JP2001233902A - Preparation of porous cross-linked polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of preparation of a high internal phase emulsion (hereinafter referred to as HIPE) polymer which prevents leakage of water in oil HIPE and which thickens the resultant layer even at the both edges and keeps the thickness and which prevents insufficient polymerization caused by decrease in oxygen and which maintains sheets such as upper sheets. SOLUTION: The preparation method of a porous cross-linked polymer comprises horizontal continuous polymerization of an HIPE, wherein walls are used at the both edges in the width direction of a,support used for the horizontal continuous polymerization of the HIPE.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a water-in-oil type high internal phase emulsion.
ase Emulsion (hereinafter abbreviated as HIPE) is subjected to horizontal continuous polymerization to form a porous cross-linked polymer, preferably an open cell (open cell; hereinafter referred to as an open cell) having a communicating hole both on the surface and inside.
When manufacturing a porous cross-linked polymer having an open cell), it is necessary to prevent leakage of HIPE, increase thickness and maintain thickness including both ends, prevent uncuring by reducing the amount of oxygen, and retain a sheet such as an upper film. HIPE non-Newtonian and thixotropic viscosity weir system,
Technology related to shape, structure, and material.

[0002]

2. Description of the Related Art As a gasket for producing an MMA-based resin plate by continuous cast polymerization of a polymerizable syrup centered on methyl methacrylate (also referred to simply as MMA), which is a low-viscosity Newtonian fluid, is disclosed in JP-B-47-49823.
And JP-B-60-31643 disclose a method of making a gasket having a thickness of about 25 to 50% of the outer diameter of the tube of the gasket as a gasket to be used after compression. Since the gasket is used, the gasket is deformed by tightening force or heat, and the thickness of the resin plate to be manufactured does not become a desired thickness, and there is a problem that the thickness variation increases. As a gasket applicable for cast polymerization including cell cast polymerization and continuous cast polymerization, JP-A-5-2539
No. 51, JP-A-5-329847, etc.
Improvements in the shape, structure, and material of the gasket as described above have been proposed. However, the compressed and used state is the same, and the gasket used has an outer diameter of 30 to 30 mm.
A method for producing a sheet having a thickness of about 90% is disclosed.
In addition, there is no proposal of cast polymerization for polymerization of non-Newtonian fluid and thixotropic viscous HIPE, and of course, no proposal has been made for a weir including a gasket for cast polymerization.

[0003]

Accordingly, a further object of the present invention is to provide a horizontal continuous polymerization of non-Newtonian, thixotropic, viscous HIPE using weirs (including gaskets) to prevent leakage of HIPE, It is an object of the present invention to provide a method for producing a HIPE polymer while controlling the thickness and maintaining the thickness including the portion, preventing unpolymerization by reducing oxygen, and holding a sheet such as an upper film.

[0004]

In order to achieve the above object, the present inventor has conducted intensive studies on a method for polymerizing a non-Newtonian fluid and thixotropic viscous HIPE. It has been completed.

That is, an object of the present invention is to provide (1) HI
A method for producing a porous cross-linked polymer by horizontally and continuously polymerizing PE, wherein weirs are used at both widthwise ends of a HIPE support used for horizontally and continuously polymerizing the HIPE. This is achieved by a method for producing a porous crosslinked polymer.

The object of the present invention is also achieved by (2) the manufacturing method according to (1), wherein the height of the weir is in the range of 0.5 to 100 mm.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a method for producing a porous crosslinked polymer by horizontally and continuously polymerizing HIPE, wherein the HIPE is used for horizontally and continuously polymerizing the HIPE.
Support (hereinafter also simply referred to as support), preferably HI
It is characterized in that weirs are used at both ends in the width direction of a PE movable support (hereinafter, also simply referred to as a movable support).

The method for producing the porous crosslinked polymer of the present invention will be described in detail below in the order of the steps.

[I] Raw Material (HIPE) (1) Composition of HIPE First, the HIPE that can be used in the method for producing a porous cross-linked polymer of the present invention is not particularly limited, and is conventionally known. Things can be used as appropriate. H
Specifically, the composition of the IPE is as follows: (a)
Polymerizable monomer having two polymerizable unsaturated groups and (b)
A monomer composition comprising a crosslinkable monomer having at least two polymerizable unsaturated groups in a molecule, (c) a surfactant,
It is sufficient that (d) water and (e) a polymerization initiator are contained as essential components, and if necessary, (f) salts,
(G) Other additives may be included as optional components.

(A) Polymerizable monomer having one polymerizable unsaturated group in the molecule One of the essential monomer compositions constituting the HIPE is:
It is a polymerizable monomer having one polymerizable unsaturated group in the molecule and is not particularly limited as long as it is polymerizable in a dispersed or water-in-oil type high-dispersion phase emulsion and can form an emulsion. Preferably, at least one part contains (meth) acrylic acid ester, more preferably contains 20% by mass or more of (meth) acrylic acid ester, and particularly preferably contains 35% or more of (meth) acrylic acid ester. % By mass or more. As a polymerizable monomer having one polymerizable unsaturated group in the molecule,
It is desirable to include a (meth) acrylic ester since a porous crosslinked polymer having high flexibility and toughness can be obtained.

Specifically, arylene monomers such as styrene; monoalkylene arylene monomers such as ethylstyrene, alpha-methylstyrene, vinyltoluene and vinylethylbenzene; methyl (meth) acrylate, (meth) acrylate
Ethyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, isodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Lauryl acrylate, stearyl (meth) acrylate,
(Meth) acrylates such as cyclohexyl (meth) acrylate and benzyl (meth) acrylate; chlorine-containing monomers such as vinyl chloride, vinylidene chloride and chloromethylstyrene; acrylonitrile compounds such as acrylonitrile and methacrylonitrile; , Vinyl acetate, vinyl propionate, N-octadecylacrylamide, ethylene, propylene, butene and the like. One of these may be used alone in the monomer composition, or two or more thereof may be used in combination.

The content of the above polymerizable monomer is in the range of 10 to 99.9% by mass based on the total mass of the monomer composition comprising the polymerizable monomer and the crosslinkable monomer. Is preferred. This is because a porous crosslinked polymer having a fine pore diameter can be obtained in this range. It is more preferably in the range of 30 to 99% by mass, and particularly preferably in the range of 30 to 70% by mass. When the content of the polymerizable monomer is less than 10% by mass, the obtained porous cross-linked polymer may become brittle or the water absorption capacity may be insufficient. On the other hand, when the content of the polymerizable monomer exceeds 99.9% by mass, the strength and elastic recovery power of the obtained porous cross-linked polymer are insufficient, or a sufficient water absorption amount and water absorption speed are secured. There are things you can't do.

(B) Crosslinkable monomer having at least two polymerizable unsaturated groups in the molecule Another one of the essential monomer compositions constituting the HIPE is at least two in the molecule. Is a crosslinkable monomer having a polymerizable unsaturated group, similarly to the polymerizable monomer, is particularly limited as long as it can be polymerized in a dispersed or water-in-oil type high dispersion phase emulsion and can form an emulsion. Not something.

Specifically, divinylbenzene, trivinylbenzene, divinyltoluene, divinylxylene, p
-Aromatic monomers such as ethyl-vinylbenzene, divinylnaphthalene, divinylalkylbenzenes, divinylphenanthrene, divinylbiphenyl, divinyldiphenylmethane, divinylbenzyl, divinylphenylether, divinyldiphenylsulfide; oxygen-containing monomers such as divinylfuran; Sulfur-containing monomers such as divinyl sulfide and divinyl sulfone; aliphatic monomers such as butadiene, isoprene and pentadiene; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth)
Acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, octanediol di (meth) acrylate, decanediol di ( (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (Meta)
Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, N, N'-methylenebis (meth) acrylamide, triallyl isocyanurate, triallylamine, tetraallyloxyethane, and hydroquinone, catechol, resorcinol, Examples thereof include an ester compound of a polyhydric alcohol such as sorbitol and acrylic acid or methacrylic acid. These are one in the monomer composition.
In addition to using the species alone, two or more species may be used in combination.

The content of the crosslinkable monomer is in the range of 0.1 to 90% by mass based on the total mass of the monomer composition comprising the polymerizable monomer and the crosslinkable monomer. Preferably, it is more preferably 1 to 70% by mass, particularly preferably 3% by mass.
It is in the range of 0 to 70% by mass. When the content of the crosslinkable monomer is less than 0.1% by mass, the strength and elastic recovery power of the obtained porous crosslinked polymer are insufficient, or the absorption amount per unit volume or unit mass is insufficient. And it may not be possible to secure sufficient water absorption and water absorption speed,
If the content of the crosslinkable monomer exceeds 90% by mass, the porous crosslinked polymer may become brittle or the water absorption capacity may be insufficient.

(C) Surfactant The essential surfactant constituting the HIPE is H
There is no particular limitation as long as the aqueous phase can be emulsified in the oil phase constituting the IPE, and the present invention is not limited to the above-mentioned examples, and conventionally known nonionic surfactants and cationic surfactants And amphoteric surfactants and the like can be used.

Among them, nonionic surfactants include nonylphenol polyethylene oxide adducts;
Block polymers of ethylene oxide and propylene oxide; sorbitan monolaurate, sorbitan monomyristylate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate,
Sorbitan fatty acid esters such as sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, and sorbitan distearate; glycerin such as glycerol monostearate, glycerol monooleate, diglycerol monooleate, and self-emulsifying glycerol monostearate Fatty acid esters; polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene higher alcohol ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene sorbitan monolaurate;
Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monooleate, etc. Ethylene sorbitan fatty acid ester; polyoxyethylene sorbitol fatty acid ester such as polyoxyethylene sorbite tetraoleate; polyoxyethylene fatty acid such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate ester;
There are polyoxyethylene alkylamine; polyoxyethylene hydrogenated castor oil; alkyl alkanolamide, and the like, and particularly those having an HLB of 10 or less, preferably 2 to 6 are preferable. Two or more of these nonionic surfactants may be used in combination, and the combined use may stabilize HIPE.

Examples of the cationic surfactant include quaternary ammonium salts such as stearyltrimethylammonium chloride, ditaurodimethylammonium methylsulfate, cetyltrimethylammonium chloride, distearyldimethylammonium chloride and alkylbenzyldimethylammonium chloride; coconut amine There are alkylamine salts such as acetate and stearylamine acetate; alkylbetaines such as lauryltrimethylammonium chloride, laurylbetaine, stearylbetaine and laurylcarboxymethylhydroxyethylimidazoliniumbetaine; and amine oxides such as lauryldimethylamine oxide. By using a cationic surfactant, excellent antibacterial properties and the like can be imparted when the obtained porous crosslinked polymer is used as a water absorbing material or the like.

In some cases, the combined use of a nonionic surfactant and a cationic surfactant may improve the stability of HIPE.

The content of the above-mentioned surfactant is 100 mass% of the whole monomer composition comprising a polymerizable monomer and a crosslinkable monomer.
It is preferable that it is 1 to 30 parts by mass with respect to parts by mass,
More preferably, it is 3 to 15 parts by mass. When the content of the surfactant is less than 1 part by mass, the high dispersibility of the HIPE may be unstable, or the original effect of the surfactant may not be sufficiently exhibited. On the other hand, when the content of the surfactant exceeds 30 parts by mass, the obtained porous cross-linked polymer may be too brittle, and a further effect corresponding to the addition exceeding this may not be expected, which is uneconomical. is there.

(D) Water In addition to pure water and ion-exchanged water, waste water obtained by producing a porous cross-linked polymer may be used as it is in order to reuse the waste water in addition to pure water and ion-exchanged water. Those that have undergone predetermined processing can be used.

The water content depends on the intended use of the porous crosslinked polymer having the desired open cells (for example, water absorbing material,
Oil absorbing material, soundproofing material, filter, etc.). For example, the HIPE may be determined so as to have a desired water phase / oil phase (W / O) ratio described later.

(E) Polymerization Initiator The polymerization initiator as an essential component constituting the above-mentioned HIPE may be any polymerization initiator that can be used in reversed-phase emulsion polymerization, and may be either water-soluble or oil-soluble. . For example,
Azo compounds such as 2,2'-azobis (2-amidinopropane) dihydrochloride; persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate; hydrogen peroxide, sodium peracetate, sodium percarbonate, cumenehydro Peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,
1,3,3-tetramethylbutyl hydroperoxide,
Peroxides such as 2,5-dimethylhexane-2,5-dihydroperoxide, benzoyl peroxide, and methyl ethyl ketone peroxide;
-Ascorbic acid, ferrous salt, formaldehyde sodium sulfoxylate, glucose, dextrose,
Redox initiators and the like in combination with a reducing agent such as diethanolamine are exemplified. These polymerization initiators may be used alone or in combination of two or more.

The content of the above-mentioned polymerization initiator depends on the combination of the above-mentioned monomer composition and polymerization initiator. It is preferably in the range of 0.05 to 15 parts by mass, more preferably 1.0 to 10 parts by mass, per 100 parts by mass. When the content of the polymerization initiator is less than 0.05 parts by mass, the amount of unreacted monomer components increases, and therefore, the amount of residual monomers in the obtained porous cross-linked polymer increases. Absent. On the other hand, when the content of the polymerization initiator exceeds 15 parts by mass, it is not preferable because control of polymerization becomes difficult and mechanical properties in the obtained porous crosslinked polymer deteriorate.

(F) Salts Salts, which are one kind of optional components constituting the HIPE, are as follows:
It may be used if necessary to improve the stability of the HIPE.

Specific examples of such salts include water-soluble salts such as halides of alkaline metals such as calcium chloride, sodium sulfate, sodium chloride, and magnesium sulfate, alkaline earth metals, sulfates, and nitrates. These salts may be used alone or in combination of two or more. These salts are preferably added to the aqueous phase. Among them, polyvalent metal salts are preferred from the viewpoint of the stability of HIPE during polymerization.

The content of such salts is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of water. If the salt content exceeds 20 parts by mass, a large amount of salts will be contained in the wastewater squeezed out of the HIPE, the cost of treating the wastewater will increase, and further effects commensurate with the addition exceeding this are expected. It is impossible and uneconomical. If the amount is less than 0.1 parts by mass, the effects of the addition of salts may not be sufficiently exhibited.

(G) Other Additives The addition of various other additives to the performance and functions of these additives leads to improvements in production conditions, the resulting HIPE characteristics, and the performance of the porous cross-linked polymer. If it can be used appropriately, for example, for pH adjustment,
Bases and / or buffers may be added. Regarding the content of these other additives, it is sufficient to add them within a range in which the performance and function and the economy can be sufficiently exhibited according to the purpose of each addition.

(2) Water phase / oil phase ratio (mass ratio) The water phase / oil phase ratio (mass ratio) of the HIPE (hereinafter simply abbreviated as “W / O”) is the desired continuous ratio. Purpose of use of the porous cross-linked polymer having cells (for example, water-absorbing material,
(Oil absorbing material, soundproofing material, filter, etc.) and the like, and are not particularly limited. For example, if W / O is in the range of 10/1 to 100/1, a diaper or A porous cross-linked polymer suitable for use as a sanitary material and other various absorbents is obtained. However, W /
Since the vacancy ratio is determined by O, the porosity is preferably 3/1 or more, more preferably 10/1 to 250.
/ 1, especially 10/1 to 100/1. W / O is 3
If the ratio is less than / 1, the ability of the porous cross-linked polymer to absorb water and energy is insufficient, the opening degree is low, and the opening degree of the surface of the obtained porous cross-linked polymer is low. There is a possibility that the liquid passage performance or the like cannot be obtained.

(3) Method for Preparing HIPE The method for producing HIPE that can be used in the present invention is not particularly limited, and any conventionally known HIPE may be used.
Can be appropriately used. Hereinafter, a typical production method will be specifically described.

First, a monomer composition comprising a polymerizable monomer and a crosslinkable monomer, an oil-soluble polymerization initiator (when a water-soluble polymerization initiator is used, May be used in combination or may not be used), and the components constituting the oil phase are stirred at a predetermined temperature to prepare a uniform oil phase.

On the other hand, at the contents specified above, a water-soluble polymerization initiator (when an oil-soluble polymerization initiator is used, it may or may not be used together). Further, if necessary, stirring is carried out while adding the constituent components of the aqueous phase composed of salts, and the mixture is heated to a predetermined temperature of 30 to 95 ° C. to prepare a uniform aqueous phase.

Next, the HIPE can be stably prepared by efficiently mixing the water phase and the oil phase and applying an appropriate shearing force. The HIPE obtained by stirring the aqueous phase and the oil phase is usually a white, high-viscosity emulsion.

(4) HIPE Manufacturing Apparatus The HIPE manufacturing apparatus is not particularly limited, and a conventionally known manufacturing apparatus can be used.
For example, as a stirrer (emulsifier) used for mixing and stirring the water phase and the oil phase, a known stirrer or kneader can be used. For example, a blade stirrer such as a propeller type, a paddle type, and a turbine type, a homomixer, a line mixer, and a pin mill can be exemplified, and any of these may be used.

The optimum temperature of the water phase and the oil phase is 20
To 100 ° C, and preferably from 40 to 95 ° C from the viewpoint of the stability of HIPE. In addition, the temperature of the oil phase and / or the aqueous phase is adjusted to a predetermined value before mixing. In the production of HIPE, the temperature of the aqueous phase is preferably adjusted to a predetermined temperature because the amount of the aqueous phase is large.

(5) HIPE Formation Temperature (Emulsification Temperature) The HIPE formation temperature (emulsification temperature) is usually from 20 to 100.
° C, and from the viewpoint of the stability of HIPE, it is preferably in the range of 30 to 95 ° C, more preferably 40 to 95 ° C.
° C, particularly preferably 45-90 ° C, most preferably 50 ° C.
~ 85 ° C. When the formation temperature of HIPE is lower than 20 ° C., the viscosity of the emulsified product becomes high, so that it becomes difficult to emulsify or to be difficult to handle, which is not preferable. On the other hand, when the formation temperature of HIPE exceeds 100 ° C. Is difficult to emulsify at normal pressure, and even if emulsified at high pressure, the emulsion becomes unstable. It is desirable that the temperature of the oil phase and / or the aqueous phase be adjusted to a predetermined formation temperature (emulsion temperature) in advance, and then stirred and mixed to emulsify to form a desired HIPE. However, in the preparation (formation) of HIPE, since the amount of the aqueous phase is large, it can be said that it is preferable to adjust at least the temperature of the aqueous phase to a predetermined formation temperature (emulsification temperature). Further, polymerization of a polymerizable monomer or a crosslinkable monomer is started during emulsification, and when a polymer is formed, HIPE may become unstable. Therefore, a polymerization initiator (including a redox polymerization initiator system) In the case of preparing a HIPE containing in advance, the formation temperature (emulsification temperature) of the HIPE is preferably a temperature at which the polymerization initiator (oxidizing agent) does not substantially cause thermal decomposition, and the polymerization initiator (oxidizing agent) It is preferable to emulsify at a temperature lower than the temperature at which the half-life of the compound is 10 hours (10-hour half-life temperature).

(6) Properties of HIPE The HIPE obtained by stirring the water phase and the oil phase is usually
It becomes a white, high-viscosity emulsion. The nature of such a HIPE is a non-Newtonian, thixotropic fluid, as described above.

The HIPE that can be used in the present invention is
Due to its thixotropic properties, a shear rate of 1
[S^-1] And 100 [s^-1] Viscosity ratio (η₁/ Η₁₀₀)But
5 or more, preferably 10 or more, more preferably 100 or less
Above. Viscosity ratio (η₁/ Η_{Ten 0}) Is less than 5
In this case, it is difficult to regulate the shape and thickness. Also, HIPE
Is a shear rate of 100 [s^-1Is less than 10 Pa · s
Below, preferably 5 Pa · s or less, more preferably 3 to
The range is 0.01 Pa · s or less. The above viscosity is 100
If it exceeds, the viscosity is too high, and the shaping is not performed by this method.
Have difficulty.

[II] Production of Porous Cross-Linked Polymer (1) HIPE Polymerization Method (Partially Includes Polymerization Apparatus) In the present invention, as the HIPE polymerization method, the porous cross-linked polymer is obtained by the above-mentioned horizontal continuous polymerization of HIPE. It is a constituent requirement to produce a united product.

In the production method of the present invention, the method of performing the horizontal continuous polymerization of the HIPE is not particularly limited. For example, the HIPE is driven in a horizontal direction by using a driving and conveying device such as a belt conveyor. The HIPE is continuously supplied to a movable support {a sheet material such as an endless belt (a heating conveyor having a combined heating function) or a film running on the belt in synchronization with the belt} and a coater. The HIP is formed into a uniform thickness by passing it through a polymerization furnace having appropriate heating means.
A method for performing polymerization of E, using a driving and transporting device for running a sheet material such as a film on a belt-like plate of a fixed support (or a fixed hot plate or the like having a heating function), and traveling in a horizontal direction of the device. HIPE is continuously supplied to a movable support (a sheet material such as a film) to be formed, formed into a uniform thickness by a coater or the like, and passed through a polymerization furnace having an appropriate heating means to polymerize the HIPE. However, the present invention is not limited to these, and the HIPE is formed into a desired shape and is formed in a substantially horizontal direction (not necessarily completely horizontal; There is no particular limitation as long as the polymer can be continuously polymerized while being conveyed in a wide width direction or a parallel flow direction. Therefore, the support does not need to be held horizontally,
Although the viscosity, viscosity, concentration and temperature of IPE are affected, HI
As long as the thickness of the PE does not become uneven in the width direction and the flow direction, a case where the PE is inclined left and right: forward and backward is also included in the embodiment of the horizontal continuous polymerization of the present invention.

Here, the horizontal continuous polymerization means that the HIP of the raw material is placed on a substantially horizontally (horizontally) conveyed support of a driving and conveying device.
A series of operations and steps until E is supplied, molded into a layer, passed through a polymerization furnace having an appropriate heating means, and polymerized (specifically, heat-treated at a predetermined curing temperature in a polymerization furnace for a predetermined time). Is performed continuously. In order to form the raw material HIPE into a layer, it may be formed simultaneously with the supply so as to form a layer at the time of supply, or may be formed into a layer using an appropriate forming member (for example, a coater) after the supply. You may. When the HIPE of the raw material is supplied onto the support that is horizontally (horizontally) transported by the drive transport device, the raw material may be supplied directly onto the support or may be supplied indirectly. The term “indirect” means a case where a sheet material is used as an oxygen concentration suppressing means for an endless belt and / or a belt-shaped plate as a support, and a raw material HIPE is supplied onto the sheet material. This has the advantage that the porous crosslinked structure of the surface layer of the contact surface of the resulting porous crosslinked polymer can be appropriately changed according to the intended use by changing the material with which the HIPE is in contact, and is used continuously. If you put HIPE directly on the endless belt,
When the porous cross-linked polymer is peeled off after the polymerization, the porous cross-linked polymer may adhere to the belt side, and it is necessary to clean and clean such an adhered substance by rotating once and mounting the HIPE again. On the other hand, when the sheet material is used, there is an advantage that such attached matter can be more easily removed (peeled), and since the cost is extremely low as compared with the endless belt, a disposable method can be used.

Next, in the present invention, a support is used on the lower surface of the HIPE for horizontal continuous polymerization of the HIPE, and at least one type selected from the group consisting of film, non-woven fabric and woven fabric is further provided on the upper surface. A sheet material may be used. This is because the sheet material effectively functions as a means for reducing the amount of oxygen in HIPE, as described later.

Among these, the support that can be used on the lower surface of the HIPE has the function of maintaining the shape of the HIPE once molded and supporting the HIPE so as not to leak out from the lower surface side, and further has the function of lowering the polymerization temperature. There is no particular limitation as long as it does not deteriorate when exposed. Therefore, it is necessary to use, alone or in combination, a material having such a strength that it can be prevented from being broken, bent or bent by losing support after molding. Therefore, as such a support, for example,
As described above, one of the movable supports constituting the drive transfer device
Even if it is a metal or resin endless belt as a seed, or a metal or resin band plate as a fixed support, it is another type of movable support used on these. It may be a sheet material such as a certain film. Further, although the “lower surface” of the HIPE is not “lower”, for example, a case in which a support such as a corrugated support, a curved support, or a concave shape is used is also within the technical scope of the present invention. Shall be included. Note that such a support will be described in the section of oxygen amount reducing means described later.

As will be described later, a sheet material that can be used on the upper surface of the HIPE is one that is not damaged even when a certain tension is applied and that does not deteriorate even when exposed to the polymerization temperature. There is no particular limitation, and at least one member selected from the group consisting of a film, a nonwoven fabric, and a woven fabric can be suitably used. Also, the HIPE was defined as “upper surface” and not “upper”, but this can be achieved by increasing the thickness of the HIPE at the center, conversely increasing the thickness at both ends, embossing the shape, trapezoidal shape, semicircular shape, etc. The reason for this is that the case of forming into a shape is also included in the technical scope of the present invention. A top sheet material that is flexible and fits well into these shapes is desirable. Note that such a sheet material will be described in the section of oxygen amount reducing means described later.

Further, in the method of the present invention for producing a porous cross-linked polymer by horizontal continuous polymerization of HIPE,
The outer surface portion of E is changed to an atmosphere or state having a lower oxygen content than ambient air by an oxygen amount reducing means, so that the HIP
It is preferred to carry out horizontal continuous polymerization of E. As a result, it is thought that various technical problems of the conventional continuous and batch combined polymerization method of WO 97/27240 (that is, the lower portion becomes thicker than at the time of filling with HIPE and the uniformity of the thickness is slightly increased by winding). , The lower part tends to be thicker due to the weight of the HIPE, and worse still, the oil phase and the liquid phase tend to be deflected upward and downward.
And the thickness and the uniformity of performance and quality are difficult to maintain, and the width and thickness cannot be freely controlled; since HIPE filling to polymerization cannot be performed continuously, HIPE Because the transition stage between the continuous filling process and the batch polymerization process is rate-determining,
The problem that the advantage of the continuous filling process cannot be maximized; the use of film bags makes it possible to obtain a porous cross-linked polymer with the same properties, but to change the properties of both sides. Problem of not being able to obtain a porous cross-linked polymer), an uncured portion may be formed on the surface layer of the outer surface of the obtained porous cross-linked polymer, or pinholes and voids may be formed. Many problems can be solved, such as the formation of an open cell, the failure to form an open cell structure, and the observation of free water when cured.

The outer surface portion of the HIPE may be brought into an atmosphere or state in which the oxygen content is lower than that of the surrounding air by the above oxygen amount reducing means.
It is desirable that the atmosphere is 0% by volume or less, more preferably 0.2% by volume or less, particularly preferably an oxygen-free atmosphere or state. If the oxygen content exceeds 2.0% by volume, the surface portion of the outer surface of the HIPE becomes unpolymerized, which is not preferable.

The means for reducing the amount of oxygen is such that the HIPE can be kept in an atmosphere or state having an oxygen content lower than that of the surrounding air until a porous crosslinked polymer is obtained by horizontal continuous polymerization of the HIPE. (A) a gas having a lower oxygen content than the ambient air, preferably an inert gas containing no oxygen, for example, nitrogen gas, argon gas, helium gas, neon gas, krypton gas, xenon gas, radon gas and A part or all, and preferably all, of the ambient air that comes into contact with the outer surface of the HIPE is gas-replaced with a mixed gas of two or more of these gases, thereby preventing the ambient air (oxygen gas) from contacting the HIPE. Blocking, preferably means for reducing the amount of oxygen using a blocking gas,
(B) By forming a liquid layer or a liquid film, preferably a water layer with water on the outer surface of the HIPE with a liquid that does not affect the polymerization, for example, water or an aqueous electrolyte solution, the ambient air is applied to the HIPE. Means for reducing the amount of oxygen using a liquid that suppresses or blocks contact, (C) a solid material that reduces or cuts the amount of contact oxygen (for example, a sheet material such as a film,
By applying a support or a weir such as an endless belt or a band-shaped plate to the outer surface of the HIPE, oxygen using a solid that suppresses or blocks the contact of ambient air (oxygen gas) with the HIPE is provided. Any of the amount reducing means can be used in combination as needed.

In particular, in the present invention, as described later, the HI
To prevent leakage of the continuously supplied HIPE from the outer surface portion at both ends in the width direction of the support used for horizontally and continuously polymerizing the PE, to keep the HIPE after molding in a fixed shape, The main constituent requirement is to use a weir (including gasket etc.) contained in a solid material, which is a versatile means such as preventing unpolymerization of the material and retaining the sheet material on the outer surface. Things. In addition,
In the present specification, the relationship between “solid material”, “sheet material”, and “film” is most broadly in “solid material”
The present invention can be applied to any of the outer surface portions (upper surface, lower surface, both ends) of PE, and includes the above-described support, sheet material, weir, and the like. Next, the "sheet material" is a broad type of solid material, and includes a film, a nonwoven fabric, and a woven fabric. Finally, "film" is the narrowest and is one of the above-mentioned sheet materials.

In this specification, "the outer surface of the HIPE is made to have an atmosphere or a state in which the oxygen content is lower than that of the surrounding air by the oxygen amount reducing means" is shown in FIGS. In addition, (1) at least to the polymerization portion (if polymerization is started from the supply portion, it is excluded here because it corresponds to the following (2) or (3)), (2) preferably at least the portion after the supply , (3) More preferably, it should be one that suppresses or blocks the contact of the surrounding air with the HIPE from the supply portion, and should not be construed narrowly. That is, in the case of the liquid and the solid material, the outer surface portion is not always necessary for the HIPE supply portion. That is, in the case of gas, the HIPE can be supplied while replacing it. In the case of a liquid and a solid material, it is sufficient to suppress or block the surrounding air with the liquid and / or the solid material after supplying the HIPE (FIG. 1, FIG. Strictly, it is not necessary to suppress or block the contact of the ambient air with the HIPE with liquid or solid material (and also in the case of gas) from the supply part. This means that the time of exposure to ambient air is short (about 5 seconds) from the supply portion to the portion where the oxygen amount reducing means is provided, so that the time of exposure to ambient temperature is also short,
This is because the effect on the properties of the obtained porous cross-linked polymer is small, and a sufficient effect can be exerted as compared with the conventional method (see Examples described later).

As a preferred embodiment of the oxygen amount reducing means, the oxygen amount reducing means using the gas of (A) is a method in which nitrogen gas is used to replace all the surrounding air in contact with the outer surface of the HIPE. A means for blocking the contact of ambient air with the HIPE, wherein the means for reducing the amount of oxygen using the liquid (B) forms an aqueous layer on the outer surface of the HIPE with an aqueous solution that does not affect polymerization. And means for cutting off the contact of ambient air with the HIPE. The means for reducing the amount of oxygen using the solid (C) described above is characterized in that the solid material support, sheet material, weir, etc. This is a means for suppressing or blocking the contact of the ambient air with the HIPE by applying it to a suitable location.

Therefore, as the means for reducing the amount of oxygen on the outer surface of the HIPE, a combination of the above-described suitable means for reducing the amount of oxygen is preferable. (A) All of the ambient air which comes into contact with the outer surface of the HIPE with nitrogen gas The gas is replaced with a means for interrupting the contact of the ambient air with the HIPE, and a solid material support, sheet material, weir, or the like is applied to an appropriate portion of the outer surface of the HIPE to thereby reduce the ambient air. (B) an aqueous solution which does not affect the polymerization,
Means for blocking ambient air from contacting the HIPE by forming a water layer on the outer surface of the IPE,
A sheet material, a weir, or the like applied to an appropriate portion of the outer surface of the HIPE to suppress or block contact of ambient air (oxygen gas) with the HIPE; A) a solid material support, sheet material, weir, or the like is applied to the entire outer surface portion of the HIPE, thereby combining a plurality of means for suppressing or blocking contact of ambient air with the HIPE. Can be Thus, by performing horizontal continuous polymerization of HIPE, the holding accuracy and the yield of the porous cross-linked polymer in maintaining the shape of the HIPE after molding are good, and the shape of the HIPE after molding (for example, Width and thickness)
Can be freely controlled, and the surface properties of the outer surface of the porous cross-linked polymer can be changed.

Of these, the oxygen reducing means using gas and the oxygen reducing means using liquid have some problems in the scattering property of the monomer, and the surface properties of the obtained porous cross-linked polymer are as follows. Open cell structure and surface smoothness are not good (slightly lower than good), but in addition, they are relatively good in pinhole and void resistance, so they can be applied to many uses. It can be said that this is one of the preferable techniques for producing a porous crosslinked polymer having a modified surface property in combination with a means for reducing the amount of oxygen using a solid.

Further, the means for reducing the amount of oxygen using the above-mentioned solid does not have the problem of scattering of the monomer, and the surface properties of the obtained porous cross-linked polymer, for example, the open cell structure and the surface of the outer surface portion Since it has good smoothness and good pinhole / void resistance, it can be applied to many uses. In addition, as a means for reducing the amount of oxygen using the above-mentioned solid, by appropriately selecting the form of a solid material (support, sheet material, weir, etc.) provided on the outer surface of the HIPE, the porous crosslinked polymer whose surface properties are changed is selected. Coalescence can be manufactured.

Further, the sheet material applied to the upper surface of the HIPE may be one having a certain level of sealing property so as to obtain a desired effect of reducing the amount of oxygen. In other words, it is difficult to use a device having low air permeability (oxygen permeability) at a certain level or higher as the oxygen amount reducing means. From such a viewpoint, the air permeability of the sheet material is
100 cm ³ / cm ² · s or less, preferably 5 cm ³ / cm
cm ² · s or less. The air permeability of the sheet material is 100
If it exceeds cm ³ / cm ² · s, the ability to reduce the amount of oxygen decreases, and depending on conditions such as W / O, there is a possibility that a problem such as formation of an uncured portion in the obtained porous crosslinked polymer may occur. It is not preferable because there is. Here, “air permeability” refers to a value measured and measured by any of the test methods defined in 6.27 air permeability of JIS L1096 (1990).

The upper limit of the air permeability is based on the case where the outside is the ambient air, and the outside is exposed to a nitrogen atmosphere. When used in combination with an oxygen amount reducing means using a gas having a low oxygen content, there is no problem even if the above range is exceeded. The air permeability exceeds 5 cm ³ / cm ² · s and is 100
Even in the range of cm ³ / cm ² · s or less, in some cases, defects such as pinholes and voids can be reduced by using other oxygen amount reducing means in combination. On the other hand, when the curing temperature of the HIPE increases, a part of the water inside may be vaporized during the polymerization. In such a case, the sheet material is
A sheet material (gas permeable film) that has a slight air permeability so that the air permeability and the sealability can be balanced more than a material with a high sealability (such as a gas barrier film or a normal film) , A porous film, a nonwoven fabric, a woven fabric, etc.) may be advantageous in reducing defects such as pinholes and voids on the surface of the porous crosslinked polymer. Therefore, when determining the sealing property (air permeability) of the sheet material, it is desirable to sufficiently consider the polymerization conditions and the like, and to conduct a preliminary experiment as necessary to select an optimal one.

The material of the sheet material that can be used in the present invention is not particularly limited as long as it can be used under polymerization conditions, and is appropriately selected from conventionally known polymer materials. It has good durability (heat resistance, weather resistance, abrasion resistance, recyclability, mechanical properties such as tensile strength, etc.) and releasability suitable for continuous polymerization, and porous cross-linking. Those capable of controlling the surface properties of the polymer are preferable, and specifically, polytetrafluoroethylene (hereinafter, also simply referred to as PTFE), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (hereinafter, also simply referred to as PFA), A tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter, also simply referred to as FEP) and a tetrafluoroethylene-ethylene copolymer (hereinafter, simply referred to as FEP) Fluororesins such as ETFE); silicone resins such as dimethylpolysiloxane and dimethylsiloxane-diphenylsiloxane copolymer; polyimides (hereinafter also simply referred to as PI), polyphenylene sulfides (hereinafter simply referred to as PPS), and polysulfones (hereinafter simply referred to as simply). Heat resistance of polyethersulfone (hereinafter also simply referred to as PES), polyetherimide (hereinafter simply referred to as PEI), polyetheretherketone (hereinafter simply referred to as PEEK), para-aramid resin, etc. Polyethylene terephthalate (hereinafter also simply referred to as PET), polybutylene terephthalate (hereinafter also simply referred to as PBT), polyethylene naphthalate (hereinafter simply referred to as PEN), polybutylene naphthalate (hereinafter also simply referred to as PBN) ), A thermoplastic polyester resin such as polycyclohexane terephthalate (hereinafter also simply referred to as PCT), a block copolymer (polyether type) composed of PBT and polytetramethylene oxide glycol, and composed of PBT and polycaprolactone. Preferred examples include thermoplastic polyester-based elastomer resins such as block copolymers (polyester-based) (hereinafter also simply referred to as TPEE elastomers). These materials may be used alone or in combination of two or more depending on the purpose. Furthermore, one sheet material may be laminated with two or more kinds of different materials, or two or more kinds of different sheet materials may be used by simply overlapping.

The thickness of the sheet material is not particularly limited. When the thickness is usually 0.01 to 3.0 mm, it is possible to obtain durability (various properties such as mechanical strength such as heat resistance, weather resistance, abrasion resistance, recyclability, and tensile strength) suitable for continuous polymerization. Yes, it can be recycled into an endless belt.

Further, the shape of the sheet material may be any of a film, a nonwoven fabric and a woven fabric, and a combination thereof. As an example, a non-breathable film (breathable: 0 to 0.0001 cm ³ / cm ² · s
Gas barrier films such as aramid film, polyvinylidene chloride (hereinafter, also referred to simply as PVDC) coated PET film; PEN film, P
ET film, PBT film, PPS film, PI
Film, ETFE film, polypropylene (hereinafter,
Examples of such films include ordinary films such as a PP film) and a PTFE film. Examples of the gas permeable film (gas permeable about 0.0001 to 35 cm ³ / cm ² · s) include a gas permeable film such as a dimethylpolysiloxane film. Films: porous films such as PTFE-based porous films and polyolefin-based porous films, etc., and examples of the woven fabric (air permeability: about 0.1 to 8 cm ³ / cm ² · s) include PET multifilament type woven fabric and the like. And a non-woven fabric (breathable 10 to 100 cm ³
/ Cm ² · s), a nonwoven fabric such as a PET spunbond type.

One of the criteria for determining the heat resistance of the sheet material is a mechanical continuous use temperature (UL746B), PET (105 ° C.), PEN (160 ° C.), PI
(200 ° C.), PPS (160 ° C.), PEEK (240
° C), PSF (150 ° C), PES (180 ° C), PE
I (170 ° C.) and an aramid film (180 ° C.) are known, and the sheet material to be used can be appropriately selected depending on the curing temperature.

The metal or resin endless belt or belt-like plate which can be used for the above-mentioned support also has the above-mentioned durability suitable for continuous polymerization and corrosion by an electrolyte such as calcium chloride which is a component of HIPE. For the purpose, it is desirable to select a type having good corrosion resistance. Therefore, it is preferable to use a metal such as stainless steel or a resin selected as the sheet material for these materials.

Further, in the above-mentioned support, an endless belt or a belt-like plate used on the side in contact with the HIPE is desirably used as the movable support using the sheet material.

Here, the reason for “using” a sheet material on an endless belt or a belt-like plate is as follows. (1) In the case of a movable endless belt, a sheet material such as a film having good durability should be at least HIPE. From the supply to the completion of the polymerization, it is sufficient to simply run the belt at the same speed and in the same direction (synchronously) so as to be in contact with the belt without sticking (including adhesion and fusion) or applying (coating). Then, a sheet material such as a film with good durability may be attached to the endless belt by a suitable adhesive or a pressure-sensitive adhesive by fusing with heat or the like,
The endless belt or the belt-shaped plate may be coated with a resin material having good durability to form a sheet material, but is not limited thereto. On the other hand, (2)
In the case of a fixed band-shaped plate, a sheet material such as a film having good durability is not attached (including adhesion or fusion) or applied (coated) at least from the supply of the HIPE to the completion of polymerization. The vehicle may be run in contact with the vehicle, but is not limited thereto.

In the production method of the present invention, it is desirable to carry out horizontal continuous polymerization while maintaining the shape of the HIPE after molding. This has the advantage that the HIPE after molding can be produced in a desired form, and that a porous cross-linked polymer having uniform properties throughout can be produced with extremely high productivity. Therefore, it is very excellent industrially.

Here, as a method of maintaining the shape of the HIPE after molding, for example, the HIPE is supplied to an internal space surrounded by a support and a weir of the driving / transporting device and molded into a desired shape. HIPE is a soft creamy or yogurt-like kinematic viscous fluid with low fluidity, and thus tends to have some irregularities on its surface. However, by providing a weir (gasket, etc.), the shape of the HIPE can be maintained after molding. In addition, it is possible to obtain the effect of preventing the continuously supplied HIPE from leaking from the outer surface, the effect of preventing unpolymerization of the HIPE, and the effect of retaining the sheet material on the outer surface. For example, using a sheet material on the outer surface of the HIPE as the oxygen amount reducing means, sandwiching the outer surface of the HIPE up and down,
Furthermore, by surrounding from the left and right using a weir, the form after molding can be more stably maintained. In this case HIP
As a method of maintaining the shape of E after molding, a method of applying tension to the sheet material, a method of uniformly applying pressure (pressing) to the HIPE from the outer surface portion by a shape adjusting plate or the like provided with the HIPE on the sheet material. Examples include, but are not limited to, methods.

(2) Molded thickness and shape of HIPE The molded thickness of HIPE is not particularly limited. This is because, as described later, the slice can be sliced into an appropriate thickness after the polymerization.

The molded thickness of the HIPE is 0.5 to 100 m
m, preferably 0.5 to 50 mm, more preferably 0.1 to 0.5 mm.
The range is 5 to 30 mm. If the thickness of the HIPE is extremely large, exceeding 100 mm, the strength of the movable support must be increased in order to secure flatness and prevent deformation, and the apparatus becomes rigid and expensive. Problems such as separation of water during polymerization are slight but undesirably occur. However, HIP
Even if the molded thickness of E exceeds 100 mm, it may be applicable if the transport speed of HIPE is adjusted so as to ensure a long polymerization curing time at a relatively low temperature. Also, HIPE
When the molded thickness after shaping is less than 0.5 mm, the handling becomes difficult. If the molded thickness is 0.5 mm or more, by using a thin porous cross-linked polymer of the obtained thickness repeatedly, depending on the intended use such as liquid absorbing material, energy absorbing material, drug impregnated base material, The required performance and quality can be sufficiently ensured. In addition, by regulating the molding thickness to a range of 0.5 to 20 mm, it is possible to rapidly raise the temperature to the desired curing temperature, and to achieve a further remarkable effect that the polymerization can be completed in a very short time. can get.

The shape of the HIPE is not particularly limited, and as described above, the cross-sectional shape may be a rectangle, a square, a trapezoid, a parallelogram or another quadrangle, a polygon, or an ellipse or a semicircle. In addition, it can take any shape such as a sheet shape and a corrugated plate shape.

(3) Curing Temperature The curing temperature of HIPE is usually in the range of room temperature to 120 ° C.
However, from the viewpoint of the stability and polymerization rate of HIPE,
Or in the range of 40 to 100 ° C., more preferably 80 to 1
00 ° C, particularly preferably in the range of 95 to 100 ° C.
The HIPE formation temperature (T₀) (= Start heating
Temperature) and curing temperature (T₁) And T₀≤T₁connection of
(“Heating up to a predetermined curing temperature
And polymerize. "
You. ). If the curing temperature is lower than normal temperature, it takes a long time for polymerization.
However, it is necessary to provide a new cooling means, which is uneconomical.
Industrially unfavorable. On the other hand, the curing temperature exceeds 120 ° C
The pore size of the resulting porous cross-linked polymer
And the absorption capacity of the porous cross-linked polymer
Is undesirably reduced. Also, T₀And T₁In the relationship
About T₀≤T₁Anything that satisfies
Preferably T₀And T₁Temperature difference [T₁-T₀Is below 50 ° C
Is desirable from the viewpoint of producing a uniform porous crosslinked polymer.
New Temperature difference [T₁-T₀] Exceeds 50 ° C,
Local heating of HIPE surface by rapid temperature increase
It becomes difficult to obtain a porous crosslinked polymer. The curing temperature (heavy
Combined temperature) [T ₁] Is to control the amount of energy from outside
A more specific temperature range (± several degrees Celsius)
Good performance, quality control and temperature control of porous crosslinked polymer
Good. However, if the temperature is within the temperature range specified above,
The polymerization temperature may fluctuate during the polymerization, and the
It does not exclude one.

After the polymerization (after the polymerization curing time),
The solution is cooled or gradually cooled to a predetermined temperature. Depending on the polymerization method, the process may proceed to a post-treatment step such as dehydration or compression described below without cooling.

(4) Heating and heating rate Next, when the curing temperature is higher than the HIPE forming temperature, the heating and heating rate up to the curing temperature when polymerizing HIPE is not particularly limited. Since it differs depending on the composition and thickness of the HIPE, the heating / heating means, etc., it cannot be uniquely defined, but is preferably 5 ° C./min or more.
When the heating rate is less than 5 ° C./min, the polymerization is slow,
It is not preferable because a large amount of water is separated during the polymerization. Preferably, the heating rate is in the range of 5 to 60 ° C./min. If the heating rate is too fast, exceeding 60 ° C./min, W /
Depending on O or the like, the emulsified state of the HIPE cannot be stably maintained, and the HIPE may be crushed.
Here, the “heating rate” refers to a predetermined curing temperature [T ₁ ] from the temperature [T ₀ ] at the start of heating of the HIPE [t ₀ ].
[T ₁ -T ₀ / (t ₁ -t ₀ )] obtained from the time [t ₁ ] to reach (stabilize) the temperature, but the temperature of the predetermined curing temperatures [T ₁ ] and [T ₀ ] 9 when the difference is 100%
[T _0.9 −T ₀ / (t _0.9 −) obtained from the time [t _0.9 ] to reach the temperature [T _0.9 ] corresponding to the temperature difference of 0%.
t ₀ )]. Here, [T _0.9 ] = [T ₀ ] +
([T ₁ ] − [T ₀ ]) × 0.9.

(5) Heating and heating time At the above heating and heating rate, the total heating and heating time
Is 15 seconds or more, preferably 15 seconds to 10 minutes, more preferably
30 seconds to 7 minutes, particularly preferably 1 to 5 minutes.
If the temperature is raised in less than 15 seconds or more than 10 minutes
HIPE is kept stable during temperature rise
May cause excessive water separation or uneven polymerization.
You. Here, the “heating time” refers to the heating time of the HIPE.
At the start of temperature [t ₀] To a predetermined curing temperature [T₁Reached
Time [t]₁] [T]₁-T
₀].

(6) Polymerization and Curing Time The polymerization and curing time of the present invention cannot be uniquely defined because it depends on the composition of the HIPE, the molded thickness “T”, etc., but the conventional continuous and batch combined polymerization method In contrast, the method of the present invention in which the supply of HIPE is continuously performed from the supply of the HIPE to the polymerization is very effective for stably performing the polymerization in a short time of several tens seconds to 60 minutes. This is because, for example, only the transfer speed needs to be controlled so that polymerization is completed when the traveling transfer device passes through an appropriate polymerization furnace.
The polymerization curing time is preferably in the range from 60 seconds to 60 minutes. When the polymerization curing time exceeds 60 minutes, it is necessary to lengthen the curing furnace or reduce the conveying speed, so that the productivity of the porous cross-linked polymer decreases. If the time is less than 60 seconds, the polymerization is not completed, so that a porous crosslinked polymer having sufficient physical properties cannot be obtained. Of course, this does not preclude the use of longer polymerization curing times. here,
The term “polymerization curing time” refers to the total time [t ₂ −t ₀ ] from the start of heating and heating [t ₀ ] to the end of polymerization [t ₂ ].

(7) Polymerization device (device including a support used for horizontally and continuously polymerizing HIPE) As a polymerization device that can be used in the present invention, HIP is used.
A support used for horizontally and continuously polymerizing E, preferably an endless belt or a movable support such as a movable sheet material, provided that weirs are provided at both ends in the width direction of the movable support, are not particularly limited. Absent.

Hereinafter, a polymerization apparatus that can be used in the horizontal continuous polymerization of the present invention will be described with reference to the drawings.

FIGS. 1 and 2 show a movable sheet material (movable support and oxygen reduction means) running on an endless belt or a plate which can be used in a polymerization apparatus used for horizontal continuous polymerization of the present invention. FIG. 2 is a schematic side view of a polymerization apparatus including the same.

As shown in FIGS. 1 and 2, a stainless steel endless belt (movable support) -type conveyor (driving and transporting) which is installed horizontally corresponding to the HIPE supply unit 119 and travels horizontally at a constant speed. The apparatus) 201 or a belt-shaped plate with a jacket (fixed support) (202) installed horizontally. HIPE is continuously extracted from the HIPE supply unit 119, and the sheet material (movable support)
On the 203, a width of about Xm and a thickness of about Ymm (the setting height of the rotating roll 209 = a weir provided at both ends in the width direction of the belt or plate as the support or the sheet material (not shown))
The HIPE is continuously supplied at the same speed and in the same direction on the belt of the conveyor 201 so as to form a smooth layer at the same time as the HIPE is continuously supplied. And an unwinding / winding-type sheet material 203 made of a PET film which runs on the support (which is a support and a means for reducing the amount of oxygen below the HIPE). A P which is placed on the upper part of a similarly formed HIPE and travels in the same direction at the same speed as the belt of the conveyor 201
ET film or PE running on strip plate 202
An unwinding / winding-type sheet material 205 (which is a means for reducing the amount of oxygen above the HIPE) made of a PET film running in the same direction at the same speed as the T film is provided.
From the viewpoint of recycling, these upper and lower sheet materials may be made of an endless belt type using a material having excellent durability and releasability. Further, it goes without saying that other oxygen amount reducing means may be employed in place of these oxygen amount reducing means. ). In the case of an endless belt type made of stainless steel, the sheet material 203
The rotation speed of the unwinding / winding rolls 208 and 212 is controlled so that the belt can travel in the same direction at the same speed as the belt. The sheet material 205 is moved on a conveyor so as to be run while applying tension so that the thickness of the HIPE becomes constant.
Rotating rolls 209 and 211 and unwinding and winding rolls 207 and 213 installed in front and behind 201 are installed at appropriate heights, and the rotation speed of the unwinding and winding rolls is controlled. As a result, the sheet materials 203 and 205 are run at the same speed in the same direction while maintaining the horizontal at a certain interval vertically. In the case of a belt-shaped plate with a jacket, the sheet material 203, 205
The rotation speeds of the unwinding / winding rolls 208, 212 and the unwinding / winding rolls 207, 213 are controlled so that the sheet material 205 is synchronously driven in the same direction at the same speed. H
The belt-shaped plate 202 with a jacket is provided so as to be run while applying tension so that the thickness of the IPE is constant.
Rolls 209 and 211 installed in front and behind
The winding rolls 207 and 213 are installed at appropriate heights, and the number of rotations of the unwinding / winding roll is controlled. Also conveyor
At both ends (both sides) on the belt of 201 or on the belt-shaped plate (202), or at both ends on the sheet material provided above these, along both sides (each edge on the long side) Movable or fixed diameter (height) Ymm
Continuous weirs (including gaskets) are provided (not shown).

Further, heating means capable of running a belt carrying the HIPE of the conveyor 201 in the horizontal direction in the middle of the conveyor 201 and heating the belt from above and below the belt while running inside the conveyor 201 Or the HIPE on the strip plate 202 can be placed in the middle of the strip plate 202 so that the PET film can run horizontally in the inside, and while running inside, the belt film jackets above and below the belt are A polymerization furnace 215 provided with a heating means capable of heating is provided so as to surround (or surround). The polymerization furnace 215 is provided with a heating / heating means 217 composed of a hot air circulation device above the belt or the belt-shaped plate as heating (heating) means. A hot water shower device (hot water shower) for blowing hot water directly to the lower part of the belt so that the HIPE can be rapidly heated and heated through the belt or the band plate and the sheet material is provided below the belt or the band plate. A heating / heating means 219 including a spraying apparatus) or a heating / heating means 220 including a hot water supply apparatus (hot water circulating apparatus) for supplying hot water to the jacket of the belt-shaped plate is provided. Further, the heating / heating means 217 stabilizes H at a predetermined curing temperature for a predetermined time.
As a heat-curing means for polymerizing the IPE, a HIPE which is heated to a curing temperature rapidly over a belt or above a belt-like plate through a sheet material on the HIPE top is heated.
Is also provided so as to be able to be maintained at the same temperature. Further, the heating / heating means 219 uses the HIPE heated and heated to the curing temperature rapidly from below the belt via the belt and the sheet material, and the heating / heating means 220 through the belt-shaped plate and the sheet material. It is also provided so that it can be maintained at a temperature. The heating temperature raising means or the heat curing means is not limited to the above, and may be a continuous output magnetron capable of irradiating active thermal energy rays such as microwaves, far infrared rays, and near infrared rays that can use radiant energy and the like. Means such as an oscillator using the above, various infrared heaters, a hot air circulation device for blowing a heat medium such as hot water or hot air, a hot water spray device, and a hot water circulation device can be used. Also,
The latter zone of the polymerization furnace 215 may be used as a cooling zone for rapidly cooling the porous crosslinked polymer after polymerization, and the temperature setting of the above-described hot air circulation device, hot water spray device, and hot water circulation device may be used. It can cope enough by making it low. If nitrogen gas is used for hot air, a nitrogen gas seal can be used instead of the sheet material, and if a hot water spray device is used on the top,
Water layer seal can be used instead of sheet material.
It can function as a heating means as well as an oxygen amount reducing means.

Further, in the present invention, in the process of forming the HIPE and producing a porous cross-linked polymer by horizontal continuous polymerization, both ends in the width direction of the support used for forming the HIPE and performing horizontal continuous polymerization. The main constituent requirement is to use a weir in the section.

That is, in the case of the HIPE described above,
Since the HIPE is a non-Newtonian fluid and has a thixotropic viscosity, there is no need to use a weir (including a gasket) in a compressed state in order to improve the sealing performance of the HIPE. Therefore, if the molded thickness of the HIPE is equal to the thickness of the weir, a porous crosslinked polymer which is a HIPE polymer having a desired thickness can be obtained. Further, by providing such a weir, oxygen on the side surface of the HIPE during the polymerization step is shut off, so that a polymer having desired open cells on the side surface can be obtained efficiently.

The weir system can be either a fixed system or a mobile system (integrated system or driven system). In the fixing method, a support (for example, an endless belt or a lower sheet material on the endless belt) is fixed so that weirs are in contact with both ends in the width direction, so that only the support that is in contact with the weir in a state in contact with the weir (See Examples 1 and 2 and FIGS. 3 and 4 to be described later). Here, in order to fix the weir so as to be in contact with both ends in the width direction of the support, for example, a weir in which a wire is passed through a tube is used, and tension is applied to the wire in the running direction, or the weir is pulled on the HIPE upper surface. What is necessary is just to pull | pull the upper surface sheet material put on it toward the both ends of the width direction of a support body. Thereby, it is possible to stabilize the weir without meandering by using a fixed weir having a support capable of stably fixing the weir, which is the tube, without meandering. In addition, in the integrated movement method,
A support (for example, an endless belt or a lower sheet material on the endless belt) may be joined to both ends in the width direction and integrated with the support (Examples 3 to 4 described later, See Figures 5-6). The support and the weir may be manufactured integrally. That is, the endless belt having a concave cross-sectional shape in the width direction may be used to have both functions of the support and the weir.
In such a case, since the height of the weir cannot be adjusted, it can be said that it is suitable for a case where the same product is industrially mass-produced. In the drive-type moving method, there are weirs placed on both ends in the width direction of a support (for example, a lower surface sheet material on an endless belt) and run (drive) at the same speed in the same direction as the support. (Example 5 described later,
See FIG. 7).

The shape and structure of the weir are not particularly limited as long as the intended purpose can be achieved. For example, the shape of the cross section is hollow (see FIGS. 3 and 4), Any shape is possible, such as circular, oval, square (see squares in FIGS. 5-6 and rectangle in FIG. 7), trapezoidal, semi-circular, and the like.

As the material of the weir, those having low elasticity and low towability can be used. Those having good releasability with respect to the porous crosslinked polymer are preferred.

Examples of the material of the weir include polyolefin resins such as polyethylene and polypropylene, saturated polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as 6-nylon and 6,6-nylon, and polyvinyl chloride resins. Acrylic resin, methacrylic resin, fluororesin, silicone resin, ABS resin, polycarbonate resin, polystyrene resin, epoxy resin, polyimide resin, polyphenylsulfide resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyetheretherketone , Para-aramid resin, ionomer resin, AS resin, EVA resin, vinylidene chloride resin, polyacetal resin, polyamideimide resin, polyarylate resin, nylon resin , Vinyl acetate resin, phenol formaldehyde resin, urea resin, melamine formaldehyde resin, furan resin, unsaturated polyester resin, vinyl ester resin, synthetic resin such as DAP resin; natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber (CR), butyl rubber (BR), nitrile rubber (NBR), silicon rubber, fluorine rubber, acrylic rubber, urethane rubber, chlorosulfonated polyethylene rubber, ethylene propylene rubber (EPDM) ), Rubber materials such as polysulfide rubbers; thermoplastic elastomers such as polyester elastomers, polyamide elastomers, urethane-based elastomers, and styrene-based elastomers;
The synthetic resin and rubber material reinforced with an inorganic filler such as graphite and an organic filler such as polyimide; a synthetic resin having a synthetic resin-based coating layer different from the material of the weir body; a metal hollow made of stainless steel or the like Metals such as a ring; a composite of a metal and a synthetic resin or rubber (including a metal coated with a synthetic resin) can be used. Swelling resistance to HIPE, HIPE
In view of the heat degradation resistance to polymerization of styrene and the releasability of the porous cross-linked polymer which is a HIPE polymer, rubber materials such as chloroprene rubber and silicone rubber, polytetrafluoroethylene, and tetrafluoroethylene-perfluoroalkylvinylether Fluororesins such as polymers, tetrafluoroethylene-hexafluoropropylene copolymers and tetrafluoroethylene-ethylene copolymers, and thermoplastic elastomers such as polyester elastomers and polyamide elastomers are preferred.

The height of the weir is equivalent to the molded thickness of the HIPE since a porous cross-linked polymer which is a HIPE polymer having a desired thickness can be obtained if the molded thickness of the HIPE is equal to the thickness of the weir. And preferably 0.5 to 1 as in the case of the HIPE molding thickness.
The range is 00 mm. If the height of the weir is less than 0.5 mm, handling of the formed HIPE becomes difficult. On the other hand, if it exceeds 100 mm, in other words, the height of the weir is higher than the thickness of the formed HIPE, and if there is a height difference between the two, a sheet material or the like for reducing the amount of oxygen on the upper surface of the HIPE, It may be difficult to adhere to the upper surface of the HIPE.

The above is one embodiment of the polymerization apparatus of the present invention, but it goes without saying that the polymerization apparatus applicable to the production method of the present invention is not limited to this.

The materials (excluding the weirs described above) of the polymerization apparatus and the like are not particularly limited, and satisfy technical requirements such as necessary strength (durability) and corrosion resistance. From among the materials, an optimal material may be appropriately selected in consideration of economic efficiency, environmental issues and recyclability, for example, made of metals (including alloys) such as aluminum, iron, and stainless steel, polyethylene, and polypropylene. , Made of synthetic resin such as fluororesin, polyvinyl chloride and unsaturated polyester resin, and made of fiber reinforced resin (F
RP) can be used. In the case of high-frequency dielectric heating using microwaves as the heating and temperature raising means, if aluminum or the like is used for the device material or sheet material, there is a risk of ignition (due to eddy current). Care must be taken in the selection of

(8) Form of Porous Cross-Linked Polymer The form of the porous cross-linked polymer obtained by the above-mentioned polymerization step is not particularly limited. As a result, it becomes a porous cross-linked polymer, so that it can take any form as in the form of the HIPE after molding.

(9) Slicing Step of Porous Crosslinked Polymer Further, in the present invention, the porous crosslinked polymer obtained by horizontally and continuously polymerizing HIPE as described above can be sliced continuously.

The method for continuously slicing the porous cross-linked polymer is not particularly limited, and a conventionally known slicing means can be appropriately used. Specifically, there is a belt conveyor type horizontal endless band knife or the like.

When the porous cross-linked polymer after polymerization is sliced continuously, for example, it is polymerized into a layered form having a thickness of (n × X) mm and then into a plate-shaped or film-shaped form having a thickness of X mm. It can also be sliced in n-1 steps and processed into n sheets or films. In this case, a method is adopted in which a plurality of the horizontal endless band knives are arranged in series on the transport path, and the slice surface (height from the transport device) is stepwise changed in a stepwise manner and sliced sequentially. be able to.

Further, if the slicing speed of the porous cross-linked polymer is too high, the porous cross-linked polymer may be broken or cracked.
m / min.

(10) Post-treatment (product production) step after molding the porous cross-linked polymer (a) The porous cross-linked polymer formed by dehydration polymerization and, if necessary, by slicing after polymerization is usually compressed, Dewater by vacuum suction and a combination of these. Generally, such dehydration dehydrates 50-98% of the water used, leaving the remainder attached to the porous cross-linked polymer.

The dehydration rate is appropriately set according to the use of the porous crosslinked polymer. Usually, a water content of 1 to 10 g per 1 g of the porous crosslinked polymer in a completely dried state,
Alternatively, the water content may be set to 1 to 5 g.

(B) Compression The porous crosslinked polymer of the present invention can be in a form compressed to a fraction of its original thickness. A form such as a compressed sheet has a smaller volume than the original porous crosslinked polymer, and can reduce transportation and storage costs. The porous cross-linked polymer in the compressed form has a property of absorbing water when coming in contact with a large amount of water and returning to its original thickness, and is characterized in that the water absorption speed is higher than that of the original thickness.

In order to form a compressed form, a compressing means corresponding to the form of the porous cross-linked polymer may be used so that pressure is applied uniformly to the entire porous cross-linked polymer so that the porous cross-linked polymer can be uniformly compressed. In the present invention, it is preferable that the subsequent steps are not continuously followed by using an appropriate transfer device even after the polymerization,
The porous crosslinked polymer obtained by polymerization is continuously dehydrated while being transported, and then may be passed between rolls or belts adjusted to a predetermined interval. Therefore, if the sheet thickness after the dehydration step is within a predetermined range, it is not necessary to newly provide a compression step.

The temperature at which the porous crosslinked polymer is compressed in the pre-dehydration and compression step is preferably higher than the glass transition temperature of the porous crosslinked polymer. If the temperature is lower than the glass transition temperature of the polymer, the porous structure may be broken or the pore size may change.

It is effective to reduce the thickness to 1/2 or less of the original thickness from the viewpoint of saving of transportation and stock space, and ease of handling. More preferably, compression is performed to 1/4 or less of the original thickness.

(C) Washing For the purpose of improving the surface condition of the porous cross-linked polymer,
An aqueous solution containing pure water or any additive,
You may wash with a solvent.

(D) Drying If necessary, the porous crosslinked polymer obtained in the above steps may be dried by heating with hot air, microwaves, or the like, or may be humidified to adjust the water content. .

(E) Cutting The porous cross-linked polymer obtained in the above steps may be cut into a desired shape and size, if necessary, and processed into products suitable for various uses.

(F) Impregnation processing Functionality can also be imparted by impregnation processing with a detergent, a fragrance or the like.

[0102]

The present invention will now be described more specifically with reference to examples.

Example 1 5.0 parts by mass of 2-ethylhexyl acrylate, 55%
To a mixture of 3.0 parts by mass of divinylbenzene, 0.4 parts by mass of diglycerin monooleate was added and uniformly dissolved to prepare an oil phase. Separately, 8.0 parts by mass of calcium chloride and 0.2 parts by mass of potassium persulfate were dissolved in 395 parts by mass of pure water to prepare an aqueous phase, which was then heated to 55 ° C. The water phase and the oil phase were continuously supplied into a dynamic mixer at a ratio of W / O = 48/1, mixed and emulsified to prepare HIPE (1).

Next, as shown in FIG. 3, an endless steel belt 303 having a width of 1.6 m and a width of 1.6 m and a thickness of 50 μm conveyed in synchronization with the belt 303 are installed horizontally.
The outer diameter is 5.0m at both ends on the lower PET film 305.
Tube 307 made of fluororesin PFA with an inner diameter of 3.0 mm
A fixed weir (31) in which a gasket 311 in which a 2.0 mm diameter stainless steel wire 309 is inserted is tensioned.
The above-mentioned HIPE (1) 321 was 1.9 kg / having a thickness of 1.5 mm and a thickness of 5 mm by a coater on a lower PET film 305 of a 1.5 m width driving and conveying device 301 having 1).
Coat continuously at a feed rate of 1 minute. Then, width 1.6
After placing the upper PET film 313 having a thickness of 50 μm and a thickness of 50 μm, a moving speed of 0.degree. C. was passed through a 15 m-long polymerization furnace in which a 90 ° C. hot air circulation to the upper PET film 313 and a 90 ° C. hot water shower to the lower steel belt 303 were set. The mixture was passed at 25 m / min and polymerized for 60 minutes to produce a porous crosslinked polymer (hereinafter, also simply referred to as “polymer”) (1). The polymer (1), which was in contact with the weir 311 due to the deflection in the width direction, was cut by 3 mm at both ends in the width direction, so that the yield was 99.6%.
Met. A small wavy was recognized on the upper surface, and the smoothness was slightly lowered, but the thickness was 5 ± 0.3 mm. The evaluation results are shown in Table 1 below, and indicate a state in which the HIPE is transported using the drive transport device provided with the weir.
FIG. 3 is a schematic cross-sectional view perpendicular to the running direction of the PE.

Example 2 In the same manner as in Example 1, HIPE (1) was produced.

Next, as shown in FIG. 4, an endless steel belt 403 having a width of 1.6 m and a width of 1.6 m and a thickness of 50 μm conveyed in synchronization with the belt 403 are provided.
The outer diameter is 4.6m at both ends on the lower PET film 405.
m, 0.2 in stainless steel pipe 407 with 2.6mm inner diameter
1.5 m wide having a gasket 411 coated with a fluorine resin PTFE 409 mm thick as a fixed weir (411)
The above-mentioned H is transferred onto the lower PET film 405 of the driving and conveying device 401 by a coater so that the width becomes 1.5 m and the thickness becomes 5 mm.
IPE (1) 421 was continuously coated at a feed rate of 1.9 kg / min. Subsequently, an upper PET film 413 having a width of 1.6 m and a thickness of 50 μm is placed thereon.
90 ° C hot air circulation to the lower steel belt 403
The mixture was passed through a 15 m-long polymerization furnace equipped with a 0 ° C. hot water shower at a moving speed of 0.25 m / min, and polymerized in 60 minutes to produce a polymer (2). The polymer (2), which had been in contact with the weir 411, was cut by 3 mm at both ends in the width direction because of the run-out in the width direction, so that the yield was 99.6%. A small wavy was recognized on the upper surface, and the smoothness was slightly lowered, but the thickness was 5 ± 0.3 mm. The evaluation results are shown in Table 1 below.
FIG. 4 is a schematic cross-sectional view perpendicular to the traveling direction of the HIPE, showing a state of transporting the PE.

Example 3 In the same manner as in Example 1, HIPE (1) was produced.

Next, as shown in FIG. 5, chloroprene rubber 511 having a width of 30 mm and a height of 20 mm was attached to both ends of a 1.6 m-wide endless steel belt 503 which was placed horizontally.
1.5 m in width and 50 μm in thickness conveyed in synchronism with a 1.5 m wide driving and conveying device 501 having a moving (integral) weir (511) in which is adhered by an epoxy resin (not shown).
1.5m with a coater on the lower PET film 505
The width of the HIPE (1) 52 is set to be 20 mm.
1 was continuously coated at a feed rate of 7.5 kg / min.
Then, the upper PET film of 1.6m width and 50μm thickness
After the 513 is placed, a 90 mC hot air circulation to the upper PET film 513 and a 90 mC hot water shower to the lower steel belt 503 are set in a 15 m-long polymerization furnace set at a moving speed of 0.25 m.
Per minute and polymerized in 60 minutes to produce a polymer (3). Since there was no deflection in the width direction and the holding property of the upper PET film was good, both ends in the width direction of the polymer (3) in contact with the weir 511 were cut by 1 mm, and the yield was 99.8. %Met. Although the upper surface was slightly wavy and the smoothness was slightly reduced, the thickness of the upper PET film was 20 ± 0.3 mm because of good holding properties.
Met. The evaluation results are shown in Table 1 below, and FIG. 5 is a schematic cross-sectional view perpendicular to the traveling direction of the HIPE, showing a state in which the HIPE is transported using the drive transport device provided with the weir.

Example 4 In the same manner as in Example 1, HIPE (1) was produced.

Next, as shown in FIG. 6, an endless steel belt 603 having a width of 1.6 m and a width of 1.6 mm was provided on both ends of a horizontal fluorinated PTFE resin having a width of 30 mm and a height of 20 mm.
Width 1 in consideration of the sealing property of HIPE conveyed in synchronization with a 1.5 m wide drive conveyance device 601 having a moving type (integral type) weir (611) in which 611 is adhered by an epoxy resin (not shown). 7.5 kg of the above HIPE (1) 621 so as to have a width of 1.5 m and a thickness of 20 mm on a thin lower PET film 605 having a thickness of .64 m and a thickness of 12 μm by a coater.
/ Min with continuous feed rate. Then, width 1.6
After placing an upper PET film 613 having a thickness of 50 μm and a thickness of 50 μm, a moving speed of 0.degree. The mixture was passed at 25 m / min and polymerized for 60 minutes to produce a polymer (4). Since the polymer (4) was in contact with the PET film having a good release property and was not in contact with the weir 611 via the PET film, there was no need to cut both ends in the width direction of the polymer (4). Met. Further, a small wavy was recognized on the upper surface, and the smoothness was slightly lowered, but the thickness was 20 ± 0.3.
mm. The evaluation results are shown in Table 1 below, and FIG. 6 is a schematic cross-sectional view perpendicular to the traveling direction of the HIPE, showing a state in which the HIPE is transported using the drive transport device provided with the weir.

Example 5 In the same manner as in Example 1, HIPE (1) was produced.

Next, as shown in FIG. 7, a moving system (drive type) made of a thermoplastic polyester elastomer having a width of 5 mm and a height of 50 mm was attached to both ends of an endless steel belt 703 having a width of 1.6 m and placed horizontally. ) Endless belt
1.5 m-wide drive transfer device 70 having 711 as a weir (711)
1.5m wide by a coater on a lower PET film 705 having a width of 1.5m and a thickness of 50μm conveyed in synchronization with 1,
The above-mentioned HIPE (1) 721 was continuously coated at a supply rate of 18.8 kg / min so as to have a thickness of 50 mm. Subsequently, an upper PET film 71 having a width of 1.6 m and a thickness of 50 μm.
After placing 3 on the upper PET film 713, the hot air circulation at 90 ° C. and the lower steel belt 703 at a 90 ° C. hot water shower were set.
And polymerized in 60 minutes to produce polymer (5). Since the polymer (5), which was in contact with the weir 711, was cut by 2 mm each in the width direction because there was no deflection in the width direction, the yield was 99.7%. A small wavy was observed on the upper surface, and the smoothness was slightly reduced, but the thickness was 50 ± 0.
3 mm. The evaluation results are shown in Table 1 below,
FIG. 7 is a schematic cross-sectional view perpendicular to the traveling direction of the HIPE, showing a state in which the HIPE is transported using the drive transport device provided with the weir.

Comparative Example 1 A HIPE (1) was produced in the same manner as in Example 1.

Next, as shown in FIG. 8, an endless steel belt 803 having a width of 1.6 m and horizontally installed is used as a driving and conveying device 801, and is 1.6 m in width and thickness conveyed in synchronization with the belt 803. On a 50 μm lower PET film 805 with a coater, 1.5 m width and 5 mm thickness,
The HIPE (1) 821 was continuously coated at a supply rate of 1.9 kg / min. Then 1.6m in width and 50μm in thickness
After placing the upper PET film 813, hot air circulation at 90 ° C. to the upper PET film 813, the lower steel belt 803
The polymer was passed through a 15 m-long polymerization furnace having a 90 ° C. hot water shower set at a moving speed of 0.25 m / min and polymerized in 60 minutes to produce a comparative polymer (1). Because weirs such as gaskets were not installed at both ends in the width direction, unpolymerized tendency was observed at the parts near both ends, and the thickness accuracy at the parts near both ends was reduced, Since both ends in the width direction of the comparative polymer (1) were cut by 10 mm, the yield was 93.3%. The thickness was 5 ± 0.5 mm. The evaluation results are shown in Table 1 below, and FIG. 8 is a schematic cross-sectional view perpendicular to the traveling direction of the HIPE, showing a state in which the HIPE is transported using the drive transport device provided with the weir.

Example 6 In the same manner as in Example 1, HIPE (1) was produced.

Next, as shown in FIG. 9, an endless steel belt 903 having a width of 1.6 m and a width of 1.6 m and a thickness of 50 μm conveyed in synchronization with the belt 903 are provided horizontally.
30m wide at both ends on the lower PET film 905
A stainless steel square pipe 907 having a height of 19.6 mm and a thickness of 19.6 mm is coated with a fluorine-based resin PTFE 909 having a thickness of 0.2 mm, and a support rod 908 is provided on the outside to prevent runout (the support rod is formed of a gasket and a side wall in a polymerization furnace). (The joining method is not shown.) A 1.5 m-wide drive transfer device 901 having a gasket with a fixed type weir 911 attached thereto.
1.5m with a coater on the lower PET film 905
The above HIPE (1) 92 so as to have a width and a thickness of 20 mm.
1 was continuously coated at a feed rate of 7.5 kg / min.
Then, the upper PET film of 1.6m width and 50μm thickness
After the 913 is put on, a 15 m long polymerization furnace with a 90 ° C. hot air circulation to the upper PET film 913 and a 90 ° C. hot water shower to the lower steel belt 903 is set at a moving speed of 0.25 m.
Per minute and polymerized in 60 minutes to produce a polymer (6). Since there was no deflection in the width direction and the holding property of the upper film was good, both ends in the width direction of the polymer (6) in contact with the weir 911 were cut by 1 mm, and the yield was 99.8.
%Met. A small wavy was recognized on the upper surface, and the smoothness was slightly lowered, but the thickness was 20 ± 0.3 mm. The evaluation results are shown in Table 1 below, and FIG. 9 is a schematic cross-sectional view perpendicular to the traveling direction of the HIPE, showing a state in which the HIPE is transported using the drive transport device provided with the weir.

Example 7 HIPE (1) was produced in the same manner as in Example 1.

Next, as shown in FIGS. 10A and 10B, a T-die having a lip width of 500 mm and a lip interval of 1 mm is used.
An endless steel belt 1003 made of SUS316 having an effective width of 1023 and a width of 500 mm, and a lower PET film 1005 having a width of 600 mm and a thickness of 50 μm conveyed in synchronization with the belt 1003, having a width of 30 mm and a height of 4.0 mm. A 6 mm stainless steel square pipe 1007 is coated with a 0.2 mm thick fluororesin PTFE 1009, and a support rod 1008 is provided on the outside to prevent runout (the support rod is used to connect the side wall and the gasket in the polymerization furnace). The joining method is not shown.) A fixed type weir 1011 comprising a gasket to which a gasket is attached.
And a movable support 1001 comprising a lower PET film 1005
HIPE (1) 1021 was continuously supplied onto the lower PET film 1005 of the above. Immediately thereafter, one knife coater 10 installed at a right angle to the traveling direction of the movable support 1001
After coating while regulating the thickness through 25, the rotation speed of the nip roll 1019 in which two rolls (upper 1015 / lower 1017) are arranged in a nip type and the speed of the movable support are adjusted and synchronized, and the upper PET After mounting the film 1013, a fixed parallel flat plate (thickness regulating plate) 1027 was set. Also,
As shown in FIG. 11, the torque of the film winder 1029 was appropriately selected from the output of a torque adjuster (not shown) to prevent wrinkles from occurring in the running direction (the longitudinal direction of the upper PET film 1013). . Subsequently, as shown in FIGS. 10B and 11, in a state where the fixed weir 1011 is installed, the tension rollers are arranged in an eight-shape from the vicinity of the polymerization furnace inlet to the inside of the polymerization furnace (not shown). While applying tension in the width direction (transverse direction of the upper PET film) by a tension roller, circulating hot air at 90 ° C., and moving through a 15 m-long polymerization furnace 1031 provided with a 90 ° C. hot water shower to the lower SUS316 belt, moving speed 0 The mixture was passed at 0.25 m / min and polymerized in 60 minutes. The obtained polymer (7) had no small waving on the upper surface and had a thickness of 5 ± 0.1 mm. Since there was no deflection in the width direction and the holding property of the upper PET film was good, both ends in the width direction of the polymer (7) in contact with the fixed weir 1011 with the support rod were cut by 1 mm, and the yield was low. 99.8%.

[0119]

[Table 1]

[0120]

According to the method for producing a porous cross-linked polymer by horizontal continuation of HIPE according to the present invention, the thickness accuracy of HIPE is regulated and controlled from the supply, shaping (molding) to polymerization stages to maintain the thickness. By providing weirs at both ends of the support on the lower surface during polymerization, a porous crosslinked polymer having good thickness accuracy can be produced. HIPE
By providing weirs at both ends in the width direction of the lower support using the non-Newtonian and thixotropic viscosity of the non-Newtonian, besides being able to obtain the thickness including both ends and maintain the thickness,
It can prevent leakage of HIPE, prevent uncuring by reducing the amount of oxygen, and improve the retention of sheet materials such as an upper film. Therefore, the yield is good, the dispersion of performance and quality in the same production lot is small, and a high-quality and high-performance porous cross-linked polymer can be stably mass-produced in a high yield.

In the method for producing a porous crosslinked polymer according to the present invention, since the quality at the production stage is stable and the productivity is excellent, it is possible to obtain a high-quality, high-performance porous crosslinked polymer at low cost. Therefore, the obtained porous cross-linked polymer can be used as (1)
Liquid absorbents; for example, they can be used as absorbents for excretions such as water and urine in diaper cores, etc., and as oils, organic solvents and other absorbents for waste oil treatment agents, waste solvent treatment agents, etc. A) energy absorbing materials; for example, sound and heat absorbing materials for automobiles, architectural sound insulating materials, heat insulating materials, and the like; and (3) drug-impregnated base materials;
It can be widely used for toiletry products impregnated with polishing agents, surface protective agents, flame retardants, etc.

[Brief description of the drawings]

FIG. 1 is a schematic side view showing a typical embodiment of a polymerization apparatus including a sheet material (movable support) running on an endless belt which can be used for horizontal continuous polymerization according to the present invention.

FIG. 2 is a schematic side view showing a representative embodiment of a polymerization apparatus including a sheet material (movable support) running on a plate which can be used for horizontal continuous polymerization according to the present invention.

FIG. 3 is a schematic diagram showing a representative embodiment of a driving and transporting device having a movable support having a fixed type weir used in horizontally and continuously polymerizing HIPE in Example 1; FIG. 3 shows a schematic cross-sectional view perpendicular to the running direction of the HIPE.

FIG. 4 is a schematic view showing another representative embodiment of the drive transfer device having a movable support having a fixed type weir used in horizontally continuous polymerization of HIPE in the second embodiment. And a schematic cross-sectional view perpendicular to the running direction of the HIPE.

FIG. 5 is a schematic diagram showing a representative embodiment of a driving and transporting device having a movable support having a moving type (integral type) weir used in horizontally and continuously polymerizing HIPE in Example 3; And a schematic cross-sectional view perpendicular to the running direction of the HIPE.

FIG. 6 shows another representative embodiment of the drive transfer device having a movable support having a moving type (integral type) weir used in horizontally continuous polymerization of HIPE in Example 4. It is a schematic diagram and shows the cross-sectional schematic perpendicular to the running direction of HIPE.

FIG. 7 is a schematic diagram showing a representative embodiment of a driving / transporting device having a movable support having a moving type (driving type) weir used in horizontally continuous polymerization of HIPE in Example 5; And a schematic cross-sectional view perpendicular to the running direction of the HIPE.

FIG. 8 is a schematic view showing a representative embodiment of a driving / transporting device having a movable support without a weir used in horizontally and continuously polymerizing HIPE in Comparative Example 1, wherein FIG. FIG. 2 shows a schematic sectional view perpendicular to the running direction.

FIG. 9 is a representative example of a drive transfer device having a movable support having a fixed type weir to which a support bar for preventing vibration is used for horizontal continuous polymerization of HIPE in Example 6; FIG. 2 is a schematic view showing a typical embodiment, and is a cross-sectional schematic view perpendicular to the traveling direction of the HIPE.

FIG. 10 is a representative example of a drive transfer device having a movable support having a fixed type weir to which a support bar for preventing runout is used for horizontal continuous polymerization of HIPE in Example 7; 1 shows a schematic diagram representing one typical embodiment. FIG. 10A shows a polymerization apparatus used in Example 7;
In particular, HIPE using two T-die and knife coater together
After the thickness is regulated from the supply of the HIPE, the upper surface is covered with a sheet material (film) while continuously improving the surface smoothness and the thickness accuracy in the running direction by the nip roll, and then the HIPE is supplied by using the thickness regulating plate together. FIG. 6 is a schematic side view illustrating a state from the time when the thickness is regulated. FIG. 10 (B) shows the traveling of the movable support after the HIPE of FIG. 10 (A) is filled in contact with a fixed type weir in which the thickness of the HIPE is regulated and a support rod for preventing deflection is attached outward. FIG. 4 is a schematic sectional view perpendicular to a direction.

FIG. 11 is a diagram showing a representative example of a drive transfer device having a movable support having a fixed type weir to which a support rod for preventing runout is used for horizontal continuous polymerization of HIPE in Example 7; Is a schematic diagram showing a typical embodiment, and shows a state until HIPE is polymerized while continuously improving surface smoothness and thickness accuracy in a running direction by nip rolls. FIG. 3 is a schematic cross-sectional view parallel to the traveling direction of FIG.

[Explanation of symbols]

119: HIPE supply unit, 201: Endless belt type conveyor (with driving and conveying device), 202: Strip plate with jacket (without driving and conveying device), 203, 205: Sheet material, 207: Unwinding roll, 209, 211 ... Rotating roll, 213 ... Winding roll, 215 ... Polymerization furnace,
217: heating / heating means, 219: hot water shower device, 220: hot water circulation jacket, 301, 4
01, 501, 601, 701, 801, 901 ... Drive and transport device, 303, 40
3, 503, 603, 703, 803, 903, 1003 ... Endless steel belt (lower steel belt), 305, 405, 505, 60
5, 705, 805, 905, 1005 ... lower PET film, 307 ...
Fluororesin PFA tube, 309: stainless steel wire inserted into the tube, 311… tube gasket, 313, 413, 513, 613, 713, 813, 913, 101
3 Upper PET film, 321, 421, 521, 621, 721, 82
1, 921, 1021… HIPE (1), 407… Stainless steel pipe, 409… Fluorine resin PTF coated on the pipe
E, 411: pipe gasket (weir), 511: chloroprene rubber (weir), 611: fluorine-based PTFE resin (weir) 711 ... endless belt (weir) made of thermoplastic polyester elastomer, 907, 1007 … Stainless steel square pipe, 908, 1008… Support rod, 909, 1009… Fluorine resin PTFE, 911, 1011… Fixed weir,
1001 ... movable support, 1015 ... upper roll,
1017… Lower roll, 1019… Nip roll,
1023 ... T die, 1025 ... Knife coater, 10
27: parallel flat plate (thickness control plate), 1029: film winder, 1031: polymerization furnace.

Continued on the front page (72) Inventor Kozo Nogi 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4J011 LA03 LA06 LA06 LA07 LB05

Claims (2)

[Claims] 1. A method for producing a porous cross-linked polymer by horizontally and continuously polymerizing a water-in-oil type high-dispersion phase emulsion, wherein both ends in the width direction of an emulsion support used for horizontally and continuously polymerizing the emulsion. A method for producing a porous cross-linked polymer, comprising using a weir in a part. 2. The method according to claim 1, wherein the height of the weir is in the range of 0.5 to 100 mm.