JP4773245B2 - Honeycomb porous film and honeycomb composite film - Google Patents

Description

  The present invention relates to a honeycomb-shaped porous film having pores formed by self-organization, a honeycomb composite film composed of the honeycomb-shaped porous film, and a method for manufacturing the honeycomb composite film.

In recent years, in the fields of optical materials and electronic materials, there are increasing demands for improving the degree of integration, increasing the amount of information, and increasing the definition of image information. For this reason, it is requested | required that the fine structure (fine patterning, fine pattern structure) is formed also in the film used for the said field | area. In research in the field of regenerative medicine, it is known that a membrane having a fine structure on the surface is effective as a base material that serves as a scaffold in cell culture (see Patent Document 1).
Various methods such as vapor deposition using a mask, photochemical reaction, photolithographic technique using a polymerization reaction, laser ablation technique and the like are known and put into practical use for fine patterning of the film.

  Further, it is known that a film having a micron-scale honeycomb structure can be obtained by casting a dilute solution of a polymer having a special structure under high humidity (see Patent Document 2 and Patent Document 3). The film having such a honeycomb structure is used as an optical material or an electronic material by containing functional fine particles. For example, it is used as a display device by containing a light emitting material in the film (see Patent Document 4).

In addition, a film on which fine patterning is formed is also used for a polarizing plate which is an optical material. For example, there is a film that exhibits an antireflection function having a moth-eye structure. Such a film has regular fine patterning of submicron to several tens of microns.
In this case, a mainstream method is to prepare a plate using a micro processing technique centering on photolithography and transfer the structure of the plate to a substrate (see Patent Document 5).

In the top-down method as described in Patent Document 5, the production of a plate for determining the fine structure is complicated and requires many steps, resulting in high costs. There is also a problem that it is difficult to produce a large-area plate.
For this reason, the self-organization having a fine structure is applied by applying “self-organization” having a regular fine structure by forming a fine structure in a self-associative manner as described in Patent Documents 2 and 3 above. A bottom-up method for producing a structured structure (honeycomb-like porous film) has been proposed.

  However, since the conventional self-assembled structure is produced using a high molecular weight material such as an amphiphilic polymer or an amphiphilic oligomer, the material diffusion rate in the solution of the material is slow, and the honeycomb structure It takes a long time for the water droplets formed on the surface of the microstructure to become a mold of the material to be surrounded by the entrainment of the material solution, and as a result of the growth of individual water droplets, the pore diameter of the honeycomb structure increases. There is a problem of end. In addition, since it is a thin film having a large number of pores, there is a problem that the strength is weak, it is easily torn, and the handleability is inferior. is the current situation.

JP 2001-157574 A JP 2002-335949 A JP 2002-347107 A JP 2003-128832 A JP 2003-302532 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides a honeycomb-shaped porous film in which the pore diameter is controlled to be small, a honeycomb composite film comprising the honeycomb-shaped porous film, and a method for efficiently manufacturing the honeycomb composite film. Objective.

  As a result of intensive studies by the present inventors in order to solve the above problems, the following knowledge has been obtained. That is, as a material for producing a self-assembled structure, a phosphate ester-based surfactant that is an oil-soluble surfactant is used instead of the amphiphilic polymer that was an essential component for obtaining a honeycomb structure. This is a finding that the fusion of water droplets serving as the mold of the pores is quickly suppressed, and as a result, the diameter of the resulting pores is controlled to be small.

This invention is based on the said knowledge by the present inventors, and the means for solving the said subject are as follows. That is,
<1> A honeycomb-like porous film comprising at least a surfactant represented by the following general formula (I).
However, in said general formula (I), R < ₁ > represents either an aliphatic group, an alicyclic compound group, an aromatic group, and a heterocyclic ring, and R < ₂ > is an aliphatic group, an alicyclic compound group. , An aromatic group, a heterocyclic ring, and a group represented by -LZ, and Q ₁ , Q ₂ and Q ₃ are each a single bond, an oxygen atom, a sulfur atom, and —N (R ₃ ) —. Any one of the groups represented, R ₃ represents either a hydrogen atom or a group represented by R ₂ , L represents a divalent linking group, and Z represents an ionic group;
<2> A film material layer is formed using a film material solution containing at least the surfactant represented by the general formula (I) and a hydrophobic organic solvent,
Air holes formed by blowing a gas having a relative humidity of 50 to 95% to the film material layer, volatilizing the hydrophobic organic solvent, generating condensation on the surface of the film material layer, and evaporating the condensation. It is a honeycomb-like porous film as described in said <1> which has.

<3> A film material layer is formed using a film material solution containing at least the surfactant represented by the general formula (I) and a hydrophobic organic solvent,
The film material layer is blown with a gas having a relative humidity of 50 to 95% to volatilize the hydrophobic organic solvent, generate condensation on the surface of the film material layer, and evaporate the condensation to form pores. A method for producing a honeycomb-shaped porous film.

<4> A honeycomb composite film characterized in that a temporary support is releasably provided on at least one surface of the honeycomb-like porous film according to any one of <1> to <2>.
<5> The honeycomb composite film according to <4>, wherein the honeycomb porous film has a release layer on at least one surface of the honeycomb-shaped porous film, and has a temporary support on the release layer.
<6> The honeycomb composite film according to any one of <4> to <5>, wherein the honeycomb-shaped porous film has release layers on both surfaces, and has a temporary support on both release layers.
<7> A release layer on one side of the honeycomb-like porous film, and a temporary support on the release layer, and a support on the side of the honeycomb-like porous film that does not have the release layer. The honeycomb composite film according to any one of <4> to <6>.
<8> The honeycomb composite film according to any one of <4> to <7>, wherein the honeycomb porous film is stretched.
<9> The honeycomb composite film according to <8>, wherein the stretching is any one of uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, and triaxial stretching.
<10> The honeycomb composite film according to any one of <4> to <9>, wherein the honeycomb porous film has a metal layer on a surface thereof.
<11> The honeycomb composite film according to <8>, wherein the metal in the metal layer is at least one selected from gold, silver, copper, aluminum, iron, nickel, titanium, tungsten, chromium, and alloys thereof. is there.
<12> The honeycomb composite film according to any one of <4> to <11>, wherein pores in the honeycomb-shaped porous film are filled with a refractive index control material.
<13> The honeycomb composite film according to any one of <4> to <12>, wherein the temporary support and the release layer are peeled off.
<14> Any one selected from a retardation film, a polarizing film, a screen, a color filter, a display member, a cell culture member, a wound protective film, a percutaneous absorption film, an acoustic vibration material, a sound absorbing material, and a vibration damping material The honeycomb composite film according to any one of <4> to <13>, which is used in the above.

<15> A release layer forming step of forming a release layer on the temporary support,
A honeycomb-shaped porous film production step of producing the honeycomb-shaped porous film according to any one of <1> to <2> on a support;
A method for manufacturing a honeycomb composite film, comprising: bonding the release layer on the temporary support to the honeycomb porous film.
<16> a release layer forming step of forming a release layer on the temporary support,
A honeycomb-shaped porous film preparation step of forming the honeycomb-shaped porous film according to any one of <1> to <2> on the release layer on the temporary support. It is a manufacturing method of a composite membrane.
<17> The method for producing a honeycomb composite film according to any one of <15> to <16>, including a stretching step of stretching the honeycomb-shaped porous film.
<18> The method for producing a honeycomb composite film according to any one of <15> to <17>, including a metal layer forming step of forming a metal layer on the surface of the honeycomb-shaped porous film.

  According to the present invention, the conventional problems can be solved, and the honeycomb-shaped porous film in which the pore diameter is controlled to be small, the honeycomb composite film composed of the honeycomb-shaped porous film, and the honeycomb composite film are efficiently used. A well-manufactured method can be provided.

(Honeycomb porous film and manufacturing method thereof)
The honeycomb-shaped porous film of the present invention contains at least a phosphate ester-based surfactant represented by the following general formula (I).
The manufacturing method of the honeycomb-shaped porous film of the present invention will be clarified through the description of the honeycomb-shaped porous film.
Here, the honeycomb structure in the honeycomb-shaped porous film means a structure in which pores having a fixed shape and a fixed size are arranged continuously and regularly. This regular arrangement is two-dimensional in the case of a single layer and regular in three dimensions in the case of a multilayer. For example, as shown in FIG. 1, this regularity is arranged so that a plurality of (for example, six) holes surround a single hole in two dimensions, and the crystal structure in three dimensions. In many cases, a close-packed structure having a face-centered cubic or hexagonal structure is exhibited, but regularity other than these may be exhibited depending on manufacturing conditions.

However, in said general formula (I), R < ₁ > represents either an aliphatic group, an alicyclic compound group, an aromatic group, and a heterocyclic ring, and R < ₂ > is an aliphatic group, an alicyclic compound group. , An aromatic group, a heterocyclic ring, and a group represented by -LZ, and Q ₁ , Q ₂ and Q ₃ are each a single bond, an oxygen atom, a sulfur atom, and —N (R ₃ ) —. Any one of the groups represented, R ₃ represents either a hydrogen atom or a group represented by R ₂ , L represents a divalent linking group, and Z represents an ionic group;

In the general formula (I), the aliphatic group represented by R ₁ is a linear or branched unsubstituted alkyl group having 1 to 40 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-amyl group, tert-amyl group, n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2- Octyldodecyl group, docosyl group, tetracosyl group, 2-decyltetradecyl group, tricosyl group, etc.), linear or branched substituted alkyl group having 1 to 40 carbon atoms (substituents are alkoxyl group, aryl group, halogen atom) , Carbo Ester group, carbonamido group, carbamoyl group, oxycarbonyl group, phosphate ester group, etc.) (for example, benzyl group, β-phenethyl group, 2-methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6- Phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, heptadecylfluorooctyl group, 12- (p-chlorophenyl) dodecyl group, 2- (diphenyl phosphate) ethyl group, etc.), linear or branched carbon An unsubstituted alkenyl group of 2 to 40 (for example, vinyl group, allyl group, 3-butenyl group, 2-methyl-2-butenyl group, 4-pentenyl group, 3-pentenyl group, 3-methyl-3-pentenyl group) 5-hexenyl group, 4-hexenyl group, 3-hexenyl group, 2-hexenyl group, 7-octenyl group, 9-decenyl group, oleyl group, linoleyl group, linoleni A linear or branched substituted alkenyl group having 2 to 40 carbon atoms (for example, 2-phenylvinyl group, 4-acetyl-2-butenyl group, 13-methoxy-9-octadecenyl group, 9,10 -Dibromo-12-octadecenyl group, etc.), linear or branched unsubstituted alkynyl group having 2 to 40 carbon atoms (for example, acetylene group, propargyl group, 3-butynyl group, 4-pentynyl group, 5-hexynyl group, 4-hexynyl group, 3-hexynyl group, 2-hexynyl group, etc.), linear or branched substituted alkynyl group having 2 to 40 carbon atoms (such as alkoxyl group, aryl group, etc.) (for example, 2-phenyl Acetylene group, 3-phenylpropargyl group, etc.) are preferred.

  The alicyclic compound group includes a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms (for example, cyclopropyl group, cyclohexyl group, 2,6-dimethylcyclohexyl group, 4-tert-butylcyclohexyl group, 4-phenyl). A cyclohexyl group, a 3-methoxycyclohexyl group, a cycloheptyl group, etc.), a substituted or unsubstituted cycloalkenyl group having 4 to 40 carbon atoms (for example, a 1-cyclohexenyl group, a 2-cyclohexenyl group, a 3-cyclohexenyl group, 2,6-dimethyl-3-cyclohexenyl group, 4-tert-butyl-2-cyclohexenyl group, 2-cycloheptenyl group, 3-methyl-3-cycloheptenyl group, etc.), etc. Substituted aryl groups having 6 to 50 carbon atoms (the substituents are alkyl groups, alkoxyl groups, aryl groups, halogen atoms, etc.) (for example, phenyl Group, 1-naphthyl group, 2-naphthyl group, anthranyl group, o-cresyl group, m-cresyl group, p-cresyl group, p-ethylphenyl group, p-tert-butylphenyl group, 3,5-di- tert-butylphenyl group, p-n-amylphenyl group, p-tert-amylphenyl group, 2,6-dimethyl-4-tert-butylphenyl group, p-cyclohexylphenyl group, octylphenyl group, p-tert- Octylphenyl group, nonylphenyl group, p-n-dodecylphenyl group, m-methoxyphenyl group, p-butoxyphenyl group, m-octyloxyphenyl group, biphenyl group, m-chlorophenyl group, pentachlorophenyl group, 2- ( 5-methylnaphthyl group) and the like are preferred.

  Heterocycles include substituted or unsubstituted cyclic ethers having 4 to 40 carbon atoms (eg, furyl, 4-butyl-3-furyl, pyranyl, 5-octyl-2H-pyran-3-yl, isobenzo A furanyl group, a chromenyl group, etc.), a substituted or unsubstituted nitrogen-containing ring having 4 to 40 carbon atoms (for example, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, indolizinyl group, morpholyl group, etc.). .

  Among these, a linear, cyclic or branched unsubstituted alkyl group having 1 to 24 carbon atoms (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group) Cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2-octyldodecyl group, docosyl group, tetracosyl group, 2-decyltetradecyl group, etc.), straight chain having 1 to 24 carbon atoms excluding the carbon number of the substituent A cyclic or branched substituted alkyl group (for example, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, heptadecylfluorooctyl group, 12- (p-chloropheny ) Dodecyl group, 4-tert-butylcyclohexyl group, etc.), linear, cyclic or branched unsubstituted alkenyl group having 2 to 24 carbon atoms (for example, vinyl group, allyl group, 2-methyl-2-butenyl group, 4-pentenyl group, 5-hexenyl group, 3-hexenyl group, 3-cyclohexenyl group, 7-octenyl group, 9-decenyl group, oleyl group, linoleyl group, linolenyl group, etc.), straight chain having 2 to 24 carbon atoms Cyclic or branched substituted alkenyl groups (for example, 2-phenylvinyl group, 9,10-dibromo-12-octadecenyl group), substituted or unsubstituted aryl groups having 6 to 30 carbon atoms (for example, phenyl group, 1-naphthyl group, 2-naphthyl group, p-cresyl group, p-ethylphenyl group, p-tert-butylphenyl group, p-tert-amylphenyl group, octylphenyl group, p-tert-octylphenyl group, nonylpheny Group, p-n-dodecylphenyl group, m-octyloxyphenyl group, biphenyl group, etc.) are particularly preferred.

Q ₁ , Q ₂ and Q ₃ are each independently selected from a single bond, an oxygen atom, a sulfur atom or —N (R ₃ ) — (R ₃ represents a hydrogen atom or R ₂ as defined above). It is. Among these, a single bond, an oxygen atom or —N (R ₃ ) — is preferable, and at least two of Q ₁ , Q ₂ and Q ₃ are particularly preferably oxygen atoms. Here, a single bond means that an element does not exist.

  L represents a divalent linking group, preferably a group represented by the following general formula.

In the formula, Y ₁ , Y ₂ and Y ₃ may be the same or different, each substituted or unsubstituted alkylene group having 1 to 40 carbon atoms, substituted or unsubstituted arylene group having 6 to 40 carbon atoms (The substituent is the same as that shown in the definition of R ₁ above), and the alkylene group is a methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1,4-cyclohexylene group, octamethylene group, decamethylene group, 2-methoxy-1,3-propylene group, etc., and arylene groups include o-phenylene group, m-phenylene group, p-phenylene group, 3-chloro- 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group and the like are preferable. Among these, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1,4-cyclohexylene group, octamethylene group, decamethylene group, m-phenylene group, p- A phenylene group.

J ₁ , J ₂ and J ₃ each represent a divalent bond unit which may be the same or different, and represent a single bond, —O—, —S—, —CO—, —COO— or —OCO—. , —CON (R ₄ ) — (R ₄ is a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted alkyl group having 1 to 6 carbon atoms excluding the carbon number of the substituent (the substituent is aryl Group, an alkoxyl group, a halogen atom, etc.)), —N (R ₄ ) CO— (R ₄ is the same as described above), —CON (R ₄ ) CO— (R ₄ is the same as above) -N (R ₄ ) CON (R ₅ )-(R ₄ and R ₅ may be the same or different, and are the same as those defined for R ₄ above), -OCON (R ₄ )-(R ₄ is the same as shown above), -N (R ₄ ) COO- (R ₄ is the same as shown above),- SO ₂ —, —SO ₂ N (R ₄ ) — (R ₄ is the same as shown above), —N (R ₄ ) SO ₂ — (R ₄ is the same as shown above), —N (COR ₄ ) — (R ₄ is the same as described above), —OP (═O) (OR ₁ ) O— (R ₁ is the same as defined above) and the like are preferable. Among these, a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —CON (R ₄ ) — (R ₃ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, ), —N (R ₄ ) CO— (R ₄ is the same as shown above), —SO ₂ N (R ₄ ) — (R ₄ is the same as shown above), —N (R ₄ ) SO ₂ — (R ₄ is the same as described above) and the like are particularly preferable.

  p, q and r are each independently an integer of 0 to 5. Preferably, p, q, and r are each independently an integer value of 0 to 3, and it is particularly preferable that p, q, and r each independently take an integer value of 0 or 1. s is an integer value of 1 to 10, preferably 1 to 5, particularly preferably 1 to 3. a and b are each independently an integer of 0 to 50. Among these, it is preferable that a and b each independently take an integer value of 0 to 20, and it is particularly preferable that a and b take an integer value of 0 to 10.

Z is preferably a hydrophilic anion or a cationic ionic group, and particularly preferably an anionic group. Examples of the anionic group include —COOM, —SO ₃ M, —OSO ₃ M, —PO (OM) ₂ —OPO (OM) ₂ (M represents a counter cation, preferably an alkali metal ion (for example, lithium ion, sodium Ions, potassium ions, etc.), alkaline earth metal ions (for example, magnesium ions, calcium ions, etc.) and ammonium ions are preferred. Sodium ions and potassium ions are particularly preferred. NH ₃ ⁺ · X ⁻ , —NH ₂ (R ₆ ) ⁺ · X ⁻ , —NH (R ₆ ) ₂ ⁺ · X ⁻ , —N (R ₆ ) ₃ ⁺ · X ⁻ (R ₆ has 1 to 3 represents an alkyl group (for example, a methyl group, an ethyl group, a 2-hydroxyethyl group, an n-propyl group, an iso-propyl group, etc.), and is preferably a methyl group or a 2-hydroxyethyl group, where X is a counter anion. Preferably halogen ions (fluorine ions, chlorine ions, bromine ions, etc.), complex inorganic anions (hydroxide ions, sulfate ions, nitrate ions, phosphate ions, etc.) and organic compound anions (oxalate ions, formate ions, acetic acid) Ion, propionate ion, methanesulfonate ion, p-toluenesulfonate ion, etc.), and particularly preferred are chloride ion, sulfate ion, nitrate ion and acetate ion.

R ₂ is a monovalent group selected from the group defined by R ₁ or the group defined by -LZ, and when selected from the definition range of R ₁ , it is present in the same molecule. It may be the same structure as R ₁ or a different structure. Even when selected from the definition range of -LZ, the structure may be the same as or different from -LZ existing in the same molecule. R ₂ is particularly preferably selected from the definition range of R ₁ . Further, the total number of carbon atoms of R ₁ and R ₂ is preferably 6 or more and 80 or less, and particularly preferably 8 or more and 50 or less.

  Specific examples of the surface active compound are illustrated below, but are not limited to these specific examples.

  The honeycomb-shaped porous film of the present invention forms a film material layer composed of a film material solution containing at least a phosphate ester-based surfactant represented by the above general formula (I) and a hydrophobic organic solvent, Air holes formed by blowing a gas having a relative humidity of 50 to 95% to the film material layer, volatilizing the hydrophobic organic solvent, generating condensation on the surface of the film material layer, and evaporating the condensation. That is, it is preferable to have pores formed by self-assembly.

  The method for manufacturing a honeycomb-shaped porous film of the present invention forms a film material layer comprising a film material solution containing at least a phosphate ester-based surfactant represented by the general formula (I) and a hydrophobic organic solvent. The film material layer is blown with a gas having a relative humidity of 50 to 95%, volatilizes the hydrophobic organic solvent, generates condensation on the surface of the film material layer, and evaporates the condensation to form pores. Including other processes appropriately selected as necessary.

  In the method for manufacturing the honeycomb-shaped porous film, when the organic solvent volatilizes, the water in the gas is condensed on the surface of the film material layer where the temperature is lowered due to the removal of latent heat to form fine droplets. Adhere to. The surface tension between water and the hydrophobic organic solvent is reduced by the action of the hydrophilic portion of the phosphate ester-based surfactant in the film material layer, aggregation of water droplets is prevented, and the organic solvent is volatilized. The droplets are transported and collected by the flow of the non-volatile organic solvent by filling from the surroundings, and are further closely packed by the transverse capillary force, and finally the water evaporates to form pores arranged in a honeycomb shape. Can be obtained.

Specifically, the holes are formed as shown in FIGS. 2A to 2D.
As shown in FIG. 2A, moisture (modeled) 43 in the gas 35 having a relative humidity of 50 to 95% is condensed on the film material layer 40 to form droplets 44. Then, as shown in FIG. 2B, the moisture 43 is condensed using the droplet 44 as a nucleus to grow the droplet 44. As shown in FIG. 2C, when the dry air 37 is blown to the film material layer 40, the hydrophobic organic solvent 42 is volatilized from the film material layer 40. At this time, water is volatilized also from the droplets 44, but the volatilization rate of the hydrophobic organic solvent 42 is faster. Therefore, the droplets 44 have a substantially uniform shape due to surface tension as the hydrophobic organic solvent 42 volatilizes. Further, when the drying proceeds, as shown in FIG. 2D, moisture evaporates from the droplets 44 of the film material layer 40 as water vapor 48. When the droplet 44 evaporates from the film material layer 40, the portion where the droplet 44 was formed becomes a hole 47, and the hole penetrated according to the thickness of the layer (a cross-sectional view is shown in FIG. 3A). Alternatively, a honeycomb-like porous film without pores (a cross-sectional view is shown in FIG. 3B) can be obtained.

  The thickness of the honeycomb-like porous film is preferably not less than the pore size and about 200 μm at the maximum. By increasing the polymer concentration in the film material solution, as shown in FIG. 3B, a thick layer without voids can be provided. In this case, the thickness of the thick layer without voids is preferably in the range of 1 to 500 μm.

  The film material solution is not particularly limited as long as it is a solution containing at least the phosphate ester surfactant represented by the general formula (I) and the hydrophobic organic solvent, and is appropriately selected depending on the purpose. And may contain a hydrophobic polymer and other components selected as appropriate.

As a compounding quantity of the said phosphate ester type surfactant, it is preferable that it is 0.005-30 mass% in the said film material solution, and it is more preferable that it is 0.01-10 mass%.
When the blending amount of the phosphoric ester surfactant is less than 0.005% by mass, the pore diameter may not be controlled to be small.

Here, in the present invention, the small pore diameter means that the pore diameter is 5 μm or less.
The pores are formed using a hexagonal close-packed structure of water droplets having a uniform particle size as a mold, so in an ideal honeycomb structure, the shape of the holes is a regular hexagon, but in practice the distance between the water droplets is long. As it becomes, it becomes circular. In the honeycomb-shaped porous film of the present invention, since the pores are often circular, the size of the pores is defined by the diameter of a circle formed on the film surface. The average pore diameter is an average value of the diameters of arbitrary 100 or more pores. On the other hand, when the hole is a regular hexagon, it is defined by the average of the longer diameter and the shorter diameter.

  The fact that the phosphate-based surfactant is contained in the honeycomb-shaped porous filter of the present invention is that the prepared honeycomb-shaped porous filter is dissolved in a suitable deuterated solvent, and 1H-NMR. This can be confirmed by measuring. Moreover, when it contains another polymer component, content ratio of this polymer component and the said phosphate ester-type surfactant can also be quantified.

<Hydrophobic polymer>
There is no restriction | limiting in particular as said hydrophobic polymer, According to the objective, it can select suitably from well-known things. A polymerizable (crosslinkable) polymer having a polymerizable group in the molecule is also preferred. For example, vinyl polymer (e.g., polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyhexafluoropropene, polyvinyl ether, polyvinyl carbazole, Polyvinyl acetate, polyvinyl carbazole, polytetrafluoroethylene, etc.), polyester (eg, polyethylene terephthalate, polyethylene naphthalate, polyethylene succinate, polybutylene succinate, polylactic acid, etc.), polylactone (eg, polycaprolactone, etc.), polyamide or polyimide (For example, nylon or polyamic acid), polyurethane, polyurea, polycarbonate, poly Matikkusu, polysulfone, polyether sulfone, polysiloxane derivatives, and the like.
From the viewpoints of solubility, optical physical properties, electrical physical properties, film strength, elasticity, etc., these may be homopolymers as necessary, or may take the form of copolymers or polymer blends. In addition, you may use these polymers as a mixture of 2 or more types of polymers as needed.

  The number average molecular weight (Mn) of the hydrophobic polymer is preferably 1,000 to 10,000,000, and more preferably 5,000 to 1,000,000.

The composition ratio of the hydrophobic polymer to the phosphate ester surfactant is preferably from 0 to 99.95, more preferably from 50 to 99.9, as mass% in the total solid content.

<Other ingredients>
As said other component, a polymerizable polyfunctional monomer (henceforth "polyfunctional monomer") can be mix | blended, for example.
As the polyfunctional monomer, polyfunctional (meth) acrylate is preferable from the viewpoint of reactivity. Examples of the polyfunctional (meth) acrylate include dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol caprolactone adduct hexaacrylate or a modified product thereof, epoxy acrylate oligomer, polyester acrylate oligomer, Urethane acrylate oligomer, N-vinyl-2-pyrrolidone, tripropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or a modified product thereof can be used. These polyfunctional monomers are used singly or in combination of two or more from the balance of scratch resistance and flexibility.

  It is also preferable to subject the honeycomb-shaped porous film produced using the film material solution containing the polyfunctional monomer to a curing treatment by a known method such as a heat curing method, an ultraviolet curing method, or an electron beam curing method.

  Polymerization of the monomer having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.

Examples of the radical photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyldione compounds, Examples include disulfide compounds, fluoroamine compounds, and aromatic sulfoniums.
Examples of the acetophenones include 2,2-ethoxyacetophenone, p-methylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and the like.
Examples of the benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Examples of the benzophenones include benzophenone, 2,4-chlorobenzophenone, 4,4-dichlorobenzophenone, p-chlorobenzophenone, and the like.
Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples of the radical photopolymerization initiator are also described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasawa, publisher; Technical Information Association, Inc., published in 1991).
Further, as a commercially available photocleavable photoradical polymerization initiator, Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals Co., Ltd. and the like are preferable examples.
The photopolymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the external photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone, and thioxanthone.

As said thermal radical initiator, an organic peroxide, an inorganic peroxide, an organic azo compound, an organic diazo compound, etc. can be used, for example.
Specific examples of the organic peroxide include benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, and butyl hydroperoxide. Examples of the inorganic peroxide include hydrogen peroxide, ammonium persulfate, and potassium persulfate. Examples of the azo compound include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), and the like. Examples of the diazo compound include diazoaminobenzene, p-nitrobenzenediazonium, and the like.

<Hydrophobic organic solvent>
Examples of the hydrophobic organic solvent include halogen-based organic solvents such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; water-insoluble such as methyl isobutyl ketone Ketones; ethers such as diethyl ether; carbon disulfide; and the like. These may be used singly or as a mixed solvent in which these solvents are combined.

  The polymer concentration in the film material solution is preferably 0 to 30% by mass, and more preferably 0.01 to 10% by mass. When the polymer concentration exceeds 30% by mass, it may be difficult to obtain a sufficient honeycomb structure.

(Honeycomb composite film)
The honeycomb composite membrane of the present invention has a temporary support that can be peeled off on at least one surface of the honeycomb-shaped porous film of the present invention.
By having the temporary support so as to be peelable, the honeycomb-like porous film that is thin and difficult to handle can be protected to improve the handleability, and the temporary support can be easily removed during use. .

Also, an embodiment having a release layer on at least one surface of the honeycomb-like porous film, and having a temporary support on the release layer, and having a release layer on both sides of the honeycomb-like porous film, An embodiment having temporary supports on both release layers is preferred.
Furthermore, it has a release layer on one side of the honeycomb-shaped porous film, a temporary support on the release layer, and a support on the side of the honeycomb-like porous film that does not have the release layer. Embodiments are preferred.
Examples of the honeycomb composite film of the present invention are shown in FIGS. 4B, 4C, and 5D.

  The honeycomb composite film shown in FIG. 4B is an aspect in which the release layer 2 is provided on one surface of the honeycomb-shaped porous film 12 and the temporary support 1 is provided on the release layer 2. The honeycomb-shaped porous film 12 of the present invention may be formed on the release layer 2 of the body 1, and the honeycomb-shaped film of the present invention formed on an arbitrary support 3 as shown in FIG. 4A. 12 may be formed by being peeled from the support 3 and bonded to the release layer 2 on the temporary support 1 having a release layer.

  The honeycomb composite membrane shown in FIG. 4C has a release layer on one side of the honeycomb-like porous film and a temporary support on the release layer, and does not have the release layer of the honeycomb-like porous film. For example, the temporary support may be formed without peeling the honeycomb film 12 of the present invention formed on the support 3 as shown in FIG. 4A from the support 3. 1 may be bonded to the release layer 2 on the substrate 1.

  The honeycomb composite film shown in FIG. 4D has a mode in which release layers are provided on both sides of the honeycomb-shaped porous film, and a temporary support is provided on both of the release layers. For example, the honeycomb composite film shown in FIG. A film formed by bonding the release layer 2 on the temporary support 1 having a release layer on the honeycomb-like porous film of the membrane.

<Peeling layer>
The release layer is preferably provided in order to improve the peelability between the honeycomb-shaped porous film and the temporary support, and more preferably, for example, is formed on the temporary support.
The release layer is not particularly limited as long as it can be peeled off without damaging the honeycomb-shaped porous film and the temporary support, and can be appropriately selected according to the purpose. Preferably it contains a mold.

The release agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, emulsion type, solvent type or solventless type silicone resin, fluororesin, aminoalkyd resin, polyester resin, wax, Etc. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as said other component, Although it can select suitably according to the objective, For example, an epoxy acrylate oligomer etc. are mentioned.

There is no restriction | limiting in particular as a formation method of the said peeling layer, According to the objective, it can select suitably, The peeling which contains the said mold release agent in the location (for example, on the said temporary support body) which forms this peeling layer. Examples thereof include a method of applying a layer forming solution.
The coating method is not particularly limited and may be appropriately selected depending on the purpose. For example, blade coating method, air knife coating method, gravure coating method, roll coating coating method, spray coating method, dip coating method, bar Examples thereof include a coating method, an extrusion coating method, and a spin coating method.
The adhesion amount of the release layer forming solution is preferably 0.4 to 3.0 g / m ² , more preferably 0.5 to 2.0 g / m ² in terms of solid content.

<Temporary support>
The temporary support is preferably a material that can protect the honeycomb-like porous film and improve handling properties, and can be easily removed at the time of use. For example, glass Inorganic materials such as metal and silicon wafers; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; polyamides, polyethers, polystyrenes, polyester amides, polycarbonates, polyphenylene sulfides, polyether esters, polyvinyl chloride, Examples thereof include organic materials having excellent organic solvent resistance such as polyacrylic acid ester, polymethacrylic acid ester, polyether ketone, and polyfluorinated ethylene; and liquids such as water, liquid paraffin, and liquid polyether.

  There is no restriction | limiting in particular as thickness of the said temporary support body, Although it can select suitably according to the objective, For example, 0.02-4.0 mm is preferable.

<Support>
The support is not particularly limited as long as the honeycomb porous film can be formed on the surface thereof, and can be appropriately selected according to the purpose. For example, the same material as the temporary support, a base material (for example, a glass substrate, an electrode material, etc.) that is made into a device by forming the honeycomb porous film on the surface, and the honeycomb porous film are manufactured. For example, a casting belt in a film manufacturing facility for performing the above-described process may be used.

<Honeycomb porous film>
The honeycomb-like porous film in the honeycomb composite film may be processed, and preferred embodiments include, for example, a stretched honeycomb-like porous film, a honeycomb-like porous film having a metal layer on the surface, Examples thereof include a honeycomb-like porous film in which pores are filled with a refractive index control material.

-Stretching-
As the stretching, for example, any one of uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, and triaxial stretching is preferable.
The method for stretching the honeycomb-shaped porous film is not particularly limited, and can be carried out using various stretching machines, for example, longitudinal uniaxial stretching for stretching in the mechanical flow direction, orthogonal to the mechanical flow direction. Tenter stretching that stretches in the direction of stretching can be suitably used.
There is no restriction | limiting in particular as a draw ratio in the said extending | stretching, According to the objective, it can select suitably, For example, when extending | stretching to one direction, it is about 1.05 to 12 times, Preferably it is 1.2 to 10 times In the case of biaxial stretching, the area magnification is 1.2 to 60 times, preferably 1.5 to 50 times.
By the stretching, elliptical or slit-like pores are formed in the honeycomb-like porous film, and in particular, pores that are open in the elliptical or slit-like shape are formed on the film surface. In this case, it is preferable that the holes are arranged in a straight line so that the wire grid function can be exhibited when a metal layer described later is formed.

-Metal layer-
A metal layer can be provided on the surface of the honeycomb-like porous film, and in particular, a metal layer is provided on the surface of the honeycomb-like porous film having pores opened in an elliptical shape or a slit shape by the stretching. Is preferred.
The metal in the metal layer is preferably at least one selected from gold, silver, copper, aluminum, iron, nickel, titanium, tungsten, chromium, and alloys thereof.

The method for forming the metal layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a plating method, a printing method, a sputtering method, a CVD method, a vacuum deposition method, and an electroforming method. Of these, vacuum deposition, plating, and electroforming are particularly preferable.
There is no restriction | limiting in particular as thickness of the said metal layer, According to the objective, it can select suitably. For example, in the case of a polarizing film in which a metal layer is formed on the honeycomb-shaped porous film, the thickness of the metal layer is preferably 50 to 1000 nm.

Moreover, it is preferable to have a metal layer in the void | hole of the said honeycomb-like porous film surface, and to have a wire grid function. That is, a structure approximated to a structure in which a large number of metal wires are arranged at equal intervals so as to be parallel to each other by arranging elliptical or slit-like holes in a straight line and having a metal layer in the holes. Can be formed.
Examples of the method for forming the metal layer in the pores on the surface of the honeycomb-shaped porous film include a method in which after the metal layer is formed on the film surface, the metal layer portion other than the pores is removed by etching.

-Refractive index control material-
The pores in the honeycomb-like porous film are preferably filled with a refractive index control material having a refractive index different from the refractive index of the film material from the viewpoint of exhibiting a retardation function.
The refractive index control material is not particularly limited as long as it is a material having a refractive index different from that of the film material constituting the honeycomb-shaped porous film, and can be appropriately selected according to the purpose. It may be any of a low refractive index material having a refractive index smaller than that of the film material, and (2) a high refractive index material having a refractive index higher than that of the film material. Particularly preferred.

  Here, the “refractive index” refers to the refractive index of each of the film material constituting the honeycomb-shaped porous film and the refractive index control material, and uses a commercially available Abbe refractometer. , ISO 489 (1999), or JIS 7142-1996 (plastic refractive index measurement method). The refractive index of the present invention is a value using D line (589 nm) as the wavelength of light. Further, the refractive index of existing polymer materials is known from various literatures, for example, J. Brandrup, EHImmergut, “Polymer Handbook”, 2nd edition, 1975 (John Wiley & Sons, Inc.) III-241- The description of 244 etc. can be referred to.

  The refractive index control material is not particularly limited as long as the material has a refractive index different from that of the film material film constituting the honeycomb-shaped porous film and can be filled in the pores. It can be appropriately selected depending on the case, and examples thereof include polymer materials, inorganic materials, and mixtures thereof. The polymer material is preferably a polymer that is dispersed or dissolved in a solvent such as water or an organic solvent, and the inorganic material is preferably a mixture of inorganic fine particles.

  Examples of the polymer used for the refractive index control material include vinyl polymers and condensation polymers (polyurethane, polyester, polyamide, polyurea, polycarbonate, polycarbodiimide, etc.).

  Examples of monomers that form the vinyl polymer include acids such as acrylic acid, 2-carboxyethyl acrylate, methacrylic acid, itaconic acid, maleic acid, acrylic esters and methacrylic esters (the ester group has a substituent). An ester group including an alkyl group or an aryl group which may have, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hexyl group 2-ethylhexyl group, tert-octyl group, 2-chloroethyl group, cyanoethyl group, 2-acetoxyethyl group, 2-hydroxyethyl group, tetrahydrofurfuryl group, 5-hydroxypentyl group, cyclohexyl group, benzyl group, hydroxyethyl Group, 3-methoxybutyl group, 2- (2-methoxy group) Toxi) ethyl group, 2,2,2-tetrafluoroethyl group, 1H, 1H, 2H, 2H-perfluorodecyl group, phenyl group, 2,4,5-tetramethylphenyl group, 4-chlorophenyl group, etc.) Is mentioned.

  Specific examples of the vinyl esters include aliphatic carboxylic acid vinyl esters which may have a substituent (for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate). , Vinyl chloroacetate, etc.), and optionally substituted aromatic carboxylic acid vinyl esters (for example, vinyl benzoate, vinyl 4-methylbenzoate, vinyl salicylate, etc.).

  Specific examples of the acrylamides include acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, N-monosubstituted acrylamide, and N-disubstituted acrylamide (the substituent is an alkyl group that may have a substituent, Aryl group, silyl group, for example, methyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, tert-octyl group, cyclohexyl group, benzyl group, hydroxymethyl group, alkoxymethyl group, Phenyl group, 2,4,5-tetramethylphenyl group, 4-chlorophenyl group, trimethylsilyl, etc.).

  Specific examples of the methacrylamides include methacrylamide, N-monosubstituted methacrylamide, N-disubstituted methacrylamide (the substituent is an alkyl group, aryl group, or silyl group which may have a substituent). For example, methyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, tert-octyl group, cyclohexyl group, benzyl group, hydroxymethyl group, alkoxymethyl group, phenyl group, 2,4, 5-tetramethylphenyl group, 4-chlorophenyl group, trimethylsilyl, etc.).

  Examples of the olefins include ethylene, propylene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, and butadiene. Examples of the styrenes include styrene, methyl styrene, isopropyl styrene, methoxy styrene, acetoxy styrene, chlorostyrene, and the like. Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the other monomers include vinyl sulfonic acid, crotonic acid ester, itaconic acid ester, maleic acid diester, fumaric acid diester, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, and N-vinyl. Examples include pyrrolidone, vinylidene chloride, methylenemalonnitrile, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2-methacryloyloxyethyl phosphate, etc. It is done.

The polyurethane is basically obtained by a polyaddition reaction using a diol compound and a diisocyanate compound as raw materials.
Specific examples of the diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 2,2- Dimethyl-1,3-propanediol, 1,4-pentanediol, 2,4-pentanediol, 3,3-dimethyl-1,2-butanediol, 2-ethyl-2-methyl-1,3-propanediol 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol, 2,4-dimethyl-2,4-pentane Diol, 2-methyl-2-propyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexa Diol, 1,2-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol (average Molecular weight = 200,300,400,600,1000,1500,4000), polypropylene glycol (average molecular weight = 200,400,1000), polyester polyol, 2,2-bis (4-hydroxyphenyl) propane, 4,4 ′ -Dihydroxyphenylsulfone, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butanoic acid and the like can be mentioned.

  Preferable specific examples of the diisocyanate include ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-toluene diisocyanate, 1,3-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m- Examples thereof include phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3′-dimethylbiphenylene diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexylisocyanate).

The polyester is basically obtained by dehydration condensation of a diol compound and a dicarboxylic acid compound.
Specific examples of the dicarboxylic acid compound include oxalic acid, malonic acid, succinic acid, glutaric acid, dimethylmalonic acid, adipic acid, pimelic acid, α, α-dimethylsuccinic acid, acetone dicarboxylic acid, sebacic acid, 1 , 9-nonanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-butyl terephthalic acid, tetrachloroterephthalic acid, acetylenedicarboxylic acid, poly (ethylene terephthalate) dicarboxylic acid 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, ω-poly (ethylene oxide) dicarboxylic acid, p-xylylene dicarboxylic acid, and the like.
These compounds may be used in the form of an alkyl ester of a dicarboxylic acid (for example, dimethyl ester) or an acid chloride of a dicarboxylic acid when performing a polycondensation reaction with a diol compound, or maleic anhydride or succinic anhydride. Alternatively, it may be used in the form of an acid anhydride such as phthalic anhydride.

As the diol compound, a compound selected from the same group as the diols described in the polyurethane can be used.
A typical method for synthesizing the polyester is a condensation reaction of the above diol compound and a dicarboxylic acid or a derivative thereof, but by condensing a hydroxycarboxylic acid such as hydroxycarboxylic acid (for example, lactic acid, 12-hydroxystearic acid). Obtainable.

The polyamide can be obtained by polycondensation of a diamine compound and a dicarboxylic acid compound, polycondensation of an aminocarboxylic acid compound, or ring-opening polymerization of lactams.
Examples of the diamine compound include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine, octamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, piperazine, 2 , 5-dimethylpiperazine, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, xylylenediamine and the like.
Examples of the aminocarboxylic acid include glycine, alanine, phenylalanine, ω-aminohexanoic acid, ω-aminodecanoic acid, ω-aminoundecanoic acid, and anthranilic acid. Examples of monomers that can be used for ring-opening polymerization include ε-caprolactam, azetidinone, and pyrrolidone.
As said dicarboxylic acid compound, the compound chosen from the same group as dicarboxylic acids demonstrated in the said polyester can be used.

  The polyurea can be basically obtained by polyaddition of a diamine compound and a diisocyanate compound or a deammonia reaction of a diamine compound and urea. The diamine compound as a raw material is the diamine described in the above polyamide, and the diisocyanate compound is in the above polyurethane. Compounds selected from the same group as the described diisocyanates can be used.

  The polycarbonate can be basically obtained by reacting a diol compound with phosgene or a carbonic acid ester derivative (for example, an aromatic ester such as diphenyl carbonate). Compounds from the same group can be used.

  The polycarbodiimide can be basically obtained by a condensation reaction of a diisocyanate compound, and the diisocyanate compound as a raw material can be a compound selected from the same group as the diisocyanates described in the polyurethane.

  Hereinafter, the polymer suitable for the refractive index control material and the refractive index value of the polymer will be shown, but the refractive index control material filled in the pores of the honeycomb-shaped porous film of the present invention is limited to these. It is not a thing. In addition, the refractive index value shown in a parenthesis is a value of solid content of each polymer.

  Polymers suitable as the refractive index control material include polytetrafluoroethylene (1.35), polytrifluoroethyl acrylate (1.407), polytrifluoroethyl methacrylate (1.437), poly t-butyl methacrylate ( 1.4638), poly-4-methylpentene (1.466), polyvinyl acetate (1.4665), polyethyl acrylate (1.4685), polymethyl methacrylate (1.4893), polycyclohexyl methacrylate (1. 5066), polyethylene (1.51), polyacrylonitrile (1.52), polymethacrylonitrile (1.52), nylon 6 (1.53), styrene-butadiene (25/75) copolymer (1. 535), polybenzyl methacrylate (1.5680), polyphenyl methacrylate Tacrylate (1.5706), polydiallyl phthalate (1.572), polyethylene terephthalate (1.576), polyvinyl benzoate (1.5775), polystyrene (1.59 to 1.592 (depending on the three-dimensional structure of the polymer) )), Poly N-benzylmethacrylamide (1.5965), poly o-chlorostyrene (1.6098), polyvinyl chloride (1.63), polysulfone (1.63), polyvinyl naphthalene (1.682), Polyvinyl carbazole (1.683), polypentabromophenyl methacrylate (1.71), etc. are mentioned.

  The inorganic material suitable as the refractive index control material is not particularly limited, and a conventionally known material can be appropriately selected according to the purpose. For example, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, oxide Zirconium, silicon oxide, tin oxide, magnesium carbonate, magnesium hydroxide, calcium carbonate, calcium sulfide, iron oxide, strontium carbonate, barium sulfate, calcium sulfate, aluminum hydroxide, silver iodide, aluminum silicate, calcium silicate, magnesium silicate, Examples thereof include colloidal silica, colloidal alumina, alumina, zeolite, kaolin, talc, clay, diatomaceous earth, satin white, and diatomaceous earth. Among these, metal oxides and metal sulfides are more preferable.

  Although the said inorganic material may be used independently and may be used as a mixture with the said polymer, when the physical characteristic of a film | membrane and the extending process performed later are taken into consideration, it is preferable to use as a mixture with the said polymer. In this case, the inorganic material is preferably used as inorganic fine particles mixed with the polymer.

  The refractive index control material preferably has a polymerizable group in the molecule. Further, a polymerizable polyfunctional monomer is blended together with the refractive index control material, and after filling the blend into the pores of the honeycomb film, a known method such as a thermosetting method, an ultraviolet curing method, an electron beam curing method or the like is used. It is also preferable to perform a curing treatment by a method. Preferred polyfunctional monomers used in combination with the refractive index control material are the same as those mentioned in the description of the hydrophobic polymer. Preferred photoradical initiators or thermal radical initiators are also the same as those mentioned in the description of the hydrophobic polymer.

The inorganic material is preferably filled in the pores together with a polymerizable polymer material and a polyfunctional monomer. At this time, it is also preferable to surface-treat the inorganic material in advance with a polymerizable surface modifier.
The method of filling the refractive index control material into the pores is not particularly limited and can be appropriately selected depending on the purpose.For example, a method of filling the refractive index control material in a molten state into the pores, Examples thereof include a method of filling pores with a solution prepared with a solvent that does not dissolve the honeycomb-like porous film, a method of polymerizing by heating or light irradiation after filling the pores with a monomer.

(Manufacturing method of honeycomb composite film)
The method for manufacturing a honeycomb composite film of the present invention includes a release layer forming step and a honeycomb porous film manufacturing step, and if necessary, a bonding step, a stretching step, a metal layer forming step, and other steps. Comprising.
Specifically, (1) a release layer forming step of forming a release layer on the temporary support, a honeycomb porous film preparation step of manufacturing the honeycomb porous film on the support, and the temporary support A first embodiment comprising at least a laminating step of laminating the release layer and the honeycomb porous film; and (2) a release layer forming step of forming a release layer on a temporary support, and a honeycomb. A second embodiment including at least a honeycomb-like porous film production step of producing a porous porous film on the release layer on the temporary support.

-Release layer formation process-
The release layer forming step is a step of forming a release layer on the temporary support.
There is no restriction | limiting in particular as a formation method of the said peeling layer, According to the objective, it can select suitably, For example, the method of apply | coating the coating liquid for peeling layers on the said temporary support body etc. are mentioned.

-Honeycomb porous film production process-
The film production step forms the film material layer using the film material solution containing at least the phosphate ester surfactant and the hydrophobic organic solvent, and the relative humidity of the film material layer is 50 to 95. % Of the gas, volatilizes the hydrophobic organic solvent, generates condensation on the surface of the film material layer, and evaporates the condensation to produce a honeycomb porous film having pores. .

  The film material layer can be formed by casting the film material solution on the support or the temporary support, and the casting method is not particularly limited and is appropriately selected depending on the purpose. Examples thereof include a slide method, an extrusion method, a bar method, and a gravure method.

As an environment for forming the pores and forming the film material layer as a honeycomb-like porous film, the relative humidity is preferably in the range of 50 to 95%, and the film material layer has a relative humidity of 50 to 95%. It is preferable to blow gas.
If the relative humidity is less than 50%, water condensation on the solvent surface may be insufficient, and if it exceeds 95%, it may be difficult to control the environment and maintain uniform film formation. is there.

The gas blown to the film material layer is preferably a steady air with a constant air volume, and the wind speed is preferably 0.1 to 20 m / s.
If the wind speed is less than 0.1 m / s, it may be difficult to control the environment, and if it exceeds 20 m / s, the solvent surface may be disturbed and a uniform film may be difficult to obtain.

  In addition, the direction of blowing the gas may be any direction as long as it is in the range of 0 to 90 ° with respect to the film material layer surface, but in order to increase the uniformity of the formed holes. Is preferably 0 to 60 °.

  As the gas, for example, in addition to air, an inert gas such as nitrogen gas or argon gas can be used, but it is preferable to perform dust removal treatment such as passing through a filter in advance. Since dust in the atmosphere acts as a condensation nucleus of water vapor and affects film formation, it is preferable to install a dust removal facility or the like at the manufacturing site.

  The environment in which the film is formed is preferably strictly controlled by using a commercially available constant dew point humidity generator or the like. The air volume is preferably controlled with a blower or the like, and it is preferable to use a closed space in order to prevent the influence of outside air. In addition, it is preferable to set a gas introduction / extraction path and a film formation environment so that the gas is replaced by a laminar flow. Furthermore, it is preferable to monitor the temperature, humidity, flow rate and the like with a measuring instrument in order to control the film formation quality. In order to control the hole diameter and film thickness with high accuracy, it is essential to strictly manage these parameters (especially humidity and flow rate).

-Stretching process-
The stretching step is a step of stretching the honeycomb-shaped porous film to form elliptical or slit-like pores.
The stretching is preferably any one of uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, and triaxial stretching.
Moreover, you may implement the said extending | stretching in any direction of a vertical direction and a horizontal direction. The stretching in the machine direction can be achieved by using one or more sets of nip rolls and increasing the transport speed on the outlet side from the transport speed on the inlet side. On the other hand, when stretching in the lateral direction, it can be achieved by a method of gripping both ends with a chuck and expanding it in the width direction (tenter stretching). Stretching may be carried out by these methods alone, or a combination of these methods.

-Metal layer formation process-
The metal layer forming step is a step of forming a metal layer on the surface of the honeycomb-like porous film. Examples of the method for forming the metal layer include a plating method, a printing method, a sputtering method, a CVD method, a vacuum deposition method, and an electroforming method. Among these, a vacuum deposition method, a plating method, and an electroforming method are particularly preferable. .
Examples of the plating method include an electrolytic plating method and an electroless plating method.
As the electroless plating method, a method using an oxidation-reduction reaction, a method using a substitution reaction, or the like can be used. For example, a method of plating gold, silver, copper, nickel, palladium, or the like by the metal ions to be plated exhibiting an autocatalytic reduction reaction in an electroless plating solution, a method using a silver mirror reaction, or the like is used. be able to.
The electroforming means production or reproduction of a metal product by electroplating.

-Bonding process-
In the first aspect, the bonding step is a step of bonding the honeycomb-shaped porous film produced on the support and the release layer on the temporary support. There is no restriction | limiting in particular as a method to bond, According to the objective, it can select suitably from a well-known method.
The bonding step yields the honeycomb composite membrane having the structure shown in FIG. 4C, and after the pasting step, the honeycomb composite membrane having the structure shown in FIG. 4B is obtained by peeling from the support. You can also.

(Honeycomb porous film manufacturing equipment, honeycomb composite film manufacturing equipment)
5 to 10 show schematic views of a film production facility suitable for producing the honeycomb-shaped porous film and the honeycomb composite film of the present invention.

  In the film manufacturing apparatus 20 shown in FIG. 5, a film material solution 21 is placed in a tank 22. The tank 22 is provided with a stirring blade 23, and the film material solution 21 is uniformly mixed by rotating the stirring blade 23. The film material solution 21 is sent to the casting die 25 by the pump 24. The casting die 25 is provided on the casting belt 26. Further, the casting belt 26 is stretched around rotating rollers 27 and 28. The rotation belts 27 and 28 are rotated by a driving device (not shown), so that the casting belt 26 travels endlessly. Further, a temperature controller 29 is attached to the rotary rollers 27 and 28. The temperature of the casting belt 26 can be adjusted by adjusting the temperature of the rotating rollers 27 and 28. Further, when the honeycomb-like porous film 40 formed on the casting belt 26 is peeled off, a peeling roller 30 that supports the honeycomb-like porous film 40 and a winder that winds the honeycomb-like porous film 40 31 is also provided.

The honeycomb porous film production process will be described with reference to FIGS. 2A to 2D.
As shown in FIG. 2A, the film material solution 21 is cast (cast) on the casting belt (support) 26 from the casting die 25 to form the film material layer 40. The surface temperature of the film material layer 40 (hereinafter sometimes referred to as “film surface temperature”) is TL (° C.). In the present invention, the film surface temperature TL is preferably 0 ° C. or higher. If the film surface temperature TL is less than 0 ° C., the droplets in the film material layer 40 may solidify and a desired hole may not be formed.

  In the film production apparatus 20 shown in FIG. 5, the casting chamber in which casting is performed is partitioned into a condensation zone 32 and a drying zone 33. The condensation zone 32 is provided with a blower 34. An air 35 adjusted for condensation is blown from the blower 34 to the film material layer 40 on the casting belt 26. As shown in FIG. 5, the blower 34 is preferably composed of a plurality of blower units composed of blower ports 34a, 34c, 34e and suction ports 34b, 34d, 34f. Thereby, it becomes easy to adjust the dew condensation conditions of the film material layer 40. Note that FIG. 5 shows a structure composed of three units, but the present invention is not limited to the illustrated form.

  A dryer 36 is provided in the drying zone 33. Drying air 37 is blown from the dryer 36 to the film material layer 40. As shown in FIG. 5, the dryer 36 is preferably composed of a plurality of air blowing units each consisting of air blowing ports 36a, 36c, 36e, 36g and suction ports 36b, 36d, 36f, 36h. Thereby, it becomes easy to adjust the drying conditions of the film material layer 40. Note that FIG. 5 illustrates a configuration including four units, but the present invention is not limited to the illustrated form.

  It is more preferable to adjust the temperature of the casting belt 26 through the rotary rollers 27 and 28 using the temperature controller 29. Examples of the method for adjusting the temperature include a method in which a liquid flow path is provided inside the rotary rollers 27 and 28 and the heat transfer medium is fed into the liquid flow path for adjustment. In adjusting the temperature, it is preferable that the lower limit value is 0 ° C. or higher. Moreover, it is preferable to make it an upper limit into the solvent boiling point or less of the film material solution 21, More preferably, it is set as (solvent boiling point-3 degreeC). Accordingly, the condensed moisture does not solidify, and the solvent of the film material solution 21 is suppressed from being rapidly evaporated, so that the honeycomb structure film 12 having an excellent shape can be obtained. Furthermore, in the temperature adjustment, the temperature distribution is within ± 3 ° C. across the width direction of the film material layer 40, so that the film surface temperature distribution is also within ± 3 ° C. By reducing the temperature distribution in the width direction of the film material layer 40, it is possible to suppress the formation of anisotropy in the formation of pores in the honeycomb structure film 12, so that the commercial value is improved.

  Further, it is preferable that the conveying direction of the casting belt 26 is within ± 10 ° with respect to the horizontal direction. The form of the droplet 44 can be adjusted by adjusting the transport direction. By adjusting the form of the droplet 44, the form of the holes can be adjusted.

  Wind 35 is blown from the blower 34. The dew point TD1 (° C.) of the wind 35 is preferably 0 ° C. ≦ (TD1-TL) ° C. with respect to the surface temperature TL (° C.) of the film material layer 40 passing through the condensation zone 32, and 0 ° C. ≦ (TD1-TL) More preferably, the temperature is more preferably from 5 ° C. to 60 ° C., particularly preferably from 10 ° C. to 40 ° C. When the (TD1-TL) ° C. is less than 0 ° C., condensation may be difficult to occur, and when it exceeds 80 ° C., condensation and drying become steep, and it is difficult to control the pore size and make it uniform. May be. Further, the temperature of the wind 35 is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 5 ° C. or higher and 100 ° C. or lower. When the temperature of the wind is less than 5 ° C., the liquid, particularly water, hardly evaporates and the honeycomb structure film 12 having a good shape may not be obtained. Moreover, when it exceeds 100 degreeC, before the droplet 44 arises in the film material layer 40, there exists a possibility of volatilizing as water vapor | steam.

As shown in FIG. 2A, moisture (modeled) 43 in the wind 35 in the condensation zone 32 is condensed on the film material layer 40 into droplets 44. Then, as shown in FIG. 2B, the moisture 43 is condensed using the droplet 44 as a nucleus to grow the droplet 44. As shown in FIG. 2C, when the drying air 37 is blown to the film material layer 40 in the drying zone 33, the organic solvent 42 is volatilized from the film material layer 40. At this time, water is volatilized also from the droplets 44, but the volatilization rate of the organic solvent 42 is faster. Therefore, the droplets 44 have a substantially uniform shape due to surface tension as the organic solvent 42 volatilizes. Further, as the drying proceeds, moisture evaporates as water vapor 48 from the droplets 44 of the film material layer 40 as shown in FIG. 2D. When the droplets 44 evaporate from the film material layer 40, the portions where the droplets 44 were formed become holes 47, and the honeycomb-shaped porous film 12 as shown in FIG. 3A or FIG. 3B is obtained.
In the present invention, the form of the honeycomb-shaped porous film 12 is not particularly limited. Specifically, the distance L2 between the adjacent holes 47 shown in FIG. 3C is 0.05 μm or more and 100 μm at the center-to-center distance. The following can be controlled.

  The blowing direction of the wind 35 is parallel to the moving direction of the film material layer 40 (cocurrent flow). When the wind is blown as a countercurrent, the film surface of the film material layer 40 may be disturbed, and the growth of droplets may be hindered. Moreover, as for the blowing speed of the wind 35, the relative speed with the moving speed of the film material layer 40 is preferably 0.1 m / s or more and 20 m / s or less, more preferably 0.5 m / s or more and 15 m / s or less, and 2 m / s. More preferably, it is s or more and 10 m / s or less. If the blowing speed is less than 0.1 m / s, the film material layer 40 may be conveyed to the drying zone 33 without the droplets 44 growing sufficiently in the film material layer 40. Moreover, when it exceeds 20 m / s, there exists a possibility that disorder may arise in the film material layer 40 surface, or condensation may not fully advance.

  The time for the film material layer 40 to pass through the condensation zone 32 is preferably 0.1 seconds or more and 100 seconds or less. If the passage time is less than 0.1 seconds, it may be difficult to form a desired hole because the droplets 44 are formed without being sufficiently grown. There is a possibility that a film having honeycomb-like pores cannot be obtained because the size becomes too large.

  The blowing speed of the drying air 37 for drying the film material layer 40 in the drying zone 33 is preferably 0.1 m / s or more and 20 m / s or more, more preferably 0.5 m / s or more and 15 m / s or less, and 2 m / s or more. 10 m / s or less is still more preferable. If the blowing speed is less than 0.1 m / s, the evaporation of moisture from the droplets 44 may not proceed sufficiently, and the productivity may be inferior. If it exceeds 20 m / s, the droplets 44 are inferior. As a result, the evaporation of moisture suddenly occurs and the shape of the formed hole 37 may be disturbed.

  When the dew point of the drying air 37 is TD2 (° C.), the relationship with the film surface temperature TL (° C.) is preferably (TL−TD2) ° C. ≧ 1 ° C. As a result, the growth of the droplet 44 of the film material layer 40 is stopped in the drying zone 33, and the water constituting the droplet can be volatilized as the water vapor 48.

  The air blowing from the blowers 34 and 37 can be dried by a reduced pressure drying method in addition to the method of blowing air with a 2D nozzle. By performing drying under reduced pressure, it is possible to adjust the evaporation rate of the organic solvent 42 and the moisture 43 of the droplets 44. By adjusting this, a droplet 44 is formed in the film material layer 40, the droplet 44 is evaporated while the organic solvent 42 is evaporated, and a hole 47 is formed at a position where the droplet is provided. The size and shape of the holes in the invention can be changed.

  Also, a method of drying by a reduced pressure drying method, or a condenser cooled from the membrane surface and having a groove on the surface at a position about 3 to 20 mm away from the membrane surface, water vapor (volatile organic solvent is also on the surface of the condenser) In addition, a method of condensing and drying can also be applied. By applying any one of the drying methods, the film material layer 40 can be dried with less dynamic influence on the film surface, so that a smoother film surface can be obtained.

  Further, by using a plurality of blower units of the blower 34 and the dryer 36 or by dividing the blower unit into a plurality of zones, different dew point conditions can be set or different drying temperature conditions can be set. By selecting these conditions, it is possible to improve the dimensional controllability of the holes 47 and the hole uniformity. The number of blower units and zones is not particularly limited, but an optimal combination is determined in terms of film quality and equipment cost.

  The relationship between the film surface temperature TL (° C.) and the dew point temperature TDn (° C.) of the condensation zone or drying zone (n means the n zone number) shall be 0 ° C. ≦ | TDn−TL | ° C. ≦ 80 ° C. Is preferred. By setting the difference to 80 ° C. or less, rapid volatilization of at least one of the organic solvent and moisture can be suppressed, and the honeycomb-shaped porous film 12 having a desired form can be obtained. In addition, when impurities are mixed in the film material layer 40, the formation of the honeycomb structure is hindered. Therefore, it is preferable that the dust levels of the air outlets 34a, 34c, 34e, 36a, 36c, 36e, and 36g be class 1000 or less. Therefore, it is preferable to attach an air conditioner 39 to the housing 38 in which the blower 34 and the dryer 36 are installed, thereby performing air conditioning in the housing 38. Thereby, the possibility that impurities are mixed into the film material layer 40 is reduced, and a good honeycomb porous film 12 can be obtained.

The dried honeycomb-like porous film 12 is peeled off from the casting belt 26 while being supported by the peeling roller 30, and taken up by the winder 32. In addition, the conveyance speed of the honeycomb-like porous film 12 is not particularly limited, but is preferably 0.1 m / min or more and 60 m / min or less. If the conveyance speed is less than 0.1 m / min, the productivity is inferior and the cost is not preferable. On the other hand, if it exceeds 60 m / min, excessive tension is applied to the honeycomb-shaped porous film when it is transported, causing defects such as a honeycomb structure disorder. The honeycomb porous film 12 can be continuously manufactured by the above method.
The obtained honeycomb-like porous film is stretched by a stretching process to form elliptical or slit-like pores.
Moreover, a metal layer can also be formed on the film surface as needed.

  FIG. 6 shows a film manufacturing facility 60 suitable for manufacturing a honeycomb-shaped porous film according to the present invention. A film 62 as a support is conveyed from the delivery device 61. The film 62 is conveyed while being wound around the backup roller 63. A slide coater 64 is provided facing the backup roller 63. The slide coater 64 is provided with a decompression chamber 65. The film material solution 67 sent from the film material solution supply device 66 by the liquid feed pump is pushed out from the slide coater 64 and applied onto the film 62 to form a film material layer 68.

  The slide coater 64 is excellent in uniform coating property in the transport direction of the film 62 and can form the film material layer 68 at a high speed. Even when the surface of the film 62 is uneven, the film 62 is smoothed when it is wound around the backup roller 63, so that it has excellent uniform coating properties. Furthermore, since the coating is performed in a non-contact manner on the film 62, uniform coating is possible without damaging the surface of the film 62.

The film material layer 68 formed on the film 62 is subjected to the condensation drying process shown in FIGS. 2A to 2D by the wind 70 of the blower 69. After passing through the condensation drying step, the obtained honeycomb porous film 71 is wound around a winding roll 72. Further, the film 62 is also taken up by the take-up roll 73. The transport direction of the film 62 on which the film material layer 68 is formed is preferably within ± 10 ° with respect to the horizontal direction. It is more preferable to use a film 62 made of a material that easily absorbs the organic solvent of the film material solution 66. These materials are not particularly limited as long as they absorb an organic solvent, and can be appropriately selected according to the purpose. For example, when methyl acetate is used as the main solvent of the film material solution 67, it is preferable to use cellulose acylate as the material of the film 62.
In addition, by winding the film 62 as the support as one of the support, the temporary support, and the temporary support on which the release layer is formed, as a film integral with the honeycomb porous film 71, A honeycomb composite film can also be manufactured.

  FIG. 7 shows a film manufacturing facility 80 according to another embodiment used in the method for manufacturing a honeycomb-shaped porous film according to the present invention. In addition, description of the same location as the film manufacturing equipment 60 shown in FIG. A film 82 serving as a support is conveyed from the delivery machine 81. The film 82 is conveyed while being wound around the backup roller 83. A multi-layer slide coater 84 is provided opposite to the backup roller 83. The multilayer slide coater 84 is provided with a decompression chamber 85. A film material solution 87 sent from a film material solution supply device 86 by a liquid feed pump is pushed out from a multilayer slide coater 84 and applied onto a film 82 as a support to form a film material layer 88. . The film material layer 88 formed on the film 82 is subjected to the condensation drying process 11 by the wind 90 of the blower 89. After passing through the condensation drying step 11, the honeycomb-shaped porous film 91 is wound around a winding roll 92. Further, the film 82 is also taken up by the take-up roll 93.

By casting (coating) the multilayer film material solution 87 on the film 82, it is possible to change the form, physical properties, and the like in the thickness direction of the honeycomb-shaped porous film 91.
In addition, by winding the film 82 as a support as a film integral with the honeycomb-shaped porous film 91 as any one of the support, the temporary support, and the temporary support with the release layer formed, A honeycomb composite film can also be manufactured.

  In FIG. 8, the film manufacturing equipment 100 of other embodiment used for the manufacturing method of the film which concerns on this invention is shown. In addition, description of the same location as the film manufacturing equipment 60 shown in FIG. 6 is abbreviate | omitted. A film 102 serving as a support is conveyed from the delivery machine 101. The film 102 is conveyed while being wound around the backup roller 103. An extrusion coater 104 is provided facing the backup roller 103. The extrusion coater 104 is provided with a decompression chamber 105. A film material solution 107 sent from the film material solution supply device 106 by a liquid feed pump is pushed out from the extrusion coater 104 and applied onto the film 102 as a support to form a film material layer 108. . The film material layer 108 formed on the film 102 is subjected to a condensation drying process by the wind 110 of the blower 109. After passing through the condensation drying step, the honeycomb-shaped porous film 111 is wound on the winding roll 112. Further, the film 102 is also taken up by the take-up roll 113.

  FIG. 9 shows and describes a film manufacturing facility 120 for manufacturing a honeycomb-shaped porous film according to the present invention. The film material solution 122 is applied to the film 123 using a wire bar applicator 121. The wire bar 124 that rotates in the moving direction of the film 123 that moves at a constant speed pulls the film material solution 122 from the primary-side film material solution tank 125 to the liquid storage portion 126 by the rotation. The film material solution 122 in the liquid storage portion 126 comes into contact with the film 123 via the wire bar 124, thereby forming a film material layer 127 having a uniform thickness. The film-like material layer 127 is subjected to the condensation drying step by the wind 129 of the blower 128, whereby the honeycomb-like porous film 130 can be obtained. In the manufacturing method of the honeycomb-shaped porous film 130 using the wire bar 124, the liquid storage portion 126 prevents air from entering the contact portion between the film material solution 122 and the film 123, so that bubbles are generated in the film material layer 127. There is an advantage that mixing is difficult.

  In addition, by winding the film 102 as a support as one of the support, the temporary support, and the temporary support formed with a release layer as a film integral with the honeycomb-shaped porous film 130, A honeycomb composite film can also be manufactured.

  FIG. 10 shows a manufacturing facility 140 for manufacturing a honeycomb composite film according to the present invention. A film 141 as one of the support, the temporary support, and the temporary support on which the release layer is formed is conveyed while being wound around the impression cylinder 142. A plate cylinder 143 is disposed opposite the impression cylinder 142. A desired pattern is formed on the surface of the plate cylinder 143. The film material solution 145 stored in the film material solution tank 144 is accumulated in the recess as the plate cylinder 143 rotates. Excess film material solution 145 is scraped off by doctor blade 146. Thereafter, the film material solution 145 is applied on the film 141 that is wound around the impression cylinder 142 and the film material layer 147 is formed.

  The condensation drying process of the film material layer 147 is performed by the blower 148. The wind 149 blown from the blower 148 is a parallel flow in the same direction as the transport direction of the film 141. As for the film material layer 147, the honeycomb-like porous film 150 is formed through the condensation drying process. The film 141 becomes the honeycomb composite film 151 in which the honeycomb porous film 150 is formed in a desired pattern.

  The honeycomb composite film of the present invention obtained according to the method for manufacturing a honeycomb composite film of the present invention may be used as it is by manufacturing it on the release layer provided on the desired temporary support from the beginning, or ethanol or the like. After immersing in an appropriate solvent, the substrate may be peeled off from the support at the time of production and then used on a desired substrate. In the case of use after peeling, an adhesive such as an epoxy resin or a silane coupling agent suitable for the material and the material of the desired substrate may be used for the purpose of improving the adhesion to a new substrate.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
-Production of temporary support with release layer-
As the temporary support, on one side of a polyethylene terephthalate film having a thickness of 200 μm, 100 parts by mass of silicone resin A (SRX-211, manufactured by Toray Silicone Co., Ltd.) and silicone resin B (Toray Silicone) are used as the release layer forming solution. Co., Ltd., SRX-212) A 3% by weight toluene solution of a mixed resin with 0.6 parts by mass is applied with a wire coater so that the thickness after drying is 1 μm, and dried at 120 ° C. for 2 minutes. Thereby, the temporary support body with a peeling layer was produced.

−Preparation of honeycomb-shaped porous film−
As a film material solution, a methylene chloride solution (polymer) in which polystyrene having a weight average molecular weight of 45,000 and a phosphate ester-based surfactant represented by the following formula (PW-6) are mixed at a mass ratio of 10: 1. 0.5 mL) was prepared as a concentration of 0.4% by mass.

Next, in a closed space that is not affected by outside air, the film material solution is fully developed on a glass substrate for HDD kept at 2 ° C. to form a film material layer, and constant humidity air with a relative humidity of 70% is applied every time. A honeycomb-like porous structure in which pores are uniformly formed by spraying from the direction of 45 ° with respect to the film material layer surface (substrate surface) at a steady flow rate of 2 liters, volatilizing methylene chloride, and evaporating condensation. A quality film was obtained.
The constant humidity air is obtained by connecting a humidity generator manufactured by Yamato Scientific Co., Ltd. to a compressor SC-820 manufactured by Hitachi Koki Co., Ltd., which has a commercially available dust removal air filter (filtration degree: 0.3 μm). Supplied. Moreover, it was 0.3 m / s when the flow velocity of the air of a spraying part was measured.

-Fabrication of honeycomb composite film-
The release layer side surface of the temporary support with release layer is bonded to the honeycomb porous film surface, the honeycomb porous film is peeled off from the HDD glass substrate, and the honeycomb composite as shown in FIG. 4B is obtained. Membrane HC-1 was obtained.
With respect to the honeycomb porous film in the obtained honeycomb composite membrane HC-1, the average pore diameter was measured by the following method. The results are shown in Table 1.

<Average pore size and particle size distribution>
The pores were observed at 1250 times using an optical microscope at any five locations in the center of the honeycomb composite film, and the average pore diameter of the pores was determined.

(Example 2)
In Example 1, in place of the phosphate ester-based surfactant represented by the formula (PW-6), the phosphate ester-based surfactant represented by the following formula (PW-29) was used to form the film. A honeycomb-shaped porous film and a honeycomb composite film HC-2 were produced in the same manner as in Example 1 except that the material solution was prepared.
About the honeycomb-like porous film in the obtained honeycomb composite film HC-2, the average pore diameter of the pores was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, in place of the phosphate ester surfactant represented by the formula (PW-6), an amphiphilic polymer having a weight average molecular weight of 50,000 represented by the following structural formula was used to form the film. A honeycomb-shaped porous film and a honeycomb composite film HC-3 were produced in the same manner as in Example 1 except that the material solution was prepared.
About the honeycomb-like porous film in the obtained honeycomb composite film HC-3, the average pore diameter of the pores was evaluated in the same manner as in Example 1. The results are shown in Table 1.

* 1: Amphiphilic polymer

  From the results in Table 1, it can be seen that the honeycomb porous film of the present invention containing a phosphate ester-based surfactant has smaller pore diameters than the conventional honeycomb porous film containing an amphiphilic polymer. It was.

  The honeycomb-shaped porous film of the present invention is controlled to have a sufficiently small pore diameter, so that the honeycomb composite film has increased strength and improved handleability, for example, a retardation film, a polarizing film, a screen, a color It is suitably used widely for filters, display members, cell culture members, wound protective membranes, transdermal absorption membranes, acoustic vibration materials, sound absorbing materials, vibration damping materials, and the like.

FIG. 1 is a schematic diagram showing an example of a honeycomb structure in a honeycomb-shaped porous film. FIG. 2A is a schematic diagram illustrating an example of a method for forming a honeycomb-shaped porous film according to the present invention and a state in which a film material layer is formed. FIG. 2B is a schematic diagram illustrating an example of a method for forming a honeycomb-shaped porous film according to the present invention, in which droplets are condensed and grow. FIG. 2C is a schematic view showing an example of a method for forming a honeycomb-shaped porous film of the present invention, and showing a state in which an organic solvent volatilizes from a film material layer by drying. FIG. 2D is a schematic view showing an example of a method for forming a honeycomb-shaped porous film of the present invention, and showing a state in which moisture is volatilized from droplets of a film material layer by drying. FIG. 3A is a cross-sectional view showing an example of a honeycomb-like porous film through which pores penetrate. FIG. 3B is a cross-sectional view showing an example of a honeycomb-shaped porous film in which pores do not penetrate. FIG. 3C is a cross-sectional view showing an example of a honeycomb-like porous film. FIG. 4A is a cross-sectional view showing an example of a honeycomb composite film according to the present invention. FIG. 4B is a cross-sectional view showing an example of a honeycomb composite film according to the present invention. FIG. 4C is a cross-sectional view showing an example of a honeycomb composite film according to the present invention. FIG. 4D is a cross-sectional view showing an example of a honeycomb composite film according to the present invention. FIG. 5 is a schematic view showing an example of a film production facility used in the method for producing a honeycomb composite film according to the present invention. FIG. 6 is a schematic view showing an example of a film production facility used in the method for producing a honeycomb composite film according to the present invention. FIG. 7 is a schematic view showing an example of a film production facility used in the method for producing a honeycomb composite film according to the present invention. FIG. 8 is a schematic view showing an example of a film production facility used in the method for producing a honeycomb composite film according to the present invention. FIG. 9 is a schematic view showing an example of a film production facility used in the method for producing a honeycomb composite film according to the present invention. FIG. 10 is a schematic view showing an example of a film production facility used in the method for producing a honeycomb composite film according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Temporary support body 2 Peeling layer 3 Support body 12 Honeycomb porous film 40 Film material layer 46 Honeycomb structure film 47 Void

Claims (11)

A honeycomb-like porous film comprising at least a surfactant represented by the following general formula (I):
However, the general formula (I), _{R 1} and _{R 2} represents an unsubstituted straight-chain alkyl group having 1 to 24 carbon _atoms, Q 1, _{Q 2} and _{Q 3} are, it represents an oxygen atom, L is , - _{(CH 2) s} - and _{- (CH 2 CH 2 O)} s - represents any, s is an integer of 1 to 10, Z is a -SO ₃ M and -OSO ₃ M Represents any one, and M represents an alkali metal ion. Forming a film material layer using a film material solution containing at least a surfactant represented by the general formula (I) and a hydrophobic organic solvent;
Air holes formed by blowing a gas having a relative humidity of 50 to 95% to the film material layer, volatilizing the hydrophobic organic solvent, generating condensation on the surface of the film material layer, and evaporating the condensation. The honeycomb-shaped porous film according to claim 1, comprising: Forming a surfactant represented by at least under following general formula (I), the film material layer with a film material solution containing a hydrophobic organic solvent,
The film material layer is blown with a gas having a relative humidity of 50 to 95% to volatilize the hydrophobic organic solvent, generate condensation on the surface of the film material layer, and evaporate the condensation to form pores. A method for producing a honeycomb-shaped porous film.
However, the general formula (I), _{R 1} and _{R 2} represents an unsubstituted straight-chain alkyl group having 1 to 24 carbon _atoms, Q 1, _{Q 2} and _{Q 3} are, it represents an oxygen atom, L is , - _{(CH 2) s} - and _{- (CH 2 CH 2 O)} s - represents any, s is an integer of 1 to 10, Z is a -SO ₃ M and -OSO ₃ M Represents any one, and M represents an alkali metal ion.   A honeycomb composite film comprising a temporary support body that can be peeled off on at least one surface of the honeycomb-shaped porous film according to claim 1.   The honeycomb composite film according to claim 4, comprising a release layer on at least one surface of the honeycomb-shaped porous film, and a temporary support on the release layer.   The honeycomb composite film according to any one of claims 4 to 5, further comprising a release layer on both surfaces of the honeycomb-like porous film, and a temporary support on both of the release layers.   5. A honeycomb porous film having a release layer on one side, a temporary support on the release layer, and a support on the side of the honeycomb porous film not having the release layer. The honeycomb composite film according to any one of items 6 to 6.   The honeycomb composite film according to any one of claims 4 to 7, which is used by peeling off the temporary support and the release layer.   Used for any one selected from a retardation film, a polarizing film, a screen, a color filter, a display member, a cell culture member, a wound protective film, a transdermal absorption film, an acoustic vibration material, a sound absorbing material, and a vibration damping material. The honeycomb composite film according to any one of claims 4 to 8. A release layer forming step of forming a release layer on the temporary support,
A honeycomb-shaped porous film production process for producing a honeycomb-shaped porous film according to claim 1 on a support;
A method for producing a honeycomb composite film, comprising: bonding the release layer on the temporary support to the honeycomb-like porous film. A release layer forming step of forming a release layer on the temporary support,
A honeycomb-shaped porous film preparation step for forming the honeycomb-shaped porous film according to any one of claims 1 to 2 on the release layer on the temporary support. Production method.