WO2004092281A1 - 吸水性樹脂複合体およびその組成物 - Google Patents
吸水性樹脂複合体およびその組成物 Download PDFInfo
- Publication number
- WO2004092281A1 WO2004092281A1 PCT/JP2004/005396 JP2004005396W WO2004092281A1 WO 2004092281 A1 WO2004092281 A1 WO 2004092281A1 JP 2004005396 W JP2004005396 W JP 2004005396W WO 2004092281 A1 WO2004092281 A1 WO 2004092281A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- absorbent resin
- fibers
- fiber
- resin composite
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/08—Processes in which the treating agent is applied in powder or granular form
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2936—Wound or wrapped core or coating [i.e., spiral or helical]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2965—Cellulosic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2973—Particular cross section
- Y10T428/2978—Surface characteristic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
Definitions
- the present invention relates to a water-absorbing resin composite and a composition containing the same.
- the water-absorbent resin composite composition of the present invention is thin, flexible and openable.
- the water-absorbent resin composite of the present invention and the composition thereof are suitably used for the production of water-absorbent articles such as sanitary materials such as disposable diapers and sanitary napkins, and industrial materials. Background art
- water-absorbing resins that absorb a large amount of water have been widely used for sanitary materials, industrial materials, and the like.
- a water-absorbent resin is used as a composite with other materials, such as disposable diapers
- the water-absorbent resin can be fixed before water absorption, fixed after water absorption, thinner as a composite, flexible, and highly absorbent. Improvement such as content increase is required.
- Japanese Patent Application Laid-Open No. 63-633723 discloses that a water-absorbent resin absorbs water or a water-containing solvent, is kneaded and dispersed with hydrophilic fibers in a state of being swollen, and then is dried and pulverized.
- a composite comprising a hydrophilic base material in which at least a part of the fiber is embedded is disclosed by polymerizing the unsaturated monomer while mixing it with the hydrophilic fiber, followed by drying and pulverization.
- a composite comprising a water-absorbing resin and fibers can be obtained.
- the complex obtained by this technique must be ground before it can be used.
- Japanese Patent Publication No. 5_58080 discloses a fibrous base material at least partially composed of hydrophobic fibers, and a water-absorbent article composed of a water-absorbent resin adhered to the base material and a force. Has been described. This water-absorbent article is characterized in that at least a part of the water-absorbent resin is substantially spherical, wraps the base fiber, and is discontinuously attached.
- the base material is a fiber
- the flexibility of the composite can be ensured.
- the water-absorbing resin is also fixed.
- the water-absorbent resin encloses the fibers, it is inevitable that the fibers hinder the swelling of the water-absorbent resin.
- the ratio of the water-absorbent resin Z fiber must be reduced.
- the base material used is limited to hydrophobic fibers due to morphology control of the water-absorbing resin.
- Japanese Patent Application Laid-Open No. 11-93073 discloses that a substantially spherical water-absorbent resin is discontinuously fixed on the surface of a non-molded fiber, and that the non-molded fiber is deposited on the surface thereof. Or a composite in which non-molded fibers are bonded to each other via the water absorbent resin. It can be said that the immobilization of the water-absorbent resin has been achieved in view of the fact that the water-absorbent resin and the fibers are bonded. However, as long as the bonding is on the surface of the fiber, the bonding form must be point bonding or line bonding, and the bonding strength in a dry state cannot be said to be sufficient.
- the fiber is stably fixed to the water-absorbent resin not only at the time of drying but also at the time of water-swelling, and the water-absorbent resin can be fixed at a high content to the fiber uniformly, and is flexible.
- An object of the present invention is to provide a composition containing a composite of a water-absorbing resin and a fiber, which can be thinned and spread, and can be uniformly mixed with other materials. As a result of intensive studies, the present inventors have found that the present invention described below can achieve the object. .
- the present invention relates to a water-absorbent resin composite including one water-absorbent resin particle and two or more fibers, wherein the water-absorbent resin particles are substantially spherical, and one of the two or more fibers At least one of the fibers is partially embedded in the resin particles and a part of the fibers is exposed from the resin particles, and at least one of the two or more fibers has a fiber of the resin particles.
- a water-absorbent resin composite wherein a part of the fiber is adhered to the surface of the resin particle without being embedded in the resin particle.
- the present invention also provides a water-absorbent resin composite composition containing the water-absorbent resin composite.
- the fibers are stably fixed to the water-absorbent resin not only at the time of drying but also at the time of water-swelling, and the water-absorbent resin is uniformly contained at a high content relative to the fibers. It can be fixed, is flexible, can be thinned and opened, and can be mixed with other materials uniformly.
- FIG. 1 is a cross-sectional view for explaining a water absorption capacity measuring instrument under pressure.
- FIG. 2 is a cross-sectional view for explaining a thickness measuring tool.
- FIG. 3 is a schematic diagram for explaining a jig for measuring rigidity by the heart loop method.
- FIG. 4 is a cross-sectional view showing the configuration of the water absorbent article.
- FIG. 5 is a schematic diagram showing a low tap type shaker.
- FIG. 6 is a cross-sectional view for explaining a jig for measuring a gel falling rate.
- FIG. 7 is a view showing a cutting line of the sample in the gel detachment rate measurement.
- FIG. 8 is a schematic view for explaining a nozzle used for producing a water-absorbent resin composite.
- FIG. 9 is a schematic diagram of the sample obtained in Example 1 and the results of observation by a scanning electron microscope (101 and 102).
- FIG. 10 shows the results of observation by a scanning electron microscope (103 and 104) of the sample obtained in Example 2.
- FIG. 11 shows the results of observation by a scanning electron microscope (105 and 106) of the sample obtained in Example 3.
- FIG. 12 shows the results of a scanning electron microscope observation (107 and 108) of the sample obtained in Example 4.
- FIG. 13 is a schematic diagram of the sample obtained in Example 5 and the results of scanning electron microscope observation (109 and 110).
- FIG. 14 is a schematic diagram of the sample obtained in Example 6 and a result of observation by a scanning electron microscope (111 and 112).
- FIG. 15 is a schematic view of the sample obtained in Comparative Example 1 and the results of observation by a scanning electron microscope (113 and 114).
- FIG. 16 is a schematic view of the sample obtained in Comparative Example 2 and a result of observation by a scanning electron microscope (115 and 116).
- 1 is an adapter
- 2 is a sample stand
- 3 is a sample
- 4 is a distance
- 1 1 is a wire mesh
- 1 2 is a cylindrical tube
- 1 3 is a petri dish
- 1 3 is a load
- 2 1 is a water-impermeable polyethylene.
- 2 2 is a tissue
- 2 4 is a high-density water-absorbent resin composite composition
- 2 5 is a tissue
- 2 6 is a water-permeable polyester fiber nonwoven fabric
- 3 1 is a water-absorbing article
- 3 2 is a cylinder
- 3 4 is an Ataryl board
- 4 1 is a center
- 4 2 is a cutting line
- 5 1 is Grab
- 52 are sample pieces Detailed description of the invention
- a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
- composition of the present invention is a composition containing the composite A as an essential component.
- the composite A includes one substantially spherical water-absorbing resin particle and two or more fibers.
- one or more fibers included in the composite A a part of the fibers is embedded in the water-absorbent resin particles and a part is exposed from the water-absorbent resin particles.
- some of the fibers adhere to the surface of the water-absorbent resin particles without the fibers being embedded in the water-absorbent resin particles. That is, the essential components of complex A are the following three types.
- partially embedded fiber Fiber partially embedded in the water-absorbent resin particles and partially exposed from the water-absorbent resin particles
- surface-adhered fibers Fibers that adhere to the surface of the water-absorbent resin particles but are not embedded in the water-absorbent resin particles (hereinafter “surface-adhered fibers”)
- the fibers bonded to the water-absorbent resin particles in the composite A that is, (1) partially embedded fibers (3) and surface-bonded fibers may be collectively referred to as “bonded fibers”.
- the dry weight ratio of the binding fiber and the water-absorbent resin particles in the composite A is from 1: 1 to 1: 1, 0000, 0000. It is more preferably 1: 2 to 1: 100,000, and still more preferably 1: 3 to 1: 10,000.
- the water-absorbing resin plays a role in the complex A to absorb liquids such as water, urine, blood, and menstrual blood according to the purpose of use.
- the water-absorbent resin in the complex A is usually a polymer having a saturated water-absorbing ability capable of absorbing liquids such as water, urine, blood, and menstrual blood at normal temperature and normal pressure by about 1 to 1,000 times its own weight. .
- a functional group having high affinity for these liquids in the polymer chain include (partially) neutralized carboxylic acids, carboxylic acids, (partially) neutralized sulfonic acids, sulfonic acids, and hydroxy. Of these, partially neutralized carboxylic acids are preferred.
- an unsaturated carboxylic acid is preferable, and acrylic acid is particularly preferable.
- this polymer may be linear, it is necessary to maintain the shape even after absorbing and swelling the desired liquid. For this reason, a crosslinked polymer having a crosslinked structure between polymer chains is usually preferable so that the polymer chains are not dissolved.
- This cross-linking may be any of chemical cross-linking such as a covalent bond or an ion bond or physical cross-linking by entanglement of polymer chains. From the viewpoint of chemical stability, chemical crosslinking is preferable, and a covalent bond is more preferable.
- a preferred water-absorbing resin is a crosslinked unsaturated carboxylic acid polymer, and more preferably a crosslinked atarilic acid polymer.
- the water-absorbing resin in the composite A is substantially spherical particles.
- substantially spherical means a shape having a true sphere and an ellipsoid as a whole, and fine irregularities (ie, wrinkles, (Projections, depressions, etc.). Also, voids such as pores or cracks may be present on the surface or inside.
- the particle size of the water-absorbent resin particles is preferably from 50 to 1,000 ⁇ . The particle size is more preferably from 100 to 900 ⁇ , and particularly preferably from 200 to 800 m.
- the substantially spherical water-absorbent resin particles used in the present invention do not have such disadvantages.
- it has the advantage that it can be densely packed because it can be densely packed compared to irregular-shaped products.
- the binding fibers are composed of partially embedded fibers and surface-bonded fibers. Hereinafter, each fiber will be described in detail.
- each fiber is firmly bonded to the water-absorbent resin before and after water absorption from the viewpoint of the fixability of the water-absorbent resin.
- the water-absorbing resin is one of the substances having the highest hydrophilicity, and in this sense, it can be said that the fibers having higher hydrophilicity have higher adhesive strength.
- the water contact angle can be used as a quantitative measure of the hydrophilicity of the fiber. That is, the smaller the contact angle (ie, the greater the hydrophilicity), the greater the adhesive strength. Conversely, the larger the contact angle (ie, the smaller the hydrophilicity), the smaller the adhesive strength.
- the contact angle of water on the surface of the fiber material is preferably 60 ° or less, more preferably 50 ° or less, and most preferably 40 ° or less.
- hydrophilic fibers examples include cellulose-based fibers such as pulp, rayon, cotton, and regenerated cellulose, and polyamide-based and polyvinyl alcohol-based fibers.
- the use of such a hydrophilic fiber not only enhances the adhesive force with the water-absorbent resin, but also enhances the hydrophilic fiber.
- fibers having low hydrophilicity from the viewpoint of water permeability and water diffusibility that is, hydrophobic fibers
- hydrophobic fibers fibers having low hydrophilicity from the viewpoint of water permeability and water diffusibility
- polyester, polyethylene, polypropylene, polystyrene, polyvinyl chloride / polyvinylidene chloride, polyacrylonitrile, polyurea, polyurethane, polyfluoroethylene, polyvinylidene cyanide Fibers may be mentioned.
- a hydrophilic fiber can be selected as the embedding fiber
- a hydrophobic fiber can be selected as the surface adhesive fiber. If such an embodiment is adopted, it can be expected that the hydrophobic fibers improve the diffusivity of water between the water-absorbing resins.
- the hydrophilicity and hydrophobicity of the series of each exemplified fiber are not absolute, and they are changed by a raw material monomer / modification or the like. For this reason, the hydrophilicity and hydrophobicity of the fibers used are evaluated by contact angle measurement.
- the contact angle depends on the shape and surface smoothness of the fiber material to be measured.
- the contact angle in the present invention means a contact angle of distilled water on a smooth surface formed by forming a fiber material into a film-to-sheet shape, and is measured using an apparatus described later.
- preferred as the binding fibers are those having an average fiber length of 50 to 50,000 ⁇ . More preferably, it is 100 to 300, 000 m, and still more preferably, 500 to: L0, 000 m. If the fiber length is too long, the fiber adheres to a plurality of water-absorbent resins, so that the independence of each water-absorbent resin composite cannot be ensured, and it tends to be difficult to open a composition containing this composite. . Conversely, if the fiber length is too short, it tends to be difficult to embed and adhere to the water absorbent resin.
- the water-absorbent resin particle size: fiber length ratio is 2: 1 to 1: 1, 0 0 0 is the preferred level.
- the ratio is more preferably 1: 1-1: 500, and particularly preferably 1: 2-1: 100.
- the bonding fiber used in the present invention is preferably a fiber having a fiber diameter of 0.1 to 500 decitex, more preferably a fiber of 0.1 to 100 decitex, still more preferably 1 to 50 decitex. And particularly preferably 1 to 10 decitattas. If the fiber diameter is too large, the rigidity of the fiber is so large that not only embedding and adhesion to the water-absorbing resin become difficult, but also compression molding becomes difficult, which may be unfavorable for thinning. Also, it is uncomfortable and uncomfortable for applications such as sanitary products. Conversely, if the fiber diameter is too small, water conductivity and diffusibility may not be ensured. In addition, the blocking phenomenon may not be prevented due to insufficient rigidity.
- the appearance of the fibers may be linear or have crimps such as crimps.
- the fiber type, fiber length, fiber diameter, and appearance are appropriately selected.
- Partially embedded fibers play a role in securing the fixability of the water absorbent resin.
- the fibers also improve the fixability of the water-absorbing resin before and after water absorption. That is, the fibers extending from the surface of the water-absorbent resin prevent the water-absorbent resin from rotating or translating when pressed. Some of these fibers are embedded in the water-absorbent resin and do not detach from the water-absorbent resin even after water absorption, so they can play an important role in the fixability after water absorption.
- the shape of the fiber used may be a hollow or side-by-side type having high rigidity in order to enhance water conductivity.
- the fibers When the partially embedded fibers are composed of hydrophilic fibers, the fibers have an effect of increasing the water conductivity of the water-absorbent resin. That is, water can be directly guided into the water-absorbent resin through the fibers. In order to exhibit this function more effectively, it is preferable to select and use the above-mentioned fibers having high water conductivity.
- these fibers also have a role of ensuring the independence of each water absorbent resin composite.
- the fibers prevent the water-absorbent resins from fusing with each other due to steric hindrance.
- fibers extending from the surface of the water-absorbent resin are combined with each other. It prevents contact between water-absorbing resins during polymerization in the precursor and prevents fusion between the water-absorbing resins.
- each water-absorbent resin composite maintains its independence, prevents adhesion to the reactor wall during the manufacturing process and the treatment process, and also allows the composition described later to have openability. it can.
- this fiber gives each of the water-absorbing composites an appropriate physical entanglement, and also gives a form retention property that, when a plurality of composites are collected and formed into a mass, the composites do not easily fall apart under their own weight. That is, the composite A has a shape retention property by itself without adding free fibers and the like. Therefore, the composite A has a remarkable feature that, when it is made into a composition, it can impart opening properties and also has shape retention.
- this fiber gives Composite A a soft, smooth feel. Combined with the fact that the water-absorbent resin is substantially spherical, the composite A gives a very soft feel when pressed even in a dry state, and is therefore suitable for applications such as sanitary materials.
- the surface adhesive fibers have an effect of securing the fixability of the water-absorbing resin before absorbing water. Furthermore, after swelling, the fibers on the surface of the water-absorbent resin form a gap between the water-absorbent resins, and have an effect of securing a water flow path. In order to obtain this effect, the fibers do not necessarily have to adhere to the water-absorbent resin even after the water absorption, but it is preferable that at least the fibers are closely arranged on the surface of the water-absorbent resin. Therefore, it is advantageous that the fibers adhere to the surface of the water-absorbent resin before water absorption as in the present invention.
- fibers having a certain rigidity in order to form a gap between the water-absorbent resins and secure a flow path for water. Further, in combination with the above-mentioned partially embedded fibers, there is also an effect of securing the fixability of the water-absorbing resin before water absorption.
- the shape of the fibers used may be hollow or side-by-side type or the like in order to enhance the diffusivity.
- the surface-adhesive fibers are composed of hydrophilic fibers
- the swelling of the water-absorbent resin when the fibers absorb water prevents the water-absorbent resins from coming into contact with each other and blocking the water flow path.
- the surface adhesive fiber is made of hydrophobic resin If so, the fibers exhibit the function of improving the diffusion of water between the water-absorbing resins. Further, this fiber has a role of ensuring the independence, shape retention, and soft and smooth feel of each water-absorbent resin composite by the same action as the above-mentioned partially embedded fiber, and gives the same effect.
- both the partially embedded fiber and the surface adhesive fiber are essential. That is, a water-absorbent resin composite having only partially embedded fibers is not sufficiently effective in preventing the blocking phenomenon during water absorption. On the other hand, a water-absorbent resin composite having only surface-adhesive fibers does not have sufficient fixability of the water-absorbent resin after absorbing water. Therefore, both fibers are indispensable in order to exhibit the above-mentioned action before and after water absorption. The coexistence of both fibers has made it possible to ensure both the fixing properties of the water-absorbent resin and the water-absorbing ability, which are originally contradictory.
- the complex A has a feature that ensures not only the retention ability but also the water absorption ability under pressure while securing sufficient fixability not only before water absorption but also after water absorption.
- the types of the two fibers may be the same or different, and are appropriately selected for the purpose of use and the respective effects.
- the complex A not only has the aggregate of the complex A possessed the shape retention property, but also has a feature that the water-absorbent resin composite composition containing the complex A can have the shape retention property.
- the binding fibers in the composite A give each of the water-absorbing composites an appropriate physical entanglement, and when the water-absorbent resin composite composition containing the composite A is formed into a lump, the composite fiber is easily weighed at its own weight. Provides form retention that does not fall apart.
- the composition of the present invention is characterized by containing the above-mentioned complex A, and may contain other components such as the following complex B, complex C and free fibers.
- the dry weight ratio of the total fiber (bonded fiber + free fiber) to the water-absorbent resin is usually 70:30 to 2:98, preferably 50:50 to 5:95, and more preferably 50:50 to 5:95. Preferably it is 30: 70-5: 95.
- the ratio of the bonding fibers to the total fibers is usually 3 to 100%.
- compositions of the present invention is preferably a bulk density of 0. 1 5 ⁇ 0. 8 5 g / cm 3, 0. 20 ⁇ 0. More preferably from 8 5 g / cm 3, 0 Even more preferably, it is from 30 to 0.85 g / cm 3 . Since each component contained in the composition of the present invention is independent and has a spreadability, the composition itself maintains the spreadability. 2.
- the composition of the present invention generally contains the complex A in a weight fraction of 1 or less, preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. .
- the average particle size of the water-absorbent resin constituting the composite A contained in the composition of the present invention is preferably 50 to: L, 00 / m, more preferably 100 to 900 ⁇ m, and 2 00 to 800 ⁇ is particularly preferred.
- the average fiber length of the fibers constituting the composite ⁇ contained in the composition of the present invention is preferably 50 to 500,000 ⁇ m, and 100 to 300,000 ⁇ m. m, more preferably 500 to 10, and particularly preferably ⁇ ⁇ ⁇ .
- the average fiber diameter of the fibers constituting the composite ⁇ ⁇ contained in the composition of the present invention is preferably from 0.1 to 500 decitex, more preferably from 0.1 to 100 decitex. And even more preferably 1 to 50 decitex, and particularly preferably 1 to 10 decitex.
- Composite B is a "water-absorbent resin composite comprising one or more water-absorbent resin particles and one or more fibers, wherein the water-absorbent resin particles are substantially spherical, and one or more fibers Is a water-absorbent resin composite in which a part of the fiber is embedded in the resin particle and a part is exposed from the resin particle, and both the fiber and the fiber do not adhere to the surface of the resin particle.
- Body At least one of the bonding fibers bonded to the water-absorbent resin of the composite B is a partially embedded fiber, and does not include the surface-bonded fiber. That is, the essential components of the composite B are the following two types, and the surface adhesive fiber is not a component.
- the fibers in the composite B can be selected in the same manner as the fibers described in the section of the binding fiber of the composite A.
- the weight fraction of the complex B in the composition of the present invention is usually 0 to 90% by weight. If the amount of the complex B is too large, the fixability of the water-absorbing resin before water absorption tends to be impaired. 3) Complex C
- “Composite C” is a “water-absorbent resin composite comprising one or more water-absorbent resin particles and one or more fibers, wherein the water-absorbent resin particles are substantially spherical, and one or more of the fibers Is a water-absorbent resin composite in which some of the fibers are adhered to the surface of the resin particles, and none of the fibers is embedded in the resin particles.
- One or more of the bonding fibers bonded to the water-absorbent resin of the composite C are surface-bonded fibers and do not include partially embedded fibers. That is, the essential components of the composite C are the following two types, and the partially embedded fiber is not a component.
- the fibers in the composite C can be selected in the same manner as the fibers described above in the section of the binding fiber of the composite A.
- the weight fraction of the complex C in the composition of the present invention is usually 0 to 90% by weight. If the amount of the complex C is too large, the gel fixability after water absorption tends to be impaired.
- Free fiber is "fiber that is neither embedded nor bonded in a water-absorbent resin”.
- the composition of the present invention may contain one or more free fibers. By adding free fibers, flexibility, softness, water conductivity, water permeability, water diffusivity, air permeability, and the like can be further improved.
- the fibers synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers, and the like can be used as in the case of the binding fibers.
- the fiber used is selected according to the purpose of use of the water-absorbent resin composite composition.
- hydrophilic fibers cellulose fibers such as pulp, rayon, cotton, and regenerated cellulose, and fibers such as polyamide and polyvinyl alcohol are selected.
- Use of such hydrophilic fibers increases the water conductivity of the composition.
- hydrophobic fibers can be used as free fibers.
- polyester-based, polyethylene-based, polypropylene-based, polystyrene-based, polychlorinated vinyl-based, polyvinylidene-based, polyacrylonitrile-based, polyurine-based, polyurethane-based, polyfluoroethylene-based, and polyvinylidene-based fibers Can be selected.
- water permeability and water diffusibility in the composition can be improved.
- the affinity of the free fiber with the water-absorbing resin or the affinity with the water-absorbing resin composite is not particularly limited.
- the type of fiber used as the free fiber may be the same as or different from the binding fiber contained in the above-described composite A, composite B, or composite C.
- a hydrophilic fiber can be selected as the binding fiber
- a hydrophobic fiber can be selected as the free fiber. If such an embodiment is adopted, the hydrophobic fiber exhibits a function of improving the diffusivity of water between the water-absorbent resin composites. From the viewpoint of blocking prevention, it is also important to select fibers in consideration of the rigidity and diameter of the fibers described later.
- Preferred free fibers used in the composition of the present invention are those having a fiber length of 50 to 100; 100,000 Aim. More preferably preferably in 1 0 0 ⁇ 5 0, 0 0 0 ⁇ m N further a 5 0 0 ⁇ 2 0, 0 0 0 m. If the fiber length is too long, it may be difficult to open the composition. On the other hand, if the fiber length is too short, the mobility of the fiber itself is large, which may cause a problem such as leakage of the fiber from the composition.
- the free fibers used in the composition of the present invention preferably have a fiber diameter of 0.1 to 500 decitex, more preferably 0.1 to 100 decitex, and still more preferably 1 to 5 decitex. It is 0 decitex, particularly preferably 1 to 10 decitex. If the fiber diameter is too large, the rigidity of the fiber is so large that not only mixing with the water-absorbent resin composite becomes difficult, but also compression molding becomes difficult, which may be unfavorable for thinning. Also, it was stiff and nervous for applications such as sanitary products Therefore, the feeling is not good either. Conversely, if the fiber diameter is too small, the above-mentioned water conductivity and diffusivity may not be ensured because the fibers are too thin. In addition, the lack of rigidity may prevent the blocking phenomenon.
- the dry weight ratio of the free fiber to the water-absorbent resin is usually 95: 5 to 0: 100, preferably 95: 5 to 5:95. If the ratio of the free fibers is too high, the effect of the water-absorbing resin may not be substantially exerted, and the bulk density may be reduced.
- the free fibers in the compositions of the present invention are usually less than 90% by weight.
- the polymerizable monomer used for preparing the water-absorbent resin particles of the composite A is not particularly limited as long as it gives a water-absorbent resin. It is particularly preferable to use a polymerizable monomer whose polymerization is initiated by a redox initiator. This monomer is usually preferably water-soluble.
- Such monomers are aliphatically unsaturated carboxylic acids or salts thereof.
- unsaturated monocarboxylic acids or salts thereof such as acrylic acid or salts thereof, methacrylic acid or salts thereof; or unsaturated dicarboxylic acids or salts thereof such as maleic acid or salts thereof, itaconic acid or salts thereof And these may be used alone or in combination of two or more.
- acrylic acid or a salt thereof and methacrylic acid or a salt thereof, and particularly preferred is acrylic acid or a salt thereof.
- aliphatic unsaturated carboxylic acid or a salt thereof is preferable as described above.
- An aqueous solution mainly containing an aliphatic unsaturated carboxylic acid or a salt thereof is preferable.
- the phrase “having an aliphatic unsaturated carboxylic acid or a salt thereof as a main component” means that the aliphatic unsaturated carboxylic acid or a salt thereof is 50 mol% or more, preferably 50 mol%, based on the total amount of the polymerizable monomer. It means that it is contained at 80 mol% or more.
- a water-soluble salt for example, an alkali metal salt, an alkaline earth metal salt, an ammonium salt and the like are usually used.
- the degree of neutralization is appropriately determined according to the purpose. In the case of acrylic acid, 20 to 90 mol% of the lipoxyl group is neutralized to an alkali metal salt or an ammonium salt. Are preferred. If the degree of partial neutralization of the acrylic acid monomer is too low, the water absorbing ability of the resulting water absorbent resin tends to be significantly reduced.
- an alkali metal hydroxide, bicarbonate or the like, or ammonium hydroxide can be used for neutralization of the acrylic acid monomer.
- Sodium and hydroxylated lime can be used for neutralization of the acrylic acid monomer.
- polymerizable monomers copolymerizable therewith such as (meth) acrylamide, (poly) ethylene glycol (meth) atarylate, 2-Hydroxityl (meth) acrylate or low water-soluble monomer, but alkyl acrylates such as methyl acrylate and ethyl acrylate are also within the range that does not lower the performance of the resulting water-absorbent resin.
- the copolymerization may be carried out in an amount.
- (meth) acryl means both “acryl” and “methacryl”.
- the one that gives the water-absorbing resin is not an auxiliary component for the aliphatic unsaturated carboxylic acid or its salt, but the main monomer of “the aqueous solution of the polymerizable monomer that gives the water-absorbing resin”. It can also be used as (Monomer concentration)
- the concentration of the polymerizable monomer in the aqueous polymerizable monomer solution containing the above-mentioned aliphatic unsaturated ruponic acid or a salt thereof as a main component is preferably 20% by weight or more, and more preferably. Or more than 25% by weight. If the concentration is less than 20% by weight, the water-absorbing resin after polymerization may not have sufficient water absorbing ability.
- the upper limit is preferably about 80% by weight from the viewpoint of handling of the polymerization reaction solution.
- Aliphatic unsaturated carboxylic acids or salts thereof, particularly acrylic acid or salts thereof, may themselves form a self-crosslinked polymer, but may be used together with a crosslinking agent to positively form a crosslinked structure.
- a cross-linking agent When a cross-linking agent is used in combination, the water-absorbing performance of the generally formed water-absorbing resin is improved.
- the crosslinking agent include polyvalent vinyl compounds copolymerizable with the polymerizable monomer, for example, N, N, —methylenebis (meth) acrylamide, (poly) ethylene glycol poly (meth) atalylates, and carboxylic acid.
- a water-soluble compound having two or more functional groups capable of reacting for example, a polyglycidyl ether such as ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether is preferably used. Particularly preferred among these are N, N, -methylenebis (meth) acrylamide.
- the amount of the crosslinking agent to be used is 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, based on the charged amount of the monomer.
- polymerization initiator used in the present invention those used in aqueous solution radical polymerization can be used.
- examples of such polymerization initiators include inorganic and organic peroxides, such as ammonium alkali metals, particularly persulfates such as potassium, hydrogen peroxide, t-butyl peroxide, and acetyl chloride. Is mentioned.
- a polymerization initiator known as an azo compound can also be used.
- 2,2, -azobis (2-amidinopropane) dihydrochloride which has a certain degree of water solubility, may be mentioned.
- the polymerization is initiated by the decomposition of the radical polymerization initiator.
- a commonly known technique is pyrolysis.
- polymerization is initiated by adding an unheated polymerization initiator to the monomer of the reaction solution that has been heated to the decomposition temperature of the polymerization initiator in advance.
- this case also belongs to the category of pyrolysis here.
- Preferred as the polymerization initiator used in the present invention is a combination of an oxidizing agent and a reducing agent which forms a redox system to some extent water-soluble.
- the oxidizing agent examples include hydrogen peroxide, persulfates such as ammonium persulfate and potassium persulfate, t-butyl peroxide peroxide, cumene hydroxide peroxide, and other ceric salts, permanganates, and chlorites. And hypochlorite. Of these, hydrogen peroxide is particularly preferred.
- the use amount of these oxidizing agents is from 0.01 to 10% by weight, preferably from 0.1 to 2% by weight, based on the polymerizable monomer.
- the reducing agent is capable of forming a redox system with the oxidizing agent.
- sodium sulfite sodium sulfite such as sodium bisulfite, sodium thiosulfate, cobalt acetate, copper sulfate, ferrous sulfate, L-ascorbic acid or alkali metal L-ascorbic acid may be mentioned.
- L-ascorbic acid or alkali metal L-ascorbic acid is particularly preferred.
- the amount of these reducing agents to be used is from 0.001 to 10% by weight, preferably from 0.01 to 2% by weight, based on the polymerizable monomer.
- the fiber type and shape are appropriately selected as described above.
- the fibers are evenly dispersed as much as possible.
- fibers tend to form tangled fiber clumps, but the apparent fiber clump diameter is preferably 20 mm or less, more preferably 10 mm or less, and most preferably 5 mm or less.
- the fibers are preferably independent of one fiber.
- a technique called fiber opening is used to ensure uniformity.
- opening includes the concept of both defibration and fiberization.
- the defibration includes turning a sheet-like material such as nylon into a strip shape or a fiber shape.
- fibrous dangling includes cutting the base paper-like cellulose into pulp.
- the method for producing the water-absorbent resin composite of the present invention is not particularly limited as long as the method can produce a water-absorbent resin composite satisfying the conditions described in the claims.
- a redox-based polymerization initiator is disposed in an aqueous solution of a polymerizable monomer that gives a water-absorbing resin, for example, an aqueous solution of a polymerizable monomer having aliphatic unsaturated ruponic acid or a salt thereof as a main component.
- the polymerization of the monomer is started, and the reaction mixture during the polymerization, including the monomer and the produced polymer after the start of the reaction, is formed into droplets in a gas phase, and is brought into contact with the dispersed fibers supplied in the gas phase to form a water-absorbent resin.
- the composite is a precursor, which completes the polymerization and is recovered as a water-absorbent resin composite.
- One preferred method of polymerizing droplets in the gas phase is a first solution comprising a polymerizable monomer aqueous solution containing one of an oxidizing agent and a reducing agent constituting a redox polymerization initiator, and a redox polymerization initiator.
- the polymerization is started by mixing the other and, if desired, a second liquid composed of an aqueous solution containing a polymerizable monomer in a gas phase.
- the first liquid and the second liquid are separated from each other so that the liquid flowing out of the nozzle has an intersection angle of 15 degrees or more and collides in a liquid column state.
- the crossing angle between the first liquid and the second liquid flowing out of each nozzle is appropriately selected according to the properties of the polymerizable monomer used, the flow ratio, and the like. For example, if the linear velocity of the liquid is high, the intersection angle can be reduced.
- the temperature of the first liquid is usually from normal temperature to about 60 ° C, preferably from normal temperature to about 40 ° C
- the temperature of the second liquid is also usually from normal temperature to about 60 ° C, preferably Is from room temperature to about 40 ° C.
- the respective aqueous solutions ejected from the nozzles collide in a liquid column state to combine the two liquids.
- a liquid column is formed, and the state is maintained for a certain time. Then, the liquid column is disassembled into droplets. The generated droplets fall while promoting polymerization in the gas phase.
- the size of the droplet should be in the range of 50 to 1,000 ⁇ . I like it. Spatial density of the droplets in the reactor 0. 1 ⁇ 1 0, 0 0 0 g is not preferable Zm is 3. If the upper limit is exceeded, a water-absorbent resin that does not come into contact with the fibers will be produced, and if it is less than the lower limit, fibers that do not come into contact with the water-absorbent resin will be produced, and the yield of the water-absorbent resin composite may be relatively reduced. .
- a gaseous phase gas that provides a reaction field for forming droplets during the progress of polymerization
- nitrogen, helium, carbon dioxide, and other inert gases are preferable, but air May be.
- the humidity in the gas Even when only water vapor is used.However, if the humidity is too low, the water in the aqueous monomer solution evaporates before the polymerization proceeds, and the monomer precipitates out. The speed may drop significantly or the polymerization may stop prematurely.
- the temperature condition of the gas is room temperature to 150 ° C., preferably room temperature to 100 ° C.
- the flow direction of the gas may be either countercurrent or cocurrent with respect to the direction of travel of the liquid column and droplets.However, when it is necessary to increase the residence time of the droplets in the gas phase, that is, the polymerization rate of the polymerizable monomer is reduced. If it is necessary to raise the viscosity of the droplets and thus the viscosity of the droplets, countercurrent (antigravity direction) is better.
- the monomer transfer ratio (hereinafter referred to as “polymerization ratio”) in the droplet when the droplet is brought into contact with the fiber is preferably in the range of 0 to 90%. It is more preferably in the range of 0 to 80%, most preferably in the range of 0 to 70%. At high polymerization rates exceeding 90%, the fibers used It may not be embedded or adhered to the aqueous resin.
- the fiber may be supplied in a one-stage reaction field having almost the same polymerization rate, but preferably, the fiber is supplied in two or more reaction fields having different polymerization rates.
- the droplets and the fibers come into contact with each other at a stage where the polymerization rate is relatively low. It is preferred to have the drops and the fibers contact.
- the difference in the degree of polymerization in the contact field between each fiber and the monomer is preferably in the range of 10% to 80%. It is more preferably in the range of 10 to 70%, and most preferably in the range of 10 to 60%.
- the polymerization rate in each contact field is appropriately determined according to the monomer type, fiber type, and the like. In order to obtain a greater structure of the composite B, it is preferable to supply the fibers at a stage where the polymerization rate is relatively low (for example, in the range of 0 to 60%). In order to obtain a large amount, it is preferable to supply the fibers at a stage where the conversion is relatively high (for example, in the range of 30 to 90%).
- the spatial density of the fibers in the reactor is preferably in the range of 0.05 to 1,000 g / m 3 when the fibers are partially embedded in the water-absorbent resin, and is preferably in the range of 0.5 to 1, The range of 0.000 g / m 3 is more preferable. If the space density is too high, fibers that are not embedded in the water-absorbent resin composite will be produced. Conversely, if the space density is too low, a water-absorbent resin that will not embed the fibers will be produced, and the yield of the water-absorbent resin composite will be reduced.
- the ratio of the spatial density of the fiber to the spatial density of the droplet is preferably in the range of 0.01 to 100, and more preferably in the range of 0.05 to 500. Is more preferable, and the range of 0.1 to 10 is more preferable. If the ratio of the spatial density of the fibers to the inter-droplet density is too small, the droplets hardly come into contact with the fibers, while if the ratio is too large, more free fibers are generated and the efficiency increases. Tend to be worse.
- the gas used here those mentioned as the gas for providing the above-described reaction field can be used. Among them, air is preferred from the viewpoint of economy and reduction of environmental load.
- the weight mixing ratio of the fiber and the gas supplied as the multiphase flow is preferably 1 or less, and the linear velocity of the gas is preferably in the range of 1 to 5 OmZ seconds. Exceeding this upper limit may disturb the trajectory of the reaction mixture during the polymerization in the reaction field, and may cause a problem of adhesion to the inner surface of the reactor. On the other hand, below the lower limit, the uniformity of the fiber may not be ensured.
- the temperature of the gas supplied as a multiphase flow within a range that does not significantly inhibit the polymerization.
- the temperature is from room temperature to 150 ° C or lower, and preferably 10 ° C or lower. It is. From the viewpoint of fiber transport, the lower the humidity in the gas is, the better the force s is. If the humidity is too low, the humidity in the reactor is reduced, and the water in the monomer aqueous solution evaporates before the polymerization proceeds, and the monomer is removed. Precipitation may result, resulting in a significant decrease in the polymerization rate or termination of the polymerization in the middle.
- other additional steps include a residual monomer treatment step, a surface cross-linking step, the above-mentioned catalyst for imparting other functions, a reducing agent, a deodorant, and human urine stability.
- a step of adding an additive such as an agent or an antibacterial agent may be added.
- Methods for treating the residual monomer include (1) a method of promoting polymerization of the monomer, (2) a method of leading the monomer to another derivative, and (3) a method of removing the monomer.
- Examples of the method of promoting the polymerization of the monomer in (1) include, for example, a method of further heating the composite of the water-absorbent resin and the fiber, and heating after adding a catalyst or a catalyst component that promotes the polymerization of the monomer to the water-absorbent resin.
- the method of further heating the water-absorbent resin composite includes heating the water-absorbent resin composite at 100 to 250 ° C. to polymerize the monomers remaining in the water-absorbent resin composite. It is.
- a method of adding a catalyst or a catalyst component that promotes the polymerization of monomers to the water-absorbent resin composite is based on the fact that, for example, when polymerization is performed using a redox polymerization initiator, the radical generator remains. Since the amount is large, a reducing agent solution may be applied to the water absorbent resin.
- the reducing agent the redox polymerization initiator is used as the agent sulfite sodium ⁇ beam, sodium bisulfite, L Asukorubin acid may be used, the water-absorbent is normally these as 0.5 to 5 wt ° / 0 solution Applied to resin composite.
- the amount of the reducing agent applied is preferably 0.1 to 2% by weight based on the dry resin.
- the application of the reducing agent solution can be performed by any method such as spraying using a sprayer or dipping in the reducing agent solution.
- the water-absorbent resin composite provided with the reducing agent is then heated to polymerize the monomer.
- the heating may be performed, for example, at 100 to 150 ° C. for about 10 to 30 minutes. This heating lowers the water content of the water-absorbing resin complex, but if the water content is high, it is further dried with a dryer to obtain a water-absorbing material for the product.
- a normal ultraviolet lamp may be used. Irradiation intensity, irradiation time, and the like vary depending on the type of fiber used, the residual monomer impregnation amount, and the like. Is an ultraviolet lamp of 10 to 20 OW / cm, preferably 30 to 120 W cm, an irradiation time of 0.1 second to 30 minutes, and a lamp-composite interval of 2 to 30 cm.
- the water content in the water-absorbent resin composite at this time is generally from 0.01 to 40 parts by weight, preferably from 0.1 to 1.0 part by weight, based on 1 part by weight of the dry water-absorbent resin. Parts by weight are employed.
- a water content of less than 0.01 parts by weight or more than 40 parts by weight is not preferred because it has a significant effect on the reduction of residual monomers.
- the atmosphere for irradiating the ultraviolet rays can be used in a vacuum, in the presence of an inorganic gas such as nitrogen, argon, or helium, or in air.
- the irradiation temperature is not particularly limited, and the object can be sufficiently achieved at room temperature.
- the method of irradiating the water-absorbent resin composite with radiation includes accelerated electrons and gamma rays. High energy radiation is used.
- the dose to be applied is a force S that varies depending on the amount of residual monomer in the complex, the amount of water, etc., generally from 0.1 to 100 Mrad, preferably from 0.1 to 50 Mrad. is there. If the dose exceeds 100 megarads, the water absorption becomes extremely small. If the dose is less than 0.01 megarads, the water absorption capacity and water absorption rate aimed at in the present invention are large, and it is difficult to obtain a particularly small residual monomer.
- the water content of the water-absorbent resin composite at this time is generally 40 parts by weight or less, preferably 10 parts by weight or less, per 1 part by weight of the water-absorbent resin. If the water content exceeds 40 parts by weight, the effect of improving the water absorption rate is small, and particularly, it has a significant effect on the reduction of unpolymerized monomers, which is not preferable.
- the atmosphere for irradiating the composite with high-energy radiation may be vacuum, in the presence of an inorganic gas such as nitrogen, argon, or helium, or in air. The preferred atmosphere is air. Irradiation in air increases water absorption capacity and water absorption rate and reduces residual monomer in particular.
- the irradiation temperature is not particularly limited, and the object can be sufficiently achieved at room temperature.
- Examples of the method for introducing the monomer (2) into other derivatives include a method of adding amine, ammonia, and the like, and a method of adding a reducing agent such as bisulfite, sulfite, or pyrosulfite.
- a method for removing the monomer in (3) for example, there is a method of extracting with an organic solvent and distilling off.
- the water-absorbent resin complex is immersed in a water-containing organic solvent to extract and remove the remaining monomer.
- Ethanol, methanol, acetone, and the like can be used as the water-containing organic solvent, and the water content thereof is preferably from 10 to 99% by weight, particularly preferably from 30 to 60% by weight.
- the higher the water content the higher the ability to remove residual monomers.
- energy consumption in the subsequent drying step increases.
- the time for immersing the complex in the water-containing organic solvent is usually about 5 to 30 minutes, and it is preferable to employ a means for promoting the extraction of the residual monomer such as rocking the complex.
- After the immersion treatment it is usually treated with a dryer and dried.
- a method of distilling off the monomer there is a method of treating the composite with superheated steam or a gas containing steam.
- the residual monomer in the water-absorbent resin can be reduced by heating saturated steam at 110 ° C to 120 to 150 ° C and contacting the composite as superheated steam.
- the surface of the water-absorbent resin can be cross-linked with a cross-linking agent for the purpose of improving the water-absorbing performance.
- a cross-linking agent for the purpose of improving the water-absorbing performance.
- the properties of resin particles are improved by applying an appropriate amount of water together with a crosslinking agent to the surface of the powdery water-absorbent resin particles and then heating and crosslinking the surface. It is considered that as a result of the formation of a cross-linked structure, it is possible to maintain its shape without impairing the swelling when swelling by absorbing water.
- a solution of the surface crosslinking agent is applied to the water-absorbent resin composite.
- the surface cross-linking agent examples include polyfunctional compounds that can be copolymerized with polymerizable monomers such as N, N, —methylenebis (meth) acrylamide, (poly) ethylene glycol bis (meth) acrylate, and (poly) ethylene glycol diglycidyl ether.
- polymerizable monomers such as N, N, —methylenebis (meth) acrylamide, (poly) ethylene glycol bis (meth) acrylate, and (poly) ethylene glycol diglycidyl ether.
- a compound having a plurality of functional groups capable of reacting with a sulfonic acid group is used.
- These surface cross-linking agents are usually used in an amount of 0.1 to 1% by weight, preferably 0.2 to 0.5% by weight, based on the water-absorbent resin composite.
- These surface cross-linking agents are diluted with water, ethanol, methanol, or the like so that the surface cross-linking agent is uniformly applied to the entire water-absorbent resin composite, and is 0.1 to 1% by weight, particularly 0.2 to 0.5%. weight. /. It is preferably used as a solution. It is usually preferable to apply the crosslinking agent solution by spraying the crosslinking agent solution onto the water-absorbent resin composite using a sprayer, or by applying the crosslinking agent solution with a mouth brush. After the crosslinker solution is applied excessively, the excess crosslinker solution may be removed by squeezing the resin particles lightly with a pressing roll or blowing air to such an extent that the resin particles are not crushed.
- the application of the crosslinking agent solution may be performed at room temperature.
- Crosslinking agent The water-absorbent resin composite to which the solution has been applied is then heated to cause a cross-linking reaction to proceed, thereby selectively forming a cross-linked structure on the surface of the water-absorbent resin.
- the conditions for the cross-linking reaction may be appropriately selected depending on the cross-linking agent used, but the reaction is usually performed at a temperature of 100 ° C. or higher for 10 minutes or longer.
- a cross-linked unsaturated carboxylic acid polymer or a cross-linked partially neutralized acrylic acid polymer can be preferably used as the water-absorbing resin.
- the water-absorbent resin composite is collected as a sediment. Since each water-absorbent resin composite is independent of each other, it can be easily opened.
- the fiber opening the fiber opening method described in the description of the fiber can be used as appropriate, but an apparatus and conditions under which the water-absorbent resin is not damaged by mechanical impact are preferable.
- additives can be added to the water-absorbent resin composite or the water-absorbent resin composite composition in order to impart a desired function depending on the intended use.
- additives include stabilizers for preventing polymer decomposition and deterioration due to the liquid to be absorbed, antibacterial agents, deodorants, deodorants, fragrances, and foaming agents.
- JP-A-63-118375 discloses a method of incorporating an oxygen-containing reducing inorganic salt and / or an organic antioxidant in a polymer
- JP-A-63-153060 discloses a method of containing an oxidizing agent.
- JP-A-63-127754 discloses a method of incorporating an antioxidant
- JP-A-63-272349 discloses a method of incorporating a sulfur-containing reducing agent
- JP-A-63-146964 discloses a metal chelating agent
- JP-A-63-15266 discloses a method containing a radical chain inhibitor
- JP-A-11-275661 discloses an amine compound containing a phosphinic acid group or a phosphonic acid group or a salt thereof.
- Method Japanese Patent Application Laid-Open No. 64-29257 discloses a method of containing a polyvalent metal acid.
- JP-A-2-255804 and JP-A-3-179008 propose a method in which a water-soluble chain transfer agent coexists during polymerization. All of these can be used in the present invention. Also, JP-A-6-306202, JP-A-7-53884, JP-A-7-62252, JP-A-7-113048, JP-A-7-145326, and JP-A-7-145263 Also, the materials and methods described in JP-A-7-228788 and JP-A-7-228790 can be used.
- human urine, human blood, and menstrual stabilizers are sometimes called human urine stabilizer, human blood stabilizer, and menstrual stabilizer, respectively.
- Antimicrobial agents are used to prevent spoilage due to the absorbed liquid.
- Examples of antibacterial agents “New development of sterilization and antibacterial technology”, pp. 17-80 (Toray Research Center (1994)), “Inspection of antibacterial and antifungal agents' Evaluation methods and product design”, pp. 128-344 ⁇ TS ⁇ (1997)), Patent No.
- JP-A-39-179114 JP-A-56-31425, JP-A-57-25813, JP-A-59-189854 JP, JP-A-59-105448, JP-A-60-158861, JP-A-61-181532, JP-A-63-113501, JP-A-63-139556, JP-A-63-139556 JP-A-63-156540, JP-A-64-5546, JP-A-64-5547, JP-A-1-153748, JP-A-1-221242, JP-A-2-253847 JP-A-3-59075, JP-A-3-103254, JP-A-3-221141, JP-A-4-11948, JP-A-4-192664, JP-A-4-138165 JP-4-two hundred sixty-six thousand nine hundred forty-seven JP, Hei 5 9344 JP, Hei 5 68694 JP, Hei 5 1616 71 JP
- alkylpyridinium salts examples thereof include alkylpyridinium salts, benzalkonium chloride, chlorhexidine gluconate, zinc pyridione, and silver-based inorganic powder.
- Representative examples of quaternary nitrogen-based antibacterial agents include methyl benzethonium chloride, benzalconium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide and hexadecyltrimethylammonium bromide. Can be mentioned.
- Heterocyclic quaternary nitrogen-based antibacterial agents include dodecylpyridinium chloride, tetradecylpyridinium chloride, cetylpyridinium chloride (CPC), tetradecyl-4-ethylpyridinium chloride, and tetradecyl monochloride. 4 Monomethylpyridinium chloride can be mentioned.
- bis-biguanides include 1,6-bis (4-chlorophenyl) diguanide hexane, which is known as a water-soluble salt thereof.
- Particularly preferred are hydrochloride, acetate and gluconate of black hexidine.
- phenols include 3,4,4,1-trichlorocarbanilide (TCC, trichlorocarpanide) and 3- (trifluoromethyl-4,4'dichlorocarbanilide (IRGASA).
- TCC 3,4,4,1-trichlorocarbanilide
- IRGASA 3- (trifluoromethyl-4,4'dichlorocarbanilide
- phenols include 5-chloro-2- (2,4-dichlorophenoxy) phenol (IRGASAN DP-300)
- metal compounds include salts of graphite and tin, such as salt.
- Rare earth salts of surfactants are disclosed in European Patent Publication No. EP 0 189 19. Rare earth salts of this type include linear C 10-18 alk A lanthanum salt of rubenzen sulfonate can be exemplified.
- deodorants, deodorants, and fragrances are used to prevent or reduce the unpleasant odor of the absorbed liquid.
- deodorants, deodorants, and fragrances include “New deodorants and deodorants, technology and prospects” (Toray Research Center (1994)), JP-A-59-105448, JP-A-60-158861 JP-A-61-181532, JP-A-1-153748, JP-A-221221242, JP-A-1-265956, JP-A-2-41155, JP-A-2- JP-A No. 253847, JP-A-3-103254, JP-A-5-269164, and JP-A-5-277143 can be appropriately selected.
- examples of deodorants and deodorants include iron complexes, tea extract components, and activated carbon.
- examples of fragrances include fragrances (citral, cinnamaldehyde, heliotopin, sofa, bornyl acetate), wood vinegar, paradichlorobenzene, surfactants, higher alcohols, terpene compounds (limonene, pinene, camphor, Polneol, eucalyptol, eugenol).
- a foaming agent and a foaming aid can be used in combination to make the water absorbent resin porous and increase the surface area in order to improve the water absorbing performance.
- the foaming agent and the foaming assistant for example, those introduced in “Rubber * Plastic Compounding Chemicals” (Rubber Digest, 1989, pp. 259 to 267) can be appropriately selected.
- sodium bicarbonate, nitros compounds, azo compounds, sulfonyl hydrazide and the like can be mentioned.
- the foaming agent is suitably added before or during the polymerization step in the process of producing the water-absorbent resin.
- Human urine stabilizers, human blood stabilizers, antibacterial agents, deodorants, and fragrances can be added in the water-absorbent resin composite production process, water-absorbent resin composite composition production process, and water-absorbent article production process. is there. Of course, it can be applied to the fiber in advance. ⁇ ⁇ .
- the composition of the present invention is prepared by mixing and dispersing a separately prepared complex B and / or complex C and Z or a free fiber with respect to the manufactured composite ⁇ .
- Post-mixing method Alternatively, it can be prepared by a method of simultaneously obtaining the composition in the polymerization step of the complex A (simultaneous mixing method). Further, if necessary, a treatment by a consolidation method or the like may be added thereafter.
- an arbitrary composition can be obtained by mixing the above-deposited composite A or the above-described opened and separated composite A with the composites B and Z or the composite C and the free or free fibers in a mixer.
- a solid mixing device capable of mixing powders, powder and fibers, or fibers can be used as a mixer.
- cylindrical mixers, V mixers, double cones examples include rotary mixers such as mold mixers, cubic mixers, etc., and fixed mixers such as screw mixers, ribbon mixers, rotating disk mixers, fluidized mixers, and the like.
- the composition of the present invention can be substantially obtained. That is, if the droplets are brought into contact with the fibers at the stage where the polymerization rate is low, a composite B-containing composition is obtained, and if the droplets are brought into contact with the droplets at the stage where the polymerization ratio is high, a composite C-containing composition is obtained.
- the fibers may be supplied, mixed, and dispersed during the production of the water-absorbent resin composite in a manner that does not substantially contact the water-absorbent resin during polymerization or the water-absorbent resin in the water-absorbent resin composite.
- a composition containing fibers is obtained.
- Consolidation is performed while appropriately adjusting conditions such as pressure, temperature, and humidity.
- press As the press, a flat press, a roll press or the like can be used.
- the pressure may be within a range where the water-absorbent resin particles are not broken. If the water-absorbent resin particles break, the broken particle pieces will separate from the fibers and leak from the absorbent product as the final product, or the water-absorbing gel will leak or move off the fibers when swelling, resulting in absorptive properties. This will degrade the performance of the article.
- the fibers When heating in the consolidation process, it can be heated to a temperature below the melting point of the fiber used. When heated above the melting point, the fibers bind together to form a network, impairing the function of the composite.
- humidifying during the consolidation process usually humidify using steam.
- the humidification conditions can improve the density of the composition and improve the adhesion of the water-absorbent resin particles to the fibers.
- the fiber can be easily opened similarly to the aggregate of the composite A.
- the fiber opening method described in the above description of the fiber can be used as appropriate. However, it is preferable to employ an apparatus and conditions under which the water-absorbent resin is not damaged by mechanical shock.
- a solution having a concentration of 1 to 10% by weight was prepared using a solvent capable of dissolving or dispersing the used fibers.
- the amount of fiber retention in the reaction field is calculated by assuming that the fiber moves from top to bottom in the air flow supplied together as a multiphase flow, and the amount of retention is calculated as the volume of the entire reaction field. By dividing, the spatial density of the fiber in the reaction field was calculated.
- the droplets drop from the nozzle at the initial discharge speed in the reaction field with the initial velocity, calculate the amount of droplets retained in the reaction field, and divide the amount of retention by the volume of all reaction fields Thus, the spatial density of the droplet in the reaction field was calculated.
- a beaker containing about 150 g of methanol was installed so that the liquid level of methanol was located at the position where the fiber was introduced, and droplets of the reaction mixture that had started polymerization were formed in the gas phase. Approximately 1 g of the polymerizing droplet was allowed to fall onto methanol in the beaker.
- the fibers are separated using an agent that selectively decomposes the water absorbent resin in the composite, and the fiber weight was determined by weighing.
- the fiber weight was determined by weighing.
- the weight of the water-absorbent resin composite A obtained in 3) was defined as Wc.
- This water-absorbent resin complex A is charged into a 50 ml closed glass container, and an aqueous solution in which 0.03 g of L-ascorbic acid is dissolved in 25 g of distilled water is added to swell, and the mixture is kept at 40 ° C for 24 hours. did.
- ⁇ Worsted wrinkled, and hardly damaged water-absorbent resin particles after worsting.
- ⁇ Worsting is felt, and when the worsting is performed, the water-absorbing resin particles after the worsting are damaged.
- the ratio of the binding fiber to the water-absorbent resin in the water-absorbent resin composite is determined in the same manner as in 3.3) above, so that the weight of the water-absorbent resin in the water-absorbent resin composite becomes about 1 g. Sucking The aqueous resin composite was collected and its weight (W1) was measured. The weight (W2) of the fibers in the water-absorbent resin composite was calculated from the ratio of the water-absorbent resin to the fibers.
- Water holding capacity S of physiological saline was calculated according to the following equation.
- the units of W1 to W3 are all g.
- AUL Water absorption capacity under pressure
- the water-absorbent resin composite was collected so that the weight of the water-absorbent resin in the water-absorbent resin composite was about 0.16 g, and the weight was measured.
- the weight of the cylindrical tube 12 with a wire mesh 11 was measured. These weights are referred to as the weight Sd (g) of the water-absorbent resin composite and the weight Td (g) of the cylindrical tube, respectively.
- water absorption in which the dry weight ratios of the composites A, B and C are a, b and c (a + b + c 1), respectively, and the dry weight ratios of the fibers forming each composite are o ;
- ⁇ and ⁇ From the water-soluble resin composite X [g / m 2 ] and the free fiber y [g / m 2 ], the basis weight of the water-absorbent resin is P [g / m 2 ], and the dry weight ratio between the free fiber and the water-absorbent resin is F [ w / w] when producing a densified water-absorbent resin composite composition
- the mixture was uniformly spread on a stainless steel plate so as to be 40 cm x 10 cm, and the stainless steel plate was further laid on top of it. A load of 0.6 MPa was applied from both sides, and after standing for 20 minutes, The pressure was released to obtain a high-density absorbent resin composite composition.
- the densified water-absorbent resin composite compositions produced by the above procedures were evaluated and measured by the following procedures, respectively.
- the densified water-absorbent resin composite composition was cut into 5 cm ⁇ 5 cm, and the thickness of the densified absorbent resin composite yarn and the composition was measured in accordance with JIS 11106. ( Figure 2).
- Thickness (mm) Sample measurement (mm) _ Planck measurement (mm)
- the densified water-absorbent resin composite and the composition were cut out to 5 cm ⁇ 5 cm, the weight was measured, and the bulk density was determined from the following equation. Five samples were measured, and the average value was determined.
- the densified water-absorbent resin composite composition was cut into 2 cm ⁇ 25 cm, and the temperature was 25. After storage at C and a humidity of 50 ° C for 24 hours, the rigidity was measured by the heart loop method used for relatively soft woven fabric of JISL-1096 shown in Fig. 3.
- a sample piece 52 was mounted in a heart loop on the horizontal bar grip 51 shown in FIG. 3 so that the effective length of the sample piece was 20 cm.
- L (cm) between the top of the horizontal bar and the lowest point of the loop was measured.
- L is defined as rigidity. Five samples were measured, and the average value was determined.
- the densified water-absorbent resin composite yarn is cut into 5 cm X 5 cm, and compressed at lOMPa for 10 minutes.Based on the thickness measurement method, 4.2) immediately after compression and at a temperature of 25 ° C The thickness after storage for 30 days under the conditions of C and humidity of 50 ° C was measured and calculated by the following equation. Five samples were measured and the average was determined.
- a diaper as a water-absorbent article was produced in the following procedure.
- the absorbent article produced by the above procedure was measured and evaluated by the following procedure.
- the water-absorbent article was cut into a size of 10 cm ⁇ 10 cm (open on all four sides), and the weight was measured. From the weight ratio of the water-absorbent resin in the water-absorbent resin composite, the total amount of the water-absorbent resin was determined.
- a water-absorbent article cut into a standard mesh sieve specified by JIS Z 8801 inner frame having an inner diameter of 150 mm, a depth of 45 mm, and a mesh of 20 was fixed to the center with a tape.
- the amount of the water-absorbing gel falling off the water-absorbing article when a force acting to rub the water-absorbing article was repeatedly applied was measured by the following procedure.
- a water-absorbent article 31 is placed on a flat surface, and a cylinder 32 with an inside diameter of 4 Omm and an open top is attached at the center, and a part surrounded by a cylinder 32 has a diameter of 5 mm.
- An acryl plate 34 (100 ⁇ 100 ⁇ 10 mm, total weight: 150 g) provided with the seven through holes 33 at substantially equal intervals was placed as shown in FIG.
- the artificial urine having the following composition was used for measuring the water absorption rate and the amount of water discharged, and 5.2) for measuring the gel shedding rate.
- the prepared solution A and solution B were mixed using the nozzle shown in FIG.
- the inner diameter of the nozzle in Fig. 8 is 0.13 mm, and five nozzles for each solution are arranged at 1 cm intervals.
- the intersection angle between solution A and solution B flowing out of the nozzle is 30 degrees, The distance of the nozzle tip was adjusted to 4 mm.
- the solution A and the solution B were heated to a temperature of 40 ° C., respectively, and supplied by a pump such that the flow rate was 5 mZ seconds.
- Solution A and solution B join at the exit of each pair of nozzles, form a liquid column of about 10 mm each, and form droplets while proceeding with polymerization in the gas phase (in air, temperature 50 ° C).
- the spatial density of the droplets in the reactor which was estimated from the space capacity of the reactor, the monomer supply amount, and the falling speed of the droplets, was 2 g / m 3 .
- the temperature of the air in the multiphase flow was room temperature, and the linear velocity was 1 ⁇ sec.
- the polymerization rates at 0.8 m and 1.6 m below the tip of the nozzle were 15% and 40%, respectively.
- the fibers used were pulp with a fiber diameter of 2.2 dtex, a length of 2.5 mm and a water contact angle of 0 °.
- the feed rates were 11.5 g / min each.
- the spatial density of the fibers in the reaction field which was estimated from the space capacity of the reaction field, the fiber supply amount, and the falling speed of the fibers, was 8 gZm 3 .
- the pressure difference between the top and bottom of the mesh was controlled to be 1,000 Pa by suction under the mesh with a blower. Further, the collected matter was dried and sieved to remove free fibers that did not bind to the water-absorbent resin, thereby obtaining a product consisting of the water-absorbent resin and fibers.
- the resin particles were substantially spherical, and were a water-absorbent resin composite containing one water-absorbent resin particle and two or more fibers.
- a part of the fibers is embedded in the resin particles and a part of the fibers is exposed from the resin particles, and at least one of the two or more fibers has at least one fiber.
- the composite was a water-absorbing composite having a structure in which a part of the fiber was bonded to the surface of the resin particle without being embedded in the resin particle.
- Fig. 9 Schematic diagram inside, 101 and 102
- Example 3 The same as in Example 1 except that polyethylene terephthalate (PET) having a fiber diameter of 1.7 decitex, a length of 0.9 mm, and a water contact angle of 80 ° was used instead of the pulp used as the fiber. Manufactured and obtained product. It was confirmed that the product was a water-absorbent resin composite having the same structure as in Example 1. (103 and 104 in FIG. 10) Example 3
- PET polyethylene terephthalate
- Example 4 Manufactured in the same manner as in Example 1 except that the pulp used as the fiber was replaced with a nipple having a fiber diameter of 1.7 decitex, a length of 0.9 mm, and a water contact angle of 50 °. Then, a product was obtained. The product was confirmed to be a water-absorbent resin composite having the same structure as in Example 1. (105 and 106 in Fig. 11) Example 4
- Example 5 In place of the pulp used as the fiber, nylon with a fiber diameter of 1.7 decitex, a length of 0.9 mm and a contact angle of water of 50 ° was used. Was manufactured in the same manner as in Example 1 except that a fiber mixture having a weight ratio of 1: 1 to rayon having a contact angle of 0 ° was used to obtain a product. The product was confirmed to be a water-absorbent resin composite having the same structure as in Example 1. (107 and 108 in FIG. 12) Example 5
- Example 2 A product was obtained in the same manner as in Example 1, except that the fiber was supplied only from the fiber supply port located 0.8 m below the tip of the nose. Observation of this product with a microscope revealed that it was a composition comprising the following two types of water-absorbent resin composites.
- Water-absorbing composite having the same structure as in Example 1
- a product was obtained in the same manner as in Example 1 except that the fiber was supplied only from the fiber supply port located 1.6 m below the tip of the nozzle. Observation of this product with a microscope revealed that it was a composition comprising the following two types of water-absorbent resin composites.
- Water-absorbent resin composite in which none of the fibers are embedded in the resin particles (schematic diagram in FIG. 14, 111 and 112)
- a substantially spherical water-absorbent resin composite containing one water-absorbent resin particle and one or more fibers, wherein one or more of the fibers have a part of the fibers adhered to the surface of the resin particles. And none of the fibers is embedded in the resin particles.
- fiber diameter 1.7 is decitex and length is 0.
- Example 1 A product was obtained in the same manner as in Example 1 except that polytetrafluoroethylene (PTFE) having a water contact angle of 108 ° and a diameter of 9 mm was used. The product was confirmed to be a water-absorbent resin composite having the same structure as in Example 1. Comparative Example 1
- PTFE polytetrafluoroethylene
- the stainless steel beaker was immersed in a bath temperature of 50 ° C., and with stirring, 0.84 g of 30% hydrogen peroxide solution was added to carry out polymerization. After about 1 minute, the maximum temperature was 110 ° C. Less than Thereafter, it was kept in a warm bath at 50 ° C. for 2 hours and then cooled to 20 ° C. to obtain a water-containing water-absorbent resin.
- a one-component spray nozzle was used in place of the nozzle of Example 1, the solution temperature was maintained at 25 ° C, and the solution was supplied by a pump so that the flow rate was 40 ml / min.
- the monomer solution is converted into droplets in the gas phase (in air, at a temperature of 2
- the spatial density of the droplets in the reactor which was estimated from the space capacity of the reactor, the amount of monomer supplied, and the falling speed of the droplets, was 3 g / m 3 .
- the temperature of the air in the multiphase flow was 25 ° C, and the linear velocity was 10 ms.
- the tip of the nozzle The polymerization rate of 0.8 m below the bottom was less than 1%.
- the fiber used was polyethylene terephthalate (PET) with a fiber diameter of 1.7 dtex, a length of 0.9 mm and a water contact angle of 80 °.
- the feed rate was 11.5 g / min.
- the spatial density of the fibers in the reaction field which was estimated from the space capacity of the reaction field, the fiber supply rate, and the falling speed of the fibers, was 8 g / m 3 .
- the pressure difference between the top and bottom of the mesh was controlled to be 1.0000 Pa by sucking it under the mesh with a blower.
- the recovered product was placed in an oven at 80 ° C, polymerization of the attached monomer aqueous solution was performed for 30 minutes, and thereafter, hot air treatment was performed at 140 ° C to obtain a water-absorbent resin composite.
- the collected material was sieved to remove free fibers, but the water-absorbent resin was also used as an adhesive between the fibers, and virtually no free fibers were found. Thus, a product comprising the water-absorbent resin and the fiber was obtained.
- water-absorbent resin composites produced in Examples 1 to 8 and Comparative Examples 1 and 2 water-absorbent resin composite compositions were prepared, and before the densification treatment, each composite and free fibers were prepared. The weight ratio and the dry weight ratio between the free fiber and the water absorbent resin were measured. It was considered that this ratio did not change due to the subsequent consolidation treatment. Further, regarding the densified water-absorbent resin composite composition obtained by the consolidation treatment of the water-absorbent resin composite composition, , Bulk density, stiffness and restoration rate were measured.
- an absorbent article was produced using the densified water-absorbent resin composite composition, and the water-absorbent resin detachment rate and the gel detachment rate were measured.
- Table 1 summarizes the results of each measurement and evaluation.
- Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 types! “F” PET Nylon Nylon Rulyon.
- Lub A. Ruge ⁇ ⁇ ⁇ ° PTFE Rev PET Average fiber length Lmm] 2.5 0.9 0.9 0.9 2.5 2.5 2.5 0.9 2.5 0.9 Bond
- Thickness 0.8 1.5 1.5 1.5 1.5 0.8 0.8 0.8 1.5 0.8 2.0 Measurement and Bulk Density [g / cm 3 ] 0.42 0.22 0.22 0.22 0.39 0.39 0.39 0.22 0.42 0.16 Evaluation Flexibility [cm] 8.5 7.5 7.5 7.5 7.5 8.5 8.0 8.0 7.5 7.5 Restoration rate [] 11 20 20 20 11 11 13 18 20 20 Water absorption measurement and removal rate of water absorbent resin [] 0.9 1.0 1.0 0.9 1.5 0.9 0.9 4.0 0.9 22 Product evaluation Gel removal rate [3 ⁇ 4] 1.8 2.0 3.0 2.0 1.8 2.5 1.9 4.0 1.9 17
- the water-absorbent resin composite of the present invention and its composition are suitably used as industrial materials such as disposable diapers, sanitary materials such as sanitary napkins, and other water-absorbent articles.
- the water-absorbent resin composite of the present invention is disclosed in JP-A-63-267370, JP-A-63-110667, JP-A-63-295251, JP-A-63-270801, JP-A-63-294716, JP-A-64-64602, JP-A-1-231940, JP-A-1-243927, JP-A-2-30522, JP-A-2-153731,
- the technology used for the sheet-like water-absorbing material proposed in Kaihei 3-21385, JP-A-4-1133728, JP-A-11-156188 and the like can also be appropriately used according to the purpose.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Public Health (AREA)
- Hematology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Dispersion Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Absorbent Articles And Supports Therefor (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA05011039A MXPA05011039A (es) | 2003-04-15 | 2004-04-15 | Compuesto polimerico absorbente de agua y su composicion. |
EP04727701A EP1616912A4 (en) | 2003-04-15 | 2004-04-15 | WATER ABSORBENT RESIN COMPOSITE COMPOSITE AND COMPOSITIONS COMPRISING SUCH COMPOSITE MATERIALS |
US11/248,191 US7354646B2 (en) | 2003-04-15 | 2005-10-13 | Water-absorbent polymer composite comprising two or more fibers, and composition thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003-110863 | 2003-04-15 | ||
JP2003110863 | 2003-04-15 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/248,191 Continuation US7354646B2 (en) | 2003-04-15 | 2005-10-13 | Water-absorbent polymer composite comprising two or more fibers, and composition thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004092281A1 true WO2004092281A1 (ja) | 2004-10-28 |
Family
ID=33295969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/005396 WO2004092281A1 (ja) | 2003-04-15 | 2004-04-15 | 吸水性樹脂複合体およびその組成物 |
Country Status (5)
Country | Link |
---|---|
US (1) | US7354646B2 (ja) |
EP (1) | EP1616912A4 (ja) |
CN (1) | CN100420719C (ja) |
MX (1) | MXPA05011039A (ja) |
WO (1) | WO2004092281A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1649928A4 (en) * | 2003-06-06 | 2008-07-09 | Mitsubishi Chem Corp | WATER ABSORBING ARTICLES AND PROCESS FOR PRODUCING THE SAME |
WO2005037875A1 (ja) * | 2003-10-16 | 2005-04-28 | Mitsubishi Chemical Corporation | レドックス重合法、吸水性樹脂複合体および吸収性物品 |
MX2007009228A (es) * | 2005-02-04 | 2007-08-21 | Procter & Gamble | Estructura absorbente con material absorbente de agua mejorado. |
EP2317007B1 (en) * | 2008-08-11 | 2015-09-30 | Kurashiki Boseki Kabushiki Kaisha | Sliver for spinning, process for producing same, and spun yarn and textile product both using same |
AT507850B1 (de) * | 2009-01-22 | 2016-01-15 | Eurofoam Gmbh | Schaumstoffelement mit darin eingelagerten hydrophilen mitteln |
RU2501743C1 (ru) * | 2012-09-06 | 2013-12-20 | Леонид Асхатович Мазитов | Способ очистки сточной воды от цианид-ионов |
CN107735516A (zh) * | 2015-06-19 | 2018-02-23 | 株式会社大赛璐 | 长条状的纤维丝束的开纤物的制造方法 |
JP7269175B2 (ja) * | 2017-02-26 | 2023-05-08 | ディーエスジー テクノロジー ホールディングス リミテッド | 吸収材料、並びにそれを製造するシステム及び方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61275355A (ja) * | 1985-05-29 | 1986-12-05 | Kao Corp | 吸収性物品 |
JPS6363723A (ja) * | 1986-09-03 | 1988-03-22 | Kao Corp | 吸液性複合体 |
JPH10113556A (ja) * | 1996-10-09 | 1998-05-06 | Mitsubishi Chem Corp | 吸水性複合体及びその製造方法 |
JPH1193073A (ja) * | 1997-09-17 | 1999-04-06 | Kao Corp | ポリマーと繊維との複合体の製造法 |
JP2002275760A (ja) * | 2001-03-21 | 2002-09-25 | Mitsubishi Chemicals Corp | 吸水性複合体の製造方法 |
JP2002370025A (ja) * | 2001-03-29 | 2002-12-24 | Mitsubishi Chemicals Corp | 吸水性複合体及びその製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2205917A1 (en) * | 1994-12-09 | 1996-06-13 | The Procter & Gamble Company | Absorbent composites and absorbent articles containing the same |
JP2000198805A (ja) * | 1998-11-06 | 2000-07-18 | Mitsubishi Chemicals Corp | 吸水性複合体およびその製造方法 |
JP3895624B2 (ja) * | 2001-03-28 | 2007-03-22 | 三菱化学株式会社 | 吸水性複合体およびその製造方法 |
-
2004
- 2004-04-15 MX MXPA05011039A patent/MXPA05011039A/es unknown
- 2004-04-15 WO PCT/JP2004/005396 patent/WO2004092281A1/ja active Application Filing
- 2004-04-15 EP EP04727701A patent/EP1616912A4/en not_active Withdrawn
- 2004-04-15 CN CNB2004800161258A patent/CN100420719C/zh not_active Expired - Fee Related
-
2005
- 2005-10-13 US US11/248,191 patent/US7354646B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61275355A (ja) * | 1985-05-29 | 1986-12-05 | Kao Corp | 吸収性物品 |
JPS6363723A (ja) * | 1986-09-03 | 1988-03-22 | Kao Corp | 吸液性複合体 |
JPH10113556A (ja) * | 1996-10-09 | 1998-05-06 | Mitsubishi Chem Corp | 吸水性複合体及びその製造方法 |
JPH1193073A (ja) * | 1997-09-17 | 1999-04-06 | Kao Corp | ポリマーと繊維との複合体の製造法 |
JP2002275760A (ja) * | 2001-03-21 | 2002-09-25 | Mitsubishi Chemicals Corp | 吸水性複合体の製造方法 |
JP2002370025A (ja) * | 2001-03-29 | 2002-12-24 | Mitsubishi Chemicals Corp | 吸水性複合体及びその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1616912A4 * |
Also Published As
Publication number | Publication date |
---|---|
CN1806013A (zh) | 2006-07-19 |
EP1616912A1 (en) | 2006-01-18 |
EP1616912A4 (en) | 2008-03-26 |
CN100420719C (zh) | 2008-09-24 |
US20060081812A1 (en) | 2006-04-20 |
MXPA05011039A (es) | 2006-04-18 |
US7354646B2 (en) | 2008-04-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2004108274A1 (ja) | 吸水性物品およびその製造方法 | |
KR101782188B1 (ko) | 초박형 유체-흡수성 코어 | |
EP1448242B1 (en) | Crosslinked polyamine coating on superabsorbent hydrogels | |
JP2004530777A (ja) | 酸性の高膨潤性ヒドロゲル | |
US20050013992A1 (en) | Crosslinked polyamine coating on superabsorbent hydrogels | |
US20060252899A1 (en) | Redox polymerization method, water-absorbent resin composite, and absorbent article | |
CN101511917A (zh) | 具有暂时疏水性的聚胺涂覆的超吸收性聚合物 | |
US20090264845A1 (en) | Absorbent composite and method for producing same, asorbent article and nozzle | |
CN101511395A (zh) | 具有优异的凝胶完整性、吸收能力和渗透性的超吸收性聚合物 | |
CN101511916A (zh) | 聚胺涂覆的超吸收性聚合物 | |
WO2000027624A1 (fr) | Composite absorbant l'eau, procede de preparation de ce dernier et article absorbant l'eau | |
US7339016B2 (en) | Method for preparing water-absorbent polymer composite and accumulated material thereof | |
US7354646B2 (en) | Water-absorbent polymer composite comprising two or more fibers, and composition thereof | |
JP2006063508A (ja) | 吸水性樹脂複合体およびその製造法並びに吸水性樹脂シートおよび吸水性物品 | |
JP4379071B2 (ja) | 吸水性材料の製造方法 | |
JP2004339678A (ja) | 吸水性樹脂複合体およびその堆積物の製造方法 | |
JP2005015995A (ja) | 吸収性物品の製造方法 | |
JP2005226042A (ja) | 吸水性樹脂複合体及びその製造方法と吸水性樹脂複合体組成物並びに吸収性物品 | |
JP5067919B2 (ja) | 吸収性複合体及びその製造方法 | |
JP2004339490A (ja) | 吸水性樹脂複合体およびその堆積物の製造方法 | |
WO2004094483A1 (ja) | 吸水性樹脂複合体およびその堆積物の製造方法 | |
JP4424193B2 (ja) | 吸水性複合体、その製造方法およびそれを用いた材料 | |
JP2004332188A (ja) | 吸水性樹脂複合体およびその組成物 | |
JP2005015994A (ja) | 吸収性物品 | |
JP2005015991A (ja) | 吸収性物品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2005/011039 Country of ref document: MX Ref document number: 11248191 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004727701 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20048161258 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 2004727701 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 11248191 Country of ref document: US |