JP2015140410A - Method of producing gel material and gel material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method capable of producing a gel material excellent in stability of characteristics, and to provide a gel material excellent in stability of characteristics.SOLUTION: The method of producing a gel material of the present invention includes: a liquid mixture application step of applying a liquid mixture containing a polymerizable compound, a crosslinking agent, and a polymerization initiator onto a substrate; a decompression step of subjecting the liquid mixture applied onto the substrate to a decompression treatment; and a polymerization step of polymerizing the polymerizable compound. The method of producing a gel material preferably includes a surface treatment step of subjecting the substrate to a surface treatment for improving a lyophilic property prior to the liquid mixture application step.

Description

  The present invention relates to a method for producing a gel material and a gel material.

  Conventionally, the production of a sheet-like (film-like, plate-like) gel material has been produced, for example, by the following method. In other words, three spacers are inserted between two rectangular glass plates and along the periphery of the three glass plates, and the two glass plates are stacked and clipped around the two glass plates so that the spacers are not displaced. Crimp. Next, while removing the clip so that the edge of the two stacked glass plates is wrapped in a U shape with a series of adhesive tapes, wrap them around the 3 surroundings of the glass plate, and put the tape on the glass plate. Then, the glass plate is tilted so that the edge surface of the remaining one side faces up, and the solution is poured from the edge to be gelled.

  However, in such a method, the glass plate stack is sealed with adhesive tape on the periphery of the glass plate 3 so that it does not leak in principle when the solution is poured. In many cases, the corners of the bends often caused poor adhesion of the tape and could not be completely sealed. These manual operations are not only time consuming but also unreliable and uneconomical.

  Therefore, in order to solve the above problems, a gel material is used by using a U-shaped frame body having a depth equal to the thickness of the glass plate so that the two glass plates can be dropped exactly. Has been proposed (see, for example, Patent Document 1).

  However, when a mixed solution containing a polymerizable compound and a polymerization initiator is applied in the method as described above, the polymerization reaction does not proceed suitably, and a gel material having excellent characteristic stability and reliability is obtained. There is a problem that can not be. Further, depending on the content of the polymerization initiator and the like, the polymerization reaction may not proceed and the gel material may not be obtained. Further, in the method as described above, since the gap between the two glass plates into which the solution is injected is fixed, only a gel material having a specific thickness can be manufactured. Moreover, the method as described above cannot produce a gel material having a laminated structure.

Japanese Patent Laid-Open No. 6-138086

  The objective of this invention is providing the manufacturing method which can manufacture the gel material excellent in stability of a characteristic, and providing the gel material excellent in stability of a characteristic.

Such an object is achieved by the present invention described below.
The method for producing a gel material of the present invention includes a mixed liquid application step of applying a mixed liquid containing a polymerizable compound, a crosslinking agent and a polymerization initiator on a substrate,
A depressurization step of applying a depressurization process to the mixed solution applied on the substrate;
A polymerization step of polymerizing the polymerizable compound.

  In the method for producing a gel material of the present invention, it is preferable to have a surface treatment step for performing a surface treatment for improving the lyophilic property on the substrate prior to the mixed solution applying step.

In the method for producing a gel material according to the present invention, the surface treatment is preferably O ₂ plasma treatment.

  In the method for producing a gel material of the present invention, the mixed solution preferably contains fine particles having an average particle size of 10 nm to 1000 nm.

  In the method for producing a gel material of the present invention, the mixed solution is preferably subjected to a desalting treatment.

  In the manufacturing method of the gel material of this invention, it is preferable that the said liquid mixture is what was deaerated.

  In the manufacturing method of the gel material of this invention, it is preferable to perform the said pressure reduction process so that the amount of dissolved oxygen in the said liquid mixture provided on the said base material may be 500 ppm or less.

  In the manufacturing method of the gel material of this invention, it is preferable to perform the said liquid mixture provision process by the inkjet method.

In the method for producing a gel material of the present invention, the depressurization step is performed in a chamber having a wall portion made of a material having ultraviolet transparency.
The polymerization step is preferably performed by irradiating ultraviolet rays through the wall portion.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭化水素基（水酸基、エーテル基またはカルボキシル基を有する炭化水素基を含む）である。また、Ｒ^１とＲ^２とは、互いに共有結合により結合し、環状をなすものであってもよい。） In the method for producing a gel material of the present invention, the mixed solution preferably contains a compound represented by the formula (1) as the polymerization initiator.

(In the formula ^{(1), R 1, R} 2, R 3 are each independently hydrogen atom or a hydrocarbon group (a hydroxyl group, including a hydrocarbon group having an ether group or a carboxyl group). In addition, ^{R 1} And R ² may be bonded to each other by a covalent bond to form a ring.)

  In the manufacturing method of the gel material of this invention, it is preferable that the content rate of the said polymerization initiator in the said liquid mixture is 0.1 to 10 mass%.

  In the manufacturing method of the gel material of this invention, it is preferable that the said liquid mixture contains what has an acrylamide group as said polymeric compound.

In the method for producing a gel material of the present invention, it is preferable that the mixed liquid contains N, N′-methylenebisacrylamide as the cross-linking agent.
The gel material of the present invention is manufactured using the manufacturing method of the present invention.

It is typical process drawing for demonstrating suitable embodiment of the manufacturing method of the gel material of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

<< Gel Material Production Method >>
First, the manufacturing method of the gel material of this invention is demonstrated.

  FIG. 1 is a schematic process diagram for explaining a preferred embodiment of the method for producing a gel material of the present invention.

  As shown in FIG. 1, the manufacturing method of this embodiment includes a surface treatment step (1a) for performing surface treatment for improving lyophilicity on a substrate 6, a polymerizable compound, a crosslinking agent, and polymerization. A mixed solution application step (1b) for applying a mixed solution 10 ′ containing an initiator onto the substrate 6, and a depressurizing step (1c) for subjecting the mixed solution 10 ′ applied on the substrate 6 to a reduced pressure treatment; And a polymerization step (1d) for polymerizing the polymerizable compound.

[Surface treatment process]
Prior to the liquid mixture application step, the surface for improving the lyophilicity (affinity of the liquid mixture 5 ′) by the surface treatment means 2 for the region to which at least the liquid mixture 10 ′ of the substrate 6 is to be applied. Processing is performed (1a).

  Thereby, the wettability with respect to the base material 6 of mixed liquid 10 'at the time of providing mixed liquid 10' to the base material 6 by a subsequent process can be made more suitable, and the desired shape The gel material 10 can be obtained more reliably. In particular, it is possible to more effectively prevent unintentional thickness variations and pattern defects in the gel material 10.

  The surface treatment performed in this step may be any surface treatment as long as it improves the lyophilicity of the substrate 6 (affinity of the mixed solution 5 ′). For example, ultraviolet irradiation, silane coupling Application of a modifying agent (lyophilic improver) such as an agent, corona treatment, plasma treatment and the like can be mentioned, and one or two or more methods selected from these can be combined.

Among these, the surface treatment performed in this step is preferably a plasma treatment, and more preferably an O ₂ plasma treatment.

  Thereby, the lyophilicity (affinity of the mixed solution 5 ′) of the substrate 6 can be more effectively improved while effectively preventing damage to the substrate 6.

  Further, when the surface treatment in this step is performed by ultraviolet irradiation, the surface treatment means 2 is preferably an excimer lamp. In the excimer lamp, ultraviolet light having a shorter wavelength (for example, ultraviolet light having a peak wavelength of 172 nm) can be used, surface treatment (lyophilic treatment) can be performed more efficiently in a shorter time, and the gel material 10 The productivity can be made particularly excellent.

When the surface treatment in this step is performed by irradiation with ultraviolet rays, the peak wavelength of the ultraviolet rays is preferably 1 nm or more and 330 nm or less, and more preferably 12 nm or more and 180 nm or less. Thereby, surface treatment (lyophilic treatment) can be performed more efficiently in a shorter time, and the productivity of the gel material 10 can be made particularly excellent. Moreover, since the active oxygen is efficiently generated by irradiating the ultraviolet ray having such a wavelength in an atmosphere containing oxygen (O ₂ ), the irradiated ultraviolet ray directly improves the lyophilicity of the substrate 6. And the effect of improving the lyophilicity of the base material 6 by the active oxygen generated by the ultraviolet rays is also exhibited. By synergistically acting these effects, it is more efficient in a shorter time. Surface treatment (lyophilic treatment) can be performed, and the productivity of the gel material 10 can be further improved.

In addition, when the surface treatment in this step is performed by applying a silane coupling agent as a modifier (lyophilic improver), for example, a silane compound containing a silyl group is used as the silane coupling agent. Specific examples thereof include, for example, hexamethyldisilazane, dimethyldimethoxysilane, diethyldiethoxysilane, 1-propenylmethyldichlorosilane, propyldimethylchlorosilane, propylmethyldichlorosilane, propyltrichlorosilane, propyltriethoxysilane Propyltrimethoxysilane, styrylethyltrimethoxysilane, tetradecyltrichlorosilane, 3-thiocyanatepropyltriethoxysilane, p-tolyldimethylchlorosilane, p-tolylmethyldichlorosilane, p-tolyltrichlorosilane P-tolyltrimethoxysilane, p-tolyltriethoxysilane, di-n-propyldi-n-propoxysilane, diisopropyldiisopropoxysilane, di-n-butyldi-n-butyroxysilane, di-sec-butyldi-sec -Butyloxysilane, di-t-butyldi-t-butyloxysilane, octadecyltrichlorosilane, octadecylmethyldiethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyldimethylchlorosilane, octadecylmethyldichlorosilane, octadecylmethoxydichlorosilane, 7-oct Tenenyldimethylchlorosilane, 7-octenyltrichlorosilane, 7-octenyltrimethoxysilane, octylmethyldichlorosilane, octyldimethylchlorosila Octyltrichlorosilane, 10-undecenyldimethylchlorosilane, undecyltrichlorosilane, vinyldimethylchlorosilane, methyloctadecyldimethoxysilane, methyldodecyldiethoxysilane, methyloctadecyldimethoxysilane, methyloctadecyldiethoxysilane, n-octylmethyldimethoxysilane , N-octylmethyldiethoxysilane, triacontyldimethylchlorosilane, triaconyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methylisopropoxysilane, methyl-n-butyroxysilane, methyltri- sec-Butyloxysilane, Methyltri-t-Butyloxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane Lan, ethyltri-n-propoxysilane, ethylisopropoxysilane, ethyl-n-butyroxysilane, ethyltri-sec-butyloxysilane, ethyltri-t-butyloxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane , Hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-propyltriethoxysilane, isobutyltriethoxysilane, n-hexyltriethoxysilane, hexadecyltri Ethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltriethoxysilane, 2- [2- (trichlorosilyl) ethyl] pyrid 4- [2- (trichlorosilyl) ethyl] pyridine, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,3- (trichlorosilylmethyl) heptacosane, dibenzyldimethoxysilane, dibenzyldiethoxysilane, phenyltrimethoxysilane, Phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, phenylmethyldiethoxysilane, phenyldimethylethoxysilane, benzyltriethoxysilane, benzyltrimethoxysilane, benzylmethyldimethoxysilane, benzyldimethylmethoxysilane, Benzyldimethoxysilane, benzyldiethoxysilane, benzylmethyldiethoxysilane, benzyldimethylethoxysilane, benzylto Ethoxysilane, dibenzyldimethoxysilane, dibenzyldiethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 4-aminobutyltriethoxysilane, ( Aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 6- (aminohexylamino) Propyl) trimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenylethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylethoxysilane, 3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, ω-aminoundecyltrimethoxysilane, amyltriethoxysilane, benzoxacilepine dimethyl ester, 5- (bicycloheptenyl) triethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 8-bromooctyltrimethoxysilane, bromophenyltrimethoxysilane, 3-bromopropyltrimethoxysilane, n-butyltrimethoxysilane, 2-chloromethyltriethoxysilane, chloromethylmethyldi Ethoxysilane, chloromethylmethyldiisopropoxysilane, p- (chloromethyl) phenyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-chloropropylmethyldimethoxy Lan, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyltrimethoxysilane, cyanomethylphenethyltri Ethoxysilane, 3-cyanopropyltriethoxysilane, 2- (3-cyclohexenyl) ethyltrimethoxysilane, 2- (3-cyclohexenyl) ethyltriethoxysilane, 3-cyclohexenyltrichlorosilane, 2- (3-cyclo Hexenyl) ethyltrichlorosilane, 2- (3-cyclohexenyl) ethyldimethylchlorosilane, 2- (3-cyclohexenyl) ethylmethyldichlorosilane, cyclohexyldimethylchlorosilane, cyclohexylethyl Rudimethoxysilane, cyclohexylmethyldichlorosilane, cyclohexylmethyldimethoxysilane, (cyclohexylmethyl) trichlorosilane, cyclohexyltrichlorosilane, cyclohexyltrimethoxysilane, cyclooctyltrichlorosilane, (4-cyclooctenyl) trichlorosilane, cyclopentyltrichlorosilane, cyclopentyltrimethoxy Silane, 1,1-diethoxy-1-silacyclopent-3-ene, 3- (2,4-dinitrophenylamino) propyltriethoxysilane, (dimethylchlorosilyl) methyl-7,7-dimethylnorpinane, (Cyclohexylaminomethyl) methyldiethoxysilane, (3-cyclopentadienylpropyl) triethoxysilane, N, N-diethyl-3-aminopropyl Trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (furfuryloxymethyl) triethoxysilane, 2-hydroxy-4- (3-triethoxypropoxy) diphenyl ketone, 3- (p-methoxyphenyl) propylmethyldichlorosilane, 3- (p-methoxyphenyl) propyltrichlorosilane, p- (methylphenethyl) methyldichlorosilane, p- (methylphenethyl) ) Trichlorosilane, p- (methylphenethyl) dimethylchlorosilane, 3-morpholinopropyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 1,2,3 , 4, , 7, -hexachloro-6-methyldiethoxysilyl-2-norbornene, 1,2,3,4,7,7, -hexachloro-6-triethoxysilyl-2-norbornene, 3-iodopropyltrimethoxylane, 3-isocyanatopropyltriethoxysilane, (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, methyl {2- (3-trimethoxysilylpropylamino) ethylamino} -3-propionate, 7-octenyltrimethoxysilane, RN-α-phenethyl-N′-tri Ethoxysil Rupropylurea, S-N-α-phenethyl-N′-triethoxysilylpropylurea, phenethyltrimethoxysilane, phenethylmethyldimethoxysilane, phenethyldimethylmethoxysilane, phenethyldimethoxysilane, phenethyldiethoxysilane, phenethylmethyldiethoxysilane , Phenethyldimethylethoxysilane, phenethyltriethoxysilane, (3-phenylpropyl) dimethylchlorosilane, (3-phenylpropyl) methyldichlorosilane, N-phenylaminopropyltrimethoxysilane, N- (triethoxysilylpropyl) dansilamide, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, 2- (triethoxysilylethyl) -5- (chloroacetoxy) bicycloheptane, S) -N-triethoxysilylpropyl-O-mentcarbamate, 3- (triethoxysilylpropyl) -p-nitrobenzamide, 3- (triethoxysilyl) propylsuccinic anhydride, N- [5- (trimethoxy Silyl) -2-aza-1-oxo-pentyl] caprolactam, 2- (trimethoxysilylethyl) pyridine, N- (trimethoxysilylethyl) benzyl-N, N, N-trimethylammonium chloride, phenylvinyldiethoxysilane , 3-thiocyanatopropyltriethoxysilane, (tridecafluoro-1,1,2,2, -tetrahydrooctyl) triethoxysilane, N- {3- (triethoxysilyl) propyl} phthalamic acid, (3, 3, 3-trifluoropropyl) methyldimethoxysilane (3,3,3-trifluoropropyl) trimethoxysilane, 1-trimethoxysilyl-2- (chloromethyl) phenylethane, 2- (trimethoxysilyl) ethylphenylsulfonyl azide, β-trimethoxysilylethyl- 2-pyridine, trimethoxysilylpropyldiethylenetriamine, N- (3-trimethoxysilylpropyl) pyrrole, N-trimethoxysilylpropyl-N, N, N-tributylammonium bromide, N-trimethoxysilylpropyl-N, N, N-tributylammonium chloride, N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, vinylmethyldiethoxylane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyl Methylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldichlorosilane, vinylphenyldichlorosilane, vinylphenyldiethoxysilane, vinylphenyldimethylsilane, vinylphenylmethylchlorosilane, vinyltriphenoxysilane, vinyltris-t-butoxysilane, adamantylethyltri Chlorosilane, allylphenyltrichlorosilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, phenyltrichlorosilane, phenyldimethylchlorosilane, phenylmethyldichlorosilane, benzyltrichlorosilane, benzyldimethylchlorosilane, benzylmethyldichlorosilane , Phenethyl diisopropylchlorosilane, phenethyl trichloro Silane, phenethyl dimethylchlorosilane, phenethylmethyldichlorosilane, 5- (bicyclo heptenyl) trichlorosilane, 5- (bicyclo heptenyl) triethoxy silane, 2- (bicycloheptyl) dimethylchlorosilane, 2- (bicycloheptyl)
Trichlorosilane, 1,4-bis (trimethoxysilylethyl) benzene, bromophenyltrichlorosilane, 3-phenoxypropyldimethylchlorosilane, 3-phenoxypropyltrichlorosilane, t-butylphenylchlorosilane, t-butylphenylmethoxysilane, t- Butylphenyldichlorosilane, p- (t-butyl) phenethyldimethylchlorosilane, p- (t-butyl) phenethyltrichlorosilane, 1,3- (chlorodimethylsilylmethyl) heptacosane, ((chloromethyl) phenylethyl) dimethylchlorosilane, ((Chloromethyl) phenylethyl) methyldichlorosilane, ((chloromethyl) phenylethyl) trichlorosilane, ((chloromethyl) phenylethyl) trimethoxysilane, chlorophenylto Chlorosilane, 2-cyanoethyltrichlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldiethoxysilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropyldimethylethoxysilane, 3- Examples thereof include cyanopropylmethyldichlorosilane, 3-cyanopropyltrichlorosilane, fluorinated alkylsilane, and the like, and one or more selected from these can be used in combination.

[Mixed liquid application process]
Next, a mixed liquid 10 ′ containing a polymerizable compound, a crosslinking agent and a polymerization initiator is applied onto the substrate 6 by the mixed liquid applying means 3 (1b).
As a result, a film of the mixed solution 10 ′ is formed on the substrate 6.

  In this embodiment, since the surface treatment (lyophilic treatment) by the surface treatment means 2 is performed on the base material 6 prior to the mixed liquid application step, the wettability of the mixed liquid 10 ′ to the base material 6 is more preferable. It has become a thing. For this reason, the unintentional repelling etc. on the base material 6 of mixed liquid 10 'are prevented effectively, and the film | membrane of a desired pattern can be formed more reliably. Therefore, even if the gel material 10 to be manufactured has a fine pattern, it can be more reliably manufactured as having a desired shape.

  In this step, the mixed liquid 10 ′ may be applied by any method, but the mixed liquid applying means 3 is preferably performed by an ink jet method using a droplet discharge means.

  Thereby, the gel material 10 of various magnitude | sizes can be manufactured suitably. Further, by adjusting the vibration waveform of the vibration element, the film thickness of the mixed liquid 10 ′ can be controlled easily and reliably. Even if the gel material 10 to be manufactured has a fine structure, pattern formation can be performed accurately. Further, in the ink jet method, a necessary amount of the mixed liquid 10 ′ is discharged, so that waste of the material (mixed liquid 10 ′) can be prevented.

In this step, a plurality of types of materials having different compositions are respectively applied to the base material 6, and the plurality of types of materials are mixed on the base material 6. As a result, a mixed solution is formed on the base material 6. You may give.
The mixed solution 10 ′ will be described in detail later.

[Decompression process]
Next, the inside of the chamber 1 in which the base material 6 (the base material 6 to which the mixed liquid 10 ′ has been applied) is placed is decompressed by a pump (decompression means) 4 (1c).

  As a result, the oxygen content (dissolved oxygen amount) in the mixed liquid 10 ′ applied on the substrate 6 is reduced, and the function of the polymerization initiator is inhibited by oxygen in the subsequent polymerization step (loss). Active) is prevented / suppressed, and the polymerization reaction can be efficiently initiated / progressed. As a result, the occurrence of inconvenience due to the polymerization reaction not proceeding as intended can be prevented, and the finally obtained gel material can be made excellent in stability of characteristics.

  Moreover, since the polymerization reaction starts and proceeds efficiently, the productivity of the gel material 10 can be made excellent.

  Although it is conceivable to include a large amount of a polymerization initiator in the mixed solution, such a method is inefficient and the quality of the gel material finally obtained is reduced (for example, the gel material). For example, a decrease in the molecular weight of the polymer material that constitutes the material.

  In addition, since the polymerization initiator contained in the mixed liquid 10 ′ can efficiently contribute to the polymerization reaction and there is no need to use an excessive polymerization initiator, components other than the polymerization initiator in the mixed liquid 10 ′ ( For example, the content of the polymerizable compound, the crosslinking agent, etc.) can be increased, and the properties of the gel material 10 finally obtained can be made particularly excellent.

  Moreover, since it is not necessary to use a polymerization initiator that does not contribute to the polymerization reaction, it is preferable from the viewpoint of saving resources and reducing the production cost of the gel material 10.

  In addition, when an excessive amount of the polymerization initiator is used, a component derived from the polymerization initiator that has not contributed to the polymerization reaction is contained in a relatively large amount in the gel material after the polymerization reaction. Since it is not necessary to use a polymerization initiator as described above, the occurrence of adverse effects caused by a relatively large amount of components derived from the polymerization initiator that did not contribute to the polymerization reaction in the final gel material (for example, the gel material In the case of a stimuli-responsive gel material, it is possible to prevent a decrease in responsiveness of the gel material). Moreover, since the refinement | purification process for removing such a component can be abbreviate | omitted or simplified, the productivity of the gel material 10 can be made especially excellent.

The pressure in the chamber 1 in this step is preferably 1.0 Pa or more and 5.0 × 10 ⁴ Pa or less, and more preferably 3.0 × 10 ¹ Pa or more and 1.0 × 10 ⁴ Pa or less. .

  As a result, the oxygen content (dissolved oxygen amount) in the mixed liquid 10 ′ applied on the base material 6 can be efficiently reduced, and the productivity of the gel material can be further improved, and the mixing can be performed. Unintentional volatilization of components such as a solvent contained in the liquid 10 ′ can be effectively prevented and suppressed.

  The decompression process in this step is preferably performed so that the amount of dissolved oxygen in the mixed liquid 10 ′ applied on the substrate 6 is 500 ppm or less.

  Thereby, in a superposition | polymerization process, the function of a polymerization initiator can be exhibited more effectively.

  The dissolved oxygen amount in the mixed solution 10 'at the end of this step (at the start of the polymerization step) is preferably 500 ppm or less, more preferably 400 ppm or less, and even more preferably 300 ppm or less. Thereby, the effect mentioned above is exhibited more notably.

  In this step, the atmosphere in which the base material 6 provided with the mixed liquid 10 ′ is placed may be depressurized, and heat treatment may be performed together with the reduced pressure.

  As a result, the efficiency of deoxygenation from the mixed liquid 10 ′ is improved, and the amount of dissolved oxygen in the mixed liquid 10 ′ can be made sufficiently low in a shorter time. As a result, the productivity of the gel material 10 can be further improved.

  In addition, by using the decompression process and the heat treatment in combination, the amount of dissolved oxygen in the mixed liquid 10 ′ can be reduced to a level that is difficult to achieve only by the decompression process. For this reason, the polymerization reaction in the polymerization step can be started and advanced more suitably, and the stability of the properties of the gel material 10 finally obtained can be further improved.

  Depending on the composition of the mixed solution 10 ′ and the like, the solvent constituting the mixed solution 10 ′ is vaporized by the depressurization process, and thus the heat of vaporization is removed, and the temperature of the mixed solution 10 ′ is greatly reduced (in an extreme case, Solidification may occur). When such a temperature drop occurs, for example, the solute in the mixed liquid 10 ′ may be deposited, and it may be difficult to suitably proceed the subsequent polymerization reaction. Therefore, the occurrence of such a problem can be prevented more effectively.

  When heat treatment is performed in this step, the heating temperature is preferably 40 ° C. or higher and 90 ° C. or lower, and more preferably 50 ° C. or higher and 85 ° C. or lower.

  Thereby, deoxidation from the mixed liquid 10 ′ can be performed more efficiently while sufficiently effectively preventing undesired modification and deterioration of the components of the mixed liquid 10 ′ and unintentional volatilization. . Further, the amount of dissolved oxygen in the mixed solution 10 'can be made particularly low.

  Further, the heat treatment time is preferably 5 seconds or more and 600 seconds or less, and more preferably 10 seconds or more and 300 seconds or less.

  As a result, the amount of dissolved oxygen in the mixed solution 10 ′ is particularly low while sufficiently preventing the undesired modification and deterioration of the components of the mixed solution 10 ′ and unintentional volatilization. it can. Further, the productivity of the gel material 10 can be made particularly excellent.

  Moreover, when performing heat processing in this process, although heat processing may be performed continuously, you may perform intermittently.

  As a result, it is possible to more effectively prevent the unintentional modification and deterioration of the components of the mixed liquid 10 ′ while sufficiently obtaining the effect of improving the deoxygenation efficiency of the mixed liquid 10 ′ by heating.

  In the configuration shown in the drawing, the chamber 1 that performs the decompression process in this step has an ultraviolet transmitting portion 11 made of an ultraviolet transparent material on the wall portion.

  Thereby, since it can irradiate with ultraviolet rays with respect to liquid mixture 10 'in the chamber 1 from the exterior of the chamber 1, when liquid mixture 10' contains an ultraviolet curable component as a polymeric compound, chamber The subsequent polymerization step can be suitably performed while the pressure in 1 is kept low. Moreover, since it is not necessary to install the ultraviolet irradiation means (polymerization means) 5 in the chamber 1 where the pressure fluctuates greatly, it is possible to effectively prevent and suppress the ultraviolet irradiation means 5 from being affected by the pressure change. The life of the ultraviolet irradiation means 5 can be increased. As a result, the maintenance of the manufacturing apparatus of the gel material 10 becomes easy, and the gel material 10 having excellent characteristic stability can be stably manufactured over a long period of time. It is also advantageous from the viewpoint.

[Polymerization process]
Thereafter, the polymerizable compound contained in the mixed liquid 10 ′ is polymerized (1d).
Thereby, the gel material 10 is obtained.

  The polymerization reaction is performed by a method corresponding to the type of polymerizable compound or the like. For example, when the mixed liquid 10 ′ includes a thermosetting material, it can be performed by heating, and when the mixed liquid 10 ′ includes a photocurable (for example, ultraviolet curable) material, It can be performed by irradiation with light (for example, ultraviolet rays).

In FIG. 1, ultraviolet rays are irradiated by ultraviolet irradiation means (polymerization means) 5.
When this step is performed by irradiation with ultraviolet rays, the peak wavelength of the irradiated ultraviolet rays is preferably 340 nm or more and 400 nm or less, and more preferably 350 nm or more and 380 nm or less.

  As a result, the target polymerization reaction can be suitably started and proceeded while sufficiently preventing Japanese modification and deterioration of the constituent material of the mixed solution 10 ′. As a result, it is possible to manufacture the gel material 10 having excellent characteristics with higher productivity and more stability.

This step is performed by using the reduced pressure state in the previous reduced pressure step.
Thereby, generation | occurrence | production of the bad influence by oxygen in a polymerization reaction can be prevented more effectively. Moreover, it can prevent and suppress more effectively that a volatile organic compound (VOC) remains in the gel material 10 finally obtained.

  This step may be performed in a state where the pump (decompression unit) 4 is operated, or may be performed in a state where the operation of the pump (decompression unit) 4 is stopped.

The pressure in the chamber 1 in this step is preferably 1.0 Pa or more and 5.0 × 10 ⁴ Pa or less, more preferably 3.0 × 10 ¹ Pa or more and 1.0 × 10 ⁴ Pa or less. preferable.
As a result, the effect as described above is remarkably exhibited.

  Note that the pressure in the chamber 1 in this step may be the same as or different from the pressure in the pressure reducing step performed previously.

  In the configuration shown in the figure, ultraviolet rays are irradiated from the ultraviolet irradiation means 5 provided outside the chamber 1 through an ultraviolet transmission portion 11 provided on the wall portion of the chamber 1.

  Thereby, it is possible to irradiate the mixed liquid 10 ′ in the chamber 1 with ultraviolet rays without installing the ultraviolet irradiating means 5 in the chamber 1 having a large pressure fluctuation. For this reason, it is possible to effectively prevent and suppress the ultraviolet irradiation means 5 from being affected by the pressure change, and to extend the life of the ultraviolet irradiation means 5. As a result, the maintenance of the manufacturing apparatus of the gel material 10 becomes easy, and the gel material 10 having excellent characteristic stability can be stably manufactured over a long period of time. It is also advantageous from the viewpoint. It is also conceivable that the ultraviolet irradiation means 5 is irradiated with ultraviolet rays after the chamber 1 is opened and the pressure inside the chamber 1 is restored after the decompression step without installing the ultraviolet irradiation means 5 in the chamber 1 having a large pressure change. However, in such a case, the mixed solution 10 ′ that has undergone the decompression step is exposed to oxygen in the atmosphere, so that the occurrence of adverse effects due to oxygen is prevented and suppressed as compared to the above case. The effect will be reduced. On the other hand, when the ultraviolet ray is irradiated from the ultraviolet ray irradiation means 5 provided outside the chamber 1 through the ultraviolet ray transmitting portion 11 provided on the wall portion of the chamber 1, the pressure in the chamber 1 is kept low. It is preferable because the polymerization reaction can be started and advanced.

  According to the method for producing a gel material of the present invention as described above, a gel material having excellent characteristic stability can be produced stably and efficiently. And the gel material manufacturing apparatus provided with the chamber, the liquid mixture provision means, the pressure reduction means, the superposition | polymerization means, etc. which were mentioned above can be used suitably for the manufacturing method of the gel material of this invention.

[Mixture]
Next, the mixed liquid 10 ′ will be described in detail.

  The mixed solution 10 ′ is used for producing the gel material 10 and contains a polymerizable compound, a crosslinking agent, and a polymerization initiator.

  Thereby, the gel material 10 containing the high molecular material which has a crosslinked structure is efficiently compoundable.

  In particular, since the polymer material can be synthesized as having a three-dimensional network structure by including the cross-linking agent, the gel material 10 has excellent solvent retention. A suitable gel state can be stably maintained over a period of time. That is, the durability of the gel material 10 is excellent.

  The composition of the mixed solution 10 ′ varies greatly depending on the type and use of the gel material 10 to be manufactured. The gel material 10 may be used for any purpose. However, in the following description, the case where the gel material 10 is a stimulus-responsive gel material will be mainly described.

  In the present invention, the stimulus-responsive gel material refers to a gel material that undergoes deformation such as swelling and shrinkage due to thermal changes, changes in the concentration of specific components (including ions), and stimulations such as electricity and light. .

  Since the stimulus-responsive gel material is deformed in response to a specific stimulus, for example, the presence or absence of a specific stimulus can be confirmed by the presence or absence of the deformation, and the specific stimulus can be determined by the amount of deformation. The amount can also be quantified.

(Reactive polymer)
Examples of the reactive polymer include acrylamide, N-methylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylacrylamide, various quaternary salts, Acrylylmorpholine, N, N-dimethylaminoethyl acrylate quaternary salts, acrylic acid, various alkyl acrylates, methacrylic acid, various alkyl methacrylates, 2-hydroxyethyl methacrylate, glycerol monomethacrylate, N-vinylpyrrolidone, acrylonitrile, styrene, polyethylene Glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate Polypropylene glycol diacrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3 -Methacryloxypropane, 2,2-bis [4- (acryloxypolypropoxy) phenyl] propane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol di Methacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxyp Bread, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) Polyethoxy) phenyl] propane, trimethylolpropane trimethacrylate, tetramethylolmethane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, dipentaerythritol hexaacrylate, N, N'-methylenebis Monomers such as acrylamide, N, N′-methylenebismethacrylamide, diethylene glycol diallyl ether, divinylbenzene, etc. are listed, and one or more selected from these are combined. So it can be used.

  In particular, the mixed liquid 10 ′ preferably contains a polymerizable compound having an acrylamide group.

  Thereby, the polymerization reaction in a polymerization process can be started and advanced more suitably, and the productivity of the gel material 10 can be made particularly excellent. Moreover, the retention power (especially water retention) of the solvent of the polymeric material obtained by polymerizing a polymerizable compound can be made more excellent. When the gel material 10 is a stimulus-responsive gel material, introduction of a partial structure (functional group) that reacts (responds) to a specific stimulus in a polymer material obtained by polymerizing a polymerizable compound, It can be introduced more easily and more reliably.

  In addition, examples of the functional group capable of interacting with a sugar include a boronic acid group (particularly, a phenylboronic acid group). Therefore, a monomer having a boronic acid group may be used. Examples of such boronic acid group-containing monomers include acryloylaminobenzeneboronic acid, methacryloylaminobenzeneboronic acid, 4-vinylbenzeneboronic acid, and the like.

  Moreover, when detecting an ionic substance (especially one containing calcium ions) as a specific component, 4-acrylamidobenzo 18-crown-6-ether, acryloylaminobenzocrown ether, methacryloylaminobenzocrown is used as a monomer. Crown ether group-containing monomers (particularly, benzocrown ether group-containing monomers) such as ether and 4-vinylbenzocrown ether can be suitably used.

  When detecting an ionic substance such as sodium chloride as a specific component, as monomers, 3-acrylamidophenylboronic acid, vinylphenylboronic acid, acryloyloxyphenylboronic acid, N-isopropylacrylamide (NIPAAm), Ethylene bisacrylamide, N-hydroxyethyl acrylamide, etc. can be used suitably. In particular, when an ionic substance such as sodium chloride is detected as a specific component, the monomer is selected from the group consisting of 3-acrylamidophenylboronic acid, vinylphenylboronic acid, and acryloyloxyphenylboronic acid. Alternatively, two or more monomers are used in combination with one or more monomers selected from the group consisting of N-isopropylacrylamide (NIPAAm), ethylenebisacrylamide and N-hydroxyethylacrylamide. Is preferred.

  When lactic acid is detected as a specific component, monomers such as 3-acrylamidophenylboronic acid, vinylphenylboronic acid, acryloyloxyphenylboronic acid, N-isopropylacrylamide (NIPAAm), ethylenebisacrylamide, N -Hydroxyethyl acrylamide etc. can be used conveniently. In particular, when detecting lactic acid as a specific component, the monomer is one or more selected from the group consisting of 3-acrylamidophenylboronic acid, vinylphenylboronic acid and acryloyloxyphenylboronic acid. It is preferable to use a monomer in combination with one or more monomers selected from the group consisting of N-isopropylacrylamide (NIPAAm), ethylenebisacrylamide and N-hydroxyethylacrylamide.

  Further, the mixed liquid 10 ′ is polymerizable with a dimer, trimer, oligomer, prepolymer, or the like containing the monomer as a constituent component instead of the monomer or together with the monomer as a polymerizable compound. It may be included as a compound.

Content X ₁ of the polymerizable compound in the mixed liquid 10 'in is preferably equal to or lower than 1.0 mass% to 25 mass%, more preferably 20 wt% or less 2.5% by mass or more.

  This makes it possible to more reliably adjust the molecular weight and the like of the polymer material obtained by the polymerization reaction to a preferable range while making the reactivity of the mixed solution 10 'particularly excellent in the polymerization step.

  Further, the content of the monomer (monomer as the polymerizable compound) with respect to the entire polymerizable compound contained in the mixed solution 10 ′ is preferably 70% by mass or more and 100% by mass or less, and 80% by mass. More preferably, it is 100 mass% or less.

  This makes it possible to more reliably adjust the molecular weight and the like of the polymer material obtained by the polymerization reaction to a preferable range while making the reactivity of the mixed solution 10 'particularly excellent in the polymerization step.

(Crosslinking agent)
As the crosslinking agent, a compound having two or more polymerizable functional groups can be used. Specifically, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, Polyglycerin, N, N′-methylenebisacrylamide, N, N-methylene-bis-N-vinylacetamide, N, N-butylene-bis-N-vinylacetamide, tolylene diisocyanate, hexamethylene diisocyanate, allylated starch, Allylated cellulose, diallyl phthalate, tetraallyloxyethane, pentaerythritol triallyl ether, trimethylolpropane triallyl ether, diethylene glycol diallyl ether, triallyl trimellitate, etc. 1 type or 2 types or more selected from these can be used in combination.

  Above all, the mixed solution 10 'preferably contains N, N'-methylenebisacrylamide as a crosslinking agent.

  Thereby, the polymerization reaction in a polymerization process can be started and advanced more suitably, and the productivity of the gel material 10 can be further improved. Moreover, the holding power (particularly water retention) of the solvent of the polymer material can be further improved. Further, when the gel material 10 is a stimulus-responsive gel material, the introduction of a partial structure (functional group) that responds (responds) to a specific stimulus can be more easily and more reliably introduced into the polymer material. Can be introduced. In addition, N, N′-methylenebisacrylamide is a commercially available material that is stable and relatively inexpensive, and is advantageous from the standpoint of stable production of the gel material 10 and manufacturing cost.

Content _{X 2} of the cross-linking agent in the mixture 10 'in is preferably equal to or lower than 0.05 mass% to 1.5 mass%, more that 0.5 mass% 0.1 mass% preferable.

  Thereby, the polymer material obtained by the polymerization reaction can have a crosslinked structure at an appropriate ratio.

The ratio ((X ₂ / X ₁ ) × 100) of the content X ₂ [% by mass] of the crosslinking agent to the content X ₁ [% by mass] of the polymerizable compound in the mixed liquid 10 ′ is 1% or more and 25%. Or less, more preferably 2.5% or more and 10% or less.

  Thereby, the polymer material obtained by the polymerization reaction can have a crosslinked structure at an appropriate ratio.

(Polymerization initiator)
Examples of the polymerization initiator include those represented by the following formula (1), the following formula (2), the following formula (3), the following formula (4), the following formula (5), and the following formula (6). 1 type selected from these, or 2 or more types can be used in combination.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭化水素基（水酸基、エーテル基またはカルボキシル基を有する炭化水素基を含む）である。また、Ｒ^１とＲ^２とは、互いに共有結合により結合し、環状をなすものであってもよい。）

(In the formula ^{(1), R 1, R} 2, R 3 are each independently hydrogen atom or a hydrocarbon group (a hydroxyl group, including a hydrocarbon group having an ether group or a carboxyl group). In addition, ^{R 1} And R ² may be bonded to each other by a covalent bond to form a ring.)

（式（２）中、Ｒ^１、Ｒ^２は、それぞれ独立に、水素原子または炭化水素基（水酸基、エーテル基またはカルボキシル基を有する炭化水素基を含む）である。また、Ｒ^１とＲ^２とは、互いに共有結合により結合し、環状をなすものであってもよい。）

(In the formula (2), R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group (including a hydrocarbon group having a hydroxyl group, an ether group or a carboxyl group), and R ¹ and R ^2. And may be bonded to each other by a covalent bond to form a ring.)

（式（３）中、Ｒ^１、Ｒ^２は、それぞれ独立に、水素原子または炭化水素基（水酸基、エーテル基またはカルボキシル基を有する炭化水素基を含む）である。また、Ｒ^１とＲ^２とは、互いに共有結合により結合し、環状をなすものであってもよい。）

(In Formula (3), R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group (including a hydrocarbon group having a hydroxyl group, an ether group, or a carboxyl group), and R ¹ and R ^2. And may be bonded to each other by a covalent bond to form a ring.)

（式（４）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭化水素基（水酸基、エーテル基またはカルボキシル基を有する炭化水素基を含む）である。また、Ｒ^１とＲ^２とは、互いに共有結合により結合し、環状をなすものであってもよい。）

(In the formula ^{(4), R 1, R} 2, R 3 are each independently hydrogen atom or a hydrocarbon group (a hydroxyl group, including a hydrocarbon group having an ether group or a carboxyl group). In addition, ^{R 1} And R ² may be bonded to each other by a covalent bond to form a ring.)

（式（５）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭化水素基（水酸基、エーテル基またはカルボキシル基を有する炭化水素基を含む）である。また、Ｒ^１とＲ^２とは、互いに共有結合により結合し、環状をなすものであってもよい。）

(In the formula ^{(5), R 1, R} 2, R 3 are each independently hydrogen atom or a hydrocarbon group (a hydroxyl group, including a hydrocarbon group having an ether group or a carboxyl group). In addition, ^{R 1} And R ² may be bonded to each other by a covalent bond to form a ring.)

（式（６）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭化水素基（水酸基、エーテル基またはカルボキシル基を有する炭化水素基を含む）である。また、Ｒ^１とＲ^２とは、互いに共有結合により結合し、環状をなすものであってもよい。）

(In the formula ^{(6), R 1, R} 2, R 3 are each independently hydrogen atom or a hydrocarbon group (a hydroxyl group, including a hydrocarbon group having an ether group or a carboxyl group). In addition, ^{R 1} And R ² may be bonded to each other by a covalent bond to form a ring.)

The formula (1) as R ^1, the R ² in is preferably an alkyl group having a carbon number of 1 to 4, more preferably a methyl group.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

In addition, R ³ in the above formula (1) is preferably a hydrocarbon group having 1 to 4 carbon atoms (including a hydrocarbon group having a hydroxyl group, an ether group or a carboxyl group), and —CH ₂ CH ₂ OH Is more preferable.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

R ¹ in the above formula (2) is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

In addition, R ² in the above formula (2) is preferably a hydrocarbon group having 1 to 4 carbon atoms (including a hydrocarbon group having a hydroxyl group, an ether group or a carboxyl group), and —CH ₂ CH ₂ COOH. Is more preferable.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

The R ^1, R ² in the formula (3), preferably an alkyl group having a carbon number of 1 to 4, more preferably a methyl group.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

The R ^1, R ² in the formula (4), preferably an alkyl group having a carbon number of 1 to 4, more preferably a methyl group.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

R ³ in the above formula (4) is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms (including a hydrocarbon group having a hydroxyl group, an ether group or a carboxyl group), CH ₂ CH ₂ COOH is more preferred.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

The R ^1, R ² in the above formula (5), preferably an alkyl group having a carbon number of 1 to 4, more preferably a methyl group.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

As the R ³ in the above formula (5), a hydrogen atom or, preferably an alkyl group having a carbon number of 1 to 4, more preferably a hydrogen atom.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

The R ^1, R ² in the formula (6), preferably an alkyl group having a carbon number of 1 to 4, more preferably a methyl group.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

As the R ³ in the above formula (6), a hydrogen atom or, preferably an alkyl group having a carbon number of 1 to 4, more preferably a hydrogen atom.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

In particular, the mixed solution 10 ′ preferably contains a compound represented by the above formula (1) as a polymerization initiator, in which R ¹ and R ² in the above formula (1) are methyl groups, and R ³ is − More preferably, it includes a compound that is CH ₂ CH ₂ OH.

  Thereby, in the polymerization process after the pressure reduction process, the polymerization reaction of the polymerizable compound can be started and progressed more suitably.

  Moreover, as a polymerization initiator other than the above, what is represented by following formula (7) and following formula (8) is mentioned, for example. Such a polymerization initiator can be used together with the polymerization initiator or in place of the polymerization initiator.

Mixture 10 'content _{X 3} of the polymerization initiator in the is preferably not more than 0.1 mass% to 10.0 mass%, not more than 0.2 mass% to 4.0 mass% More preferred.

  Thereby, generation | occurrence | production of the bad effect by containing an excess polymerization initiator can be prevented more effectively, making the reaction rate of the polymerization reaction in the superposition | polymerization process after a pressure reduction process faster.

The ratio ((X ₃ / X ₁ ) × 100) of the content X ₃ [% by mass] of the polymerization initiator to the content X ₁ [% by mass] of the polymerizable compound in the mixed liquid 10 ′ is 1.5%. It is preferably 40% or less and more preferably 4.0% or more and 16% or less.

  Thereby, generation | occurrence | production of the bad effect by containing an excess polymerization initiator can be prevented more effectively, making the reaction rate of the polymerization reaction in the superposition | polymerization process after a pressure reduction process faster.

(solvent)
The mixed solution 10 ′ may include a solvent having a function of dissolving or dispersing other components in addition to the polymerizable compound, the crosslinking agent, and the polymerization initiator.

  By including the solvent, the polymerization reaction can be started and proceeded more suitably. In addition, each constituent component can be more uniformly present in each part of the mixed liquid 10 ′, and effectively prevent unintentional compositional variation in the finally obtained gel material 10. be able to. In addition, when the polymer material is synthesized by the polymerization reaction, the reaction product can be suitably gelled, so that the productivity of the gel material 10 is superior to the case of gelation after the polymerization reaction. It can be. In addition, after synthesizing a polymer material by a polymerization reaction, the occurrence of unintentional variation in the composition at each part of the gel material is more effective than when the polymer material is mixed with a solvent and gelled. Can be prevented.

  As the solvent, various organic solvents and inorganic solvents can be used. More specifically, for example, water; various alcohols such as methanol and ethanol; ketones such as acetone; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide Amides such as: Chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; Cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatics such as benzene, toluene and xylene One or two or more selected from these can be used in combination, but those containing water are particularly preferred.

  Thereby, a polymerization reaction can be started and advanced more suitably, and the characteristic of the gel material 10 obtained can be made especially excellent. Moreover, since water can be suitably used as a constituent component of the final gel material 10, the purification treatment after the polymerization reaction can be omitted or simplified. In particular, the fact that the polymerization reaction starts and proceeds efficiently and the purification process can be omitted or simplified synergistically work to make the productivity of the gel material 10 particularly excellent. it can.

  The content of the solvent in the mixed liquid 10 ′ is preferably 50% by mass to 95% by mass, and more preferably 65% by mass to 90% by mass.

  Thereby, a polymerization reaction can be started and advanced more suitably. In addition, each constituent component can be present more uniformly in each part in the mixed liquid 10 ′, and it is possible to more effectively prevent unintentional compositional variation in the finally obtained gel material 10. can do. Moreover, the content rate of the solvent in the gel material obtained by a polymerization reaction can be adjusted to a suitable range.

(Fine particles)
The mixed liquid 10 ′ may include fine particles.

  Thereby, when the gel material 10 (stimulus responsive gel material) manufactured using the mixed liquid 10 ′ is deformed by a specific stimulus, the structural color due to the colloidal crystal is easily visually recognized. Detection can be performed more easily and more reliably. Further, since the structural color due to the colloidal crystal is easily visually recognized, for example, the amount of stimulation can be determined more easily and more accurately by the color tone.

  The constituent materials of the fine particles include inorganic materials such as silica and titanium oxide; polystyrene, polyester, polyimide, polyolefin, poly (meth) acrylate methyl, polyethylene, polypropylene, polyethylene, polyether sulfone, nylon, polyurethane, polyvinyl chloride, Examples thereof include organic materials (polymers) such as polyvinylidene chloride, and the fine particles are preferably silica fine particles. Thereby, the stability of the shape of the fine particles can be made particularly excellent, and the durability and reliability of the gel material 10 can be made particularly excellent. In addition, silica fine particles are relatively easy to obtain as those having a sharp particle size distribution (monodispersed fine particles), which is advantageous from the viewpoint of stable production and supply of the gel material 10.

  The shape of the fine particles is not particularly limited, but is preferably spherical. Thereby, the structural color by the colloidal crystal is visually recognized more reliably, and detection of a specific stimulus can be performed more easily and more reliably.

  The average particle diameter of the fine particles is not particularly limited, but is preferably 10 nm or more and 1000 nm or less, and more preferably 20 nm or more and 500 nm or less.

  Thereby, when the gel material 10 receives a specific stimulus, the structural color due to the colloidal crystal is more easily recognized, so that the specific stimulus can be detected more easily and more reliably. Further, since the structural color due to the colloidal crystal is more easily recognized, for example, the amount of stimulation can be determined more easily and more accurately by the color tone.

  In the present invention, the average particle diameter means a volume-based average particle diameter. For example, a dispersion obtained by adding a sample to methanol and dispersing for 3 minutes with an ultrasonic disperser is used as a Coulter Counter particle size distribution analyzer (COULTER ELECTRONICS). INS TA-II type) can be obtained by measuring with a 50 μm aperture.

The mixed solution 10 ′ may include a plurality of different types of fine particles.
The content of the fine particles in the mixed liquid 10 ′ is preferably 2.0% by mass or more and 30% by mass or less, and more preferably 5.0% by mass or more and 20% by mass or less.

  Thereby, the effect as mentioned above by gel material 10 containing fine particles is exhibited more notably.

(Other ingredients)
The mixed solution 10 ′ may include components other than those described above (other components).

  Examples of such components include colorants, slip agents (leveling agents), antifungal agents, preservatives, and antioxidants.

  Moreover, it is preferable that the liquid mixture 10 'used in the liquid mixture application step has been subjected to a desalting treatment.

  Thereby, inhibition of the function of the polymerization initiator is more effectively prevented / suppressed, and the polymerization reaction in the polymerization process can be started / progressed more efficiently. As a result, it is possible to more effectively prevent the occurrence of inconvenience due to the fact that the polymerization reaction does not proceed as intended, and the gel material 10 finally obtained can be made particularly excellent in stability of characteristics. . Further, the content of the polymerization initiator in the mixed liquid 10 'can be further reduced.

  Moreover, it is preferable that the liquid mixture 10 ′ provided for the liquid mixture application step has been subjected to a deaeration process.

  Thereby, the oxygen content rate (dissolved oxygen amount) in the mixed liquid 10 ′ applied on the substrate 6 can be reduced in advance. As a result, even if the decompression process in the decompression step is performed in a shorter time, the oxygen content (dissolved oxygen amount) in the mixed liquid 10 ′ applied on the substrate 6 can be made sufficiently low. . Moreover, the deaeration process with respect to liquid mixture 10 '(liquid mixture 10' before provision to the base material 6) provided to a liquid mixture provision process is from the pressure reduction process with respect to liquid mixture 10 'provided on the base material 6. Can be easily performed in a short time. For this reason, the productivity of the gel material 10 can be further improved. Further, the ejection stability of the mixed liquid 10 ′ by the ink jet method is improved.

《Gel material》
Next, the gel material of the present invention will be described.

The gel material of the present invention is manufactured using the method of the present invention as described above.
Thereby, the gel material excellent in the stability of the characteristic can be provided.

[Overall shape of gel material]
The gel material 10 may have any shape, and examples thereof include a sheet shape (film shape), a plate shape, a block shape, a string shape, a cylindrical shape, and a particle shape.

[Constituent material of stimuli-responsive gel material]
(Polymer material)
The gel material 10 includes a polymer material having a crosslinked structure.

  The content of the polymer material in the gel material 10 is preferably 0.7% by mass or more and 36.0% by mass or less, and more preferably 2.4% by mass or more and 27.0% by mass or less.

(solvent)
The gel material 10 contains a solvent.
Thereby, the polymeric material mentioned above can be gelatinized.

  The solvent may have the same composition as the solvent used in the polymerization reaction in the production method described above, or may have a different composition.

  As the solvent constituting the gel material 10, various organic solvents and inorganic solvents can be used. More specifically, for example, water; various alcohols such as methanol and ethanol; ketones such as acetone; tetrahydrofuran, diethyl ether and the like Ethers; amides such as dimethylformamide; chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene, toluene And aromatics such as xylene, and the like, particularly those containing water.

  The content of the solvent in the gel material 10 is preferably 30% by mass or more and 95% by mass or less, and more preferably 50% by mass or more and 90% by mass or less.

(Fine particles)
The gel material 10 may include fine particles.

  Thereby, when the gel material 10 receives a specific stimulus, the structural color due to the colloidal crystal is easily visually recognized. Therefore, the specific stimulus can be detected more easily and more reliably. In addition, since the structural color due to the colloidal crystal is easily visually recognized, the amount of stimulation can be determined more easily and more accurately by, for example, the color tone.

  The fine particles can be introduced into the gel material 10 by being included as a constituent component of the mixed liquid 10 ′ in the manufacturing method described above, but may not be introduced in this way.

  The fine particles constituting the gel material 10 preferably satisfy the same conditions as those described as the constituent components of the mixed liquid 10 ′.

  The content of the fine particles in the gel material 10 is preferably 1.6% by mass or more and 36% by mass or less, and more preferably 4.0% by mass or more and 24% by mass or less.

  Thereby, the effect as mentioned above by gel material 10 containing fine particles is exhibited more notably.

[Use of gel material]
The use of the gel material 10 is not particularly limited, and examples thereof include a gel material for electrophoresis, a stimulus-responsive gel material, and a buffer material.

  In particular, the stimulus-responsive gel material is required to have a sensitivity to respond stably to a specific stimulus. However, when the present invention is applied to a stimulus-responsive gel material, the stimulus-responsive gel material is stable to a specific stimulus. The sensitivity to react is reliably obtained. Therefore, when the present invention is applied to a stimulus-responsive gel material, the effects of the present invention are more remarkably exhibited.

  When the gel material of the present invention is used as a stimulus-responsive gel material, the stimulus-responsive gel material can stably detect a specific stimulus. For example, as a sensor (detection means) for a specific stimulus Can be used.

  Further, since the amount of the specific component incorporated into the stimulus-responsive gel material can be stably identified, it can be suitably used as a separation / extraction means for separating / extracting the specific substance contained in the test object. it can. That is, when the amount of a specific component incorporated in the stimulus-responsive gel material is saturated or is likely to saturate, contact with the contact liquid is stopped and replaced with another stimulus-responsive gel material as necessary. Can do. Thereby, the specific component can be recovered from the contact liquid without waste.

  When the gel material of the present invention is applied to a stimulus-responsive gel material, more specific uses of the stimulus-responsive gel material include, for example, biological substances (for example, various cells such as cancer cells and blood cells, Detection means for proteins such as antibodies (including glycoproteins etc.), components of body fluids or exocrine secretions (eg blood, saliva, sweat, urine etc.) (eg lactic acid, uric acid, sugar etc.) Detection means, separation / extraction means for biological substances (especially trace biological substances such as hormones), separation / extraction means for metals (especially rare metals, noble metals, etc.), detection means for antigens (allergic substances) such as pollen, Included in food, separation / extraction means for toxic substances, harmful substances, environmental pollutants, etc., detection means for viruses, bacteria, etc., detection means for components contained in soil, detection means for components contained in waste liquid (including wastewater) Component detection means, underwater Included components (e.g., brackish, rivers, salt or the like contained in the paddy field, etc.) detection means include a cell culture monitoring and the like.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

  For example, in the above-described embodiment, the case where the surface treatment process is included prior to the mixed liquid application process has been described. However, the manufacturing method of the present invention includes a mixed liquid application process, a pressure reduction process, and a polymerization process. It suffices to have a surface treatment step.

  Moreover, in the manufacturing method of this invention, you may perform a pre-processing process, an intermediate processing process, and a post-processing process as needed.

  For example, you may have the process of adjusting the amount of solvent in a gel material, and the process of substituting at least one part of a solvent after a superposition | polymerization process.

  In the production method of the present invention, a series of steps may be repeated. Thereby, the gel material as a laminated body can be obtained suitably. For example, the gel material may be manufactured as a laminate by repeatedly performing a series of steps including a mixed liquid application step, a pressure reduction step, and a polymerization step. Moreover, after repeating a series of processes including the mixed liquid application process and the decompression process, the polymerization process may be performed on the laminate in which layers (droplets) of the mixed liquid are stacked.

  When manufacturing the gel material as a laminated body by the above methods, the gel material which has the area | region comprised with the different material can also be obtained suitably. Moreover, the gel material as a three-dimensional structure which has a complicated shape can also be suitably manufactured by adjusting the application pattern of the liquid mixture to laminate | stack.

  In the above-described embodiment, the polymerization step is described as being performed under reduced pressure using the reduced pressure state in the pressure reduction step. However, at least a part of the polymerization step is mixed on the base material 6 subjected to the pressure reduction treatment. You may carry out in the state which raised the pressure of the atmosphere of liquid 10 '(return pressure). For example, the polymerization process includes a first process that is started under reduced pressure, and a second process that causes the polymerization reaction to proceed while the pressure in the chamber 1 is higher (for example, while returning to atmospheric pressure). It may be what performs. Further, after the decompression step, the polymerization reaction may be performed in a state where the atmosphere of the mixed liquid 10 ′ on the base material 6 subjected to the decompression process is returned to the atmospheric pressure.

  DESCRIPTION OF SYMBOLS 10 ... Gel material 10 '... Mixed liquid 1 ... Chamber 11 ... Ultraviolet transmission part 2 ... Surface treatment means 3 ... Mixed liquid provision means 4 ... Pump (pressure reduction means) 5 ... Ultraviolet irradiation means (polymerization means) 6 ... Base material

Claims (14)

A liquid mixture application step for applying a liquid mixture containing a polymerizable compound, a crosslinking agent and a polymerization initiator on the substrate;
A depressurization step of applying a depressurization process to the mixed solution applied on the substrate;
A method for producing a gel material, comprising: a polymerization step of polymerizing the polymerizable compound.   The manufacturing method of the gel material of Claim 1 which has a surface treatment process which performs the surface treatment for improving the lyophilic property to the said base material prior to the said liquid mixture provision process. The method for producing a gel material according to claim ₂ , wherein the surface treatment is an O ₂ plasma treatment.   The method for producing a gel material according to any one of claims 1 to 3, wherein the mixed solution contains fine particles having an average particle size of 10 nm to 1000 nm.   The method for producing a gel material according to any one of claims 1 to 4, wherein the mixed solution is subjected to a desalting treatment.   The method for producing a gel material according to any one of claims 1 to 5, wherein the mixed solution is subjected to a deaeration process.   The method for producing a gel material according to any one of claims 1 to 6, wherein the depressurization treatment is performed so that a dissolved oxygen amount in the mixed liquid applied on the base material is 500 ppm or less.   The method for producing a gel material according to claim 1, wherein the liquid mixture applying step is performed by an ink jet method. The decompression step is performed in a chamber having a wall portion made of a material having ultraviolet transparency,
The method for producing a gel material according to claim 1, wherein the polymerization step is performed by irradiating ultraviolet rays through the wall portion. The method for producing a gel material according to any one of claims 1 to 9, wherein the mixed solution contains a compound represented by the formula (1) as the polymerization initiator.

(In the formula ^{(1), R 1, R} 2, R 3 are each independently hydrogen atom or a hydrocarbon group (a hydroxyl group, including a hydrocarbon group having an ether group or a carboxyl group). In addition, ^{R 1} And R ² may be bonded to each other by a covalent bond to form a ring.)   The method for producing a gel material according to any one of claims 1 to 10, wherein a content of the polymerization initiator in the mixed solution is 0.1 mass% or more and 10 mass% or less.   The method for producing a gel material according to any one of claims 1 to 11, wherein the mixed liquid contains an acrylamide group as the polymerizable compound.   The method for producing a gel material according to any one of claims 1 to 12, wherein the mixed solution contains N, N'-methylenebisacrylamide as the cross-linking agent.   A gel material produced using the method according to any one of claims 1 to 13.

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