JPH1088009A - Micro-cellular impregnated composite and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite which can contain a large quantity of a functional material with excellent retentivity and sustained release properties by mixing a syndiotactic 1,2-polybutadiene with a low-molecular material, removing the low-molecular material from the mixture, and filling a functional material into the voids. SOLUTION: A syndiotactic 1,2-polybutadiene is mixed with a low-molecular material at such a ratio as to provide a content of the polybutadiene of at most 40wt.% to give a polymer network structure wherein the low-molecular material is held in the three-dimensional continuous meshed skeleton formed from the polybutadiene. The low-molecular material is then removed, and a functional material that is liquid or solid at ordinary temperature is filled into the voids freed of the low-molecular material, thus giving an objective composite. Since the cells of the three-dimensional continuous meshed skeleton are very dense and uniform, this composite is excellent in both retention and sustained release of the functional material contained therein.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an electrolyte, an ink,
Microcell-impregnated composites in which functional materials such as adhesives, fragrances, and medicinal ingredients are incorporated in a microscopic, uniform, three-dimensional continuous network skeleton to utilize the exudation and sustained release of these substances and a method for producing the same About.

[0002]

2. Description of the Related Art As is well known, a typical porous material is a polyurethane foam, a plastic foam, or a sponge. It is manufactured by injecting nitrogen gas or carbon dioxide gas and / or foaming the material by mechanical stirring.

[0003] However, although such a method is simple in terms of manufacturing method, it is difficult to obtain cells (bubbles) obtained by foaming.
Is very large, and it is difficult to obtain a micro cell.

For this reason, for example, when a conventional porous material is impregnated with ink, a medicinal component, or the like, and these functional materials are to gradually exude or diffuse, the cells are large and the retention is poor. Since it was sufficient, sustained release could not be expected.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and can hold a large amount of various functional materials, and can gradually release the built-in functional materials. It is an object of the present invention to provide a microcell-impregnated composite having excellent properties and a method for producing the same.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that syndiotactic 1,2-polybutadiene and a low-molecular material are syndiotactic 1,2-polybutadiene. Content of 40
By mixing so as to have a ratio of not more than 1% by weight, a polymer network structure in which the low-molecular-weight material is held between three-dimensional continuous network frames formed of syndiotactic 1,2-polybutadiene is obtained. After removing the low molecular weight material held by the polymer network, the voids from which the low molecular material has been removed are filled with a liquid or solid functional material at room temperature to obtain syndiotactic 1,2- A microcell-impregnated composite formed from polybutadiene and containing a liquid or solid functional material at room temperature in a microporous body composed of a three-dimensional continuous network skeleton having an average skeleton diameter of 5 μm or less and an average cell diameter of 150 μm or less The body can be obtained, the cells of this three-dimensional continuous network skeleton are very dense and uniform, so it has excellent retention of the built-in functional material and excellent sustained release, Utilizing this property, by selecting a wide range of functional materials such as electrolytes, inks, drugs, and fragrance components, it has excellent sustained release properties as semi-solid electrolytes, printing members, medicinal coating agents, fragrances, etc. It has been found that a complex of the type described above can be obtained, and the present invention has been accomplished.

Accordingly, the present invention provides (1) a method in which syndiotactic 1,2-polybutadiene is mixed with a low molecular weight material and then the low molecular weight material is removed, and the average diameter of the skeleton is 5 μm or less; (2) a microcell-impregnated composite comprising a microporous body composed of a three-dimensional continuous network skeleton having an average cell diameter of 150 μm or less and incorporating a liquid or solid functional material at room temperature; and The syndiotactic 1,2-polybutadiene and the low molecular weight material are mixed so that the content of the syndiotactic 1,2-polybutadiene is 40% by weight or less, thereby forming the syndiotactic 1,2-polybutadiene. Obtaining a polymer network structure in which the low molecular weight material is held between three-dimensional continuous network skeletons, and then a low molecular weight material held in the polymer network structure The method for producing a microcell-impregnated composite according to the above (1), wherein a liquid or solid functional material is filled at room temperature in the space from which the low-molecular material has been removed after removing the material. .

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The microcell-impregnated composite of the present invention is composed of a three-dimensional continuous network skeleton formed from syndiotactic 1,2-polybutadiene as described above. A liquid or solid functional material is built in a microporous body at room temperature.

The microporous body has a three-dimensional continuous network skeleton having an internal communication space, and the three-dimensional continuous network skeleton is formed of syndiotactic 1,2-polybutadiene.

[0010] The three-dimensional continuous network skeleton preferably has a hard block portion such as a crystal structure or an aggregated structure and a soft block portion such as an amorphous structure together. Polybutadiene has a crystallinity of 10% by weight or more and 50% by weight or less,
Also, the 1,2 bond is 80% by weight or more, especially 90% by weight.
The above is preferred.

The syndiotactic 1,2-
The three-dimensional continuous network skeleton formed from polybutadiene
For example, addition and modification of a hydrophilic group such as a hydroxyl group or a lipophilic group such as a nitro group is also effective for some applications.

Such syndiotactic 1,2-
A three-dimensional continuous network skeleton composed of polybutadiene
It has a microstructure as shown in FIG. In FIG. 1, reference numeral 1 denotes a three-dimensional continuous network skeleton made of the syndiotactic 1,2-polybutadiene, and reference numeral 2 denotes an internal communication space. In the internal communication space 2, a low molecular material described later is held. Here, in FIG. 1, the average diameter d of the skeleton 1 is shown.
Is 8 μm or less, or in the range of 0.5 to 5 μm, and the average cell diameter D is 80 μm or less, preferably 1 to 50 μm.
Is preferably in the range of Further, the porosity is desirably 40% or more, preferably in the range of 50 to 95%.

This microporous material is obtained by mixing the above-mentioned predetermined amount of syndiotactic 1,2-polybutadiene and a low-molecular material with a mixture in which the syndiotactic 1,2-polybutadiene can form a three-dimensional continuous network skeleton structure. It can be obtained by mixing under conditions.

More specifically, it is recommended to use a high-speed stirrer such as a high-shear mixer to mix at a stirring speed of 300 rpm or more, preferably 500 rpm or more, and more preferably 1000 rpm or more. If high-speed stirring is not performed, for example, using a roll, rotor-type mixer, or cylinder-type mixer and mixing at a low speed, a uniform three-dimensional continuous network skeleton structure of the target syndiotactic 1,2-polybutadiene can be obtained. It is difficult. The mixing temperature is preferably in the range of 60 to 150 ° C, and the mixing time is preferably in the range of 1 to 120 minutes.

After the above-mentioned mixing, crosslinking can be carried out by mixing a vulcanizing agent such as sulfur or an organic peroxide, or by irradiating an electron beam.

Here, the low-molecular material mixed with the syndiotactic 1,2-polybutadiene may be a solid or a liquid, and various materials can be used depending on the application. If the low molecular weight material is an organic material, its number average molecular weight is less than 20,000, preferably 10,000,
Further, it is better to be 5,000 or less. Although there is no particular limitation on the low molecular material family, the following can be exemplified. Softeners: Various types of rubbers such as mineral oils, vegetable oils, and synthetic oils, and softeners for resins, and mineral oils include aromatic, naphthene, and paraffinic process oils. Vegetable oils include castor oil, cottonseed oil,
Linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, wood wax, pine oil, olive oil, etc. Plasticizer: phthalic acid ester, phthalic acid mixed ester,
Various ester plasticizers such as aliphatic dibasic acid ester, glycol ester, fatty acid ester, phosphate ester, stearic acid ester, epoxy plasticizer, plasticizer for other plastics, or phthalate, adipate,
NBR plasticizers such as sebacate, phosphate, polyether and polyester. Tackifiers: various tackifiers (tackifiers) such as coumarone resin, coumarone-indene resin, phenol terpine resin, petroleum hydrocarbons, and rosin derivatives. Oligomer: Crown ether, fluorinated oligomer, polybutene, xylene resin, chlorinated rubber, polyethylene wax, petroleum resin, rosin ester rubber, polyalkylene glycol diacrylate, liquid rubber (polybutadiene, styrene-butadiene rubber, butadiene-acrylonitrile rubber, polychloroprene Various oligomers such as silicone-based oligomers and poly-α-olefins. Lubricants: hydrocarbon lubricants such as paraffin and wax, fatty acid lubricants such as higher fatty acids and oxy fatty acids, fatty acid amide lubricants such as fatty acid amides and alkylene bis fatty acid amides, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty alcohols , Polyhydric alcohols, polyglycols, alcoholic lubricants such as polyglycerol,
Various lubricants such as metal soaps and mixed lubricants.

In addition, latex, emulsion, liquid crystal, bituminous composition, clay, natural starch, sugar, inorganic silicone oil, phosphazene and the like can also be used. In addition, animal oils such as cow oil, pig oil, horse oil, bird oil,
Dairy products such as fish oil, honey, fruit juice, chocolate, yogurt, hydrocarbons, halogenated hydrocarbons, alcohols, phenols, ethers, acetals, ketone fatty acids, esters, nitrogen compounds, sulfur compounds Organic solvents such as a system, or various medicinal ingredients, soil conditioners,
Fertilizers, petroleums, water, aqueous solutions and the like can also be used.

This polymer network structure has a low molecular material held between three-dimensional continuous network frames (in the internal communication space) composed of syndiotactic 1,2-polybutadiene as described above. However, in this case, it is desirable to form the three-dimensional continuous network skeleton with as little syndiotactic 1,2-polybutadiene as possible.

Here, the amount of syndiotactic 1,2-polybutadiene constituting the three-dimensional continuous network skeleton is represented by A,
When the amount of the other materials is B, the weight fraction of the syndiotactic 1,2-polybutadiene [{A / (A +
B) × 100}] is 30% or less, preferably 7 to 25%.
% Is desirable.

The polymer network obtained in this manner is formed between the three-dimensional continuous network skeleton of syndiotactic 1,2-polybutadiene (in the internal communication space).
Having a structure in which the low-molecular material described above is retained, and by removing a large amount of the low-molecular material from the polymer network structure as described above, the microporous body of the present invention A three-dimensional continuous network skeleton of tactic 1,2-polybutadiene can be obtained.

The method for removing the low-molecular material is not particularly limited. For example, a method in which the low-molecular material is dissolved and extracted using an appropriate solvent and the remaining solvent is volatilized and dried is suitable.

Here, as the solvent that can be used, any one can be used as long as the syndiotactic 1,2-polybutadiene is insoluble or hardly soluble and the low molecular weight material and other components are easily soluble. For example, aromatic hydrocarbons such as xylene, toluene and benzene, unsaturated aliphatic hydrocarbons such as hexene and pentene, saturated aliphatic hydrocarbons such as hexane and pentane, ketones such as acetone and methyl ethyl ketone, ethanol and butanol Alcohols such as methylene chloride and chloroform; alicyclic hydrocarbons such as cyclohexanone; ethers such as dioxane and tetrahydrofuran; esters such as butyl acetate; and water, an aqueous alkaline solution, and an acid. Aqueous solution and the like. One of these may be used alone or a mixture of two or more may be used once. It can be used in multiple extraction procedure.

When dissolving and extracting with these solvents, specifically, a polymer network structure containing a low molecular material is formed into small pieces or a thin film, and then immersed in the solvent to extract the low molecular material. Is preferred.

In this case, in order to effectively recover the low-molecular material, especially when the low-molecular material is in a liquid state, the polymer network structure is compressed by a roll or a press before the dissolution extraction with a solvent, It is recommended to remove most of the low molecular weight material by applying physical force using a suction machine, a vacuum machine, a centrifuge, an ultrasonic device or the like, and then to perform a dissolution extraction with a solvent.

It is also effective to add a post-treatment to the microporous body obtained by such an extraction operation to change its characteristics. For example, thermal stability can be increased by crosslinking the polymer component with ultraviolet light, electron beams, or heating. In addition, for example, an organic acid having a double bond is impregnated and heat-treated. Alternatively, it is also effective to change the hydrophilicity, hydrophobicity, electrical properties, optical properties, strength, and the like of the microporous body by etching, plasma treatment, sputtering, or the like with a surfactant, a coupling agent, or a gas.

In the present invention, a liquid or solid functional material is filled and held at room temperature in the void (internal communication space) of the microporous body thus obtained from which the low molecular material has been removed. .

As a method of filling this functional material,
If the functional material is liquid, a method of impregnating it as it is or diluting it with an appropriate solvent is preferable, and if it is a solid, a method of impregnating it by melting it or dissolving it in a solvent that dissolves the solid However, other known methods for adsorbing a powder or the like into pores may be employed.

When the functional material is retained after the removal of the low molecular material, if the compatibility between the microporous material (syndiotactic 1,2-polybutadiene) and the functional material is poor, the low molecular material may be used. It is difficult to impregnate these functional materials into the microporous body after completely removing the solvent used for the extraction. Therefore, in this case, it is preferable to sequentially replace the solvent and the functional material in a state where the solvent is contained in the microporous material.

When the compatibility between the microporous body and the functional material is very poor (for example, when one is hydrophilic while the other is hydrophobic or water repellent), the microporous In order to improve the compatibility between the porous body and the functional material, modification of the microporous body at the molecular level, blending with a modifier, or coupling of the three-dimensional continuous network skeleton of the microporous body with a coupling agent It is very effective to adopt a method such as surface modification by using a method such as the above. It is also effective to mix a slight amount of a surfactant in one or both of the microporous body and the functional material.

When the compatibility of the solvent used for extracting the low molecular weight material with the functional material is poor, a method of dissolving the functional material in another solvent capable of dissolving and sequentially replacing both solvents is adopted. You can also.

Further, when the functional material is a solid or powder that does not dissolve even at high temperature, it can be mixed with another liquid or solid that melts at high temperature in advance, and then replaced with a low molecular weight material by the above method.

Next, the types of functional materials and their uses will be described. The functional materials and applications in the microcell-impregnated composite of the present invention are not limited to those described below.

<When the functional material is liquid at room temperature> When the functional material is an organic or inorganic electrolytic solution, it is impregnated into a microporous body to obtain a semi-solid electrolyte.
It can be used for products such as electrochromic devices. In the case of the plating solution, by impregnating the microporous body with this and sandwiching it between the plating material and the material to be plated,
Dry plating becomes possible. In the case of a liquid crystal, it can be impregnated to form a light control element, and can be applied to products such as a liquid crystal display and a variable transmittance blind. Further, in the case of a magnetic fluid, it can be applied to a flexible magnet, a clean sealing or the like, and in the case of an electrorheological fluid, it can be applied to various vibration preventing devices. Further, in the case of a reactive organic material, the organic materials which react with each other are impregnated into separate microporous bodies, and the microporous materials are brought into close contact with each other to react, so that the reactants of these organic materials are syndiotactic 1 and 2. -A resin reinforced with a three-dimensional continuous network skeleton of polybutadiene is obtained, and is applicable to, for example, dry bonding of a reactive two-component adhesive, two-component reactive paint, and the like. In addition, by using a coloring component as a functional material,
An excellent printing member can be obtained. That is, it can be obtained by mixing a coloring component with various softeners, plasticizers, tackifiers, oligomers, lubricants and the like.

In addition, latex, emulsion, bituminous composition, clay, natural starch, sugar, inorganic silicone oil, phosphazene and the like can also be used. In addition, animal oils such as beef oil, pig oil, horse oil, etc., bird oil, fish oil, dairy products such as honey, fruit juice, chocolate, yogurt, hydrocarbons, halogenated hydrocarbons, alcohols, phenols, and ethers , Organic solvents such as acetal, ketone, fatty acid, ester, nitrogen-containing, and sulfur compounds, or various medicinal ingredients, soil conditioners, fertilizers, petroleum, water, aqueous solutions, etc. it can.

By using a drug component as the functional material, an excellent medicinal coating agent (poultice) can be obtained. In this case, the medicinal ingredient is not particularly limited as long as it is a drug that can be administered to the skin. For example, in the case of a drug intended for local action, the drug can be penetrated deeply, while in the case of a systemic action, the drug can be promptly transferred to the blood. The molecular weight of the drug component is 1,000 or less, preferably 700 or less, and more preferably 500 or less.

Further, by using an aromatic component as the functional material, an excellent fragrance can be obtained. In this case, as the aromatic component, for example, lemon oil, lime oil,
Spearmint oil, jasmine oil, orange oil, pine oil, seaweed oil, eucalyptus oil, lavender oil, natural flavors such as musk oil, or synthetic flavors using these flavors as raw materials, such as limonene, linamol, eugenol, citranerol, vanillin, Carvone, yonon, muscone,
Rose oxide, indole, geranyl acetate, ethyl benzoate and the like can be mentioned. These can be used alone or in combination of two or more.

<When the functional material is solid at room temperature> As such a functional material, a polymer material can be mentioned first. For example, the functional material may be a conductive polymer such as polyaniline, polypyrrole, or polyacetylene, a photoelectric conversion polymer composed of a phthalocyanine-based material, a water-absorbing polymer such as chitin, chitosan or an acrylic acid-based polymer, or PVA (polyvinyl alcohol). it can. Also, barium titanate, zinc zirconate, which exhibits piezoelectricity,
Powders such as ceramics such as titanium oxide having light absorbency, metals having conductivity or magnetism, and carbon having conductivity, gas adsorption, and deodorization are also effective. Furthermore, when a general thermoplastic or thermosetting polymer material or organic material is used as the functional material, the impact resistance, strength, elongation, etc. of these thermoplastic resins and thermosetting resins have been improved. A composite can be obtained.

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

[Examples 1 to 3] First, syndiotactic 1,2-polybutadiene (15% by weight) having the physical properties shown in Table 1 and a low molecular weight material were mixed with a high shear mixer under the stirring conditions shown in the same table. After mixing, a polymer network was obtained.

With respect to the obtained polymer network structure, the average diameter d of the skeleton and the average diameter D of the cells were determined. Next, the low-molecular material was dissolved and extracted using acetone to obtain a microporous body, and the average diameter d of the skeleton of the microporous body and the average diameter D of the cell were measured. The results are also shown in Table 1.

[0041]

[Table 1]

The obtained microporous body was impregnated with the liquids shown in Table 2 in the amounts shown in Table 2 to obtain microcell-impregnated composites.

[0043]

[Table 2]

Next, the electric resistance of the microcell-impregnated composite in which the functional material was an electrolytic solution was measured. The electric resistance was 23.69Ω, which confirmed that the composite could be used as a separator for batteries and the like. The electric resistance was measured by using the cell for resistance measurement shown in FIG.
This is a value measured by an LCR meter between the electrodes when an AC voltage of 1 kHz is set between the S electrodes.

[0045]

Industrial Applicability The microcell-impregnated composite of the present invention can incorporate a liquid or solid functional material at room temperature with good retention and has excellent sustained release of the functional material, and can be applied to various application fields. is there. According to the method for producing a microcell-impregnated composite of the present invention, such a microcell-impregnated composite can be produced easily and reliably.

[Brief description of the drawings]

FIG. 1 is a schematic view showing the structure of a microporous body of the present invention.

FIG. 2 is a schematic diagram of a cell for resistance measurement.

[Explanation of symbols]

 1 Three-dimensional continuous mesh structure 2 Internal communication space

Claims (2)

[Claims] 1. A mixture obtained by mixing a syndiotactic 1,2-polybutadiene and a low molecular weight material and then removing the low molecular weight material. The average diameter of the skeleton is 5 μm or less, and the average diameter of the cell is 150 μm or less. A microcell-impregnated composite comprising a liquid or solid functional material incorporated at room temperature in a microporous body composed of a three-dimensional continuous network skeleton. 2. Syndiotactic 1,2-polybutadiene and a low molecular weight material are synthesized with syndiotactic 1,2-polybutadiene.
The polybutadiene content was mixed so as to be 40% by weight or less to obtain a polymer network structure in which the low-molecular-weight material was held between three-dimensional continuous network skeletons formed of the polymer. 2. The method according to claim 1, wherein after removing the low-molecular material held by the polymer network structure, the gap from which the low-molecular material has been removed is filled with a liquid or solid functional material at room temperature. A method for producing a microcell-impregnated composite.