JP2023004571A - Production method of resin structure, and production apparatus of resin structure - Google Patents

Abstract

To solve a problem that it is difficult to obtain a resin structure of a high porosity and polymerization rate, since the structure and property of a porous resin change according to polymerization conditions in the production of a resin structure having a porous structure formed when polymerizing a polymerizable compound.SOLUTION: A production method of a resin structure includes a preparation step for preparing a liquid composition containing a polymerizable compound and a solvent, a first irradiation step for irradiating the prepared liquid composition with first active energy rays, and a second irradiation step for irradiating the liquid composition irradiated with the first active energy rays with second active energy rays. The resin structure has a porous structure having a resin skeleton. The porous structure is formed by irradiating the polymerizable compound in the liquid composition with the first active energy rays and the second active energy rays. The irradiation intensity of the second active energy rays is higher than that of the first active energy rays.SELECTED DRAWING: None

Description

The present invention relates to a resin structure manufacturing method and a resin structure manufacturing apparatus.

In general, porous resins can be used for various purposes. For example, by appropriately selecting the shape and size of the pores in the porous resin, the surface properties of the skeleton portion, and the like, it is possible to provide a separation layer that transmits or blocks only a specific substance. As another example, by utilizing the vast surface area and void volume of the porous resin, it is possible to provide an efficient reaction field and storage field for gases and liquids taken in from the outside. Therefore, if a liquid composition for forming a porous resin, which is excellent in handleability and can be easily applied to many places, can be provided, the range of applications of the porous resin will be greatly expanded.

As such a liquid composition for forming a porous resin, for example, in Patent Document 1, a photopolymerizable monomer (A) and an organic compound (B) incompatible with the photopolymerizable monomer (A) , a porous-forming photocurable resin composition comprising, as essential components, a common solvent (C) compatible with a photopolymerizable monomer (A) and an organic compound (B) and a photopolymerization initiator (D). ing.

However, in the production of a resin structure in which a porous structure is formed as a result of polymerization of a polymerizable compound, the structure, properties, etc. of the porous resin change based on the polymerization conditions, resulting in high porosity and high polymerization rate. There is a problem that it is difficult to obtain a resin structure.

The present invention includes an application step of applying a liquid composition containing a polymerizable compound and a solvent, a first irradiation step of irradiating the applied liquid composition with a first active energy ray, the first and a second irradiation step of irradiating a second active energy ray to the liquid composition irradiated with the active energy ray, wherein the resin structure comprises a resin The porous structure is formed by irradiating the polymerizable compound in the liquid composition with the first active energy ray and the second active energy ray and the irradiation intensity of the second active energy ray is higher than the irradiation intensity of the first active energy ray.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method and manufacturing apparatus which can improve a porosity and a polymerization rate in the resin structure in which a porous structure is formed with polymerization of a polymerizable compound can be provided.

FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus for a resin structure. FIG. 2 is a schematic diagram showing an example of a material jet modeling apparatus.

An embodiment of the present invention will be described below.

<<Method for manufacturing resin structure>>
The method for producing a resin structure according to the present embodiment comprises an applying step of applying a liquid composition containing a polymerizable compound and a solvent, and a first step of irradiating the applied liquid composition with a first active energy ray. and a second irradiation step of irradiating the liquid composition irradiated with the first active energy ray with the second active energy ray. In addition, the method for manufacturing a resin structure according to the present embodiment may include, if necessary, a removal step of removing the solvent from the resin structure after the second irradiation step.

<Addition process>
The applying step is a step of applying a liquid composition containing a polymerizable compound and a solvent to an object to be applied such as a substrate. The applied liquid composition preferably forms a liquid composition layer, which is a liquid film of the liquid composition, on the applied object. The method of applying the liquid composition is not particularly limited, and examples thereof include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, Various printing methods such as slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reversal printing method and inkjet printing method can be used. Among these, a liquid ejection method such as an inkjet printing method is preferable from the viewpoint that the position to which the liquid composition is applied can be controlled.

-Liquid composition-
The liquid composition contains other ingredients such as a polymerizable compound, a solvent, and optionally a polymerization initiator. In addition, the liquid composition is cured to form a resin structure (also referred to as “porous resin” in the following description) having a porous structure with a resin skeleton.
In the present disclosure, the liquid composition forms a porous resin, but this applies not only to the case where the porous resin is formed in the liquid composition, but also to the precursor of the porous resin in the liquid composition ( For example, it is meant to include the case where a porous resin skeleton is formed and the porous resin is formed in a subsequent step (for example, a heating step, etc.). In addition, the liquid composition forms a porous resin means that some components (polymerizable compound, etc.) in the liquid composition are cured (polymerized) to form the skeleton of the porous resin, It also means that other components (solvent, etc.) are not cured to form a porous resin.

--Polymerizable compound--
The polymerizable compound forms a resin by polymerizing to form a porous resin when polymerized in the liquid composition. The resin formed by the polymerizable compound is preferably a resin having a network structure formed by application of active energy rays (for example, irradiation of light, application of heat, etc.). Resins, methacrylate resins, urethane acrylate resins, vinyl ester resins, unsaturated polyester resins, epoxy resins, oxetane resins, vinyl ether resins, and resins formed by ene-thiol reactions are preferred. In addition, acrylate resins, methacrylate resins, and urethane acrylate resins, which are resins formed from polymerizable compounds having a (meth)acryloyl group, can be easily formed using highly reactive radical polymerization. Resins and vinyl ester resins, which are resins formed from a polymerizable compound having a vinyl group, are more preferable from the viewpoint of productivity. These may be used individually by 1 type, and may use 2 or more types together. When two or more types are used in combination, the combination of polymerizable compounds is not particularly limited and can be appropriately selected according to the purpose. It is preferable to mix the resin. In addition, in the present disclosure, a polymerizable compound having an acryloyl group or a methacryloyl group is referred to as a polymerizable compound having a (meth)acryloyl group.

The polymerizable compound preferably has at least one radically polymerizable functional group. Examples thereof include monofunctional, difunctional, trifunctional or higher radically polymerizable compounds, functional monomers, and radically polymerizable oligomers. Among these, bifunctional or higher radically polymerizable compounds are preferred.

Examples of monofunctional radically polymerizable compounds include 2-(2-ethoxyethoxy) ethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2- ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexylcarbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate , phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer, and the like. These may be used individually by 1 type, or may use 2 or more types together.

Examples of bifunctional radically polymerizable compounds include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, neopentyl glycol diacrylate, tricyclodecanedimethanol diacrylate, etc. is mentioned. These may be used individually by 1 type, or may use 2 or more types together.

Trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, and trimethylolpropane triacrylate. Acrylates, HPA-modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH-modified glycerol triacrylate, EO-modified glycerol triacrylate, PO-modified glycerol triacrylate, tris(acryloxyethyl ) isocyanurate, dipentaerythritol hexaacrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol tri acrylates, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxy tetraacrylate, EO-modified phosphoric acid triacrylate, 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate, and the like. These may be used individually by 1 type, or may use 2 or more types together.

The content of the polymerizable compound in the liquid composition is preferably 5.0% by mass or more and 70.0% by mass or less, more preferably 10.0% by mass or more and 50.0% by mass or less, relative to the total amount of the liquid composition. It is preferably 20.0% by mass or more and 40.0% by mass or less is more preferable. When the content of the polymerizable compound is 70.0% by mass or less, the pore size of the obtained porous resin is not too small, such as several nm or less, and the porous resin has an appropriate porosity, It is preferable because it can suppress the tendency of liquid or gas to hardly permeate. In addition, when the content of the polymerizable compound is 5.0% by mass or more, the three-dimensional network structure of the resin is sufficiently formed, a sufficient porous structure is obtained, and the obtained porous structure has a high strength. It is preferable because it shows a tendency to improve.

--solvent--
Solvents (also referred to as “porogens” in the following description) are liquids that are compatible with polymerizable compounds. The solvent is a liquid that becomes incompatible with the polymer (resin) produced in the process of polymerizing the polymerizable compound in the liquid composition (causes phase separation). By containing the solvent in the liquid composition, the polymerizable compound, when polymerized in the liquid composition, in other words, emits the first active energy ray and the second active energy ray sequentially in the liquid composition. Forms a porous resin when irradiated. Moreover, it is preferable that a compound (polymerization initiator described later) that generates a radical or an acid by light or heat can be dissolved. A solvent may be used individually by 1 type, or may use 2 or more types together. Note that the solvent does not have polymerizability.

The boiling point of one kind of porogen alone or the boiling point of two or more porogens used in combination is preferably 50° C. or higher and 250° C. or lower, more preferably 70° C. or higher and 200° C. or lower at normal pressure. When the boiling point is 50° C. or higher, vaporization of the porogen at around room temperature is suppressed, handling of the liquid composition is facilitated, and control of the content of the porogen in the liquid composition is facilitated. Moreover, since the boiling point is 250° C. or lower, the time required for drying the porogen after polymerization is shortened, and the productivity of the porous resin is improved. In addition, since the amount of porogen remaining inside the porous resin can be suppressed, it is possible to use the porous resin as a functional layer such as a substance separation layer for separating substances or a reaction layer as a reaction field. Improve quality.
Also, the boiling point of one type of porogen alone or the boiling point of two or more types in combination is preferably 120° C. or higher at normal pressure.

Examples of porogens include ethylene glycols such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, and dipropylene glycol monomethyl ether; esters such as γ-butyrolactone and propylene carbonate; and amides such as NN dimethylacetamide. can be mentioned. Liquids with relatively large molecular weights such as methyl tetradecanoate, methyl decanoate, methyl myristate, and tetradecane can also be used. Liquids such as acetone, 2-ethylhexanol, and 1-bromonaphthalene can also be used.
Note that the liquids exemplified above do not always correspond to porogens. As described above, the porogen is a liquid that is compatible with the polymerizable compound, and is incompatible with the polymer (resin) generated in the process of polymerizing the polymerizable compound in the liquid composition (phase separation ) is a liquid. In other words, whether or not a liquid corresponds to a porogen is determined by the relationship between the polymerizable compound and the polymer (resin formed by polymerizing the polymerizable compound).
In addition, since the liquid composition only needs to contain at least one porogen having the above-mentioned specific relationship with the polymerizable compound, the range of material selection when producing the liquid composition is widened, and the liquid composition can be design becomes easier. By expanding the range of materials to be selected when producing the liquid composition, the range of responses to the properties required for the liquid composition other than the formation of the porous structure can be expanded. For example, when a liquid composition is ejected by an inkjet method, it is required that the liquid composition has ejection stability and the like from the standpoints other than the porous formation. Easier to design.
As described above, the liquid composition should contain at least one porogen having the above specific relationship with the polymerizable compound. may additionally contain liquids that do not have However, the content of the liquid that does not have the above-mentioned specific relationship with the polymerizable compound (liquid that is not a porogen) is preferably 10.0% by mass or less with respect to the total amount of the liquid composition. It is more preferably 0.0% by mass or less, still more preferably 1.0% by mass or less, and particularly preferably not contained.

The porogen content in the liquid composition is preferably 30.0% by mass or more and 95.0% by mass or less, more preferably 50.0% by mass or more and 90.0% by mass or less, relative to the total amount of the liquid composition. 60.0% by mass or more and 80.0% by mass or less is more preferable. When the porogen content is 30.0% by mass or more, the pore size of the resulting porous body is not too small, such as several nanometers or less, and the porous body has an appropriate porosity and is suitable for liquids and liquids. This is preferable because it can suppress the tendency of gas permeation to occur less easily. Further, when the porogen content is 95.0% by mass or less, a three-dimensional network structure of the resin is sufficiently formed, a sufficient porous structure is obtained, and the strength of the resulting porous structure is also improved. It is preferable because a trend can be seen.

The mass ratio of the polymerizable compound content to the porogen content (polymerizable compound: porogen) in the liquid composition is preferably 1.0:0.4 to 1.0:19.0, and 1.0: 1.0 to 1.0:9.0 is more preferred, and 1.0:1.5 to 1.0:4.0 is even more preferred.

---Polymerization-induced phase separation---
Porous resins are formed by polymerization-induced phase separation. Polymerization-induced phase separation represents a state in which the polymerizable compound and the porogen are compatible, but the polymer (resin) generated in the process of polymerizing the polymerizable compound and the porogen are not compatible (phase separation occurs). There are other methods for obtaining a porous resin by phase separation, but by using the method of polymerization-induced phase separation, a porous body having a network structure can be formed, so a porous resin with high resistance to chemicals and heat can be obtained. body can be expected. In addition, compared with other methods, the process time is short and surface modification is easy.

Next, a process for forming a porous resin using polymerization-induced phase separation will be described. A polymerizable compound undergoes a polymerization reaction by light irradiation or the like to form a resin. During this process, the solubility of the porogen in the growing resin decreases and phase separation between the resin and the porogen occurs. Eventually, the resin forms a porous structure with porogens and the like filling the pores. When this is dried, the porogen and the like are removed, leaving a porous resin. Therefore, in order to form a porous resin having an appropriate porosity, the compatibility between the porogen and the polymerizable compound and the compatibility between the porogen and the resin formed by polymerizing the polymerizable compound are examined.

Compatibility between the porogen and the polymerizable compound is judged as follows.
First, the liquid composition is injected into a quartz cell, and the transmittance of light (visible light) at a wavelength of 550 nm of the liquid composition is measured while being stirred at 300 rpm using a stirrer. In the present disclosure, when the light transmittance is 30% or more, the polymerizable compound and the porogen are in a compatible state, and when it is less than 30%, the polymerizable compound and the porogen are in an incompatible state. to decide. Various conditions for the measurement of light transmittance are shown below.
・Quartz cell: special micro cell with screw cap (product name: M25-UV-2)
・Transmittance measurement device: USB4000 manufactured by Ocean Optics
・Agitation speed: 300 rpm
・Measurement wavelength: 550 nm
・Reference: Obtained by measuring the transmittance of light at a wavelength of 550 nm when the inside of the quartz cell is air (transmittance: 100%)

The compatibility between the porogen and the resin formed by polymerizing the polymerizable compound is determined as follows.
First, resin fine particles are uniformly dispersed on a non-alkali glass substrate by spin coating to form a gap agent. Subsequently, the substrate coated with the gap agent is attached to the non-alkali glass substrate to which the gap agent is not coated so as to sandwich the surface coated with the gap agent. Next, the liquid composition is filled between the bonded substrates by utilizing the capillary phenomenon to produce a "element for haze measurement before UV irradiation". Subsequently, the element for haze measurement before UV irradiation is irradiated with UV to cure the liquid composition. Finally, by sealing the periphery of the substrate with a sealant, a "haze measuring element" is produced. Various conditions during fabrication are shown below.
・ Alkali-free glass substrate: manufactured by Nippon Electric Glass, 40 mm, t = 0.7 mm, OA-10G
・Gap agent: Sekisui Chemical Co., Ltd., resin fine particle Micropearl GS-L100, average particle size 100 μm
・Spin coating conditions: 150 µL of dispersed droplets, rotation speed of 1000 rpm, rotation time of 30 s
Amount of filled liquid composition: 160 μL
・UV irradiation conditions: UV-LED used as light source, light source wavelength 365 nm, irradiation intensity 30 mW/cm ² , irradiation time 20 s
・Sealant: TB3035B (manufactured by Three Bond)
Next, the haze value (cloudiness) is measured using the manufactured element for haze measurement before UV irradiation and the element for haze measurement. Using the measured value of the haze measuring element before UV irradiation as a reference (haze value 0), the increase rate of the measured value (haze value) of the haze measuring element with respect to the measured value of the haze measuring element before UV irradiation is calculated. The haze value in the haze measuring element increases as the compatibility between the resin formed by polymerizing the polymerizable compound and the porogen decreases, and decreases as the compatibility increases. In addition, the higher the haze value, the easier it is for the resin formed by polymerizing the polymerizable compound to form a porous structure. In the present disclosure, when the haze value increase rate is 1.0% or more, the resin and the porogen are in a non-compatible state, and when it is less than 1.0%, the resin and the porogen are in a compatible state. I judge. In addition, the apparatus used for the measurement is shown below.
・Haze measuring device: Haze meter NDH5000 manufactured by Nippon Denshoku Industries

--Polymerization initiator--
A polymerization initiator is a material capable of generating active species such as radicals and cations by energy such as light and heat to initiate polymerization of a polymerizable compound. As the polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used singly or in combination of two or more. Among them, photoradical polymerization initiators can be used. preferable.

A photoradical generator can be used as the photoradical polymerization initiator. For example, photoradical polymerization initiators such as Michler's ketone and benzophenone known under the trade names of Irgacure and Darocure, more specific compounds include benzophenone, acetophenone derivatives such as α-hydroxy- or α-aminocetophenone, -aroyl-1,3-dioxolane, benzyl ketal, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, pp'-dichlorobenzophene, pp '-Bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzyl dimethyl ketal, tetramethylthiuram monosulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutyronitrile, benzoin peroxide, di-tert-butyl peroxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methylbenzoyl Formate, benzoin isopropyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin n-propyl, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(η5-2,4- Cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2 -methyl-1[4-(methylthio)phenyl]-2-morifolinopropan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173), bis(2, 6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one mono Acylphosphine oxide, bisacyl Phosphine oxide or titanocene, fluorescene, anthraquinone, thioxanthone or xanthone, lophine dimer, trihalomethyl compound or dihalomethyl compound, active ester compound, organoboron compound and the like are preferably used.
Furthermore, a photocrosslinkable radical generator such as a bisazide compound may be contained at the same time. In the case of polymerizing only with heat, a thermal polymerization initiator such as azobisisobutylonitrile (AIBN), which is a normal radical generator, can be used.

In order to obtain a sufficient curing rate, the content of the polymerization initiator should be 0.05% by mass or more and 10.0% by mass or less, when the total mass of the polymerizable compounds is 100.0% by mass. It is preferably 0.5% by mass or more and 5.0% by mass or less.

--others--
The liquid composition of the present disclosure can be a non-dispersed composition that does not contain a dispersion in the liquid composition or a dispersed composition that contains a dispersion in the liquid composition, but the non-dispersed composition preferably a system composition. This is because the liquid composition can be used for various applying means because the liquid composition is a non-dispersion composition. For example, it is preferable because it can be stably used in an ink jet system in which maintenance of ejection stability is important.

-Method for producing liquid composition-
The liquid composition is preferably prepared through the steps of dissolving the polymerization initiator in the polymerizable compound, further dissolving the porogen and other components, and stirring to obtain a uniform solution.

-Physical properties of the liquid composition-
The viscosity of the liquid composition is preferably 1.0 mPa·s or more and 150.0 mPa·s or less, more preferably 1.0 mPa·s or more and 30.0 mPa·s at 25° C. from the viewpoint of workability when applying the liquid composition. The following are more preferable, and 1.0 mPa·s or more and 25.0 mPa·s or less are particularly preferable. When the viscosity of the liquid composition is 1.0 mPa·s or more and 30.0 mPa·s or less, good ejection properties can be obtained even when the liquid composition is applied to an inkjet method. Here, the viscosity can be measured using, for example, a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.).

<First irradiation step>
The first irradiation step is a step of irradiating the liquid composition applied in the application step with a first active energy ray. The first irradiation step improves the porosity of the finally produced porous resin, thereby improving, for example, the uptake of fluids such as liquids or gases in the porous resin. Specifically, by irradiating the liquid composition with the first active energy ray, a porous precursor having a porous structure that serves as a basis for forming a porous resin with a high porosity is formed. In the first irradiation step, the polymerizable compound may remain as an unreacted component as long as the porous precursor is formed.

The first active energy ray is not particularly limited as long as it can impart the energy necessary for proceeding with the polymerization reaction of the polymerizable compound. Examples include ultraviolet rays, electron beams, α rays, and β rays. , γ-rays, and X-rays. Among these, ultraviolet rays are preferable. In particular, when using a high-energy light source, the polymerization reaction can proceed without using a polymerization initiator.

The reason why the porous precursor is formed by the first irradiation step will be explained.
As described above, when a porous resin is formed by polymerization-induced phase separation, the structure, properties, etc. of the porous resin change based on the polymerization conditions. For example, when forming a porous resin under conditions that promote the polymerization of a polymerizable compound by irradiating a liquid composition with an active energy ray having a high irradiation intensity, polymerization occurs before sufficient phase separation occurs. tends to progress, making it difficult to produce a porous resin with a high porosity.
Therefore, in the first irradiation step for the purpose of forming a porous precursor having a porous structure that is the basis for forming a porous resin with a high porosity, the first active energy ray to be irradiated is set not too high. Specifically, the irradiation intensity of the first active energy ray is higher than the irradiation intensity of the second active energy ray irradiated in the second irradiation step described later for the purpose of promoting the polymerization reaction of the polymerizable compound as an unreacted component. Set to low intensity.
More specifically, the irradiation intensity of the first active energy ray is preferably 1 W/cm ² or less, more preferably less than 300 mW/cm ² , and even more preferably 100 mW/cm ² or less. However, if the irradiation intensity of the first active energy ray is too low, the phase separation proceeds excessively, which tends to cause variation and coarsening of the porous structure, and furthermore, the irradiation time becomes longer, resulting in a decrease in productivity. Therefore, it is preferably 10 mW/cm ² or more, more preferably 30 mW/cm ² or more. When the first irradiation step is performed while the light source that irradiates the first active energy ray and the liquid composition move relative to each other, the irradiation intensity on the surface of the liquid composition changes continuously. The irradiation intensity in such a case represents an average value of irradiation intensities measured at a plurality of locations evenly (uniformly) selected from within the region where the first irradiation step is performed.

The time for irradiating the first active energy ray in the first irradiation step is preferably longer than or equal to the structure determination time for determining the porous structure that is the basis for forming a porous resin with a high porosity. By setting the time for irradiating the first active energy ray to be equal to or longer than the structure determination time, it is possible to avoid executing the second irradiation step described later in a state in which the formation of the porous structure is insufficient. As a result, a porous resin having a high porosity can be produced.

The structure determination time can be calculated by the following method using the liquid composition.
First, resin fine particles are uniformly dispersed on a non-alkali glass substrate by spin coating to form a gap agent. Subsequently, the substrate coated with the gap agent is attached to the non-alkali glass substrate to which the gap agent is not coated so as to sandwich the surface coated with the gap agent. Next, the space between the bonded elements is filled with the liquid composition using capillary action, and finally, the periphery of the substrate is sealed with a sealant to prepare a "structure determination time measurement element". Various conditions during fabrication are shown below.
・ Alkali-free glass substrate: manufactured by Nippon Electric Glass, 40 mm, t = 0.7 mm, OA-10G
・Gap agent: Sekisui Chemical Co., Ltd., resin fine particle Micropearl GS-L100, average particle size 100 μm
・Spin coating conditions: 150 µL of dispersed droplets, rotation speed of 1000 rpm, rotation time of 30 s
Amount of filled liquid composition: 160 μL
・Sealant: TB3035B (manufactured by Three Bond)
Next, the fabricated device for structure determination time measurement is irradiated with a first active energy ray under the same conditions as in the first irradiation step. Using the transmittance of the element before irradiation as a reference, the attenuation of the measured value (transmittance) of the element during irradiation is measured. The attenuation rate is calculated assuming that the transmittance is 100% when there is no change in attenuation due to excessive irradiation of the first active energy ray. The decay rate increases as the polymerization forms a porous structure. In the present disclosure, the structure determination time is defined as the time required from the start of irradiation until the transmittance attenuation rate reaches 50%. In addition, the apparatus used for the measurement is shown below.
・Transmittance measurement device: LCD-5200 manufactured by Otsuka Electronics Co., Ltd.

<Second irradiation step>
The second irradiation step is a step of irradiating the liquid composition irradiated with the first active energy ray with the second active energy ray. In the second irradiation step, the polymerization rate of the porous resin is improved by promoting the polymerization reaction of the polymerizable compound remaining as an unreacted component in the first irradiation step, thereby improving the strength of the porous resin, for example. improve. Specifically, the polymerization rate of the porous resin is preferably 90% or more. In addition, when the porous resin is used as an insulating layer (separator) for a power storage element, it is possible to suppress the remaining polymerizable compound, which is an unreacted component. decrease (for example, gas generation, etc.) can be suppressed. In the present disclosure, the “liquid composition irradiated with the first active energy ray” to be irradiated with the second active energy ray means that the liquid composition is irradiated with the first active energy ray in the first irradiation step. Specifically, it is a composite of a porous precursor produced in the first irradiation step, a polymerizable compound as an unreacted component, and a solvent.

The second active energy ray is not particularly limited as long as it can impart the energy necessary for proceeding with the polymerization reaction of the polymerizable compound. Examples include ultraviolet rays, electron beams, α rays, and β rays. , γ-rays, and X-rays. Among these, ultraviolet rays are preferable. In particular, when using a high-energy light source, the polymerization reaction can proceed without using a polymerization initiator.
Also, the types of the first active energy ray and the second active energy ray may be the same or different, but are preferably the same, and both are preferably ultraviolet rays. When both the first active energy ray and the second active energy ray are ultraviolet rays, the peak wavelengths may be the same or different, but are preferably the same.

The reason why the second irradiation step promotes the polymerization reaction of the polymerizable compound remaining as an unreacted component in the first irradiation step will be explained.
As described above, when a porous resin is formed by polymerization-induced phase separation, the structure, properties, etc. of the porous resin change based on the polymerization conditions. Specifically, the first irradiation step described above is performed for the purpose of forming a porous precursor having a porous structure that is the basis for forming a porous resin with a high porosity. Since the irradiation intensity of the active energy ray is set so as not to be too high, the polymerizable compound may remain as an unreacted component in the first irradiation step, and it is difficult to produce a porous resin with a high polymerization rate. tends to be difficult.
Therefore, in the second irradiation step for the purpose of forming a porous resin with a high polymerization rate, the irradiation intensity of the second active energy ray is set to be higher than the irradiation intensity of the first active energy ray. be done.
Specifically, the irradiation intensity of the second active energy ray is preferably 300 mW/cm ² or higher, more preferably 400 mW/cm ² or higher, and even more preferably 1 W/cm ² or higher. In addition, when the second irradiation step is performed while the light source for irradiating the second active energy ray and the object to be irradiated (liquid composition irradiated with the first active energy ray) are relatively moving, the irradiated The irradiation intensity on the object surface changes continuously. The irradiation intensity in such a case represents an average value of irradiation intensities measured at a plurality of locations evenly (uniformly) selected from within the region where the second irradiation step is performed.
The irradiation intensity of the second active energy ray is preferably 5 times or more, more preferably 10 times or more, that of the first active energy ray.

The method for measuring the polymerization rate of the porous resin is not particularly limited, but examples thereof include a method of measuring by infrared spectroscopy. Specifically, the peak value of 820 to 800 cm ⁻¹ corresponding to =CH out-of-plane bending vibration, the peak value of 1430 to 1400 cm ⁻¹ corresponding to =CH in-plane bending vibration, or C=C corresponding to C It is calculated by reading the peak value at 1640 to 1620 cm ⁻¹ and comparing it with the value at the time of non-irradiation.

<Removal process>
The removing step is a step of removing the solvent from the porous resin after the second irradiation step. A method for removing the solvent is not particularly limited, and an example thereof includes a method of removing the solvent from the porous resin by heating. At this time, it is preferable to heat under reduced pressure because the removal of the solvent is further accelerated and the residual of the solvent in the porous resin can be suppressed.

<<Resin Structure Manufacturing Equipment>>
The apparatus for manufacturing a resin structure according to the present embodiment includes applying means for applying a liquid composition containing a polymerizable compound and a solvent, and a first means for applying a first active energy ray to the applied liquid composition. irradiating means; and second irradiating means for irradiating the liquid composition irradiated with the first active energy ray with the second active energy ray. In addition, the apparatus for manufacturing a resin structure according to the present embodiment may have, if necessary, removal means for removing the solvent from the resin structure after irradiation by the second irradiation means.

Details of the apparatus for manufacturing a resin structure will be described with reference to FIG. FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus for a resin structure.
A porous resin manufacturing apparatus 100, which is an example of a resin structure manufacturing apparatus, is an apparatus for manufacturing a porous resin using the liquid composition described above. The porous resin manufacturing apparatus 100 includes a printing process unit 10 that performs a process of applying a liquid composition to a printing substrate 4, which is an example of a substrate, to form a liquid composition layer, and a printing process unit 10 that forms a liquid composition layer. A polymerization process unit 20 and a polymerization process unit 21 for performing a step of activating a polymerization initiator to polymerize a polymerizable compound to obtain a porous resin 6, and a step of heating the porous resin 6 to remove the solvent are performed. A heating process section 30 is provided. The porous resin manufacturing apparatus 100 includes a conveying section 5 that conveys the printing base material 4. The conveying section 5 carries out the printing base material in the order of the printing process section 10, the polymerization process section 20, the polymerization process section 21, and the heating process section 30. 4 is conveyed at a preset speed.

<Printing process department>
The printing process unit 10 includes a printing device 1a, which is an example of applying means for realizing a step of applying the liquid composition onto the printing base material 4, a container 1b containing the liquid composition, and a container 1b. and a supply tube 1c for supplying the liquid composition stored in the printer 1a to the printer 1a.

The storage container 1b stores the liquid composition 7, and the printing process unit 10 ejects the liquid composition 7 from the printing device 1a, applies the liquid composition 7 onto the printing substrate 4, and produces the liquid composition. The layer is formed into a thin film. The container 1b may be integrated with the porous resin manufacturing apparatus 100, or may be detachable from the porous resin manufacturing apparatus 100. FIG. Moreover, it may be a container that is integrated with the porous resin production apparatus 100 or a container that is used for adding to a storage container that is detachable from the porous resin production apparatus 100 .

The printing apparatus 1a is not particularly limited as long as it can apply the liquid composition 7. Examples of the printing apparatus 1a include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar Various printing methods such as coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method, etc. Any printing device suitable for the method can be used.

The storage container 1b and the supply tube 1c can be arbitrarily selected as long as they can store and supply the liquid composition 7 stably. It is preferable that the materials forming the storage container 1b and the supply tube 1c have light shielding properties in the relatively short wavelength regions of ultraviolet light and visible light. This prevents the liquid composition 7 from being polymerized by outside light.

<Polymerization process department>
As shown in FIG. 1, the polymerization process unit 20 is a light irradiation device which is an example of a first irradiation means for polymerizing a polymerizable compound by irradiating a liquid composition with an active energy ray such as heat or light. 2a and a polymerization inert gas circulation device 2b for circulating the polymerization inert gas. The light irradiation device 2a irradiates the liquid composition formed by the printing process section 10 with light in the presence of a polymerization inert gas to form a porous precursor.

As shown in FIG. 1, the polymerization process section 21 irradiates the liquid composition irradiated with the first active energy ray in the polymerization process section 20 with an active energy ray such as heat or light to produce a polymerizable compound. and a polymerization inert gas circulation device 2d for circulating the polymerization inert gas. The light irradiation device 2 c irradiates the liquid composition irradiated with the first active energy ray in the polymerization process section 20 with light in the presence of a polymerization inert gas to form the porous resin 6 .

The light irradiation devices 2a and 2c are appropriately selected according to the absorption wavelength of the photopolymerization initiator contained in the liquid composition layer, and are not particularly limited as long as they can initiate and progress the polymerization of the compound in the liquid composition layer. Examples include ultraviolet light sources such as high-pressure mercury lamps, metal halide lamps, hot cathode tubes, cold cathode tubes, and LEDs. However, it is preferable to select the light source according to the thickness of the porous film to be formed, since light with a shorter wavelength generally tends to reach deeper areas.

Next, the polymerization inert gas circulators 2b and 2d reduce the concentration of polymerization-active oxygen contained in the atmosphere, allowing the polymerization reaction of the polymerizable compound in the vicinity of the surface of the liquid composition layer to proceed without hindrance. play a role. Therefore, the polymerization inert gas to be used is not particularly limited as long as it satisfies the above functions, and examples thereof include nitrogen, carbon dioxide and argon.

In addition, considering that the inhibition reduction effect can be effectively obtained as the flow rate of the polymerization inert gas, it is preferable that the O ₂ concentration is less than 20% (environment with a lower oxygen concentration than the atmosphere), and 0% It is more preferably 15% or less, and even more preferably 0% or more and 5% or less. In addition, it is preferable that the polymerization inert gas circulation devices 2b and 2d are provided with a temperature control means capable of controlling the temperature in order to realize stable polymerization progress conditions.

<Heating process part>
As shown in FIG. 1, the heating process section 30 has a heating device 3a which is an example of a removing means, and the solvent remaining in the porous resin 6 formed by the polymerization process section 20 and the polymerization process section 21 is removed by the heating device. Heat dry and remove according to 3a. The heating process section 30 may perform the solvent removal process under reduced pressure.
The heating process section 30 may remove the photopolymerization initiator remaining in the porous resin 6 by heating and drying it with the heating device 3a.

The heating device 3a is not particularly limited as long as it satisfies the above functions, and examples thereof include an IR heater and a hot air heater.
Moreover, the heating temperature and the heating time can be appropriately selected according to the boiling point of the solvent contained in the porous resin 6 and the formed film thickness.

<Print base material>
As a material for the printing substrate 4, any material can be used regardless of whether it is transparent or opaque. That is, transparent substrates include glass substrates, resin film substrates such as various plastic films, and composite substrates thereof, and opaque substrates include silicon substrates, metal substrates such as stainless steel, or laminates thereof. Various substrates can be used, such as
The printing substrate 4 may be a recording medium such as plain paper, glossy paper, special paper, or cloth. Also, the recording medium may be a low-permeability base material (low-absorbent base material). A low-permeability substrate means a substrate having a surface with low water permeability, absorption, or adsorption, and includes materials that have many cavities inside but are not open to the outside. Examples of low-permeability substrates include recording media such as coated paper used in commercial printing, and paperboard in which waste paper pulp is blended in the middle layer and back layer and the surface is coated.
In addition, the printing base material 4 may be a porous resin sheet used as an insulating layer for an electric storage element or an electric power generation element.

Moreover, as for the shape, even if it has a curved surface or an uneven shape, it can be used as long as it is applicable to the printing process section 10, the polymerization process section 20, and the polymerization process section 21. FIG.

<<resin structure>>
The film thickness of the resin structure (porous resin) having a porous structure with a resin skeleton formed by the liquid composition is not particularly limited, but it is 0.01 μm or more in consideration of curing uniformity during polymerization. It is preferably 500 µm or less, more preferably 0.01 µm or more and 100 µm or less, still more preferably 1 µm or more and 50 µm or less, and particularly preferably 10 µm or more and 20 µm or less. When the film thickness is 0.01 μm or more, the surface area of the obtained porous resin is increased, and the function of the porous resin can be sufficiently obtained. Further, when the film thickness is 500 μm or less, unevenness of light and heat used during polymerization in the film thickness direction is suppressed, and a porous resin uniform in the film thickness direction can be obtained. By producing a porous resin that is uniform in the film thickness direction, it is possible to suppress unevenness in the structure of the porous resin and suppress a decrease in liquid or gas permeability. Incidentally, the film thickness of the porous resin is appropriately adjusted according to the application in which the porous resin is used. For example, when a porous resin is used as an insulating layer for an electric storage element, the thickness is preferably 10 μm or more and 20 μm or less.
The porous resin to be formed is not particularly limited, but from the viewpoint of ensuring good liquid and gas permeability, it has a three-dimensional branched network structure of a cured resin as a skeleton, and a plurality of porous resins in the porous resin. It preferably has a co-continuous structure (also called a monolithic structure) in which pores are continuously connected. That is, it is preferable that the porous resin has a large number of pores, and that one of the pores has communication with other surrounding pores and spreads three-dimensionally. When the pores communicate with each other, the penetration of liquid and gas occurs sufficiently, and functions such as substance separation and reaction field can be efficiently exhibited.
One of the physical properties obtained by having a co-continuous structure is air permeability. The air permeability of the porous resin is measured according to JIS P8117, for example, and is preferably 500 seconds/100 mL or less, more preferably 300 seconds/100 mL or less. At this time, the air permeability is measured using, for example, a Gurley densometer (manufactured by Toyo Seiki Seisakusho).
The cross-sectional shape of the pores of the formed porous resin may be various shapes and sizes such as substantially circular, substantially elliptical, and substantially polygonal. Here, the size of the hole refers to the length of the longest portion in the cross-sectional shape. The pore size can be determined from a cross-sectional photograph taken with a scanning electron microscope (SEM). Although the size of the pores of the porous resin is not particularly limited, it is preferably 0.01 μm or more and 10 μm or less from the viewpoint of liquid or gas permeability. Moreover, the porosity of the porous resin is preferably 30% or more, more preferably 50% or more. The method for adjusting the pore size and porosity of the porous resin to these ranges is not particularly limited. Examples include a method of adjusting the content of porogen in the composition within the above range and a method of adjusting the irradiation conditions of active energy rays.

<<Use of resin structure>>
<Electricity Storage Element Application or Power Generation Element Application>
A resin structure (porous resin) having a porous structure having a resin skeleton formed using the above liquid composition (porous resin) can be used, for example, as an insulating layer for a power storage device or a power generation device. When used for these applications, it is preferable, for example, to form an insulating layer (separator) by applying a liquid composition onto an active material layer previously formed on an electrode substrate.
As an insulating layer for a storage device or a power generation device, it is known to use, for example, a film-like porous insulating layer having pores of a predetermined size or a porosity. On the other hand, when the above liquid composition is used, the pores and porosity can be appropriately changed by appropriately adjusting the content of the polymerizable compound, the content of the porogen, the irradiation conditions of the active energy ray, and the like. , the degree of freedom in designing the performance of the storage element and the power generation element can be improved. In addition, since the above liquid composition can be applied to various application methods, it can be applied, for example, by an inkjet method, and the degree of freedom in designing the shape of the storage element and the power generation element can be improved.
The insulating layer is a member that separates the positive electrode and the negative electrode and ensures ion conductivity between the positive electrode and the negative electrode. In addition, the term “insulating layer” in the present disclosure is not limited to a layered shape.
In addition, the above liquid composition is applied on the insulating layer (first insulating layer) for the storage element or the power generation element, thereby additionally forming an insulating layer (second insulating layer) made of a porous resin layer. insulating layer) can be formed. By forming the second insulating layer on the first insulating layer, it is possible to add or improve various functions of the insulating layer as a whole, such as heat resistance, impact resistance, and high-temperature shrinkage resistance.

The electrode substrate is not particularly limited as long as it has conductivity, and can be suitably used for secondary batteries and capacitors, which are generally electrical storage devices, especially lithium ion secondary batteries. Aluminum foil, copper foil, stainless steel Foils, titanium foils, etched foils obtained by etching them with fine holes, electrode substrates with holes used in lithium ion capacitors, and the like are used. In addition, carbon paper fiber-like electrodes used in power generation devices such as fuel cells may be used in a non-woven or woven flat form, and the perforated electrode substrates having fine holes may also be used. Furthermore, in the case of a solar device, in addition to the above electrodes, a transparent semiconductor thin film such as an indium-titanium oxide or zinc oxide is formed on a flat substrate such as glass or plastic, or a conductive film is formed. A thinly vapor-deposited electrode film can be used.

The active material layer is formed by dispersing a powdery active material or catalyst composition in a liquid, coating the liquid on the electrode substrate, fixing it, and drying it. It is formed by drying after application and printing using pull-up coating.

The positive electrode active material is not particularly limited as long as it is a material that can reversibly occlude and release alkali metal ions. Typically, an alkali metal-containing transition metal compound can be used as the positive electrode active material. Examples of lithium-containing transition metal compounds include composite oxides containing lithium and at least one element selected from the group consisting of cobalt, manganese, nickel, chromium, iron and vanadium. Examples include lithium-containing transition metal oxides such as lithium cobaltate, lithium nickelate and lithium manganate, olivine-type lithium salts such as _LiFePO4 , chalcogen compounds such as titanium disulfide and molybdenum disulfide, and manganese dioxide. A lithium-containing transition metal oxide is a metal oxide containing lithium and a transition metal or a metal oxide in which a part of the transition metal in the metal oxide is replaced with a different element. Examples of dissimilar elements include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, B, etc. Among them, Mn, Al, Co, Ni and Mg is preferred. The dissimilar element may be one kind or two or more kinds. These positive electrode active materials can be used alone or in combination of two or more. Nickel hydroxide etc. are mentioned as said active material in a nickel-hydrogen battery.

The negative electrode active material is not particularly limited as long as it is a material that can reversibly occlude and release alkali metal ions. Typically, a carbon material containing graphite having a graphite-type crystal structure can be used as the negative electrode active material. Examples of such carbon materials include natural graphite, spherical or fibrous artificial graphite, non-graphitizable carbon (hard carbon), and easily graphitizable carbon (soft carbon). Materials other than carbon materials include lithium titanate. In addition, from the viewpoint of increasing the energy density of lithium ion batteries, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxides, silicon nitrides, and tin oxides can also be suitably used as negative electrode active materials.

As the active material in the nickel-metal hydride battery, the hydrogen absorbing alloy is exemplified by AB2 or A2B hydrogen absorbing alloys.

Positive or negative electrode binders include, for example, PVDF, PTFE, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, poly Acrylate hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene-butadiene rubber, Carboxymethyl cellulose and the like can be used. Two types selected from tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene Copolymers of the above materials may also be used. Two or more selected from these may be mixed and used. Examples of the conductive agent contained in the electrode include graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black, carbon fibers and metal fibers. Conductive fibers such as carbon fluoride, metal powders such as aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, organic conductors such as phenylene derivatives and graphene derivatives material is used.

The active material in a fuel cell is generally used as a catalyst for a cathode electrode or an anode electrode, in which fine particles of metal such as platinum, ruthenium or platinum alloy are supported on a catalyst carrier such as carbon. In order to support the catalyst particles on the surface of the catalyst carrier, for example, the catalyst carrier is suspended in water, and a precursor of the catalyst particles (chloroplatinic acid, dinitrodiaminoplatinum, platinic chloride, platinous chloride, bisacetylacetate Nath platinum, dichlorodiammine platinum, dichlorotetramine platinum, platinum (II) sulfate, ruthenic chloride, iridic acid chloride, rhodic acid chloride, ferric chloride, cobalt chloride, chromium chloride, gold chloride, silver nitrate, rhodium nitrate, palladium chloride, nitric acid alloy components such as nickel, iron sulfate, and copper chloride) are added, dissolved in the suspension, alkali is added to generate a metal hydroxide, and the catalyst carrier is supported on the surface of the catalyst carrier get By coating such a catalyst carrier on an electrode and reducing it in a hydrogen atmosphere or the like, an electrode having a surface coated with catalyst particles (active material) is obtained.

In the case of solar cells and the like, active materials include tungsten oxide powder, titanium oxide powder, and oxide semiconductor layers such as SnO ₂ , ZnO, ZrO ₂ , Nb ₂ O ₅ , CeO ₂ , SiO ₂ and Al ₂ O ₃ . , a dye is supported on the semiconductor layer. Compounds such as complexes, ruthenium-cis-diaqua-bipyridyl complexes, phthalocyanines and porphyrins, organic-inorganic perovskite crystals can be mentioned.

<For white ink>
Since the liquid composition described above whitens by forming a porous resin and then removing the porogen, it is preferably used, for example, as a white ink applied onto a recording medium. In the present disclosure, the white ink is not particularly limited as long as it is an ink capable of forming a white image. included.

As a white ink, one that exhibits a white color by containing an inorganic pigment such as titanium oxide as a coloring material is generally known. However, since the specific gravity of the coloring material is high, such a white ink tends to cause sedimentation, resulting in poor storage stability and ejection stability. In this respect, the white ink composed of the above liquid composition can exhibit white color without containing a white colorant such as a pigment or dye as a component other than the liquid composition, and therefore has good storage stability and Ejection stability can be improved. The white ink of the present embodiment may contain a white colorant, but preferably does not substantially contain a white colorant. When substantially no white colorant is contained, the content of the white colorant is preferably 0.1% by mass or less, and 0.05% by mass or less, relative to the mass of the white ink. More preferably, it is 0.01% by mass or less, even more preferably below the detection limit, and particularly preferably not contained. Since the white ink does not substantially contain a white coloring material, the white image formed by the white ink can be made lighter. It can be preferably used as.

Also, as white inks, those containing a plurality of types of polymerizable compounds, which become cloudy due to phase separation of these polymers during curing, are also known. However, such a white ink exhibits whiteness due to phase separation between polymers and does not exhibit whiteness due to an air layer, and thus has a problem of inferior whiteness. In this regard, when the liquid composition of the present embodiment is used as a white ink, the porous resin having pores as an air layer exhibits a white color, and thus a high degree of whiteness can be exhibited. In addition, white is a color commonly referred to as “white”, and whiteness can be evaluated by measuring lightness (L ^* ) with a spectrophotometric densitometer such as X-Rite 939. For example, when it is applied at a duty of 100% or more or in an amount that sufficiently covers the surface of the recording medium, the lightness (L ^* ) and chromaticity (a ^* , b ^* ) are 70 ≤ L ^* ≤ 100 , −4.5≦a ^* ≦2 and −6≦b ^* ≦2.5.

In addition, since the white ink of the present embodiment forms a layer composed of a porous resin when applied onto a recording medium, the fixability of another ink (such as an ink containing a coloring material) applied thereafter is reduced. It may be used as a primer ink for producing a base layer (primer layer) that improves the
In general, when a low-permeability or non-permeability substrate such as coated paper, a glass substrate, a resin film substrate, or a metal substrate is used as a recording medium, the problem is that the fixability of the ink to the substrate is reduced. There is In this regard, when the white ink (primer ink) of the present embodiment is used, the fixability of the white ink (primer ink) to a low-permeability substrate or a non-permeability substrate is high. It is possible to improve the fixability of another ink to be applied. In addition, another ink (such as an ink containing a coloring material) applied later is a permeable ink (such as a water-based ink) that is difficult to use on a low-permeable or non-permeable substrate. However, the coloring material can be fixed on the surface of the porous resin while penetrating and diffusing the ink component into the porous resin.
In addition, since the white ink (primer ink) forms a white receiving layer, it hides the color and transparency of the recording medium and reduces the image density of other inks (inks containing coloring materials, etc.) that are applied later. can also be improved.

<Solid modeling applications>
Since the liquid composition described above can form a porous resin layer having a layer thickness in the height direction, a three-dimensional object can be formed by laminating a plurality of the porous resin layers. Generally, in three-dimensional modeling, there is a problem of distortion of a three-dimensional model due to curing shrinkage. In this regard, since the three-dimensional modeling composition containing the liquid composition of the present embodiment forms a porous body having a network structure as a result of polymerization-induced phase separation, the network structure relaxes the internal stress during polymerization. , distortion of the model due to curing shrinkage is suppressed.

Next, a modeling apparatus and a modeling method for modeling a three-dimensional object will be described with reference to FIG. FIG. 2 is a schematic diagram showing an example of a material jet modeling apparatus. The modeling apparatus in FIG. 2 includes ejection means (an example of application means) that ejects the liquid composition by an inkjet method or the like, and curing means (first irradiation method) that irradiates the ejected liquid composition with an active energy ray to cure it. means and an example of a second irradiation means), and forms a three-dimensional object by sequentially repeating ejection by the ejection means and curing by the curing means. Further, the modeling method realized by the modeling apparatus of FIG. 2 includes an ejection step (an example of an ejection step) of ejecting a liquid composition by an inkjet method, and irradiating an active energy ray to the ejected liquid composition to cure it. and a curing step (an example of a first irradiation step and a second irradiation step), and forming a three-dimensional object by sequentially repeating the discharging step and the curing step.
The modeling apparatus and the modeling method will be specifically described. The modeling apparatus 39 of FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged, and applies the first three-dimensional modeling composition from the object ejection head unit 30 to the support ejection head unit 31. , 32, a second composition for three-dimensional modeling having a composition different from the first composition for three-dimensional modeling is discharged, and these three-dimensional modeling compositions are laminated while being cured by adjacent ultraviolet irradiation means 33 and 34. It is. More specifically, for example, the second three-dimensional modeling composition is discharged from the support discharge head units 31 and 32 onto the modeled object support substrate 37, and irradiated with active energy rays to be solidified to form a reservoir. After forming the first support layer having the By repeating the step of forming the model layer a plurality of times while lowering the vertically movable stage 38 according to the number of times of stacking, the support layer and the model layer are laminated to manufacture the three-dimensional model 35.例文帳に追加After that, the support laminate 36 is removed as needed. In FIG. 2, only one ejection head unit 30 for a modeled object is provided, but two or more may be provided.

<Use for carrier>
When the above liquid composition is mixed with a functional substance to form a porous resin, it is possible to produce a carrier in which the functional substance is supported on the surface of the porous resin. Here, the surface of the porous resin is meant to include not only the external surface of the porous resin but also the internal surface communicating with the outside. In this way, the functional substance can be supported in the voids communicating with the outside, so the surface area capable of supporting the functional substance is increased.

When the carrier-forming composition of the present embodiment is used, the pores and porosity can be changed by appropriately adjusting the content of the polymerizable compound, the content of the porogen, the irradiation conditions of the active energy ray, and the like. It is possible to improve the degree of design freedom in terms of the performance of the carrier. In addition, since the carrier-forming composition of the present embodiment can be applied to various application methods, it can be applied, for example, by an ink jet method, thereby improving the degree of freedom in designing the shape of the carrier. can. Specifically, the carrier can be uniformly formed not only on a flat surface but also on a curved surface, and the trouble of adjusting the shape by cutting the carrier according to the shape of the target can be omitted. In addition, droplets are formed by discharging by an inkjet method, and active energy rays are irradiated to droplets in flight or independent droplets attached to a substrate, thereby forming a carrier having a particle shape. can also be formed.

The functional substance is a substance that directly or indirectly exerts a predetermined function, and is preferably a substance that increases or improves the function as the area supported by the porous resin increases. The functional substance is a substance that exhibits the function when positioned on the external surface and/or the internal surface that communicates with the outside (in other words, the function does not function when positioned on the internal surface that does not communicate with the outside). Substances whose performance is suppressed) is more preferable. The functional substance may be a substance that dissolves or disperses in the liquid composition, but is preferably a substance that disperses. Examples of functional substances include, but are not particularly limited to, photocatalysts and physiologically active substances.

A photocatalyst is a substance that exhibits photocatalytic activity when irradiated with light in a specific wavelength range (excitation light having energy equal to or higher than the bandgap between the valence band and conduction band of the photocatalyst). By showing the photocatalytic activity, the photocatalyst can exert various actions such as antibacterial action, deodorizing/deodorizing action, and action of decomposing harmful substances such as volatile organic compounds (VOC).

Examples of photocatalysts include anatase-type or rutile-type titanium (IV) oxide (TiO ₂ ), tungsten oxide (III) (W ₂ O ₃ ), tungsten oxide (IV) (WO ₂ ), tungsten oxide (VI) ( WO3), zinc oxide (ZnO), iron( _III ) oxide _{( Fe2O3} ), strontium titanate (SrTiO3) _, bismuth( _III ) oxide (Bi2O3), bismuth vanadate _{( BiVO4} ), tin (II) oxide (SnO), tin (IV) oxide (SnO ₂ ), tin (VI) oxide (SnO ₃ ), zirconium oxide (ZrO ₂ ), cerium (II) oxide (CeO), cerium (IV) oxide (CeO ₂ ), barium titanate (BaTiO ₃ ), indium (III) oxide (In ₂ O ₃ ), copper (I) oxide (Cu ₂ O), copper (II) oxide (CuO), potassium tantalate (KTaO ₃ ), metal oxides such as potassium niobate (KNbO3); metal sulfides such as cadmium sulfide (CdS), zinc sulfide (ZnS), indium sulfide (InS); cadmium selenate _{( CdSeO4} ), zinc selenide metal selenides such as (ZnSe); metal nitrides such as gallium nitride (GaN); titanium (IV) oxide (TiO ₂ ), tin oxide (IV) (SnO ₂ ), tungsten (III) oxide; (W ₂ O ₃ ), tungsten oxide (IV) (WO ₂ ), and tungsten oxide (VI) (WO ₃ ), anatase titanium oxide (IV) (TiO ₂ ) is more preferred.

Physiologically active substances are active ingredients that are used to exert physiological effects on living organisms. For example, low-molecular-weight compounds including pharmaceutical compounds, food compounds, and cosmetic compounds, as well as proteins and DNA such as antibodies and enzymes. , macromolecular compounds including biopolymers such as nucleic acids such as RNA. In addition, the term “physiological effect” refers to an effect caused by a physiologically active substance exerting its physiological activity at a target site. to bring about meaningful change and impact. In addition, "physiological activity" means that a physiologically active substance acts on a target site (for example, a target tissue, etc.) to change or affect it. The target site is preferably, for example, a cell surface or intracellular receptor. In this case, the physiological activity of the physiologically active substance binding to a specific receptor transmits a signal to the cell, resulting in the exertion of a physiological effect. A physiologically active substance may be a substance that exhibits a physiological effect by binding to a specific receptor after being converted to a mature form by an enzyme in vivo. In this case, in the present application, the physiologically active substance includes the substance before being converted to the mature form. The physiologically active substance may be a substance produced by an organism (human or non-human organism), or may be an artificially synthesized substance. When a liquid composition containing such a physiologically active substance is used to form a particulate carrier, particles that deliver the physiologically active substance to a target site, that is, drug delivery, are used to exhibit desired physiological effects. It can be used as particles used in systems (DDS) and sustained release particles that continue to release drugs for a long period of time. Further, when a sheet-shaped carrier is formed using a liquid composition containing a physiologically active substance, it can be used as a sustained-release sheet that continuously releases a drug over a long period of time.

<Surface modification applications>
The outer surface of the porous resin formed from the above liquid composition has fine irregularities derived from the porosity, which can control the wettability. Specifically, when the resin constituting the porous resin is hydrophilic, the outer surface of the porous resin can be endowed with hydrophilicity higher than the hydrophilicity of the planar surface formed by the resin. . Further, when the resin constituting the porous resin is water repellent, the outer surface of the porous resin can be imparted with a higher water repellency than the planar surface formed by the resin. Therefore, by applying the surface-modifying liquid containing the liquid composition of the present embodiment to the surface of the object, the surface-modifying layer is formed, and the wettability of the surface of the object can be easily modified.

In addition, when the liquid composition of the present embodiment is used, the content of the polymerizable compound, the content of the porogen, the irradiation conditions of the active energy ray, etc. (unevenness derived from the porosity) can be changed, and the degree of freedom in designing the performance of the surface modified layer can be improved. In addition, since the liquid composition of the present embodiment can be applied to various application methods, for example, it can be applied by an inkjet method, and the degree of freedom in designing the shape of the surface-modified layer can be improved. . Specifically, the surface modification layer can be uniformly formed not only on flat surfaces but also on curved surfaces.

<Separation layer use or reaction layer use>
When the porous resin formed from the above liquid composition is permeable to a fluid such as a liquid or gas, the porous resin can be used as a flow path for the fluid. When a porous resin can be used as a fluid channel, the porous resin can be used as a separation layer that separates a predetermined substance from a fluid or as a reaction layer (microreactor) that provides a minute reaction field to a fluid. It can be used for purposes such as In other words, the liquid composition of the present embodiment is preferably contained in the separation layer forming composition or the reaction layer forming composition. It is preferable that the porous resin used for these purposes is capable of uniformly and efficiently permeating the fluid inside the porous resin. In this regard, since the porous resin formed by the liquid composition of the present embodiment is formed by phase separation, the pores are continuously connected to each other, and the fluid can be uniformly and efficiently permeated. It has a possible structure.
The case where the porous resin is permeable to fluids such as liquids and gases is not particularly limited, but for example, the case where the air permeability measured according to JIS P8117 is 500 seconds/100 mL or less. Preferably, it is 300 seconds/100 mL or less, more preferably. At this time, the air permeability is measured using, for example, a Gurley densometer (manufactured by Toyo Seiki Seisakusho).
Separation means that a predetermined substance contained in a fluid mixture can be removed or concentrated. Moreover, the removal is not limited to the case where the predetermined substance is completely removed from the fluid mixture, and may be the case where a part of the substance is removed.
Note that the reaction field is a place where a predetermined chemical reaction proceeds through passage of a predetermined substance contained in the fluid.

When used for a separation layer, the liquid composition preferably contains a polymerizable compound having a functional group capable of interacting with a predetermined substance contained in the fluid. When the porous resin is formed using the liquid composition, functional groups capable of interacting with a predetermined substance are arranged on the surface (inner surface and outer surface) of the porous resin, effectively separating the predetermined substance. It can be carried out. The polymerizable compound having a functional group capable of interacting with a predetermined substance contained in the fluid may be part or all of the polymerizable compound contained in the liquid composition. In the present application, the term "functional group capable of interacting with a given substance" refers to the case where the functional group itself is capable of interacting with the given substance, and in addition to the case where the functional group itself is capable of interacting with the given substance It also includes cases where it becomes operable.

When used for reaction layer applications, the liquid composition described above preferably contains a polymerizable compound having a functional group that provides a reaction site to the fluid. When the porous resin is formed using the liquid composition, functional groups that provide a reaction field to the fluid are arranged on the surface (inner surface and outer surface) of the porous resin to effectively provide a reaction field. can. The polymerizable compound having a functional group that provides a reaction field to the fluid may be part or all of the polymerizable compound contained in the liquid composition. In the present application, a functional group that provides a reaction field to a fluid means a case where the functional group itself can provide a reaction field, and a case where a reaction field can be provided by additionally performing graft polymerization. Also includes

The separation layer and the reaction layer are formed, for example, by filling a container such as a glass tube capable of forming a fluid inflow portion and a fluid outflow portion with a liquid composition and curing the composition. Further, by printing the liquid composition on a substrate by an inkjet method or the like, it is possible to prepare (drawing) a separation layer and a reaction layer which are formed of a porous resin and have channels of a desired shape. Since the channels of the separation layer and the reaction layer can be printed, it is possible to provide the separation layer and the reaction layer in which the channels can be appropriately changed according to the purpose.

When the composition for forming the separation layer and the composition for forming the reaction layer of the present embodiment are used, the content of the polymerizable compound, the content of the porogen, the irradiation conditions of the active energy ray, and the like can be appropriately adjusted to obtain a porous structure. The pores and porosity of the organic resin can be changed, and the degree of freedom in designing the performance of the separation layer and the reaction layer can be improved.

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

<Adjustment of liquid composition>
A liquid composition was prepared by mixing materials in the proportions shown below.
・Tricyclodecane dimethanol diacrylate (Daicel-Ornex Co., Ltd.): 29.0% by mass
・ Tetradecane (manufactured by Kanto Chemical Industry Co., Ltd.): 70.0% by mass
・ Irgacure 184 (manufactured by BASF): 1.0% by mass

In the prepared liquid composition, the transmittance of light at a wavelength of 550 nm was measured by the above method while stirring, and it was 30% or more. Further, the rate of increase in haze value of the element for haze measurement produced using the prepared liquid composition was measured by the above method and found to be 1.0% or more.
Further, the viscosity of the prepared liquid composition at 25° C. was measured by the above method and found to be 1.0 mPa·s or more and 30.0 mPa·s or less.

<Production of resin structure>
(Example 1)
- Granting process -
First, the prepared liquid composition is filled in the apparatus for manufacturing a resin structure shown in FIG. A continuous film of the liquid composition was formed so that the thickness of the porous resin formed after the removal step described later was 20 μm. As the printing device 1a, an inkjet head (GEN5 head, manufactured by Ricoh Printing Systems Co., Ltd.) was used. Also, as the printing base material 4, a glass base material on which ITO having a thickness of 8 μm was sputtered and an electrode base material on which an active material layer manufactured by the following method was laminated were used.
In addition, ejection of the liquid composition from the inkjet head was stable, and no ejection failure nozzles, ejection bending, and the like were observed.

--Production of Electrode Substrate Laminated with Active Material Layer--
97.0 parts by mass of graphite particles (average particle size 10 μm) as an active material, 1.0 parts by mass of cellulose as a thickener, and 2.0 parts by mass of acrylic resin as a binder are uniformly dispersed in water. to obtain an active material dispersion. This dispersion was applied to a copper foil having a thickness of 8 μm as an electrode substrate, and the resulting coating film was dried at 120° C. for 10 minutes and then pressed to obtain an electrode substrate laminated with an active material layer having a thickness of 60 μm.

-First irradiation process-
Next, the printing substrate 4 after the imparting process is transported into the polymerization process section 20, which is filled with nitrogen by the polymerization inert gas circulation device 2b so that the oxygen concentration is 0%, and the light irradiation device UV irradiation was performed for 3 seconds at an irradiation intensity of 30 mW/cm ² from 2a. The light irradiation device 2a was a UV-LED and had a peak wavelength of 365 nm.
In addition, when the structure determination time was calculated by the above method using the prepared liquid composition, it was 1.2 seconds. It was longer than the decision time (1.2 seconds).

- Second irradiation process -
Next, the printing substrate 4 after the first irradiation step is transported into the polymerization process section 21, which is filled with nitrogen by the polymerization inert gas circulation device 2d so that the oxygen concentration is 0%, UV irradiation was performed for 3 seconds at an irradiation intensity of 400 mW/cm ² from the light irradiation device 2c. The light irradiation device 2c was a UV-LED and had a peak wavelength of 365 nm.

-Removal process-
Further, the printing substrate 4 after the second irradiation step is transported into the heating process section 30 heated to 120° C. by the heating device 3a, and the remaining solvent and the like are removed in the atmosphere to form a co-continuous structure. A white porous resin with

(Example 2)
A porous resin was produced in the same manner as in Example 1, except that the UV irradiation time in the first irradiation step was changed to 5 seconds and the UV irradiation time in the second irradiation step was changed to 1 second. bottom.

(Example 3)
A porous resin was produced in the same manner as in Example 1, except that the UV irradiation time in the first irradiation step was changed to 1 second and the UV irradiation time in the second irradiation step was changed to 5 seconds. bottom.

(Comparative example 1)
A porous resin was produced in the same manner as in Example 1, except that the UV irradiation time in the first irradiation step was changed to 6 seconds and the second irradiation step was not performed.

(Comparative example 2)
A porous resin was produced in the same manner as in Example 1, except that the first irradiation step was not performed and the UV irradiation time in the second irradiation step was changed to 6 seconds.

Next, evaluation of porosity and evaluation of polymerization rate in the produced porous resin were performed by the following methods. Table 1 shows the evaluation results.

[Porosity]
The porous resin formed on the electrode substrate on which the active material layer is laminated is filled with unsaturated fatty acid (commercially available butter), and after being dyed with osmium, the internal cross-sectional structure is cut out with FIB and SEM is used. The porosity in the porous resin was measured using The measurement results of the porosity of the porous resin were evaluated based on the following evaluation criteria.
(Evaluation criteria)
a+: porosity is 50% or more a: porosity is 30% or more and less than 50% b: porosity is less than 30%

[Polymerization rate]
The degree of polymerization in the porous resin formed on the ITO-sputtered glass substrate was measured by infrared spectroscopy. The polymerization rate was calculated by reading the peak value of 820 to 800 cm ⁻¹ corresponding to =CH out-of-plane bending vibration and comparing it with the value when not irradiated. The measurement results of the polymerization rate of the porous resin were evaluated based on the following evaluation criteria.
(Evaluation criteria)
a: polymerization rate is 90% or more b: polymerization rate is less than 90%

From the results of Comparative Example 1, it can be seen that it is difficult to produce a porous resin with a high degree of polymerization when the second irradiation step is not performed.
From the results of Comparative Example 2, it can be seen that it is difficult to produce a porous resin with a high porosity when the first irradiation step is not performed.

1a: Printing device 1b: Storage container 1c: Supply tube 2a: Light irradiation device 2b: Polymerization inert gas circulation device 2c: Light irradiation device 2d: Polymerization inert gas circulation device 3a: Heating device 4: Printing substrate 5: Conveyance Part 6: Porous resin 7: Liquid composition 10: Printing process part 20: Polymerization process part 21: Polymerization process part 30: Heating process part

Patent No. 4426157

Claims (18)

an applying step of applying a liquid composition containing a polymerizable compound and a solvent;
a first irradiation step of irradiating the applied liquid composition with a first active energy ray;
a second irradiation step of irradiating the liquid composition irradiated with the first active energy ray with a second active energy ray,
The resin structure has a porous structure with a resin skeleton,
The porous structure is formed by irradiating the polymerizable compound in the liquid composition with the first active energy ray and the second active energy ray,
The method for producing a resin structure, wherein the irradiation intensity of the second active energy ray is higher than the irradiation intensity of the first active energy ray. The polymerizable compound and the solvent are compatible,
2. The production of a resin structure according to claim 1, wherein the porous structure is formed by incompatibility between the solvent and the polymer produced in the process of polymerizing the polymerizable compound in the liquid composition. Method. 3. The method for producing a resin structure according to claim 1, wherein the time for irradiating the first active energy ray in the first irradiation step is longer than or equal to the structure determination time calculated using the liquid composition. . The method for manufacturing a resin structure according to any one of claims 1 to 3, wherein the irradiation intensity of the first active energy ray is 1 W/ ^cm2 or less. The method for manufacturing a resin structure according to any one of claims 1 to 4, wherein the irradiation intensity of the second active energy ray is 300 mW/ ^cm2 or more. The method for manufacturing a resin structure according to any one of claims 1 to 5, wherein the irradiation intensity of the second active energy ray is five times or more the irradiation intensity of the first active energy ray. 7. The method for manufacturing a resin structure according to claim 1, further comprising a removing step of removing the solvent from the resin structure after the second irradiation step. The method for manufacturing a resin structure according to any one of claims 1 to 7, wherein the removing step is a step of removing the solvent from the resin structure by heating. The light transmittance of the liquid composition at a wavelength of 550 nm measured while stirring the liquid composition is 30% or more,
9. The method for producing a resin structure according to any one of claims 1 to 8, wherein the haze measuring element produced using the liquid composition has a haze value increase rate of 1.0% or more. The method for manufacturing a resin structure according to any one of claims 1 to 9, wherein the resin structure has a co-continuous structure in which a plurality of pores are continuously connected. The method for manufacturing a resin structure according to any one of claims 1 to 10, wherein the resin structure has a porosity of 30% or more. The method for manufacturing a resin structure according to any one of claims 1 to 11, wherein the resin structure has a thickness of 0.01 µm or more and 500 µm or less. The method for manufacturing a resin structure according to any one of claims 1 to 12, wherein the resin structure has a polymerization rate of 90% or more. 14. The method of manufacturing a resin structure according to any one of claims 1 to 13, wherein the applying step is a step of applying the liquid composition to an active material layer formed on an electrode substrate. The method for manufacturing a resin structure according to any one of claims 1 to 14, wherein the application step is a step of ejecting the liquid composition by an inkjet method. The method for producing a resin structure according to any one of claims 1 to 15, wherein the liquid composition has a viscosity of 1.0 mPa·s or more and 150.0 mPa·s or less at 25°C. The method for producing a resin structure according to any one of claims 1 to 16, wherein the liquid composition has a viscosity of 1.0 mPa·s or more and 30.0 mPa·s or less at 25°C. applying means for applying a liquid composition containing a polymerizable compound and a solvent;
a first irradiation means for irradiating the applied liquid composition with a first active energy ray;
a second irradiation means for irradiating the liquid composition irradiated with the first active energy ray with a second active energy ray,
The resin structure has a porous structure with a resin skeleton,
The porous structure is formed by irradiating the polymerizable compound in the liquid composition with the first active energy ray and the second active energy ray,
The apparatus for manufacturing a resin structure, wherein the irradiation intensity of the second active energy ray is higher than the irradiation intensity of the first active energy ray.

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