JPH06269664A - Porous oil absorbing material - Google Patents

Abstract

PURPOSE:To obtain an oil absorbing material efficiently absorbing oil, developing the oil retentivity of absorbed oil and having oil recovery efficiency by supporting a particulate material consisting of an oil absorbable crosslinked polymer obtained by polymerizing a hydrophobic monomer having a specific solubility parameter in the presence of a prosslinkable monomer and a water- insoluble compd. on a porous base material. CONSTITUTION:A particulate material III consisting of 30-90 pts.wt. of a crosslinked polymer I obtained by polymerizing monomer components consisting of 96-99.999wt.% of a monomer A having one polymerizable unsaturated group in its molecule and based on a monomer having a solubility parameter (SP value) of 9 or less and 0.001-4wt.% of a crosslinkable monomer B having at least two polymerizable unsaturated groups in its molecule (the sum of the monomers A, B is 100wt.%) and 1-70 pts.wt. of a water-insoluble compd. II (e.g. metal soap) is supported in a porous base material (e.g. nonwoven fabric). As a result, a porous oil absorbing material efficiently absorbing oil and developing the oil retentivity of absorbed oil and having high oil absorbing efficiency can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an oil absorbing material. More specifically, it efficiently absorbs even oil mixed with oil and thin film oil floating on the surface of the water, and exhibits the oil retaining performance of the oil absorbed by contact with oil for a short time. The present invention relates to an oil absorbent material having a high oil recovery efficiency in which re-release (oil sag etc.) of oil once absorbed is significantly reduced.

[0002]

2. Description of the Related Art In recent years, the recovery of oil spilled into the sea and oil in waste water has become a major environmental issue. Further, there is a strong demand for a simple method for treating leaked oil such as small-scale waste oil discarded in homes and factories and machine oil in factories.

[0003] As one of the effective means for recovering these oil spills and oil components in waste water or treating waste oil and oil leaks, a method of adsorbing oil with an oil absorbent and then incineration or other post-treatment has been conventionally used. Has been. As such an oil absorbing material,
For example, a synthetic fiber oil absorbing material made of a hydrophobic fiber such as polypropylene fiber, polystyrene fiber, polyethylene fiber or a nonwoven fabric thereof has been used. However, the conventional synthetic fiber-based oil absorbent material is inferior in oil retention performance after oil absorption because the oil absorbing action is due to adsorption and holding of the oil in the voids existing in the oil absorbent material due to the capillary phenomenon, so that it is less than the low viscosity oil. Has substantially no oil retaining ability, and since the oil that was easily absorbed is re-released even with viscous oil with a slight external pressure, liquid sagging easily occurs and post-treatment becomes extremely complicated. Was.

As an attempt to solve these problems, the present inventors have prepared a crosslinked polymer obtained by copolymerizing a specific hydrophobic unsaturated monomer with a crosslinkable monomer as a hydrophobic porous group. Oil absorption material supported on a material (Japanese Patent Laid-Open No. 04-41583)
And a crosslinked polymer obtained by post-crosslinking a copolymerization prepolymer of a specific hydrophobic unsaturated monomer and a condensable functional group-containing monomer with a crosslinkable condensing agent is uniformly supported on a porous substrate. By the oil absorption material (Japanese Patent Application No. 4-25062)
A method has been proposed in which the oil once adsorbed on the porous base material is further absorbed by the cross-linked polymer to develop the oil retaining ability. But,
Since the cross-linked polymer used in this method takes a long time to absorb the oil, this method should improve the oil retaining ability substantially if the contact time between the oil absorbent and the oil is not sufficiently given. I couldn't.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above problems of conventional oil absorbent materials. That is, the object of the present invention is excellent in handleability, efficiently absorbs oil even in oil-water mixed system and thin film oil floating on the water surface, and moreover, it absorbs by contact with oil for a short time. Another object of the present invention is to provide an oil-absorbing material having a high oil-recovering efficiency, which exhibits the oil-retaining performance of the above-mentioned oil and remarkably reduces the re-release (oil dripping etc.) of the oil once absorbed.

[0006]

The present inventors have found that the above object can be achieved by supporting a particulate material comprising a specific crosslinked polymer and a water-insoluble compound on a porous substrate. The invention was completed.

That is, according to the present invention, a monomer (A) 96 to 9 having one polymerizable unsaturated group in a molecule whose main component is a monomer having a solubility parameter (SP value) of 9 or less.
9.999% by weight and 0.001 to 4 crosslinkable monomer (B) having at least two polymerizable unsaturated groups in the molecule
% By weight (however, the sum of monomers (A) and (B) is 10
The cross-linked polymer (I) obtained by polymerizing a monomer component consisting of 0% by weight) and 30 to 99 parts by weight of a water-insoluble compound (II) and 1 to 70 parts by weight of a particulate material (III) are porous. The present invention relates to a porous oil absorbing material supported on a porous base material.

[0008]

The solubility parameter (SP value) is generally used as a measure of the polarity of a compound, and in the present invention, the value derived by substituting the Hoy cohesive energy constant into the Small calculation formula is applied. And the unit (cal /
It can be expressed in cm ³ ) ^1/2 .

The monomer constituting the main component of the monomer (A) used when producing the crosslinked polymer (I) in the present invention is
A monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in the molecule, and having a solubility parameter (SP value) of more than 9 is referred to as a monomer (A). When it is used as the main component, only a crosslinked polymer having insufficient oil absorption performance can be obtained, which is not preferable.

Examples of the monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in the molecule include, for example, methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth). Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate,
Dodecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, octylphenyl (meth) acrylate, nonylphenyl (meth) acrylate, dinonylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, menthyl (meth) Unsaturated carboxylic acid esters such as acrylate, isobornyl (meth) acrylate, dibutyl maleate, didodecyl maleate, dodecyl crotonate, didodecyl itaconate; (di) butyl (meth) acrylamide, (di) dodecyl (meth) acrylamide ,
(Meth) acrylamide having a hydrocarbon group such as (di) stearyl (meth) acrylamide, (di) butylphenyl (meth) acrylamide, (di) octylphenyl (meth) acrylamide; 1-hexene, 1-octene, isooctene, Α-Olefins such as 1-nonene, 1-decene, 1-dodecene; alicyclic vinyl compounds such as vinylcyclohexane; allyl ethers having a hydrocarbon group such as dodecyl allyl ether; vinyl caproate, vinyl laurate, palmitic acid Vinyl ester having a hydrocarbon group such as vinyl and vinyl stearate;
Vinyl ether having a hydrocarbon group such as butyl vinyl ether and dodecyl vinyl ether; aromatic vinyl compounds such as styrene, t-butyl styrene, octyl styrene and the like can be mentioned, and one or more of these monomers can be used. You can Among these, as a monomer that gives better oil absorption performance and oil retention performance,
It has at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms, and is alkyl (meth) acrylate, alkylaryl (meth) acrylate, alkyl (meth) acrylamide, alkylaryl (meth) acrylamide,
The monomer (A) containing as a main component at least one unsaturated compound (a) selected from the group consisting of fatty acid vinyl ester, alkylstyrene and α-olefin is particularly preferable.

Such solubility parameter (SP value)
Is 9 or less, the amount used in the monomer (A) is
The proportion is 50% by weight or more, more preferably 70% by weight or more, based on the total amount of the monomer (A). When the amount of the monomer having the solubility parameter (SP value) of 9 or less in the monomer (A) is less than 50% by weight, only a crosslinked polymer having poor oil absorption performance and oil retention performance can be obtained.

Therefore, in the present invention, 5 monomers having a solubility parameter (SP value) of 9 or less are included in the monomer (A).
It is necessary that the content of the solubility parameter (SP) is 50% by weight or less in the monomer (A), although the content of SP is 0% by weight or more.
A monomer having one polymerizable unsaturated group may be contained in a molecule whose value) exceeds 9. Examples of such a monomer include (meth) acrylic acid, acrylonitrile, maleic anhydride, fumaric acid, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. You can

Examples of the crosslinkable monomer (B) used in producing the crosslinked polymer (I) in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and polyethylene glycol di. (Meth) acrylate, polyethylene glycol-polypropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, N, N'-methylenebisacrylamide, N, N'-propylenebisacrylamide, glycerin tri (meth) acrylate, trimethylolpropane Poly (functional) compound obtained by esterification of (meth) acrylic acid with alkylene oxide adduct of tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, polyhydric alcohol (eg glycerin, trimethylolpropane or tetramethylolmethane) (Meth) acrylate, divinylbenzene, etc. can be mentioned.
One kind or two or more kinds can be used.

The ratio of the monomer (A) and the crosslinkable monomer (B) in the monomer component used for producing the crosslinked polymer (I) is such that the monomer (A) and the crosslinkable The amount of the monomer (A) is 96 to 99.9 with respect to the total amount of the monomer (B).
99% by weight, the crosslinkable monomer (B) is 0.001-
It is in the range of 4% by weight.

When the amount of the monomer (A) is less than 96% by weight or the amount of the crosslinkable monomer (B) exceeds 4% by weight, the crosslinking density of the obtained crosslinked polymer becomes too high and a large amount of oil is obtained. It is not preferable because it cannot be absorbed. Further, the monomer (A) is 9
If it exceeds 9.999% by weight or the crosslinkable monomer (B) is less than 0.9.
If the amount is less than 001% by weight, the solubility of the obtained crosslinked polymer in oil increases, and the crosslinked polymer fluidizes after oil absorption, and the oil retaining ability cannot be obtained, which is not preferable.

The crosslinked polymer (I) in the present invention can be produced by polymerizing the above-mentioned monomer components by a conventionally known method. Among them, monomer components in an aqueous medium, for example, polyvinyl alcohol, hydroxyethyl cellulose, protective colloid agents such as gelatin and sodium alkyl sulfonate, sodium alkylbenzene sulfonate, polyoxyethylene alkyl ether, surfactant such as fatty acid soap The method in which the polymer is dispersed in the presence and is subjected to suspension polymerization with an oil-soluble radical polymerization initiator is a cross-linked polymer (I suitable for preparing granules (III) by granulation molding with a water-insoluble compound (II) described below. It is preferable because the granular material of 1) can be obtained. If necessary, the monomer component may be dissolved in a water-insoluble organic solvent and then suspension-polymerized.

Examples of the oil-soluble radical polymerization initiator include benzoyl peroxide, lauroyl peroxide,
Organic peroxides such as cumene hydroperoxide; 2,
Azo compounds such as 2'-azobisisobutyronitrile and 2,2'-azobisdimethylvaleronitrile can be used. The polymerization temperature can be appropriately selected within the range of 0 to 150 ° C. depending on the type of monomer component and the type of polymerization initiator.

In the present invention, as a method for producing the particles of the cross-linked polymer (I), a method of polymerizing the cross-linked polymer (I) by bulk polymerization and then adjusting the particle size by adding an operation such as pulverization. I can give you. Bulk polymerization may be carried out, for example, by pouring a monomer component into a mold in the presence of the above-mentioned polymerization initiator and conducting the polymerization under the condition of 50 to 150 ° C.

In the present invention, the cross-linked polymer (I) has an average particle size of 0. 1 by introducing a pre-suspension step using a homomixer or the like during suspension polymerization and adjusting stirring power during polymerization.
It is preferable that the particles are in the range of 5 to 500 μm.
If the average particle diameter of the particles of the crosslinked polymer (I) is less than 0.5 μm, the surface area is reduced due to the Mamako phenomenon due to the aggregation of the crosslinked polymers, and it is difficult to obtain an oil absorbing material with an improved oil absorption rate. Becomes Further, if the average particle size of the particles of the crosslinked polymer (I) exceeds 500 μm, the oil absorption rate also decreases as the surface area of the crosslinked polymer decreases, which is not preferable.

Water-insoluble compound (II) used in the present invention
There is no particular limitation as long as it is water-insoluble or sparingly water-soluble, having a solubility of 1 g or less in 100 g of water at 20 ° C., minerals such as silica, talc and diatomaceous earth, metals such as iron and aluminum, calcium carbonate. Examples thereof include inorganic salts such as and the like, organic salts such as metal soaps, resins such as polystyrene, polyethylene and polyvinyl acetate, organic compounds such as wax, fibers such as cotton and pulp, and one of these or Two or more types can be used. When a water-soluble compound such as starch or polyvinyl alcohol is used instead of the water-insoluble compound (II), the cross-linked polymer (I) becomes a lump that is solidly and tightly integrated with the water-soluble compound, resulting in a porous material having an improved oil absorption rate. No oil absorbent material can be obtained. However, these water-soluble compounds can be used as granulation aids during preparation of granules (III) composed of crosslinked polymer (I) and water-insoluble compound (II) within a range that does not impair the oil absorption performance of oil-absorbent materials. You can do it.

Water-insoluble compound (II) used in the present invention
Is preferably used as a powder having an average particle size of 0.05 to 300 μm. This average particle size is 0.05 μm
If it is less than 1, the water-insoluble compounds may coagulate with each other and the oil absorption rate of the oil absorbing material may be reduced, which is not preferable. On the other hand, if the average particle size exceeds 300 μm, it becomes difficult to uniformly carry out mixed granulation molding with the crosslinked polymer (I), and the oil absorption rate of the oil absorbent cannot be improved, which is not preferable.

To produce the granular material (III) used in the present invention, the crosslinked polymer (I) and the water-insoluble compound (I
I) may be mixed and granulated. Further, in the case of mixed granulation molding, the crosslinked polymer (I) and the water-insoluble compound (II)
Is preferably used in the form of particles or powder having the above-mentioned average particle size.

As a mixing method, either wet mixing or dry mixing can be adopted. The wet mixing may be carried out, for example, by dispersing and mixing the crosslinked polymer (I) and the water-insoluble compound (II) in water in the presence of a surfactant, if necessary, and by subjecting the resulting mixture to a granulation molding method described below. Granules (II
Process to I). The dry mixing can be carried out, for example, by mixing the crosslinked polymer (I) and the water-insoluble compound (II) with a colloid mill, a kneader or a mixer. In particular, wet mixing is preferable because the aqueous dispersion of the crosslinked polymer (I) obtained by the suspension polymerization can be mixed with the water-insoluble compound (II) as it is. Further, a method of mixing the crosslinked polymer (I) obtained by bulk polymerization and the water-insoluble compound (II) while adjusting the particle size by a pulverizing operation or the like can also be adopted.

As a method for granulating the mixture of the crosslinked polymer (I) and the water-insoluble compound (II) to prepare the granules (III), the granules or powders are aggregated or aggregated to form a large mixture. It is possible to adopt a conventionally known method for forming particles, for example, a method of granulating at the same time as mixing by heteroaggregation or hydrophobic interaction in an aqueous medium, and then filtering and drying, both of which are water. A method of granulating by using water as a granulation aid by reducing the water content while mixing from a dispersed state, drying and granulating, a pressure-sensitive adhesive or adhesive other than water, such as the above-mentioned water-soluble compound. A method of granulating and granulating using a granulating aid, a method of granulating by adding an aggregating agent to both aqueous dispersions and aggregating and then filtering and drying,
A method of granulating by drying both aqueous dispersions with a spray dryer can be used.

The average particle size of the granules (III) thus obtained may be adjusted according to the method of supporting the granules on the porous base material and the required performance of the porous oil absorbing material. The diameter is preferably in the range of 0.01 to 20 mm. If it is less than 0.01 mm, the loading efficiency on the porous base material may be reduced, or the oil-absorbent material after loading may be left with no residue, which is not preferable. On the other hand, when it exceeds 20 mm, the oil absorption rate is lowered and it is difficult to support the porous substrate, which is not preferable.

The mixing ratio of the crosslinked polymer (I) and the water-insoluble compound (II) in the granular material (III) used in the present invention is 30 to 99 parts by weight of the crosslinked polymer (I) and the water-insoluble compound ( II) is 1 to 70 parts by weight. If the amount of the water-insoluble compound (II) is less than 1 part by weight, the particles of the crosslinked polymer (I) aggregate with each other and the oil absorption rate of the oil absorbing material decreases, which is not preferable. Further, when a large amount of the water-insoluble compound (II) is used in an amount exceeding 70 parts by weight, the saturated oil absorption amount of the oil absorbent and the oil retaining performance are deteriorated, which is not preferable. The porous oil-absorbing material of the present invention is obtained by supporting a particulate material (III) comprising a crosslinked polymer (I) and a water-insoluble compound (II) on a porous substrate.

Therefore, the method for producing the porous oil-absorbing material of the present invention is not particularly limited as long as it can be supported and fixed on the porous substrate to such an extent that the particulate matter (III) is not detached from the porous substrate. For example, a method may be used in which the fibrous material capable of forming a porous substrate by molding and the granular material (III) are mixed in a wet or dry manner, and then the granular material (III) is supported on the porous substrate by molding. A method of supporting the granular material (III) on the formed porous substrate may be used.

The fibrous material used for molding the porous substrate may be a material capable of forming a porous substrate such as a nonwoven fabric having a large surface area capable of effectively supporting the particulate matter and voids for absorbing and retaining oil. There is no particular limitation, and examples thereof include polyolefin such as polypropylene and polyethylene, polyester, nylon, polyurethane, cellulose, viscose, rayon, cupra, acetate, pulp, cotton, glass, fiber fleece and adhesive fiber made of metal. . In addition, an adhesive, a pressure-sensitive adhesive, or the like may be used to form the porous base material from the fiber material and to increase the strength of the resulting porous oil-absorbing material.

As a method for mixing the fibrous material as the porous base material and the granular material (III) by molding to form the porous oil-absorbing material, a general nonwoven fabric manufacturing method can be adopted. For example, Rand Web Method, Scan Web method, Karl Krioyer method, Honshu method, etc., dry air-laid pulp method, wet method, spunlace method, melt blow method,
The spunbond method, flash spinning method and the like can be mentioned.

According to the method for producing the dry non-woven fabric, the granular material (II
I) and a fiber fleece or adhesive fiber and an adhesive as necessary or mixed and laminated, and formed into a sheet by a needle punch method, a spun bond method, a water jet method or a heat treatment, and a granular material (III ) Can be dispersed and fixed in a nonwoven fabric.

According to the method for producing a wet non-woven fabric, the granular material (II
I), fibers, fleeces, adhesive fibers and adhesives may be mixed and mixed in water, and then dried or heat-treated to form a sheet, and the particulate matter (III) may be dispersed and fixed in the nonwoven fabric. it can. In the case of wet type,
A crosslinked polymer (I) and a water-insoluble compound (II) are mixed in water in place of the granulated product (III) preliminarily granulated and agglomerated and granulated in water to produce granules (III). This may be dispersed and fixed in the non-woven fabric.

Granules (II
As the porous substrate used in the method of supporting I),
There is no particular limitation as long as it is a porous substrate having a large surface area capable of effectively supporting the particulate matter (III) and a void for absorbing and retaining oil, for example, polyolefin such as polypropylene or polyethylene, polyester, nylon, polyurethane, cellulose, viscose. Examples thereof include rayon, cupra, acetate, pulp, cotton, glass, non-woven fabric and sponge made of metal, paper, and sintered body.

Granules (II
As a method of supporting I), for example, a method of adhering and fixing the particulate matter to the porous substrate using an adhesive material or an adhesive, a method of spraying the granular material on the porous substrate and then vibrating as necessary A method of uniformly dispersing the particulate matter in the porous substrate by giving it and then carrying it by a heat treatment, etc., and after applying an aqueous dispersion of the particulate matter on the porous substrate, give vibration etc. if necessary As a result, a method of uniformly dispersing the granular material in the porous substrate and then drying and fixing it can be mentioned.

The granular material (II) comprising the crosslinked polymer (I) and the water-insoluble compound (II) in the porous oil-absorbing material of the present invention (II
The amount of I) supported on the porous substrate is not particularly limited, but it is preferable that the ratio of the particulate matter (III) to 10 to 20000 parts by weight relative to 100 parts by weight of the porous substrate. . When the amount of the particulate matter (III) supported is less than 10 parts by weight,
The oil absorption performance and oil retention performance may be insufficient, which is not preferable. Further, when a large amount of the particulate matter (III) is loaded in excess of 20,000 parts by weight, the particulate matter (III) fills the voids in the porous base material, and as a result, the oil absorbing performance of the oil absorbing material may decrease, which is preferable. Absent.

The porous oil-absorbent material of the present invention is pasted with an oil-permeable sheet material such as paper or cloth, and the porous oil-absorbent material is pasted with a non-oil-permeable sheet material such as a plastic film or metal foil. Thus, the strength and printability of the porous oil absorbing material can be improved. Further, the porous oil-absorbing material of the present invention can be used by wrapping it in an oil-permeable sheet material such as paper or cloth or filling an oil-permeable container such as a non-woven bag or a perforated container.

[0036]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the examples, parts represent parts by weight unless otherwise specified.

[0037]

[Reference Example 1] In a 500 ml flask equipped with a thermometer, a stirrer, a gas introduction tube and a reflux condenser, polyoxyethylene alkyl ether (manufactured by Nippon Shokubai Co., Ltd., trade name: Sophthanol 150, this product is also used in the following examples. 3 parts (used) was dissolved in 300 parts of water and charged, and the inside of the flask was replaced with nitrogen under stirring, and the mixture was heated to 40 ° C. under a nitrogen stream.
Then, 99.794 parts of nonylphenyl acrylate (SP value: 8.3) as the monomer (A), 0.206 parts of 1,6-hexanediol diacrylate as the crosslinkable monomer (B), and a polymerization initiator. Was added to the flask all at once, and the mixture was vigorously stirred under the condition of 750 rpm.

Then, the temperature inside the flask was raised to 80 ° C. and maintained at the same temperature for 2 hours to carry out the polymerization reaction. Then, the temperature inside the flask was further raised to 90 ° C. and maintained for 2 hours to complete the polymerization. By doing so, an aqueous dispersion (pure resin content: 25% by weight) containing the crosslinked polymer (1) having an average particle size of 30 μm was obtained.

Next, 5 parts of a fine powder of aluminum monostearate (average particle size 10 μm) was added to an aqueous solution prepared by dissolving 1.5 parts of sodium stearate in 150 parts of water, and 3 parts was added.
The mixture was stirred at 00 rpm to obtain an aqueous dispersion of aluminum monostearate. Then, 60 parts of an aqueous dispersion containing the crosslinked polymer (1) obtained in the previous polymerization was gradually added to the mixture, and
Stirring was continued for a minute to obtain an aggregate composed of the crosslinked polymer (1) and aluminum monostearate. The aggregate was filtered off, washed with water, and dried at 80 ° C. to obtain a granular material (1) composed of 15 parts of the crosslinked polymer (1) and 5 parts of aluminum monostearate. This granular material (1)
Was granulated to an average particle size of 3 mm.

[0040]

Reference Example 2 Hexadecyl methacrylate (SP value: 7.8) 49.93 as the monomer (A) in Reference Example 1
0 part and N-octyl methacrylamide (SP value:
8.6) 49.930 parts, divinylbenzene O.V. as the crosslinkable monomer (B). An aqueous dispersion containing a crosslinked polymer (2) having an average particle size of 300 μm (resin content of 25% by weight) was prepared in the same manner as in Reference Example 1 except that 140 parts were used instead and the rotation speed was changed to 200 rpm. Got

Further, 5 parts of fine powder of calcium stearate (average particle size 8 μm) was added to an aqueous solution prepared by dissolving 1.5 parts of the polyoxyethylene alkyl ether in 150 parts of water, and stirred under the condition of 300 rpm and calcium stearate was added. A water dispersion of Then, 180 parts of an aqueous dispersion containing the crosslinked polymer (2) was gradually added, and stirring was continued for 10 minutes to obtain an aggregate containing the crosslinked polymer (2) and calcium stearate. The aggregate was filtered and dried at 80 ° C. to obtain a granular material (2) composed of 45 parts of the crosslinked polymer (2) and 5 parts of calcium stearate. This granular material (2) was granulated to have an average particle size of 5 mm.

[0042]

Reference Example 3 Monomer (A) was added to an aqueous solution prepared by dissolving 3 parts of the polyoxyethylene alkyl ether in 300 parts of water.
As dodecyl acrylate (SP value: 7.9) 57.
772 parts and N, N-dioctyl acrylamide (S
P value: 8.2) 38.515 parts, polypropylene glycol dimethacrylate (molecular weight 4000) 3.713 parts as the crosslinkable monomer (B), and 2 as the polymerization initiator.
2'-azobisisobutyronitrile O. A solution consisting of 5 parts was added and mixed with a homomixer at 10,000 rpm for 10 minutes to obtain an aqueous dispersion of a monomer.

Then, an aqueous dispersion of the above monomer was charged into a 500 ml flask equipped with a thermometer, a stirrer, a gas introduction tube and a reflux condenser, and the inside of the flask was replaced with nitrogen while vigorously stirring at 400 rpm. . Subsequently, the temperature inside the flask was raised to 70 ° C. under a nitrogen stream, the temperature was maintained for 2 hours to carry out a polymerization reaction, and then the temperature was further raised to 90 ° C. to complete the polymerization, and crosslinking with an average particle size of 5 μm was performed. An aqueous dispersion containing the polymer (3) (resin content of 25% by weight) was obtained.

Further, 5 parts of talc fine powder (average particle size 2 μm) was added to an aqueous solution prepared by dissolving 1.5 parts of the polyoxyethylene alkyl ether in 150 parts of water to obtain 300 rp.
The mixture was stirred under the condition of m to obtain an aqueous dispersion of talc. Then,
Gradually add 30 parts of an aqueous dispersion containing the cross-linked polymer (3) 1
Stirring was continued for 0 minutes to obtain an aggregate composed of the crosslinked polymer (3) and talc. Further, the agglomerate was filtered off and dried at 80 ° C. to obtain a granular material (3) composed of 7.5 parts of the crosslinked polymer (3) and 5 parts of talc. This granular material (3) was granulated to have an average particle size of 3 mm.

[0045]

[Reference Example 4] 99.823 parts of dodecyl acrylate (SP value: 7.9) as the monomer (A) in Reference Example 1,
As the crosslinkable monomer (B), ethylene glycol diacrylate O. By the same method as in Reference Example 1 except that 177 parts was used instead, an aqueous dispersion containing a crosslinked polymer (4) having an average particle diameter of 30 μm (resin content of 25% by weight) was obtained.

Next, 5 parts of fine powder of aluminum monostearate (average particle size 8 μm) was added to an aqueous solution prepared by dissolving 1.5 parts of sodium stearate in 150 parts of water, and added to 30 parts.
The mixture was stirred at 0 rpm to obtain an aqueous dispersion of aluminum monostearate. Then, 60 parts of an aqueous dispersion containing the crosslinked polymer (4) obtained by the previous polymerization was gradually added, and stirring was continued for 10 minutes to obtain an aggregate composed of the crosslinked polymer (4) and aluminum monostearate. It was The aggregate was filtered off, washed with water, and dried at 80 ° C. to obtain a granular material (4) consisting of 15 parts of the crosslinked polymer (4) and 5 parts of aluminum monostearate. This granular material (4)
Was granulated to an average particle size of 3 mm.

[0047]

[Reference Example 5] t-Butylstyrene (SP value: 7) as a monomer (A) was placed in a glass casting polymerization container (a tray shape having a size of 5 x 5 x 1 cm) equipped with a thermometer and a gas introduction tube. ．
9) 54.881 parts and 1-decene (SP value: 7.
0) 44.903 parts, divinylbenzene O.V. as the crosslinkable monomer (B). 216 parts and 2, as a polymerization initiator
A mixed solution consisting of 0.1 part of 2'azobisdimethylvaleronitrile was injected, and the mixture was heated at 60 ° C for 2 hours under a nitrogen stream to carry out a polymerization reaction, then heated to 80 ° C and maintained for 2 hours to carry out polymerization. Completed. After cooling, the polymerization product was peeled off from the container to obtain a crosslinked polymer (5). Then, the cross-linked polymer (5) was crushed with a colloid mill to give an average particle size of 5
Granules of the crosslinked polymer (5) having a size of μm were obtained.

75 parts of granules (average particle size 5 μm) of this crosslinked polymer (5) and 25 parts of silica fine powder (average particle size 2 μm) were mixed using a colloid mill, and the resulting mixture was 1%. A polyvinyl alcohol aqueous solution was sprayed and dried and granulated to obtain granules (5) having an average particle diameter of 2 mm, which consisted of 75 parts of the crosslinked polymer (5) and 25 parts of silica.

[0049]

Reference Example 6 Nonylphenyl acrylate (SP value: 8.3) 74.79 as the monomer (A) in Reference Example 1
3 parts and hydroxyethyl acrylate (SP value: 1
0.3) The same method as in Reference Example 1 except that 24.931 parts was used instead and the amount of 1,6-hexanediol diacrylate as the crosslinkable monomer (B) was changed to 0.276 parts. Thus, an aqueous dispersion (pure resin content: 25% by weight) containing the crosslinked polymer (6) having an average particle diameter of 30 μm was obtained.

2.5 parts of fine silica powder (average particle size 2 μm) and 2.5 parts of diatomaceous earth (average particle size 10 μm) were added to an aqueous solution prepared by dissolving 1.5 parts of the polyoxyethylene alkyl ether in 150 parts of water. Parts were added and stirred under the condition of 300 rpm to obtain an aqueous dispersion of a water-insoluble compound. Then, 60 parts of an aqueous dispersion containing the crosslinked polymer (6) was gradually added, stirring was continued for 10 minutes, and heating was further performed in an oil bath to remove water until the solid content concentration in the aqueous dispersion became 55% by weight. While boiled down, an aggregate consisting of the crosslinked polymer (6), silica and diatomaceous earth was obtained. The aggregate was filtered off and dried at 80 ° C. to give 15 parts of crosslinked polymer (6), silica 2.
A granular material (6) consisting of 5 parts and 2.5 parts of diatomaceous earth was obtained. This granular material (6) was granulated to have an average particle size of 3 mm.

[0051]

Reference Example 7 In Reference Example 1, 99.811 parts of vinyl laurate (SP value: 7.9) was used as the monomer (A), and trimethylolpropane triacrylate O.V. was used as the crosslinkable monomer (B). Reference Example 1 except that 187 parts were used instead
By the same method as described in (1), an aqueous dispersion containing a crosslinked polymer (7) having an average particle diameter of 30 μm (resin content of 25% by weight) was obtained.
Also, the polyoxyethylene alkyl ether 1.5
2.5 parts of fine powder of polyethylene wax (average particle size 8 μm) and 2.5 parts of calcium carbonate (average particle size 20 μm) were added to an aqueous solution prepared by dissolving 150 parts of water in an amount of 300 rp.
The mixture was stirred under the condition of m to obtain an aqueous dispersion of polyethylene wax and calcium carbonate. Then, 60 parts of an aqueous dispersion containing the crosslinked polymer (7) was gradually added and stirring was continued for 10 minutes to obtain an aggregate consisting of the crosslinked polymer (7), polyethylene wax and calcium carbonate. Further, the aggregate is filtered off and dried at 80 ° C. to obtain a crosslinked polymer (7) 1.
A granular material (7) consisting of 5 parts, polyethylene wax 2.5 parts and calcium carbonate 2.5 parts was obtained. This granular material (7) was granulated to have an average particle size of 3 mm.

[0052]

Comparative Reference Example 1 An average particle size of 30 μm was obtained in the same manner as in Reference Example 4, except that the amount of dodecyl acrylate was changed to 94.637 parts and the amount of ethylene glycol diacrylate was changed to 5.363 parts. An aqueous dispersion containing the comparative polymer (1) was obtained. Using this aqueous dispersion and the same aluminum monostearate as used in Reference Example 4, Comparative Polymer (1) 15 was prepared in the same manner as in Reference Example 4.
Parts and 5 parts of aluminum monostearate were obtained as comparative granulate (1). This comparative granular material (1) was granulated to have an average particle size of 3 mm.

[0053]

Comparative Reference Example 2 In Reference Example 4, 39.854 parts of dodecyl acrylate and 59.780 parts of methacrylic acid (SP value: 10.1) were used instead of the monomer (A) consisting of 99.823 parts of dodecyl acrylate. , An average particle diameter of 30 μm was measured in the same manner as in Reference Example 4 except that the amount of ethylene glycol diacrylate was changed to 0.366 part.
An aqueous dispersion containing m of the comparative polymer (2) was obtained. Using this aqueous dispersion and the same aluminum monostearate as used in Reference Example 4, in the same manner as in Reference Example 4, a comparative granule comprising 15 parts of Comparative Polymer (2) and 5 parts of aluminum monostearate. (2) was obtained. This comparative granular material (2) was granulated to have an average particle size of 3 mm.

[0054]

[Comparative Reference Example 3] Crosslinkable monomer (B) in Reference Example 4
An aqueous dispersion containing the comparative polymer (3) having an average particle diameter of 30 μm was obtained by the same method as in Reference Example 4 except that the above was not used. Using this aqueous dispersion and the same aluminum monostearate as used in Reference Example 4, in the same manner as in Reference Example 4, a comparative granular material comprising 15 parts of Comparative Polymer (3) and 5 parts of aluminum monostearate. (3) was obtained. This comparative granular material (3) was granulated to have an average particle size of 3 mm.

[0055]

[Comparative Reference Example 4] 1 part of the same fine powder of aluminum monostearate as used in Reference Example 4 was added to an aqueous solution prepared by dissolving 1.5 parts of the polyoxyethylene alkyl ether in 150 parts of water under the condition of 300 rpm. The mixture was stirred underneath to obtain an aqueous dispersion of aluminum monostearate. Then, 400 parts of an aqueous dispersion containing the crosslinked polymer (4) obtained by the polymerization of Reference Example 4 was gradually added and stirring was continued for 10 minutes to obtain an aggregate containing the crosslinked polymer (4) and aluminum monostearate. Got Further, the agglomerates were separated by filtration, pulverized with a colloid mill and dried at 80 ° C. to obtain comparative granules (4) consisting of 100 parts of the crosslinked polymer (4) and 1 part of aluminum monostearate. This comparative granular material (4) was granulated to have an average particle size of 7 mm.

[0056]

[Comparative Reference Example 5] 5 parts of the same fine powder of aluminum monostearate as used in Reference Example 4 was added to an aqueous solution prepared by dissolving 1.5 parts of the polyoxyethylene alkyl ether in 150 parts of water under the condition of 300 rpm. The mixture was stirred underneath to obtain an aqueous dispersion of aluminum monostearate. Then, 8 parts of an aqueous dispersion containing the crosslinked polymer (4) obtained in Reference Example 4 was gradually added and stirring was continued for 10 minutes to obtain an aggregate consisting of the crosslinked polymer (4) and aluminum monostearate. It was Further, this agglomerate was filtered off and dried at 80 ° C. to obtain a comparative granular material (5) consisting of 2 parts of the crosslinked polymer (4) and 5 parts of aluminum monostearate. This comparative granular material (5) was granulated to have an average particle size of 3 mm.

[0057]

Example 1 Granules (1) obtained in Reference Examples 1 to 7
(7) and 90 parts of each of the comparative granules (1) to (5) obtained in Comparative Reference Examples 1 to 5 were coated with a corrugated cardboard waste paper 70.
Weight% and rayon fiber (diameter 3d, length 5mm) 30
After mixing 5 parts by weight of fiber and 5 parts of low melting point polyethylene powder as an adhesive, the mixture was sucked and deposited on a 100 mesh wire mesh to form a nonwoven fabric having a basis weight of 700 g / m ² , and then 110 The oil-absorbing materials (1) to (7) and the comparative oil-absorbing materials (1) to (5) in which the fibers and the particles are fixed by heat treatment in a heating furnace at ℃, and the particles are carried on the dry non-woven mat. Obtained.

[0058]

Example 2 A polypropylene chop (manufactured by Chisso Corporation) was added to 90 parts each of the granular material (4) obtained in Reference Example 4 and the comparative granular materials (4) to (5) obtained in Comparative Reference Examples 4 to 5. PP chop, diameter 3d, length 3 mm) 50% by weight and heat-fusible fiber (ES fiber manufactured by Chisso Co., diameter 3d, length 5)
mm) 50 parts by weight of a fiber composed of 50% by weight are mixed, and the mixture is mixed with a polyester spunbonded nonwoven fabric (basis weight: 50 g /
m ² ), sucking and depositing it on top to form a nonwoven fabric with a basis weight of 800 g / m ² , and then placing a polyester spunbond nonwoven fabric (basis weight 50 g / m ² ) on top of it and heating furnace at 130 ° C. Were heat-treated in accordance with the above procedure to fix the fibers and the particles, and to obtain the oil absorbent material (8) and the comparative oil absorbent materials (6) to (7) in which the dry nonwoven fabric mat was loaded with the particles.

[0059]

Example 3 90 parts of each of the granular material (4) obtained in Reference Example 4 and the comparative granular materials (4) to (5) obtained in Comparative Reference Examples 4 to 5 were mixed with acrylic fiber (Kanebuchi Kagaku). Kanecaron KCE2, an acrylic fiber manufactured by the company, diameter 3d, length 10m
m) 70% by weight and nylon fiber (diameter 5d, length 26)
mm) 30 parts by weight of fibers and 5 parts of low melting point polyethylene powder as an adhesive are mixed in 1000 parts of water, and an aqueous dispersion of the mixture is deposited by filtration on a wire net and dehydrated, and then dried at 120 ° C. with a dryer. By drying, it was formed into a non-woven fabric having a basis weight of 200 g / m ² , and oil-absorbent material (9) and comparative oil-absorbent materials (8) to (9) were obtained by supporting a granular material on a wet-laid nonwoven fabric mat.

[0060]

Example 4 To 99 parts of each of the granular material (4) obtained in Reference Example 4 and the comparative granular materials (4) to (5) obtained in Comparative Reference Examples 4 to 5, a heat-welding fiber (Chisso) was used. 1 part of ES fiber manufactured by the company, diameter 3d, length 5 mm) is mixed in 1000 parts of water, and an aqueous dispersion of the mixture is filtered and deposited on a wire net to be dehydrated and then dried with a dryer at 120 ° C. It was formed into a non-woven fabric with an amount of 200 g / m ² .

One piece of non-woven fabric carrying this granular material was
Cut into m-square, sandwich this between 12 cm-square acrylic non-woven fabric (basis weight 50 g / m ² ) and 12 cm-square acrylic film (film thickness 0.05 mm), heat seal the four sides to 12 cm-square To obtain an oil-absorbing material (10) and comparative oil-absorbing materials (10) to (11) obtained by molding the non-woven fabric carrying granular material into the bag.

[0062]

Example 5 15 parts each of the granular material (4) obtained in Reference Example 4 and the comparative granular materials (4) to (5) obtained in Comparative Reference Examples 4 to 5 and an acrylic emulsion adhesive (stock A water dispersion obtained by mixing 10 parts of PS-4517 manufactured by Nihon Shokubai Co., Ltd., 50% water dispersion) was applied onto a polypropylene spunbonded nonwoven fabric (basis weight 50 g / m ² ) and a porous polypropylene nonwoven fabric (basis weight 100 g). / M ² , bulk specific gravity of 0.
1 g / cm ³ ) was sprayed onto 15 parts of the laminated non-woven fabric substrate and then shaken to apply vibration to permeate the aqueous dispersion into the substrate. Then, polypropylene spunbonded non-woven fabric (basis weight: 50 g / m ² ) was superposed on the porous polypropylene non-woven fabric and dried in a heating oven at 130 ° C. to fix the fibers and the granules, and the dry non-woven mat was coated with the granules. The supported oil absorbing material (11) and comparative oil absorbing materials (12) to (13) were obtained.

[0063]

[Example 6] 10 cm square needle-punched nonwoven fabric made of polypropylene (basis weight: 200 g / m ² , bulk specific gravity: 0.1 g /
m ³ on both surfaces of) mixture was allowed to uniformly spray drying the solvent type pressure-sensitive adhesive of acrylic resin, Reference Example 4 obtained in granules (4) and Comparative Example Comparative granules obtained in 4-5 The particles were supported on the non-woven fabric by spraying (4) to (5) on the non-woven fabric. The amount of particulate matter attached to this nonwoven fabric was 600 g / m ² .

One piece of non-woven fabric carrying this granular material is 24 ×
12cm square polyester non-woven fabric (basis weight 50g / m ² )
Oil-absorbing material (12) and comparative oil-absorbing material (14) obtained by folding and sandwiching each of them in a 12 cm square and heat-sealing the three sides to form a 12 cm square bag, and enclosing the granular material-supported nonwoven fabric in the bag. ~ (15) was obtained.

[0065]

[Embodiment 7] Oil absorbing materials (1) obtained in Examples 1 to 6
Each of (12) and comparative oil-absorbing materials (1) to (15) was immersed in kerosene at 20 ° C. for 1 minute, then pulled up, and left on a 200-mesh wire net for 1 minute to remove oil. After that, the oil absorption amount and the oil absorption rate per 1 g of the oil absorbing material were weighed and calculated according to the following equation.

Oil absorption amount (g) = weight of oil absorbing material weighed after removing oil-weight of oil absorbing material before immersion in kerosene Oil absorption rate (%) = (oil absorption amount / weight of oil absorbing material before immersion in kerosene) ×
100 Then, the oil-absorbing material after oil absorption was placed on a 200-mesh wire net, a load of 20 g / cm ² was applied to the upper part for 1 minute, the amount of oil that flowed out was measured, and the oil retention rate after loading was calculated according to the following formula.

Oil retention rate (%) = {(oil absorption amount−oil amount washed away by load) / oil absorption amount} 100 Further, the porous polypropylene nonwoven fabric used in Example 5 (basis weight 100 g / m ² , bulk specific gravity) Oil absorbing materials (1) to (12) and comparative oil absorbing material (1) to 0.1 g / cm ³ )
The oil absorption rate and oil retention rate were measured in the same manner as in (15).

The measurement results are shown in Table 1.

[0069]

[Table 1]

[0070]

The oil-absorbing material of the present invention comprises a porous base material containing a particulate material comprising a specific cross-linked polymer and a water-insoluble compound, and the oil content adsorbed by the porous base material is added to the particulate material. Has an oil-absorption function of quickly absorbing and swelling, and thus exhibits high oil-retaining performance by contact with oil for a short time,
Post-treatment is extremely easy without dripping.

Furthermore, since the oil absorbent of the present invention has a structure in which the liquid permeability and air permeability are sufficiently ensured by the voids of the porous substrate, it is easy to fill the column and install it in the ventilation system. Is.

Therefore, the oil-absorbing material of the present invention is used for treating household waste oil, industrial waste oil, leak oil, waste water, pits, harbors, floating oil that has flowed out into lakes and the sea,
It is extremely effective for applications such as water treatment filters and oil mist filters.

Front Page Continuation (72) Inventor Hideyuki Tahara 14-1 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Shokubai Kawasaki Laboratory

Claims (4)

[Claims] 1. A monomer (A) having one polymerizable unsaturated group in a molecule containing a monomer having a solubility parameter (SP value) of 9 or less as a main component in an amount of 96 to 99.999% by weight, and 0.001 to 4% by weight of a crosslinkable monomer (B) having at least two polymerizable unsaturated groups in the molecule (however, the total amount of the monomers (A) and (B) is 100% by weight). Crosslinked polymer (I) obtained by polymerizing a monomer component comprising
30-99 parts by weight and water-insoluble compound (II) 1-70
A porous oil-absorbing material which comprises a porous base material on which a granular material (III) consisting of parts by weight is supported. 2. The monomer (A) has at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms and is alkyl (meth) acrylate, alkylaryl (meth) acrylate, alkyl (meth) acrylamide. , Alkylaryl (meth) acrylamide, fatty acid vinyl ester,
The oil absorbent according to claim 1, which contains at least one unsaturated compound (a) selected from the group consisting of alkylstyrene and α-olefin as a main component. 3. The average particle diameter of the granular material (III) is 0.01 to.
The oil absorbing material according to claim 1, wherein the oil absorbing material has a range of 20 mm. 4. The oil absorbing material according to claim 1, wherein the granular material (III) is obtained by granulating the granular material of the crosslinked polymer (I) and the powder of the water-insoluble compound (II).