JP2010150338A - Methods for producing resin film and shading film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method by which a resin film having an uneven shape on the surface and useful for various kinds of applications is efficiently and continuously produced by using the excellent unevenness-transferring properties and by sufficiently preventing the planarization of the uneven shape formed by the curing, and to provide a method by which a shading film having excellent various properties such as heat resistance and shading properties is efficiently produced by using the production method. <P>SOLUTION: The method for producing the resin film having the uneven shape on the surface includes a step of forming the uneven shape on the surface of a thermosetting resin film constituted of a thermosetting resin composition by a transfer method, and a step of curing the thermosetting resin film. The concentration of the solid content in the thermosetting resin film to be subjected to the surface unevenness-forming step is 60-80 mass% based on 100 mass% of the whole mass of the thermosetting resin film in the production method. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a resin film and a method for producing a light-shielding film. More specifically, a method for producing a resin film useful for various uses such as an optical member, an optical device member, a display device member, a mechanical component, and an electric / electronic component, and a light-shielding film using the production method. Regarding the method.

A resin film is a film-like molded product obtained by drying, solidifying, curing, or reacting a resin composition. For example, various types of optical members, optical device members, display device members, mechanical parts, electrical / electronic parts, etc. Widely used in applications. In such a resin film, a film having a concavo-convex shape on its surface has been developed in order to reduce its gloss and suppress reflection. For example, as a light-shielding film, optical noise is generated inside the lens unit. And is used to suppress enlargement.

Regarding the resin film having a surface uneven shape, as a method for forming the uneven shape on the resin film, for example, a method of sandblasting a polyester film mixed with carbon black (see, for example, Patent Document 1), an organic filler (matte). Agent) is bonded to the surface of the base black film with a binder resin to form irregularities based on the fine particles (see, for example, Patent Document 2), organic filler and black fine particles are applied to the surface of the base transparent film with a binder resin. A method of binding and forming irregularities based on fine particles and blackening (for example, see Patent Document 3) is disclosed. Moreover, after apply | coating the coating material which consists of a radiation curable resin composition on a base film, it dries and forms the uneven | corrugated shape (for example, refer patent document 4), The coating liquid containing a photocurable composition is supported. A method of forming an uneven shape by applying and drying on the surface of a body (see, for example, Patent Document 5), applying or laminating an ultraviolet curable resin composition on a polymer film sheet raw material, A method (for example, refer to Patent Document 6), in which a roll having a concavo-convex shape in close contact with a roll having a concavo-convex shape and irradiating ultraviolet rays to transfer and mold the roll concavo-convex surface, is disclosed. Furthermore, as another method for forming the uneven shape, there is a method in which a photosensitive polyimide precursor composition is applied onto a metal conductor to form a precursor layer, and then exposed to light, and a mask pattern is transferred to the precursor layer as a latent image. (For example, refer to Patent Document 7).
JP-A-1-120503 JP 2003-147275 A JP 2003-266580 A JP 2001-152027 A JP 2003-272228 A JP 2003-272228 A JP 2006-98514 A

As described above, various techniques for forming an uneven shape on the surface of a resin film have been developed. However, for example, in the techniques described in Patent Documents 1 to 3, it cannot be said that the unevenness transferability is at a sufficient level, and the uneven shape cannot be formed continuously, so these points need to be improved. Moreover, since the composition used for the technique of patent documents 4-7 is photocurable or photosensitivity, when a black material is mix | blended, for example, desired unevenness | corrugation is difficult, a light-shielding film etc. It is difficult to obtain a resin film for use in optical members. Accordingly, it is possible to form a concavo-convex shape even for a resin composition that can be used for more applications such as optical members, and to improve the concavo-convex transfer property, and to suitably produce a resin film useful for various applications. There was room for ingenuity.

The present invention has been made in view of the above-described present situation, has excellent concavo-convex transferability, sufficiently suppresses flattening of the concavo-convex shape formed by curing, has a concavo-convex shape on the surface, and has various A method capable of efficiently and continuously producing a resin film useful for applications, and using the production method, efficiently producing a light-shielding film excellent in various performances such as heat resistance and light-shielding properties. It aims to provide a possible method.

The inventors of the present invention have studied various methods for producing a resin film having a concavo-convex shape on the surface, and by producing a production method using a transfer method, it is possible to efficiently produce a resin film suitable for an optical member or the like. Found (PCT / JP2008 / 063812). And in such a manufacturing method, it has the process of shape | molding uneven | corrugated shape by the transfer method on the surface of the thermosetting resin film comprised from a thermosetting resin composition, and the process of hardening a thermosetting resin film When the solid content concentration of the thermosetting resin film used for the manufacturing method and the surface unevenness forming step is specified, the unevenness transferability is greatly improved and the flatness of the formed unevenness can be sufficiently suppressed. I found what I could do. In addition, it has also been found that a resin film can be continuously produced by adopting such a production method. Furthermore, if such a manufacturing method is used, it has excellent heat resistance, light shielding properties, etc., and light shielding properties useful for various applications such as optical members, optical device members, display device members, mechanical parts, electrical / electronic parts, etc. It has also been found that a film can be produced efficiently and at low cost, and the inventors have conceived that the above-mentioned problems can be solved brilliantly and have reached the present invention.

That is, the present invention is a method for producing a resin film having a concavo-convex shape on the surface, wherein the above-described production method forms a concavo-convex shape on the surface of a thermosetting resin film composed of a thermosetting resin composition by a transfer method. And the step of curing the thermosetting resin film, and the solid content concentration of the thermosetting resin film used for the surface irregularity forming step is 100% by mass of the total mass of the thermosetting resin film. , 60 to 80% by mass of the resin film production method.
The present invention is also a method for producing a light-shielding film provided with a light-shielding layer formed from a thermosetting resin composition, wherein the production method uses a resin film production method as described above. It is also a method for producing a light-shielding film to be produced.
The present invention is described in detail below.

The present invention is a method for producing a resin film having a concavo-convex shape on the surface, and the structure (configuration) of the resin film may be appropriately selected according to the use of the resin film. For example, (1) The form which is a laminated film which consists of a base material, the layer (single side) formed from a thermosetting resin composition, and the layer which has another function as needed, (2) Base material and a thermosetting resin In the form of a laminated film composed of layers (both sides) formed from the composition and layers having other functions as required, (3) a single layer film of a layer formed from the thermosetting resin composition Certain forms are preferred. Especially, when using a resin film for the use for which size reduction and thickness reduction are calculated | required, it is suitable that it is a form of (3), ie, a single layer structure.
In addition, the layer formed from a thermosetting resin composition means the layer formed by hardening | curing the thermosetting resin film comprised from a thermosetting resin composition.

The said thermosetting resin composition (henceforth only "resin composition") should just be a composition containing resin (thermosetting resin) hardened | cured by heating, according to the use of a resin film. It is preferable to include other components as appropriate.
Examples of the thermosetting resin include compounds having at least one epoxy group (epoxy group-containing compound), polyhydric phenol compounds, compounds having a polymerizable unsaturated bond, poly (amide) imide resins, and the like. The raw material etc. are mentioned, It can use individually or can use 2 or more types together. Especially, it is preferable to use a poly (amide) imide resin or its raw material (precursor polymer), More preferably, it uses a poly (amide) imide resin raw material (precursor polymer). That is, it is preferable that the thermosetting resin composition contains a poly (amide) imide resin raw material, whereby the obtained resin film can exhibit heat resistance comparable to that of inorganic glass, Excellent properties such as excellent workability can be exhibited. Specific forms of these compounds and the like are as described later.

When the resin film is used as a light-shielding film, the thermosetting resin composition preferably further includes a black material in order to impart light-shielding properties. That is, the form in which the said thermosetting resin composition contains a thermosetting resin and a black material is also one of the suitable forms of this invention.
Examples of the black material include carbon black fine particles such as carbon black and graphite; inorganic black fine particles such as metal oxide black fine particles such as titanium black; black organic fine particles such as aniline black (organic black fine particles). It is preferable to use black fine particles such as anthraquinone, indigoid, diazo black organic dyes and the like.
The inorganic black fine particles (inorganic black material) include magnetite, cuprous oxide (cuprous oxide), composite oxide black fine particles containing copper and chromium as main metal components, copper, other than the above titanium black, copper Complex oxide black fine particles containing copper and iron as main metal components, composite oxide black fine particles containing copper, iron and manganese as main metal components, and complex oxide black fine particles containing cobalt, chromium and iron as main metal components Etc. is also one of the preferred forms.

Among the black materials, fine-particle black materials (black fine particles) are preferable, and various black fine particles can be used. Among the black fine particles, carbon black fine particles and inorganic black fine particles are preferable in terms of excellent heat resistance. Carbon-based materials such as carbon-based fine particles are preferable in terms of excellent light-shielding performance in the visible light region. Also, ultra-fine particles give excellent black color to the light-shielding film due to excellent dispersibility in the resin composition. Carbon black is more preferable because it can be used. In addition to excellent heat resistance, carbon black is preferable because it has a high degree of black and is inexpensive.

The black fine particles preferably have a primary particle diameter of 1 μm or less. More preferably, it is 0.1 μm or less. Moreover, the particle | grains by which secondary aggregation was suppressed are preferable. Further, when the black fine particles are dispersed in the resin composition, it is preferable that the black fine particles have a particle diameter of 1 μm or less. The particle size of the black fine particles when dispersed in the resin composition is more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. When the black fine particles are dispersed in the resin composition, the hue (black) becomes uniform when the black fine particles are dispersed with a fine particle diameter. Further, when the treatment for forming irregularities on the surface of the light-shielding film is performed, if the black fine particles have a particle size of 1 μm or less, there is no generation of defects due to the coarse particles of the black fine particles, and the uniform thickness Resin with no unevenness in surface unevenness due to transfer, which can be applied to the surface, and even when adjusted to a predetermined solid content concentration (60 to 80% by mass), can provide a film thickness uniformity and surface smoothness. A film is obtained.
The primary particle diameter can be evaluated by a transmission electron microscope image.
The black fine particles may exist in such a way that the primary particles exist independently without secondary aggregation or association, or the primary particles form a structure in which the primary particles aggregate in one, two, or three dimensions. The primary particle diameter means the size of the primary particle in any case. For example, in the case of carbon black, the primary particles are substantially spherical or granular (having a contour due to microcrystals, and are more difficult to be divided).
The size of the primary particles can be usually evaluated by a transmission electron microscope image, and the number average value (average primary particle diameter) is more preferably in the above range. In determining the average primary particle size, it is preferable to measure the size of 20 or more primary particles and determine the average of the measured values.
Further, when it is difficult to evaluate the size of the primary particles from the transmission electron microscope image, B.I. E. T. T. The specific surface area diameter calculated by the following formula using the specific surface area value measured by the method can be substituted as the average primary particle diameter.
Specific surface area diameter (μm) = 6 / (ρ × S)
(In the formula, ρ represents the true specific gravity. S represents the specific surface area (m ² / g).)
The particle size of the black fine particles when dispersed in the resin composition described above is measured by using a dynamic light scattering type particle size distribution measuring device such as LB-500 (manufactured by Horiba). In the present invention, a volume-based arithmetic average value is adopted.

When the black fine particles are carbon black, dibutyl phthalate oil absorption can be used as a dispersibility index, and the oil absorption is preferably 300 ml / 100 g or less. When the oil absorption exceeds 300 ml / 100 g, the dispersibility of the carbon black is deteriorated, the hue (black) is not sufficiently uniform, coarse particles of the carbon black are formed, and a process for forming irregularities on the surface is performed. There is a possibility that the processability at the time may not be sufficiently excellent. The oil absorption is more preferably 250 ml / 100 g or less, and still more preferably 200 ml / 100 g or less.

The oil absorption amount indicates characteristics of carbon black itself (of powdered carbon black), and indicates characteristics of carbon black in a state before being dispersed in a resin composition or the like. The amount of oil absorption increases when carbon black is aggregated and decreases when dispersed. As the carbon black is more dispersed, the uniformity in the light-shielding film is improved. Therefore, it is preferable that the oil absorption is smaller. Thus, the resin composition preferably has a form in which black fine particles are dispersed.

As content of the said black material, it is preferable that it is 1-50 mass% with respect to 100 mass% of solid content total of a thermosetting resin and a black material. If it is less than 1% by mass, the light-shielding property may not be sufficient. If it exceeds 50% by mass, the resin composition has a too high viscosity, so that it is difficult to form a uniform thickness and the surface is flat. In addition, it is difficult to obtain a thermosetting resin film having excellent properties, and there is a possibility that it may be easily broken. More preferably, it is 3-40 mass%, More preferably, it is 5-30 mass%.

As a form of inclusion of the black material in the resin composition, it is preferable that a black material (preferably black fine particles) is dispersed or dissolved in the resin composition. If the black material does not exist in a dispersed or dissolved state, when the light shielding layer is formed on the light shielding film or the like, the light shielding layer may not be sufficiently black and may not exhibit better light shielding properties. There is.
As a method for dispersing or dissolving the black material, that is, a method for producing a resin composition in which the black material is dispersed or dissolved, various methods can be suitably used. For example, a thermosetting resin is dissolved in a solvent. A method in which a black material is mixed with a dispersed resin binder solution and dispersed or dissolved; a method in which a thermosetting resin is dissolved in a dispersion in which a black material is dispersed; a dispersion in which a thermosetting resin is dispersed in fine particles A method of mixing and dispersing or dissolving a black material; a method of melting and kneading a mixture of a thermosetting resin and black fine particles, and the like, are appropriately selected and used depending on the black material and the thermosetting resin be able to.

Here, the thermosetting resin is preferably solvent-soluble, and the thermosetting resin composition preferably further contains a solvent. Thereby, since it becomes easy to disperse or dissolve the black material uniformly in the resin composition, a thermosetting resin composition in which the black material is sufficiently uniformly dispersed or dissolved is obtained. It becomes possible to obtain a film having a sufficiently uniform distribution and excellent light shielding properties. Thus, the form in which the said thermosetting resin is solvent-soluble is also one of the preferable forms of this invention.
In this case, as a method for producing the resin composition, a method of mixing and dispersing a solution in which a black material is dispersed or dissolved in a solution (resin binder solution) in which a thermosetting resin is finely dispersed or dissolved is used. Is preferred. Thereby, for example, when a light shielding layer (black layer) is formed by coating or the like using this resin composition, a more uniform blackness can be obtained as the light shielding layer, and excellent light shielding properties can be exhibited. It becomes possible.

The solvent is appropriately selected according to the type of thermosetting resin, and examples thereof include ketones such as methyl ethyl ketone (2-butanone), methyl isobutyl ketone (4-methyl-2-pentanone), cyclohexanone, and the like; PGMEA ( 2-acetoxy-1-methoxypropane), glycol derivatives such as ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol ethyl ether acetate (ether compounds, ester compounds, ether ester compounds, etc.); N, N- Amides such as dimethylacetamide; Esters such as ethyl acetate, propyl acetate, and butyl acetate; Pyrrolidones such as N-methyl-2-pyrrolidone (more specifically, 1-methyl-2-pyrrolidone, etc.); Toluene, Aromatic carbonization such as xylene Motorui; cyclohexane, aliphatic hydrocarbons such as heptane; ethers such as diethyl ether and Djibouti ether and the like. More preferred are N, N-dimethylacetamide, xylene, 1-methyl-2-pyrrolidone (NMP) and the like.

The amount of the solvent used is preferably 150 parts by weight or more and preferably 1900 parts by weight or less with respect to 100 parts by weight of the thermosetting resin. More preferably, it is 200 parts by weight or more and 1400 parts by weight or less.

A preferable form of the thermosetting resin composition is a coating composition, and in particular, a black material and a thermosetting resin (including a curing agent and a curing accelerator described later, respectively) and further. And the solid content (total amount of the thermosetting resin and the black material described above) is 5 with respect to 100% by mass of the thermosetting resin composition (assuming that the solvent is also included). The form which is -40 mass% is suitable. When the solid content in the thermosetting resin composition is in the range, a thermosetting resin film excellent in film thickness uniformity and surface flatness can be easily obtained by coating, and a surface unevenness forming step described later It is easy to adjust the solid content concentration of the thermosetting resin film to be provided to 60 to 80% by mass in a short time. The more preferable range of solid content in the said thermosetting resin composition is 10-30 mass%.

In the method for producing the resin composition, the black material is produced so as to be contained in the resin composition as particles (black material-containing particles) dispersed and contained in other components such as a resin. It may be a form to do. The preferred resin component constituting the black material-containing particles is not particularly limited, and examples thereof include the resins described above as the thermosetting resin constituting the resin composition, and among them, the thermosetting constituting the resin composition. It is preferable that it is a thermosetting resin of the same type or the same refractive index as the resin.

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

The thermosetting resin composition may further contain a curing agent. In particular, when the epoxy group-containing compound is included, it is preferable to include a heat latent cation generator as a curing agent.
The thermal latent cation generator is also called a cationic polymerization initiator, and exhibits a substantial function as a curing agent when the resin composition reaches a curing temperature. By using a cation generator, for example, even when an organic material that cures at room temperature is used, curing can be prevented from proceeding at room temperature, and the curing reaction can be easily handled. become. In addition, the moisture resistance of the resulting cured product (light-shielding layer) is dramatically improved, and it retains the excellent optical properties of the resin composition even in harsh usage environments and can be suitably used for various applications. It becomes.

Normally, when water having a high refractive index is contained in the resin composition or its cured product, it causes turbidity, but when the resin composition containing the thermal latent cation generator is used, excellent moisture resistance is obtained. Since it can exhibit, such turbidity etc. are suppressed and it can use suitably for an optical use. Especially in applications such as in-vehicle cameras and bar code readers for home delivery companies, there are concerns about yellowing and deterioration of strength due to prolonged UV irradiation and high temperature exposure in summer. It is thought that the generation of oxygen radicals is caused by the synergistic effect of heat ray exposure. By improving moisture resistance, moisture absorption into the cured resin composition is suppressed, and generation of oxygen radicals due to a synergistic effect of ultraviolet irradiation or exposure to heat rays is also suppressed. Exhibits excellent heat resistance for a long time without causing it.

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

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

Specific products of the heat latent cation generator include the following products.
Diazonium salt type: AMERICURE series (American Can), ULTRASET series (Adeka), WPAG series (Wako Pure Chemical Industries)
Iodonium salt type: UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone-Poulenc), WPI series (manufactured by Wako Pure Chemical Industries)
Sulfonium salt type: CYRACURE series (manufactured by Union Carbide), UVI series (manufactured by General Electric), FC series (manufactured by 3M), CD series (manufactured by Satomer), optomer SP series, optomer CP series (manufactured by Adeka) ), Sun Aid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), CPI series (manufactured by San Apro)
Etc.

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

When the thermosetting resin composition contains an epoxy group-containing compound, it is preferable to use a curing accelerator. As a hardening accelerator, 1 type (s) or 2 or more types, such as organic phosphorus compounds, such as a triphenyl phosphine, a tributyl hexadecyl phosphonium bromide, a tributyl phosphine, a tris (dimethoxyphenyl) phosphine, are suitable, for example.

The thermosetting resin composition further includes, for example, a reactive diluent, a saturated compound having no unsaturated bond, a pigment, a dye, an antioxidant, an ultraviolet absorber, a light stabilizer, and a plasticizer as necessary. , Non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic and organic fillers, adhesion improvers such as coupling agents, thermal stabilizers, antibacterial and antifungal agents Agent, flame retardant, matting agent, antifoaming agent, leveling agent, wetting / dispersing agent, anti-settling agent, thickener / anti-sagging agent, anti-coloring agent, emulsifier, anti-slip / scratch agent, anti-skinning agent In addition, one or more of a desiccant, an antifouling agent, an antistatic agent, a conductive agent (electrostatic aid), and the like may be contained.

The thermosetting resin composition preferably has a viscosity (viscosity at 25 ° C. as a resin solution) of 10 cP to 100,000 cP (centipoise). When it is in this range, the thermosetting resin composition makes it easy to obtain a coating film having excellent film thickness uniformity and surface flatness, and the solid content concentration during use in the surface irregularity forming step is adjusted to 60 to 80% by mass. In the thermosetting resin film thus obtained, uneven surface roughness due to solvent removal is unlikely to occur, and a resin film with no unevenness in surface irregularities is easily obtained by transfer. In addition, it is possible to suppress the flattening of the formed uneven surface shape. More preferably, it is 500 cP to 50,000 cP.
The viscosity can be measured by, for example, a B-type viscometer.

The method for producing a resin film of the present invention is also referred to as a step of forming a concavo-convex shape by a transfer method on the surface of a thermosetting resin film composed of the thermosetting resin composition described above (also referred to as “surface concavo-convex forming step”). ) And a step of curing the thermosetting resin film (also referred to as “curing step”), it may further include other steps as necessary.
As a thermosetting resin film used for the surface unevenness forming step, the solid content concentration is suitably 60 to 80% by mass with respect to 100% by mass of the total mass of the thermosetting resin film. . If it is less than 60% by mass, a thermosetting resin film is deposited on the surface of the transfer material, and the shape of the transfer material cannot be sufficiently transferred, and a resin film may not be obtained continuously. . Further, when a resin film having a single layer structure is manufactured as described later, it is preferable to remove the resin film from the base material before performing the surface unevenness forming step. It may be difficult to peel from the material. Further, if it exceeds 80% by mass, the thermosetting resin film is likely to be broken, so that it may not be possible to impart an uneven shape, and when a resin film having a single layer structure is produced, a peeling process may be performed. May be difficult. The lower limit of the solid content concentration range is preferably 65% by mass, more preferably 70% by mass, and the upper limit is preferably 77% by mass, more preferably 75% by mass.

The thermosetting resin film is, for example, after the thermosetting resin composition is applied to the substrate by a normal coating method or after being formed into a film by a film (film) forming method such as melt extrusion molding. The solid content concentration can be obtained by drying, solidifying, curing, or reacting (reacting from a precursor or a monomer into a resin state) until the solid content concentration is in the above-described range. Especially, the method to apply | coat is preferably employ | adopted at the point which is easy to adjust the thermosetting resin film whose solid content concentration mentioned above is 60-80 mass%. In that case (that is, by the coating method), it is preferable to adjust the solid content concentration to the above-mentioned range by removing (drying) the solvent. Further, it is also preferable to proceed with curing or reaction (reaction (for example, reaction to partially imidize the polyamideimide precursor polymer) or the like from the precursor or the monomer by heating). . It is also preferable to remove the solvent by heating and simultaneously proceed with the above curing or reaction.
Note that the thermosetting resin film is not chemically or compositionally final (dried, solidified, cured or reacted), but is in an intermediate state (semi-dried, semi-solidified, semi-cured or unreacted).・ Semi-reactive state).

The thermosetting resin film used for the surface irregularity forming step preferably has a glass transition temperature (Tg) of 110 to 260 ° C. In this case, the thermosetting resin film is dried, solidified, cured, or reacted (reaction from the precursor or monomer to the resin state) until the glass transition temperature of the thermosetting resin film falls within the range. It is preferable to perform a surface unevenness forming step on the resin film. When Tg is within this range, the transfer process (surface unevenness forming step) and the peeling step from the base material before the surface unevenness forming step can be performed more easily, more continuously and efficiently. It becomes possible to obtain a resin film. More preferably, it is 150-240 degreeC. A method of producing a resin film having a concavo-convex shape on the surface, the step of forming a concavo-convex shape by a transfer method on the surface of a thermosetting resin film composed of a thermosetting resin composition, and thermosetting And a method for producing a resin film having a glass transition temperature (Tg) of 110 to 260 ° C. of the thermosetting resin film used for the surface unevenness forming step. The same effect can be exhibited.

The glass transition temperature (Tg) can be measured as follows.
(Tg measurement method)
TA Instruments, Inc., RSAIII use measurement conditions: temperature rising speed 10 ° C./min,
1Hz frequency
In addition, although Tg of the polyimide film completely baked (imidized) varies depending on the composition, it is usually 280 to 400 ° C. and, for example, 380 ° C. for aromatic polyimide.

The thermosetting resin film may also be subjected to a surface unevenness forming step in a state of being present on the base material depending on the structure (configuration) of the target resin film, or may be peeled off from the base material to form the surface unevenness. You may use for a formation process. Especially, when it is going to obtain the resin film of a single layer structure, it is preferable to peel from a base material and to use for a surface unevenness | corrugation formation process. In this case, after applying the thermosetting resin composition to the base material, it may be peeled off from the base material when the solid content concentration is in the range described above, and may be used for the surface unevenness forming step, or peeled off from the base material. After that, the solid content concentration in the above-described range may be subjected to the surface unevenness forming step. Among these, from the viewpoint of improving work efficiency and the like, it is preferable that the solid concentration is peeled off from the base material when it falls within the above-described range and used for the surface unevenness forming step. That is, it is preferable that the solid content concentration of the thermosetting resin film at the time of peeling from the substrate is in the same solid content concentration range as that used in the surface unevenness forming step. The glass transition temperature of the thermosetting resin film at the time of peeling from the substrate is also preferably in the same temperature range as that suitable for use in the surface irregularity forming step.

The thermosetting resin film obtained by peeling from the base material has a glossy surface on the side that was in contact with the thermosetting resin composition. The base material contact surface) has high glossiness, but the surface that was not in contact with the base material (base material non-contact surface) is less glossy than the base material contact surface, probably because of solvent evaporation. Tend. Therefore, when trying to obtain a resin film with low glossiness, the surface unevenness is formed on the substrate non-contact surface (the surface on which the substrate is not in contact) of the thermosetting resin film obtained by peeling. It is preferable to perform the forming step. Of course, it is also preferable to process both sides.

As the base material, a smooth material is suitable, but the material may be any of an organic material, an inorganic material, an organic / inorganic composite material, or a metal material, and these are one type or two or more types. May be used. Organic materials (for example, thermoplastic resin compositions and curable resin compositions) are suitable because they are easy to handle, inorganic materials (for example, glass) are excellent in thermal expansion coefficient, and organic / inorganic composite materials are suitable for both characteristics It is. Any of these materials can be suitably used. However, when the thermosetting resin film obtained by peeling from the substrate as described above is subjected to the surface unevenness forming step, a material having excellent releasability is used. It is preferable to use it. Moreover, when not peeling from a base material (for example, when aiming at the resin film which has a base material), it is preferable to use the material which has reflow resistance. Moreover, if it can peel from a base material, the film or glass etc. which have uneven | corrugated shape may be sufficient.

Specifically, the material having reflow resistance is selected from the group consisting of fluorinated aromatic polymers, polycyclic aromatic polymers, poly (amide) imide resins, fluorine-containing polymer compounds, glass films, and polyether ketone resins. It is preferable that at least one of them is included.
In addition, since these materials are excellent also in the mold release property, they can be used suitably also when performing the peeling process from a base material.

When not peeling from the substrate (for example, when a resin film having a substrate is intended), the substrate is also preferably a heat-resistant material. More preferably, it is a heat resistant resin film (a film which essentially requires a heat resistant resin). As the heat resistant temperature of the substrate, the 10% decomposition temperature is preferably 200 ° C or higher, more preferably 250 ° C or higher, still more preferably 300 ° C or higher, and most preferably 350 ° C or higher. Tg is preferably 80 ° C. or higher, more preferably 150 ° C. or higher, further preferably 200 ° C. or higher, and most preferably 250 ° C. or higher. By using a base material having such heat resistance, it can be suitably applied to automatic mounting of a resin film.

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

The thickness of the substrate can be appropriately selected according to the presence or absence of the peeling step, the thickness of the resin film to be obtained, and the like. For example, when glass is used as the substrate, the thickness of the glass is preferably 30 to 500 μm, more preferably more than 100 μm. In the case of using a resin as the substrate, for example, a sheet having a thickness of about 100 μm can be suitably used for polyimide, kapton, etc., but a film having a thickness of less than 100 μm is preferable.

As mentioned above, Preferably, the thermosetting resin composition containing a solvent is apply | coated to a base material, a part of solvent is removed by heating, and solid content concentration in a film | membrane is adjusted to 60-80 mass%. Thus, a thermosetting resin film suitable for use in the surface unevenness forming step can be obtained. In this case, a resin film composed of a thermosetting resin film single layer can be obtained by peeling the film from the substrate as necessary after coating or after adjusting the solid content concentration.
Further, in the above heating, by adjusting Tg to 110 to 260 ° C., a more suitable thermosetting resin film that is used for the surface unevenness forming step can be obtained.

The step of forming the concavo-convex shape by the transfer method on the surface of the thermosetting resin film is a step of forming the concavo-convex shape by bringing the thermosetting resin film into contact with a transfer material (also referred to as a transfer layer). Good. By using the transfer method, it is possible to form a concavo-convex shape at a fine level with good reproducibility, and it is possible to precisely control the form such as the size and depth of the concavo-convex shape. That is, it is possible to impart a matting property to the surface based on a uniform and fine uneven shape while having excellent flatness.

Examples of the transfer material (transfer layer) include frosted glass; mat films such as mat-treated PET film (mat pet film), mat-treated PP film, and mat PC film (mat-treated polymer film); conventionally known mat rolls ( Also called embossing roll). Among them, a roll transfer method using a mat roll (emboss roll) is suitable, and by this, an uneven shape can be formed on the surface of the thermosetting resin film in the embossing process with the mat roll, enabling continuous production and manufacturing. Cost can be kept low. In addition, it is possible to make both sides uneven by adopting embossing with a mat roll. In addition, it is preferable that the transfer material is usually excellent in releasability in order to separate from the light-shielding film, and the uneven shape of the transfer material is appropriately selected according to the uneven shape of the resin film to be obtained. Just choose.
Moreover, as a method for forming the unevenness, a roll transfer method and a mold transfer method are suitable.

The transfer material is preferably brought into contact with the resin film while being heated and held at 60 to 200 ° C. in the process of forming the surface unevenness. When the temperature is less than 60 ° C., the uneven shape changes due to heat curing, and the shape of the transfer material may not be sufficiently transferred. If the temperature exceeds 200 ° C., a thermosetting resin film is deposited on the surface of the transfer material, and the shape of the transfer material cannot be sufficiently transferred, and there is a possibility that a resin film cannot be obtained continuously. . The lower limit value of the temperature range of the transfer material is more preferably 80 ° C., still more preferably 100 ° C., and the upper limit value is more preferably 190 ° C., still more preferably 180 ° C.

What is necessary is just to perform the said hardening process by the normal thermosetting method. Moreover, although it changes with the kind of thermosetting resin which comprises a film | membrane, the kind of hardening | curing agent, and a hardening accelerator, it is preferable that it is the range of 100-400 degreeC as hardening temperature. More preferably, it is 150 degreeC or more, More preferably, it is 200 degreeC or more, Most preferably, it is 250 degreeC or more, On the other hand, as an upper limit temperature, 400 degrees C or less is preferable. More preferably, it is 350 degrees C or less. The curing time is preferably 5 minutes to 3 hours, more preferably 10 minutes to 1 hour.
In addition, in the manufacturing method of this invention, it is appropriate to perform the process (curing process) of hardening a resin film after the said surface uneven | corrugated formation process.

In the above manufacturing method, when it is intended to obtain a resin film having uneven shapes on both surfaces, it is most preferable to perform the above-described surface unevenness forming step on both surfaces, for example, other methods are used in combination. It is also possible. In any case, from the viewpoint of efficiency, it is preferable to form concave and convex shapes on both surfaces simultaneously and / or continuously.
In addition, when forming an uneven shape on both surfaces at the same time, it is preferable that the time for forming the uneven shape on one side and the time for forming the uneven shape on the other surface overlap at least partially. .

Other methods include, for example, a method of forming a concavo-convex shape by applying a thermosetting resin composition to a transfer material, and then drying, solidifying, curing, or reacting to form a film (this is a substrate mold transfer method). Can also be used. This method is a method for forming a concavo-convex shape before or in the course of drying, solidifying, curing, or reacting the thermosetting resin composition, but it is usually formed from a transfer material after the concavo-convex shape is formed. The thermosetting resin composition (cured thermosetting resin film) thus peeled off.
As the transfer material, among the above-mentioned transfer materials, either frosted glass or mat film (surface unevenness PET or the like) is preferable. In addition, as the unevenness forming method, a normal coating method such as a solvent casting method, a spin coating method, a bar coater method, a roll coater method, a gravure coater method, or a knife coating method can be employed.

When the other methods are used in combination, it is preferable to perform the surface unevenness forming step of the present invention after performing the substrate template transfer method. For example, in the case of a resin film having a single layer structure, first, an uneven shape is formed on one surface of a thermosetting resin film by a substrate mold transfer method, and the solid content concentration of the thermosetting resin film is within the above-described range. It is preferable to dry, solidify, cure, or react until the surface becomes, and then perform the surface unevenness forming step of the present invention described above for the other surface. Such a process is schematically shown in FIG.
The resin composition is applied to the transfer layer 11, and unevenness is formed on the surface in contact with the transfer layer 11 while being semi-dried or semi-cured. At this time, pressure is applied with a roll 9 as necessary. Subsequently, the resin composition is brought into contact with the mat roll type transfer layer 10 to form a concavo-convex shape on the other surface, the transfer layer 11 is peeled off, and both surfaces have a concavo-convex shape. A light-shielding film having a layer structure can be obtained continuously.

The present invention is also a method for producing a light-shielding film provided with a light-shielding layer formed from a thermosetting resin composition, wherein the production method uses a resin film production method as described above. It is also a method for producing a light-shielding film to be produced.
Such a light-shielding film has a function of shielding light having a desired wavelength by scattering / absorbing light having a desired wavelength. For example, when mounted on a lens unit, it has the function of shielding light in the visible light region, ultraviolet region, infrared region, etc. that the photoelectric conversion sensor senses, and it generates and expands optical noise inside the lens unit. It suppresses and removes the generated optical noise.

What is necessary is just to use the thermosetting resin composition mentioned above as a thermosetting resin composition which forms the said light shielding layer, and it is especially using the thermosetting resin composition containing a thermosetting resin and a black material. Is preferred.
The light-shielding layer is a layer formed from the thermosetting resin composition, that is, a layer formed by curing a thermosetting resin film composed of the thermosetting resin composition), and at least one surface thereof Has an uneven shape (uneven structure). By having an uneven surface shape, the light-shielding film is not glossy, light reflection is prevented, and the light-shielding property is excellent. More preferably, both surfaces have a concavo-convex shape, whereby the effect is more fully exhibited.

As the uneven shape, for example, the surface may not be smooth to the extent that incident light is scattered without being specularly reflected. Moreover, it is preferable that the unevenness | corrugation of the surface is a magnitude | size suitable for scattering the light which it wants to shield. For example, when a light-shielding film is used for a lens unit, it effectively scatters light in the visible light region, the ultraviolet region, the infrared region, and the like.
In this case, Ra (arithmetic average roughness) of the line roughness (JIS 2001) of the film is preferably 0.5 μm or more. More preferably, it is 0.7 micrometer or more, More preferably, it is 1.0 micrometer or more, Most preferably, it is 2.0 micrometers or more. The maximum height Rz of the film is preferably 10 μm or more. More preferably, it is 15 micrometers or more, More preferably, it is 20 micrometers or more, Most preferably, it is 25 micrometers or more. Further, the average height Rc is preferably 5 μm or more. More preferably, it is 8 micrometers or more, More preferably, it is 10 micrometers or more, Most preferably, it is 15 micrometers or more.

Here, the line roughness (JIS 2001) of the film is obtained using a calculation formula according to JIS B 0601-2001 surface roughness-definition.
As shown in FIG. 1, the arithmetic average roughness (Ra) represents an average of absolute values in the reference length, and can be obtained from the following formula (i). In the formula, Rn represents the height of the nth measurement line when the height of the average line of the roughness curve is 0.

As shown in FIG. 2, the maximum height Rz is represented by the sum of the highest mountain height (Rp) and the deepest valley depth (Rv) in the contour curve at the reference length. It can be obtained from the following formula (ii). In addition, a mountain means a portion above the average line, and a valley means a portion below the average line.
Rz = Rp + Rv (ii)

As shown in FIG. 3, the average height Rc represents the average value of the height (Rti) of the contour curve (roughness curve) element at the reference length, and is obtained from the following formula (iii). Can do. The contour element is a set of adjacent peaks and valleys. In this case, the peak (valley) constituting the contour element has a minimum height and a minimum length, and the height (depth) is 10% or less of the maximum height, or the length is the length of the calculation section. If it is 1% or less, the noise is assumed to be a part of the valley (mountain) that follows the front and rear.

Although it does not specifically limit as long as it has the unevenness | corrugation of the shape mentioned above as the said surface uneven | corrugated shape, It is preferable that uneven | corrugated shape is formed, without making fine particles other than black material contain in a light-shielding film. When the concave and convex shape is formed by containing fine particles, since the fine particles are usually white or light-colored fine particles, the fine particles existing near the surface of the light-shielding film serve as a light transmission path, and the light-shielding property of the light-shielding film. May not be excellent enough. The fine particles that can be contained in the light-shielding film of the present invention preferably have high heat resistance, but particles having high heat resistance such as spherical silica and silicone resin particles are white. When such white (or light) fine particles are used, it becomes a blackening inhibiting factor for obtaining excellent light-shielding properties. Therefore, it is necessary to add a large amount of black fine particles. Is disadvantageous. Moreover, when forming uneven | corrugated shape using microparticles | fine-particles, the particle | grains with uniform particle size distribution are required for uniform uneven | corrugated formation, and there exists a possibility that it may become expensive.

A light-shielding film having such a light-shielding layer can be obtained using the above-described method for producing a resin film. That is, the method includes a step of forming a concavo-convex shape by a transfer method on the surface of a thermosetting resin film (light-shielding film) composed of a thermosetting resin composition, and a step of curing the thermosetting resin film, It can obtain by using the manufacturing method whose solid content concentration of the thermosetting resin film | membrane used for a surface unevenness | corrugation formation process is 60-80 mass% with respect to 100 mass% of total mass of a thermosetting resin film.

The structure of the light-shielding film is not particularly limited as long as it has the light-shielding layer, but may have other components as necessary. For example, when the light shielding layer is a thin film that does not have sufficient strength, it is preferable to include a base material in order to obtain sufficient strength.
Specifically as a structure of the said light-shielding film, for example, (1) Form which is a laminated film which consists of a base material, a light shielding layer (one side), and a layer which has another function as needed, (2) The form which is a laminated film which consists of a base material, a light shielding layer (both surfaces), and a layer having other functions as required, and (3) a form which is a light shielding layer single layer film are suitable.
The schematic diagram of these forms is shown in FIG. 4A shows the form of (1), (b) shows the form of (2), and (c-1) and (c-2) show the form of (3). In FIGS. 4A and 4B, a laminated film composed of a base material and a light shielding layer is schematically shown. However, if necessary, a layer having other functions may be provided. .

In the forms of (1) and (2) above, since the strength of the light-shielding film can be obtained by the base material, the light-shielding layer can be made thin. By thinning the light-shielding layer, it is easy to control the film thickness when applying the resin composition, and the solvent contained in the composition can be removed by evaporation in a short time when drying. There is an advantage that it is easy to obtain a light-shielding layer in which the generation of defects in the film that causes a reduction in light-shielding performance, such as the generation of accompanying bubbles, is suppressed. In these forms, the arrangement positions of the light shielding layer and the base material are not particularly limited, and any of them is the incident light surface, so that the effect of the present invention is not particularly limited. A form in which the layer is disposed on the incident light surface is preferable.
The preferred forms such as the material and thickness of the substrate are as described above.

In the forms (1) and (2), the thickness of the light shielding layer is preferably 5 μm or more. More preferably, it is 10 μm or more. Moreover, as an upper limit of the thickness of a light shielding layer, it is preferable that it is 80 micrometers or less, More preferably, it is 50 micrometers or less, More preferably, it is 30 micrometers or less. Moreover, as a particularly preferable range, it is 10-30 micrometers.
In addition, in this specification, the thickness of a light shielding layer means the thickness which measured the light shielding layer with the micrometer.

A layer having other functions may be appropriately set in the light-shielding film of the above forms (1) and (2). In the case of forming a layer having other functions, for example, in the case of forming an infrared cut layer, usually, a low refractive index material and a high refractive index material (for example, an inorganic oxide) are vapor-deposited on a substrate, It will be laminated. And when heating at the time of vapor deposition, the heat resistance with respect to the heat at the time of vapor deposition is required, and it is preferable to use the material which has reflow resistance as a base material since an infrared cut layer can be formed easily. In addition, when forming a layer having other functions other than the light shielding layer, sufficient heat resistance may be required. For example, when vapor-depositing an infrared cut layer (inorganic multilayer film or film that reflects or blocks infrared rays), the temperature of the substrate (substrate material) is usually high because a temperature of several hundred degrees Celsius or higher is required during vapor deposition. Necessary. Therefore, by making the base material sufficiently heat resistant, various infrared blocking materials can be formed by various methods.

In the form (3) in which the light-shielding layer is a single layer (form in which the light-shielding layer alone forms a light-shielding film), the thickness of the light-shielding layer varies depending on the form of the light-shielding film and the application to be applied. It is preferable that it is 1000 micrometers. Thereby, the light-shielding film of this invention becomes thin, For example, when this light-shielding film is used for an optical member, an optical path can be shortened. Thereby, this optical member (for example, camera module etc.) can be reduced in thickness. The lower limit of the thickness of the light shielding layer is more preferably 10 μm or more, more preferably 10 μm or more from the viewpoint of easy post-processing of the film and excellent mechanical strength, although it depends on the thermosetting resin composition used in the light shielding layer. It is 20 μm or more, particularly preferably 30 μm or more. Although the upper limit of the thickness of the light shielding layer depends on the material of the light shielding layer, it is preferably 200 μm or less, more preferably 100 μm or less in view of sufficient light shielding performance and application to a lens unit that is highly required to be thin. Particularly preferably, it is 80 μm or less. The thickness range of the light shielding layer is more preferably 10 to 200 μm, still more preferably 20 to 100 μm, and particularly preferably 30 to 80 μm.

A particularly preferred form of the light-shielding film is a single layer structure. That is, a form constituted by the light shielding layer alone having the form (3) is suitable. By adopting such a form, the thickness of the light-shielding film can be reduced, and when used for optical applications (lens units), the optical path can be shortened, and the lens unit can be reduced in size and thickness. It becomes possible. A schematic diagram of a light-shielding film having a single layer structure is shown in FIG. FIG. 4 (c-1) is a form in which the unevenness is formed on one side, and (c-2) is a form in which the unevenness is formed on both sides.

The light-shielding film preferably has a thickness of less than 1000 μm. By setting the thickness to less than 1000 μm, for example, when used as an optical member, the optical path can be shortened and the optical member can be made small. More preferably, it is 200-10 micrometers, More preferably, it is 100-20 micrometers.

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

The light-shielding film obtained by the above production method has excellent heat resistance. The heat resistance of the light-shielding film can be evaluated by a change in film shape when the film is heated at a high temperature. As the change in film shape, the smaller the change in film dimensions (longitudinal and transverse lengths in the plane, the length in the thickness direction) before and after heating, the better the shape retention. Preferably there is. As a specific example of having excellent shape retainability (having heat resistance), when heated at 200 ° C. for 1 minute, the rate of change (dimensional change rate) of each length after heating with respect to before heating is 10% or less. It is to become. When the dimensional change rate is 10% or less, the characteristics of the light-shielding film can be sufficiently exhibited under the conditions normally used in the above-described applications. For example, generation and expansion of optical noise inside the lens unit can be achieved. Can be suppressed. More preferably, it is 5% or less, further preferably 3% or less, and particularly preferably 1% or less.
In addition, what is necessary is just to select suitably the magnitude | size of the sample when measuring a dimensional change rate, for example, the sample of size 50.0 mm x 10.0 mm x width 35-80 micrometers can be used.

The dimensional change rate may be measured under more severe conditions, and the heating temperature is preferably 250 ° C. The heating and holding time is preferably 2 minutes. More preferably, it is 5 minutes, More preferably, it is 10 minutes. A light-shielding film having a dimensional change rate in the above range under such severe conditions is more preferable.
More preferably, the rate of dimensional change is more preferably 10% or less after each heating after heating at 260 ° C. for 2 minutes (dimensional change rate). Measurement conditions are preferably performed in an air atmosphere. That is, in the light-shielding film, when the film is heated at 260 ° C. for 2 minutes in an air atmosphere, the dimensional change rate of the length, width, and thickness after heating with respect to before heating is 10% or less. preferable. When the above-mentioned light-shielding film is used for a lens unit, it should be able to sufficiently withstand the solder reflow process because the dimensional change is small by heating at 260 ° C. for 2 minutes (the dimensional change rate is 10% or less). Can do. The dimensional change rate in this case is more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1% or less.

The shape of the light-shielding film can be appropriately selected according to the application. When the lens is attached to the lens unit, it can be effectively transmitted / lighted except for the optical path by sticking it to the heel that fixes the lens. Reflection can be suppressed, and optical noise can be reduced. That is, in a lens unit application, as schematically shown in FIG. 5, it is preferable that a light-shielding film (in particular, a light-shielding layer) is attached to a bag for fixing the lens, and the position of the lens and the light-shielding layer in the lens unit. The relationship is preferably that schematically shown in FIG. 6 when viewed as a sectional view of the lens unit. In this case, the light shielding layer in the light shielding film preferably has a planar shape (ring shape) as schematically shown in FIG. 7 when viewed from the lens unit incident light side. The center of the ring may be a cavity, a transparent film that transmits visible light, or a lens. Preferably, the center of the ring is a cavity.

In the present specification, “having heat resistance” means having high resistance to heat. For example, when used for optical applications, in materials such as thermosetting resins, it is preferable to satisfy at least one of high Tg or high decomposition temperature (preferably high 10% decomposition temperature). The material, the light-shielding film, and the lens unit preferably satisfy at least one of excellent shape retention, low dimensional change rate, and high decomposition temperature (preferably high 10% decomposition temperature). . Further, “having reflow resistance” means having sufficient resistance to the temperature used in the reflow process, and in the same way as having heat resistance, for example, when used for optical applications, In a material such as a curable resin, it is preferable to satisfy at least one of a high Tg or a high decomposition temperature (preferably a high 10% decomposition temperature). Preferably satisfies at least one of excellent shape retention and high decomposition temperature (preferably high 10% decomposition temperature). As preferable requirements for Tg, decomposition temperature, shape retention, and the like, it is preferable to satisfy the preferable requirements for the above-described characteristics.

In the following, a compound having at least one epoxy group (epoxy group-containing compound), a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, and a poly (amide) that are preferably used as the thermosetting resin of the present invention ) The imide resin will be further described.
In addition, an epoxy group means an organic group having an oxirane ring, and an epoxy group is included in an organic group having an oxirane ring such as a glycidyl group. "Glycidyl group" is included.

As said epoxy group containing compound, the following compounds etc. can be used conveniently, for example.
Epibis type glycidyl ether type epoxy resin obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and epihalohydrin, and these bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc. High molecular weight epibis type glycidyl ether type epoxy resin obtained by further addition reaction with other bisphenols; phenols such as phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol And formaldehyde, acetoaldehyde, propionaldehyde, benzaldehyde, hydroxybenzaldehyde Obtained by condensation reaction of polyhydric phenols obtained by condensation reaction of hydride, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc. with epihalohydrin. Novolak aralkyl type glycidyl ether type epoxy resin; aromatic crystalline epoxy resin obtained by condensation reaction of tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol and the like with epihalohydrin, and the above bisphenols and tetramethyl Aromatic crystalline epoxy tree obtained by addition reaction of biphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc. High molecular weight of;

Alicyclic glycols hydrogenated aromatic skeletons such as the above bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalenediol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, PEG600, propylene glycol, Dipropylene glycol, tripropylene glycol, tetrapropylene glycol, PPG, glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and its multimer, pentaerythritol and its multimer, glucose, fructose, lactose, maltose, etc. / Aliphatic glycidyl ether type epoxy resin obtained by condensation reaction of polysaccharides and epihalohydrin; (3 4-epoxycyclohexane) epoxy resin having an epoxycyclohexane skeleton such as methyl 3 ′, 4′-epoxycyclohexyl carboxylate; tetrahydrophthalic acid, hexahydrophthalic acid, glycidyl ester obtained by condensation reaction of benzoic acid and epihalohydrin Type epoxy resin; tertiary amine-containing glycidyl ether type epoxy resin solid at room temperature obtained by condensation reaction of hindatoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin.

Among them, epibis type glycidyl ether type epoxy resin; novolak aralkyl type glycidyl ether type epoxy resin; aromatic crystalline epoxy resin; aliphatic glycidyl ether type epoxy resin; epoxy resin having epoxy cyclohexane skeleton; glycidyl ester Type epoxy resin; tertiary amine-containing glycidyl ether type epoxy resin and the like are preferable. For the purpose of suppressing appearance deterioration during light irradiation, the above aliphatic glycidyl ether type epoxy resins and epoxy resins having an epoxycyclohexane skeleton are more preferably used.

Examples of the polyhydric phenol include phenols such as phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, and fluorene bisphenol, and formaldehyde, acetoaldehyde, propionaldehyde, benzaldehyde, and hydroxybenzaldehyde. And compounds obtained by condensation reaction of salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, and the like.

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

The poly (amide) imide resin means a polyimide resin in a narrow sense (resin including an imide bond and not including an amide bond) and a polyamideimide resin (resin including an amide bond and an imide bond). There are two types of such poly (amide) imide resins, thermosetting resins and thermoplastic resins. In the present invention, thermosetting poly (amide) imide resins are preferred, and more preferably aromatic It is a group thermosetting poly (amide) imide resin.
The poly (amide) imide resin imidizes a precursor polymer (raw material of poly (amide) imide resin) obtained by reacting a polyvalent carboxylic acid compound with a polyvalent amine compound and / or a polyvalent isocyanate compound. Although it can be obtained by reaction, the form in which the thermosetting resin composition contains such a precursor polymer is one of the preferred forms of the present invention. More preferably, the precursor polymer has an aromatic ring.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As said precursor polymer (raw material of poly (amide) imide resin), following formula (3);

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

In the above formula (3), R ⁵ preferably contains an aliphatic cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring from the viewpoint of heat resistance. More preferably, R ⁵ is an aliphatic cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring, and is a trivalent or tetravalent group having 4 to 30 carbon atoms. Specifically, for example, phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenylsulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoropropane group, cyclobutyl group, cyclopentyl group, cyclohexane Although a hexyl group etc. are mentioned, it does not specifically limit and various organic groups can be used.

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

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

In the general formula (3), n represents the number of repeating structural units represented by the general formula (3) in the precursor polymer, and is an integer of 1 to 1000. Preferably, it is 2 or more, and if the viscosity becomes too high, the compatibility with the black material may not be sufficient, so that it is preferably 500 or less.

In the precursor polymer containing the structural unit (3), the content of the structural unit (3) is preferably 30 to 100% by mass with respect to 100% by mass of the polymer. More preferably, it is 50-100 mass%.

In the above general formula (3), as a precursor polymer mainly composed of the structural unit (3) where r = 2, for example, polyamic acid (polyimide precursor) synthesized from tetracarboxylic dianhydride and diamine Polymer). Moreover, as a precursor polymer which has the structural unit (3) which is r = 1 as a main component, for example, a polyvalent carboxylic acid compound containing a tricarboxylic acid compound, a polyvalent amine compound and / or a polyvalent isocyanate compound A polyamideimide precursor polymer obtained by the reaction is preferable.

Since the method for producing a resin film of the present invention has the above-described configuration, it has excellent concavo-convex transferability and has a concavo-convex shape on the surface by sufficiently suppressing flattening of the concavo-convex shape formed by curing. In addition, resin films useful for various applications can be produced efficiently and continuously. Moreover, if such a manufacturing method is used, it will be excellent in various performances, such as heat resistance and light-shielding property, and light-shielding property useful for various uses, such as an optical member, an optical device member, a display device member, a mechanical component, and an electrical / electronic component. A film can be produced efficiently.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by mass”.
In the following examples and the like, the solid content of the thermosetting resin film (before transfer) subjected to the transfer treatment (surface unevenness forming step) was determined as follows. That is, using a small piece of resin film as a sample, TG-DTA (manufactured by BRUKER AXS, TG-DTA2000SA) was used to measure the weight loss from room temperature to 350 ° C. at a heating rate of 10 ° / min. The amount was the solvent content, and the residue was the solid content (solid content concentration, unit: mass%). Further, the glass transition temperature (Tg) of the thermosetting resin film (before transfer) was determined as described above.

Examples 1-1 to 1-3
[Preparation of varnish solution in which carbon black is dispersed in polyamic acid solution]
A reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirrer was prepared. In this reactor, a polyamic acid solution, a black material, and a surface conditioner were charged in the proportions (mass%) shown in Table 1, mixed under the mixing conditions shown below, and then made of SUS using the pressure filter shown below. Each varnish liquid as a thermosetting resin composition was obtained by carrying out pressure filtration with 300 mesh.
In addition, as a polyamic acid solution, Ube Industries, Ltd. polyimide varnish U-varnish A (solid content: 18.5%), or I.V. S. Polyimide varnish Pire-ML RC5083 (solid content: 19.0%) manufactured by T company was used. As the black material, Graft carbon black dispersion Epotone LY (carbon black concentration 7.8%) manufactured by Nippon Shokubai Co., Ltd. is used, and BYK-306 (solid content: 12.5) manufactured by Big Chemie Japan Co., Ltd. is used as the surface conditioner. %) Was used.
(Mixing conditions)
Stirring blade: 2-stage paddle mixing time: 60 minutes stirring, under nitrogen atmosphere (pressure filtration)
Pressure filter used: ADVANTEC, KST-293-10-JA

Examples 2-1 to 2-5, Comparative Examples 1-2
[Creation of thermosetting resin film]
By coating each varnish obtained in Examples 1-1 to 1-3 on a mat pet film manufactured by Teijin DuPont (brand: PSG, thickness 100 μm), drying, and then peeling from the substrate PET A thermosetting resin film (resin films A to C) was obtained.
The solid content in each resin film was 67% for resin film A, 73% for resin film B, and 58% for resin film C.
The coating conditions and drying conditions are shown below.
(Coating conditions)
Coating method: Slot die coating width: 26cm
Drying furnace temperature: 140 ° C. (for resin films A and C), 145 ° C. (for resin film B)

The obtained resin films A, B, and C were further heat-treated (dried) with a hot air drier to adjust the solid content concentration.
What heat-processed resin film A for 10 minutes at 150 degreeC was made into resin film A-C1,
What heat-processed the resin film B for 120 minutes at 120 degreeC was made into resin film B-C2,
A resin film C-C3 was obtained by heating the resin film C at 120 ° C. for 5 minutes.
The solid content of each resin film was A-C1: 85%, B-C2: 77%, and C-C3: 69%.

[Surface unevenness forming process (transfer process)]
A transfer process (surface unevenness forming process) was performed on the surface of the obtained resin film on the non-contact side of the base material PET. A mat roll was used as the transfer material. Details regarding the apparatus used, processing conditions, etc. are shown below.
Used machine: Electric heating type embossing machine Mat roll 1: Fine embossed receiving roll: Resin roll Test temperature: 120 ° C, 150 ° C
Compressive load: 5 tons (linear pressure 185N / mm)
Speed: 2m / min

[Curing process (imidization)]
Each of the resin films was subjected to the above transfer treatment (test) and then cured by heat curing under the following conditions in an inert oven to obtain a resin film made of a polyimide resin.
Heat curing conditions: after curing at 200 ° C. for 20 minutes, curing at 250 ° C. for 10 minutes, and further curing at 300 ° C. for 10 minutes.

Each resin film (or resin film after transfer treatment) thus obtained was evaluated and measured for glossiness, line roughness, heat resistance and light transmittance by the following evaluation methods. The results are shown in Table 2.
1. Measurement of glossiness The glossiness of the transfer-treated surface of the resin film after the transfer treatment and the curing treatment was measured. The glossiness was determined by measuring the glossiness at a measurement angle (θ) of 60 ° using a gloss meter (VG-2000) manufactured by Nippon Denshoku Industries Co., Ltd.

2. Measuring method of line roughness (JIS2001) The measurement was performed with the following models and measurement conditions, and analysis was performed.
Model: Color 3D laser microscope (VK-9700) manufactured by KEYENCE
Measurement setting objective lens: 20 times Zoom: 1.0 times Measurement pitch: RPD
Measurement mode: Surface shape measurement area: Surface measurement quality: Ultra high definition analysis software: VK-9700 / VK-8700 Shape analysis application VK-HIAI
Analysis surface (image) tilt correction: quadratic surface correction (automatic)
Analysis length (reference length l): 500 μm
Analysis line tilt correction: straight line (automatic)

3. A heat resistance test was performed on the polyimide film (resin film) after curing.
Test piece: Film cut to a size of 50 mm × 10 mm Test condition: Dimensional change before and after the test at 260 ° C. for 2 minutes was measured.
As a result of measuring the dimensional change for the resin films obtained in Examples 2-1 to 2-5, all the samples were 50 mm × 10 mm and had no thickness change, and no dimensional change was observed.

4. Light transmittance The spectral transmittance of each resin film obtained in Examples 2-1 to 2-5 was measured using a spectrophotometer (Shimadzu autograph spectrophotometer UV-3100 manufactured by Shimadzu Corporation). As a result, in any resin film, the light transmittance with respect to the wavelength region of 300 to 800 nm was 0.1% or less. Moreover, as a result of measuring similarly also after the heat resistance test of each resin film, in any resin film, the light transmittance with respect to the wavelength of 300-800 nm was 0.1% or less.

In Tables 1 and 2, “-” means not measured.
In Comparative Example 1, unevenness could not be formed because the curable resin film was deposited on the roll during the transfer process, and in Comparative Example 2, unevenness could not be applied because the film was hard and brittle. Thus, since the transfer process could not be performed in Comparative Examples 1 and 2, an evaluation test after transfer (and after firing) could not be performed.

From Table 2, the solid content concentration of the thermosetting resin film (before transfer) used for the surface unevenness forming step (transfer process) is 60 to 80% by mass with respect to 100% by mass of the total mass of the thermosetting resin film. As a result, it was found that an advantageous effect was exhibited in producing a resin film having a concavo-convex shape on the surface, which was remarkable.
Regarding the technical significance of the upper limit and the lower limit of the numerical range, Comparative Example 1 (58 mass%) slightly below the lower limit, and Comparative Example 2 (85 mass%) slightly above the upper limit, and within the above range It is clear when certain Examples 2-1 to 2-5 are compared. In Comparative Example 1 where the solid content concentration is lower than the lower limit value, the thermosetting resin film is deposited on the transfer material. In Comparative Example 2 where the solid content concentration is higher than the upper limit value, the thermosetting resin film is hard and brittle. None of them were able to continue work. On the other hand, in Examples 2-1 to 2-5 in which the solid content concentration is within the above range, the operation was not interrupted in this way, and the resin film was efficiently obtained, and the glossiness and linear roughness were obtained. From the results of the measurement test and the heat resistance test, it can be seen that a resin film at a high level as a product could be manufactured. In addition, since the thermosetting resin film hardly adhered to the transfer materials used in Examples 2-1 to 2-5, continuous operation of the transfer operation is possible.

FIG. 1 shows one of schematic cross-sectional views of a light-shielding film when the line roughness (Ra) of the light-shielding film is determined. FIG. 2 shows one of the cross-sectional schematic diagrams of the light-shielding film when the maximum height (Rz) of the light-shielding film is obtained. FIG. 3 shows one of the schematic cross-sectional views of the light-shielding film when the average height (Rc) of the light-shielding film is obtained. FIG. 4 is a schematic cross-sectional view showing one preferred form of the light-shielding film. FIG. 5 is a schematic cross-sectional view showing the configuration of a camera module which is one of the preferred forms of the lens unit. FIG. 6 is a schematic cross-sectional view showing the relationship between the light-shielding film and the lens in the lens unit. FIG. 7 is a schematic plan view showing one preferred form of the light-shielding film in the lens unit. FIG. 8 is a schematic view showing a form in which the surface unevenness forming step of the present invention is performed after performing the substrate mold transfer method when forming uneven shapes on both surfaces of the thermosetting resin film.

Explanation of symbols

1: light shielding layer 2: base material 3: light shielding film 4: lens 5: infrared cut filter 6: barrel 7: sensor lens 8: edge 9: roll 10: mat roll type transfer layer 11: transfer layer

Claims (4)

A method for producing a resin film having an uneven shape on the surface,
The manufacturing method includes a step of forming a concavo-convex shape by a transfer method on the surface of a thermosetting resin film composed of a thermosetting resin composition, and a step of curing the thermosetting resin film.
The solid content concentration of the thermosetting resin film used for the surface unevenness forming step is 60 to 80% by mass with respect to 100% by mass of the total mass of the thermosetting resin film. The said thermosetting resin composition contains a thermosetting resin and a black material, The manufacturing method of the resin film of Claim 1 characterized by the above-mentioned. The method for producing a resin film according to claim 1 or 2, wherein the thermosetting resin film used for the surface unevenness forming step has a glass transition temperature (Tg) of 110 to 260 ° C. A method for producing a light-shielding film comprising a light-shielding layer formed from a thermosetting resin composition,
This manufacturing method manufactures a light-shielding film using the manufacturing method of the resin film in any one of Claims 1-3, The manufacturing method of the light-shielding film characterized by the above-mentioned.

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