a 5 μm film on one side of a glass film (30 μm), the same operation is performed on the other side of the glass surface, followed by drying at 150 ° C. so that FPEK / glass / FPEK film This was used as a substrate (7).

(8) Preparation of fluorene epoxy / FPEK / glass / fluorene epoxy / FPEK film 1.0 g of FPEK and 0.5 g of fluorene epoxy (Osaka Gas Chemical Co., Ltd., ONCOAT EX-1020) were added to 10 g of propylene glycol monomethyl ether acetate. And stirred uniformly. Thereafter, the temperature was set to 40 ° C. or less, and 0.016 g (solid content: 32%) of a cationic polymerization initiator (Sanshin Chemical Co., Ltd., Sun-Aid SI-60L) was uniformly stirred. Film formation was performed in the same manner as in (7) above by spin coating, to obtain a fluorene epoxy / FPEK / glass / fluorene epoxy / FPEK film, which was used as the substrate (8).

2. Production of laminated film Multilayer film [silica (SiO ₂ : film thickness 120) reflecting infrared rays at a deposition substrate temperature of 150 ° C. on both surfaces of each of the base materials ((1) to (8)) having a side of 60 mm. ˜190 nm) layers and titania (TiO ₂ : film thickness: 70 to 120 nm) layers are alternately laminated, and the number of laminated layers is 25 layers on one side by vapor deposition: 50 layers in total. Films ((1) to (8)) were produced.

3. Different shape <Punching>
These laminated films were laid flat on a die and punched from above using a Thomson blade to obtain a circular light selective transmission filter. Thomson blades having a diameter of 12 mm, 6.8 mm, 2.2 mm, and 2.0 mm were used. The results are shown in Table 1. In Table 1, the light selective transmission filter that was not cracked or cracked was evaluated as “◯”, and the one that was cracked or cracked was evaluated as “x”.

The light selective transmission filter using the substrates (1) to (3) and punched to a diameter of 12 mm and a diameter of 6.8 mm did not crack, but the light punched to a diameter of 2.2 mm and a diameter of 2.0 mm The selective transmission filter has cracked the inorganic layer.
When the substrate (4) was used, the inorganic layer or the inorganic layer and the substrate were cracked regardless of the diameter of the Thomson blade.
In the base material containing the glass of the base materials (6) to (8), the inorganic layer and the base material were cracked regardless of the diameter of the Thomson blade.

<Laser cut molding>
Perform laser cutting of the laminated film using a HITACHI Co. CO ₂ laser, to obtain a circular light selective transmission filter of 6mm diameter and 2mm diameter. The results are shown in Table 2. In Table 2, “◯” and “x” are the same as those in Table 1.
The glass film of the base material (6) (glass single base material) has cracked both the inorganic layer and the base material during laser cutting, but a laminate containing other resin layers can be molded without cracking. It was found that laser cut molding is possible.

The appearance of a 2 mm diameter light selective transmission filter obtained by laser cut molding was evaluated. The results are shown in Table 3.
Although the glass film (glass single base material) of the base material (6) was cracked and cracked, the laminate including the other resin layers was free from cracks and cloudiness due to laser cutting. However, only the ARTON film of the substrate (5) lacked the light selective transmission layer in the range of 0.2 mm from the outer periphery.

<Protective layer>
Laser cutting was performed with the protective layer provided to obtain a plurality of 2 mm diameter light selective transmission filters. The results are shown in Table 4. The protective layer was provided in the configuration of FIG. 1, FIG. 2 or FIG.
In the configuration of FIG. 1, Panaprotect CT (25 μm, PET) manufactured by Panac Corporation was used for the upper protective film a, and a masking film P-30 (55 μm, polyethylene) manufactured by Daiwa Kasei was used for the lower protective film c.
In the configuration of FIG. 2, Panaprotect CT (25 μm, PET) manufactured by Panac is used for the upper protective film a, and Panaprotect ST (100 μm, PET) manufactured by Panac is used for the lower protective film c.
In the configuration of FIG. 3, Panaprotect CT (25 μm, PET) manufactured by Panac is used for the upper protective film a, Panaprotect CT (25 μm, PET) manufactured by Panac is used for the lower protective film c, and Daiwa Kasei is used for d. Masking film P-30 (55 μm, polyethylene) was used.

Here, when laser cutting is performed without a protective layer, foreign matter generated by laser cutting adheres to the surface of the light selective transmission filter. However, by providing a protective layer, foreign matter adheres to the surface of the light selective transmission filter. Improved. By adopting the protective layer structure as shown in FIGS. 1, 2, and 3, the laser cut processability is not impaired, and the light selective transmission filter after cutting is held by the lowermost protective layer. Since it is integrated, it was easy to handle. When laser cutting was performed with the protective layer of FIG. 1 provided, the cut surface of the light selective transmission filter (the portion in contact with the protective layer c) was somewhat messy, and the smoothness was not sufficient. 2 and 3 were provided, and the lower protective layer was also laser-cut simultaneously to obtain a light selective transmission filter having a smoother cut surface. In each case, the arton film of the substrate (5) had a messy cut surface.

Since it is necessary to remove the protective layer when incorporating the light selective transmission filter into the lens unit, the removal of the protective layer from the light selective transmission filter after laser cutting was examined.
The light selective transmission filters of the base materials (1) to (5) made of only the resin could easily remove the protective layer, but the base material contains glass (6) and (7) when peeling the protective layer. The light selective transmission filter was cracked. It has been found that a light selective transmission filter using a substrate made of only a resin has an advantage in terms of handleability compared to a light selective transmission filter containing glass.
After laser cutting, peel off unnecessary parts (parts other than circles with a diameter of 2 mm or upper protective films remaining on circles with a diameter of 2 mm), and re-apply the protective film, so that a light selective transmission filter as shown in FIG. A support film could be obtained.

4. Evaluation of light selective transmission filter The transmittance of the laminated film before laser cutting and the transmittance of a 2 mm diameter light selective transmission filter obtained by laser cutting were measured. The results are shown in Table 5.
The light selective transmission filter using the substrates (1), (3-1), (3-2) and (4) has almost no change in transmittance even after laser cutting, and has excellent performance as a light selective transmission filter. Indicated. The light selective transmission filter using the substrate (2) had a slight decrease in transmittance, but could be used as a light selective transmission filter. On the other hand, the light selective transmission filter using the base material (5) has a low transmittance and is not usable.

a: Protective film b: Film (laminated film comprising a base material and a light selective transmission layer)
c: protective film d: protective film e: light selective transmission filter f: adhesive sheet / film g: laser light h: table / sheet 1: lens 2: light selective transmission filter 3: sensor

Claims (7)

A method for producing a light selective transmission filter having at least a base material and a light selective transmission layer, wherein the manufacturing method comprises light selection by a laser from a laminated film having a light selective transmission layer on at least one surface of the base material. Including a step of cutting the transmission filter,
The substrate comprises a resin layer formed of at least one organic material selected from a fluorinated aromatic polymer, a polycyclic aromatic polymer, a poly (amide) imide resin, a fluorine-containing polymer compound, and a curable resin. A method for producing a light selective transmission filter, which is a resin film or a glass film having the resin layer. The method for producing a light selective transmission filter according to claim 1, wherein the light selective transmission filter and the laminated film further include a protective layer. The method for producing a light selective transmission filter according to claim 1, wherein the laser is a carbon dioxide laser. The said selective light transmission filter and laminated film have a selective light transmission layer on both surfaces of a base material, The manufacturing method of the selective light transmission filter in any one of Claims 1-3 characterized by the above-mentioned. A light selective transmission filter obtained by the production method according to claim 1. A light selective transmission filter support film comprising a plurality of the light selective transmission filters according to claim 5 on a support film. A lens unit comprising the light selective transmission filter according to claim 5.

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