CA2356925C - Water-swellable hot-melt-type adhesive - Google Patents
Water-swellable hot-melt-type adhesive Download PDFInfo
- Publication number
- CA2356925C CA2356925C CA002356925A CA2356925A CA2356925C CA 2356925 C CA2356925 C CA 2356925C CA 002356925 A CA002356925 A CA 002356925A CA 2356925 A CA2356925 A CA 2356925A CA 2356925 C CA2356925 C CA 2356925C
- Authority
- CA
- Canada
- Prior art keywords
- water
- hot
- swellable
- melt adhesives
- swellable hot
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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
- D06M17/00—Producing multi-layer textile fabrics
- D06M17/04—Producing multi-layer textile fabrics by applying synthetic resins as adhesives
- D06M17/06—Polymers of vinyl compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- 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
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Abstract
Water-swellable hot-melt adhesives based on a tackifying resin, a water-dispersible EVA wax, an ethylene/acrylic ester copolymer, a water-soluble homo- or co-polymer and a super absorber polymer powder having an average particle size of less than 80 µm display a clearly improved swelling behavior in comparison with the prior art. Furthermore, the swelling agent is significantly more homogeneously distributed in the matrix. Such hot-melt adhesives are suitable for ensuring longitudinal water impermeability in modern cable structures, as water-swellable jointing compounds in the building industry in the area of building conservation and restoration. Such hot-melt adhesives are further suitable for the manufacture of absorbent textile fabrics in the personal hygiene sector.
Description
. '~.
WATER-SWELLABLE HOT-MELT-TYPE ADHESIVE
FIELD OF THE INVENTION
This invention relates to a water-swellable hot-melt adhesive and to the use of such hot-melt adhesive to manufacture cables, for sealing purposes, for general assembly applications and for bonding non-woven articles.
io BACKGROUND OF THE INVENTION
Water-absorbing or water-swellable compositions are widely used for sealing purposes, for assembly applications and as binders for non-wovens in the manufacture of personal hygiene products. Water-absorbing and water-swellable compositions are used, for example, in pipeline construction to ensure longitudinal water impermeability in multi-layer pipe structures is and in the building industry as jointing compounds in the area of building conservation or restoration. Cables that are laid in the ground or under water represent a further field of application. These cables have to be protected against water penetration in the event of damage to the outer jacket and at transition points and joints. Power, telecommunications and optical cables in particular are long-lived capital goods, the reliability of which has to be 2 o assured over a very long service period. In the event of damage to the external insulation and/or defective transition points, water penetrates into the interior of such cable structures, and these intrusions of water may cause substantial damage to the cables. The water may spread rapidly along the longitudinal axis of the cable, rendering unusable long sections of cable damaged in this way.
Water-swellable sealing compounds or sealing structures have been used for some time now to prevent the penetration of water into cable structures and pipeline structures as well as to form seals in building conservation. JP-A-58-215334 (1983) describes in general terms, heat-curable sealing compounds based on rubbers. and a water-swellable polyurethane resin based on ethylene oxide copolymers.
JP-A-02 155 953 describes salt water-resistant water-swellable materials for seals based on vulcanisable rubbers and water-absorbing resins consisting of acrylic acid derivatives. These materials have to be vulcanised in presses at temperatures of about 160 C for about 30 minutes.
EP-A-0 188 959 describes a multi-layer sealing strip consisting of a support made from paper, textile materials or plastics, which is coated with a layer of a water-swellable polymeric powder and a water-soluble binder and optionally also a surfactant.
US-A-5 020 875 describes cable structures in which the layer designed to prevent water intrusion by swelling consists of a multi-layer laminate. This laminate consists of two support strips made from hydrophobic material, such as polyester. A water-swellable super absorber type polymer or copolymer is interlayered between these two support strips.
US-A-5 188 883 describes a multi-layer composite structure consisting of a metal strip as one layer and a layer of a swellable water-blocking material, whereby the two layers and surfaces are bonded by means of an adhesive.
US-A-5 179 611 describes a cable structure for a fiber optic cable having a water-absorbing element that has been applied to a support by means of a coating method. To this end, a water-absorbing composition consisting of a thermoplastic elastomer, a water-absorbing resin and a water-soluble resin is mixed, this mixture is dissolved or dispersed in a solvent and this solution or suspension is coated onto a flat substrate, such as a textile material or paper, whereupon the solvent is evaporated off by drying.
WO-A-98/27559 describes swellable hot-melt adhesives based on a water-insoluble component consisting of one or more thermoplastic polymers and one or more resins having a saponification value other than 0, together with a water-soluble or water-dispersible component and a water-swellable component belonging to the class of super absorbers.
According to this publication, these are suitable for use as water-swellable hot-melt adhesives in the manufacture of water-tight structures, particularly in the manufacture of longitudinally water-tight cable structures. The components should be mixed together homogeneously, i.e.
there must be no macroscopic inhomogeneities present. No mention is made of the particle size of the water-swellable components.
Although the swellable hot-melt adhesives according to the latest prior art are already characterised by great ease of use in the manufacture of longitudinally water-tight cable structures, there is a need for further improvement in the latter compositions in terms of the speed of swelling on exposure to water. An object was therefore to provide a hot-melt adhesive that is as easy to process as possible and exhibits a high and very rapid swellability on exposure to water. At the same time this adhesive should demonstrate low surface tack at room temperature.
DESCRIPTION OF THE INVENTION
Accordingly, the present invention provides a water-swellable hot-melt adhesive containing:
at least one tackifying resin at least one water-dispersible EVA wax io at least one ethylene/acrylic acid copolymer at least one water-soluble homo- or co-polymer and at least one powdered super absorber polymer having an average particle size of less than 80 pm.
The tackifying resin is used in this context as a bonding agent and compatibility agent and all known tackifying resins that are used for hot-melt adhesives may be used here.
Particularly suitable in this respect are the various colophony derivatives, i.e.
particularly the resin esters of abietic acid and hydrogenation products thereof. These colophony derivatives are also known as colophony esters of various mono- and poly-functional alcohols.
Polyterpenes and terpene phenolic resins may also be used as tackifying resin.
Water-dispersible EVA waxes are polyethylene waxes based on an ethylene/vinyl acetate copolymer having a vinyl acetate content of up to 15 % and molecular weights of between 500 and about 10,000 (determined by viscometry). These specialised polyethylene waxes are characterised by the hydrophilic properties thereof, for example, they are dispersible in water.
Flexibilising ethylene copolymers, particularly ethylene/alkyl acrylate copolymers having an alkyl acrylate proportion of 15 to 40 wt.%, are suitable as hydrophobic matrix components for binding the super absorbers. The longer-chain alkyl acrylic esters are particularly suitable as comonomers in this respect, particularly the C4-C12 alkyl acrylates. These ethylene/alkyl acrylate copolymers generally exhibit a softening point of between 80 and 100 C (ring and ball method, ASTM E 28).
A large number of known homo- or co-polymers may be used as water-soluble homo-or co-polymers, particularly polyethylene glycol, ethylene oxide/propylene oxide copolymers (either as block copolymers or as random copolymers having a predominate proportion of ethylene oxide), polyvinyl methyl ether, polyvinyl pyrrolidone, polyvinyl alcohol and copolymers of such monomers with other olefinically unsaturated monomers. These water-soluble polymers have molecular weights of between 1000 and 20,000, they may be liquid at room temperature or are preferably solid and waxy in cases where higher molecular weights are used.
Suitable powdered super absorber polymers include known homo- and co-polymers of acrylic acid or methacrylic acid ((meth)acrylic acid for short), (meth)acrylonitrile, (meth)acrylamide, io vinyl acetate, vinyl pyrrolidone, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, vinyl sulfonic acid or hydroxyalkyl esters of such acids, 0 to 95 wt.% of the acid groups being neutralised with alkali or ammonium groups and these polymers/copolymers are crosslinked by means of polyfunctional compounds. Such polymers are known, for example, from EP-A-0 700 414 or EP-A-0 701 587. The latter publication discloses that the polymer powders should have a particle size of between 90 and 630 pm. According to the present invention, however, the average particle size of the super absorber polymer powders is less than 80 pm. Particle sizes of between 60 and 2 pm are particularly preferred for the super absorber polymer powders.
2 o Graft copolymers of starch or cellulose with the above comonomers are also known to be suitable as super absorbers, albeit again with the precondition that the particle size of the super absorber polymer powder is less than 80 pm.
The hot-melt adhesives according to the present invention may further contain known commercial stabilisers that guarantee the temperature stability of the formulations; these include, for example, conventional antioxidants based on sterically hindered phenols.
Particularly preferred swellable hot-melt adhesives contain the essential components in the following quantities:
10 to 25 % tackifying resin 20 to 40 % water-dispersible EVA wax 5 to 25 wt.% flexibilising ethylene/acrylic ester copolymer 15 to 35 wt.% water-soluble homo- or co-polymer 20 to 40 wt.% super absorber polymer powder.
The water-swellable hot-melt adhesives according to the present invention are suitable, for example, for coating metal foils or glass fiber-reinforced plastics reinforcing elements in cable construction. One example of a particularly preferred application is the direct coating of the central reinforcing element in optical cables. This central element may be coated with the version of the adhesive that does not exhibit surface tack and then rolled and placed in temporary storage. In conventional optical cables the individual optical fibers are arranged concentrically around this central element. After reactivation of the non-surface-tacky version io of the adhesive on the central element, these optical fibers may be bonded directly onto the central element prior to undergoing additional fabrication steps. The outer side of the plastics tubes that contain the optical fiber(s) may optionally also be coated with the hot-melt adhesive according to the present invention. Use of the hot-melt adhesives according to the present invention may avoid the need for sheathing the optical fibers with a water-swellable multi-layer is adhesive tape or a multi-layer flowing material or for longitudinal waterproofing of the void between the central element and the tubes with a grease (petroleum jelly), as is necessary according to the present prior art. The voids that are a structural feature of cable construction may be ignored, since in the event of water penetration the water-swellable hot-melt adhesive completely fills these voids by virtue of the swelling process, thereby ensuring a reliable 20 longitudinal water seal. This type of construction provides a simplified joining method, the option of working without grease and a significant weight saving in cable construction. A higher production speed may also be achieved in comparison to the processing of laminar flow.
In addition to the above fields of application in the manufacture of longitudinally water-tight 25 optical cables, the water-swellable hot-melt adhesives according to the present invention are also suitable for ensuring the longitudinal water impermeability of various types of power and telecommunications cables based on copper conductors.
The water-swellable hot-melt adhesives according to the present invention are further suitable 30 for use as jointing compounds in the area of building conservation or restoration to form a seal against the penetration of moisture or water into buildings. A further field of application is pipeline construction, for example to ensure the longitudinal water impermeability of multi-layer coaxial pipe structures. The hot-melt adhesives according to the present invention are also suitable for use as binders for non-woven products in the personal hygiene sector, such as _g.
nappies, incontinence pads, incontinence products, sanitary towels, panty liners or mattress covers. Use of the hot-melt adhesives according to the present invention is also conceivable for recyclable bonded joints, where bonds need to be released again subsequently (following the action of water); this is very greatly encouraged by swelling in water.
The water-swellable hot-melt adhesives may be manufactured as follows:
tackifying resin, for example resin ester, EVA wax and ethylene/acrylic ester copolymer are melted at 110 to 160 C and homogenised. The water-soluble homo- or co-polymer(s) is/are then added and homogenised. Finally the powdered super absorber polymer powder is incorporated and io homogenised. The homogeneous melt is then poured into the corresponding packing units and cooled at room temperature.
The compositions according to the present invention are illustrated in greater detail by means of the following Examples, which represent only a limited selection and are in no way intended to restrict the scope of the present invention.
Method of determining the water absorption of water-swellable hot-melt adhesives using the Atea bag testa method Preparation of samples:
A 1 mm thick sheet, as free from bubbles as possible, is produced from a homogeneously manufactured adhesive sample in a heated press at an appropriate temperature.
Two square test pieces whose edges measure 5 x 5 cm are cut from it to provide test pieces having a surface area of 52 cm2.
The test pieces should be as fresh and as free from water as possible. The test pieces are optionally dried overnight in a drying cabinet or desiccator.
The mass of the test pieces mt is determined. Each test piece is placed in a commercial tea filter made from filter paper. This is attached to a commercial plastics holder (the Teekanne range of tea filters and holders, for example, is particularly suitable). The mass of the filter and holder mFH is determined.
Performing the measurement:
The sample is immersed in a 600 ml beaker filled with the desired test liquid.
The test liquid may be demineralised water, tap water, salt water or another aqueous solution.
After exactly s one minute, the support is removed from the liquid and allowed to drip into a larger beaker for 5 minutes without being touched. The weight mtoc of the filter, holder, sample and bound water is then determined and the water absorption of the test piece calculated as follows:
Water absorption mW [g water] = mtOt B(m, + mFH) io The swelling capacity of the product to be tested may be given by relating the absorbed quantity of water to the surface area and mass of the sample:
Swelling capacity [g/(gxcm2)] = mw /(m, x 52) 15 For comparative purposes this value is quoted accurate to three decimal places.
Following the 5 minute dripping time and determination of the weight, the sample is suspended in the test liquid for a further test period and the above procedure is repeated.
Example 1 2 Comp.1 Comp.2 Tackifying resin(') 19.0 10.0 10.0 19.0 Ethylene/acrylic ester copolymer(z) 15.0 10.0 10.0 15.0 Water-soluble polymer(3) 20.0 22.5 22.5 20.0 EVA wax") 20.8 32.3 32.3 20.8 Irganox 1010 0.2 0.2 0.2 0.2 Super absorber (> 100 pm) 25.0 25.0 Super absorber (60-2 pm) 25.0 25.0 Control total 100.0 100.0 100.0 100.0 Softening point C 94.6 96.8 94.5 92.4 Viscosity 140 C [mPa.s] (n=lrpm) 56000 39750 44250 58750 Viscosity 160 C [mPa.s] (n=2.5rpm) 20300 13700 28900 35000 Homogeneity of the swelling agent 15 15 8 8 (15=homog; 0=inhomog) Swelling behavior B tea bag test: 0.047 0.031 0.030 0.023 water absorption (1 min) [g/(gxcm2)]
Swelling behavior B tea bag test: 0.346 0.416 0.264 0.224 water absorption (10 min) [g/(gxcm2)]
Colophony pentaerythritol ester (2) Ethylene butyl acrylate copolymer m.p. 94 C (ring & ball) (3) Polyethylene glycol, MW 12000 (4) EVA content about 9 %, MW about 6500 In relation both to the homogeneous distribution of the swelling agent and to the swelling behavior in the tea bag test, after short-term water absorption and after longer-term water absorption, the hot-melt adhesives according to the present invention display significantly better properties than the comparative examples containing the coarser super absorber io polymer powder.
WATER-SWELLABLE HOT-MELT-TYPE ADHESIVE
FIELD OF THE INVENTION
This invention relates to a water-swellable hot-melt adhesive and to the use of such hot-melt adhesive to manufacture cables, for sealing purposes, for general assembly applications and for bonding non-woven articles.
io BACKGROUND OF THE INVENTION
Water-absorbing or water-swellable compositions are widely used for sealing purposes, for assembly applications and as binders for non-wovens in the manufacture of personal hygiene products. Water-absorbing and water-swellable compositions are used, for example, in pipeline construction to ensure longitudinal water impermeability in multi-layer pipe structures is and in the building industry as jointing compounds in the area of building conservation or restoration. Cables that are laid in the ground or under water represent a further field of application. These cables have to be protected against water penetration in the event of damage to the outer jacket and at transition points and joints. Power, telecommunications and optical cables in particular are long-lived capital goods, the reliability of which has to be 2 o assured over a very long service period. In the event of damage to the external insulation and/or defective transition points, water penetrates into the interior of such cable structures, and these intrusions of water may cause substantial damage to the cables. The water may spread rapidly along the longitudinal axis of the cable, rendering unusable long sections of cable damaged in this way.
Water-swellable sealing compounds or sealing structures have been used for some time now to prevent the penetration of water into cable structures and pipeline structures as well as to form seals in building conservation. JP-A-58-215334 (1983) describes in general terms, heat-curable sealing compounds based on rubbers. and a water-swellable polyurethane resin based on ethylene oxide copolymers.
JP-A-02 155 953 describes salt water-resistant water-swellable materials for seals based on vulcanisable rubbers and water-absorbing resins consisting of acrylic acid derivatives. These materials have to be vulcanised in presses at temperatures of about 160 C for about 30 minutes.
EP-A-0 188 959 describes a multi-layer sealing strip consisting of a support made from paper, textile materials or plastics, which is coated with a layer of a water-swellable polymeric powder and a water-soluble binder and optionally also a surfactant.
US-A-5 020 875 describes cable structures in which the layer designed to prevent water intrusion by swelling consists of a multi-layer laminate. This laminate consists of two support strips made from hydrophobic material, such as polyester. A water-swellable super absorber type polymer or copolymer is interlayered between these two support strips.
US-A-5 188 883 describes a multi-layer composite structure consisting of a metal strip as one layer and a layer of a swellable water-blocking material, whereby the two layers and surfaces are bonded by means of an adhesive.
US-A-5 179 611 describes a cable structure for a fiber optic cable having a water-absorbing element that has been applied to a support by means of a coating method. To this end, a water-absorbing composition consisting of a thermoplastic elastomer, a water-absorbing resin and a water-soluble resin is mixed, this mixture is dissolved or dispersed in a solvent and this solution or suspension is coated onto a flat substrate, such as a textile material or paper, whereupon the solvent is evaporated off by drying.
WO-A-98/27559 describes swellable hot-melt adhesives based on a water-insoluble component consisting of one or more thermoplastic polymers and one or more resins having a saponification value other than 0, together with a water-soluble or water-dispersible component and a water-swellable component belonging to the class of super absorbers.
According to this publication, these are suitable for use as water-swellable hot-melt adhesives in the manufacture of water-tight structures, particularly in the manufacture of longitudinally water-tight cable structures. The components should be mixed together homogeneously, i.e.
there must be no macroscopic inhomogeneities present. No mention is made of the particle size of the water-swellable components.
Although the swellable hot-melt adhesives according to the latest prior art are already characterised by great ease of use in the manufacture of longitudinally water-tight cable structures, there is a need for further improvement in the latter compositions in terms of the speed of swelling on exposure to water. An object was therefore to provide a hot-melt adhesive that is as easy to process as possible and exhibits a high and very rapid swellability on exposure to water. At the same time this adhesive should demonstrate low surface tack at room temperature.
DESCRIPTION OF THE INVENTION
Accordingly, the present invention provides a water-swellable hot-melt adhesive containing:
at least one tackifying resin at least one water-dispersible EVA wax io at least one ethylene/acrylic acid copolymer at least one water-soluble homo- or co-polymer and at least one powdered super absorber polymer having an average particle size of less than 80 pm.
The tackifying resin is used in this context as a bonding agent and compatibility agent and all known tackifying resins that are used for hot-melt adhesives may be used here.
Particularly suitable in this respect are the various colophony derivatives, i.e.
particularly the resin esters of abietic acid and hydrogenation products thereof. These colophony derivatives are also known as colophony esters of various mono- and poly-functional alcohols.
Polyterpenes and terpene phenolic resins may also be used as tackifying resin.
Water-dispersible EVA waxes are polyethylene waxes based on an ethylene/vinyl acetate copolymer having a vinyl acetate content of up to 15 % and molecular weights of between 500 and about 10,000 (determined by viscometry). These specialised polyethylene waxes are characterised by the hydrophilic properties thereof, for example, they are dispersible in water.
Flexibilising ethylene copolymers, particularly ethylene/alkyl acrylate copolymers having an alkyl acrylate proportion of 15 to 40 wt.%, are suitable as hydrophobic matrix components for binding the super absorbers. The longer-chain alkyl acrylic esters are particularly suitable as comonomers in this respect, particularly the C4-C12 alkyl acrylates. These ethylene/alkyl acrylate copolymers generally exhibit a softening point of between 80 and 100 C (ring and ball method, ASTM E 28).
A large number of known homo- or co-polymers may be used as water-soluble homo-or co-polymers, particularly polyethylene glycol, ethylene oxide/propylene oxide copolymers (either as block copolymers or as random copolymers having a predominate proportion of ethylene oxide), polyvinyl methyl ether, polyvinyl pyrrolidone, polyvinyl alcohol and copolymers of such monomers with other olefinically unsaturated monomers. These water-soluble polymers have molecular weights of between 1000 and 20,000, they may be liquid at room temperature or are preferably solid and waxy in cases where higher molecular weights are used.
Suitable powdered super absorber polymers include known homo- and co-polymers of acrylic acid or methacrylic acid ((meth)acrylic acid for short), (meth)acrylonitrile, (meth)acrylamide, io vinyl acetate, vinyl pyrrolidone, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, vinyl sulfonic acid or hydroxyalkyl esters of such acids, 0 to 95 wt.% of the acid groups being neutralised with alkali or ammonium groups and these polymers/copolymers are crosslinked by means of polyfunctional compounds. Such polymers are known, for example, from EP-A-0 700 414 or EP-A-0 701 587. The latter publication discloses that the polymer powders should have a particle size of between 90 and 630 pm. According to the present invention, however, the average particle size of the super absorber polymer powders is less than 80 pm. Particle sizes of between 60 and 2 pm are particularly preferred for the super absorber polymer powders.
2 o Graft copolymers of starch or cellulose with the above comonomers are also known to be suitable as super absorbers, albeit again with the precondition that the particle size of the super absorber polymer powder is less than 80 pm.
The hot-melt adhesives according to the present invention may further contain known commercial stabilisers that guarantee the temperature stability of the formulations; these include, for example, conventional antioxidants based on sterically hindered phenols.
Particularly preferred swellable hot-melt adhesives contain the essential components in the following quantities:
10 to 25 % tackifying resin 20 to 40 % water-dispersible EVA wax 5 to 25 wt.% flexibilising ethylene/acrylic ester copolymer 15 to 35 wt.% water-soluble homo- or co-polymer 20 to 40 wt.% super absorber polymer powder.
The water-swellable hot-melt adhesives according to the present invention are suitable, for example, for coating metal foils or glass fiber-reinforced plastics reinforcing elements in cable construction. One example of a particularly preferred application is the direct coating of the central reinforcing element in optical cables. This central element may be coated with the version of the adhesive that does not exhibit surface tack and then rolled and placed in temporary storage. In conventional optical cables the individual optical fibers are arranged concentrically around this central element. After reactivation of the non-surface-tacky version io of the adhesive on the central element, these optical fibers may be bonded directly onto the central element prior to undergoing additional fabrication steps. The outer side of the plastics tubes that contain the optical fiber(s) may optionally also be coated with the hot-melt adhesive according to the present invention. Use of the hot-melt adhesives according to the present invention may avoid the need for sheathing the optical fibers with a water-swellable multi-layer is adhesive tape or a multi-layer flowing material or for longitudinal waterproofing of the void between the central element and the tubes with a grease (petroleum jelly), as is necessary according to the present prior art. The voids that are a structural feature of cable construction may be ignored, since in the event of water penetration the water-swellable hot-melt adhesive completely fills these voids by virtue of the swelling process, thereby ensuring a reliable 20 longitudinal water seal. This type of construction provides a simplified joining method, the option of working without grease and a significant weight saving in cable construction. A higher production speed may also be achieved in comparison to the processing of laminar flow.
In addition to the above fields of application in the manufacture of longitudinally water-tight 25 optical cables, the water-swellable hot-melt adhesives according to the present invention are also suitable for ensuring the longitudinal water impermeability of various types of power and telecommunications cables based on copper conductors.
The water-swellable hot-melt adhesives according to the present invention are further suitable 30 for use as jointing compounds in the area of building conservation or restoration to form a seal against the penetration of moisture or water into buildings. A further field of application is pipeline construction, for example to ensure the longitudinal water impermeability of multi-layer coaxial pipe structures. The hot-melt adhesives according to the present invention are also suitable for use as binders for non-woven products in the personal hygiene sector, such as _g.
nappies, incontinence pads, incontinence products, sanitary towels, panty liners or mattress covers. Use of the hot-melt adhesives according to the present invention is also conceivable for recyclable bonded joints, where bonds need to be released again subsequently (following the action of water); this is very greatly encouraged by swelling in water.
The water-swellable hot-melt adhesives may be manufactured as follows:
tackifying resin, for example resin ester, EVA wax and ethylene/acrylic ester copolymer are melted at 110 to 160 C and homogenised. The water-soluble homo- or co-polymer(s) is/are then added and homogenised. Finally the powdered super absorber polymer powder is incorporated and io homogenised. The homogeneous melt is then poured into the corresponding packing units and cooled at room temperature.
The compositions according to the present invention are illustrated in greater detail by means of the following Examples, which represent only a limited selection and are in no way intended to restrict the scope of the present invention.
Method of determining the water absorption of water-swellable hot-melt adhesives using the Atea bag testa method Preparation of samples:
A 1 mm thick sheet, as free from bubbles as possible, is produced from a homogeneously manufactured adhesive sample in a heated press at an appropriate temperature.
Two square test pieces whose edges measure 5 x 5 cm are cut from it to provide test pieces having a surface area of 52 cm2.
The test pieces should be as fresh and as free from water as possible. The test pieces are optionally dried overnight in a drying cabinet or desiccator.
The mass of the test pieces mt is determined. Each test piece is placed in a commercial tea filter made from filter paper. This is attached to a commercial plastics holder (the Teekanne range of tea filters and holders, for example, is particularly suitable). The mass of the filter and holder mFH is determined.
Performing the measurement:
The sample is immersed in a 600 ml beaker filled with the desired test liquid.
The test liquid may be demineralised water, tap water, salt water or another aqueous solution.
After exactly s one minute, the support is removed from the liquid and allowed to drip into a larger beaker for 5 minutes without being touched. The weight mtoc of the filter, holder, sample and bound water is then determined and the water absorption of the test piece calculated as follows:
Water absorption mW [g water] = mtOt B(m, + mFH) io The swelling capacity of the product to be tested may be given by relating the absorbed quantity of water to the surface area and mass of the sample:
Swelling capacity [g/(gxcm2)] = mw /(m, x 52) 15 For comparative purposes this value is quoted accurate to three decimal places.
Following the 5 minute dripping time and determination of the weight, the sample is suspended in the test liquid for a further test period and the above procedure is repeated.
Example 1 2 Comp.1 Comp.2 Tackifying resin(') 19.0 10.0 10.0 19.0 Ethylene/acrylic ester copolymer(z) 15.0 10.0 10.0 15.0 Water-soluble polymer(3) 20.0 22.5 22.5 20.0 EVA wax") 20.8 32.3 32.3 20.8 Irganox 1010 0.2 0.2 0.2 0.2 Super absorber (> 100 pm) 25.0 25.0 Super absorber (60-2 pm) 25.0 25.0 Control total 100.0 100.0 100.0 100.0 Softening point C 94.6 96.8 94.5 92.4 Viscosity 140 C [mPa.s] (n=lrpm) 56000 39750 44250 58750 Viscosity 160 C [mPa.s] (n=2.5rpm) 20300 13700 28900 35000 Homogeneity of the swelling agent 15 15 8 8 (15=homog; 0=inhomog) Swelling behavior B tea bag test: 0.047 0.031 0.030 0.023 water absorption (1 min) [g/(gxcm2)]
Swelling behavior B tea bag test: 0.346 0.416 0.264 0.224 water absorption (10 min) [g/(gxcm2)]
Colophony pentaerythritol ester (2) Ethylene butyl acrylate copolymer m.p. 94 C (ring & ball) (3) Polyethylene glycol, MW 12000 (4) EVA content about 9 %, MW about 6500 In relation both to the homogeneous distribution of the swelling agent and to the swelling behavior in the tea bag test, after short-term water absorption and after longer-term water absorption, the hot-melt adhesives according to the present invention display significantly better properties than the comparative examples containing the coarser super absorber io polymer powder.
Claims (9)
1. A water-swellable hot-melt adhesive containing at least:
(a) one tackifying resin;
(b) one water-dispersible EVA wax having a molecular weight of between 500 to 000 determined by viscometry and a vinyl acetate content of up to 15%;
(c) one ethylene/acrylic ester copolymer;
(d) one water-soluble homo- or co-polymer having a molecular weight of between 1000 to 20 000; and (e) one powdered super absorber polymer having an average particle size of less than 80 µm.
(a) one tackifying resin;
(b) one water-dispersible EVA wax having a molecular weight of between 500 to 000 determined by viscometry and a vinyl acetate content of up to 15%;
(c) one ethylene/acrylic ester copolymer;
(d) one water-soluble homo- or co-polymer having a molecular weight of between 1000 to 20 000; and (e) one powdered super absorber polymer having an average particle size of less than 80 µm.
2. The water-swellable hot-melt adhesive as claimed in claim 1, wherein the particle size of the super absorber (e) is between 60 and 2 µm.
3. The water-swellable hot-melt adhesive as claimed in claim 1 or claim 2, wherein a colophony derivative, a polyterpene or a terpene phenolic resin is used as tackifying resin (a).
4. The water-swellable hot-melt adhesive as claimed in any one of claims 1 to 3, wherein the water-soluble homo- or co-polymer (d) is selected from polyethylene glycol, ethylene oxide/propylene oxide copolymers, polyvinyl methyl ether, polyvinyl pyrrolidone, polyvinyl alcohol and copolymers thereof with other olefinically unsaturated monomers.
5. The water-swellable hot-melt adhesive as claimed in any one of claims 1 to 4, wherein the powdered super absorber is selected from homo- and/or co-polymers of (meth)acrylic acid, (meth)acrylonitrile, (meth)acrylamide, vinyl acetate, vinyl pyrrolidone, maleic acid, maleic acid anhydride, itaconic acid, itaconic acid anhydride, vinyl sulfonic acid and hydroxyalkyl esters thereof, 0 to 95 wt.% of acid groups of the powdered super absorber polymer are neutralised and the homo- and/or co-polymers of (meth)acrylic acid, (meth)acrylonitrile, (meth)acrylamide, vinyl acetate, vinyl pyrrolidone, maleic acid, maleic acid anhydride, itaconic acid, itaconic acid anhydride, vinyl sulfonic acid and hydroxyalkyl esters thereof, are crosslinked by means of polyfunctional compounds.
6. Use of the water-swellable hot-melt adhesives as claimed in any one of claims 1 to 5 to provide power, telecommunications and/or optical cables with longitudinal water impermeability.
7. Use of the water-swellable hot-melt adhesives as claimed in any one of claims 1 to 5 in the building industry for sealing joints in building conservation or building restoration and in pipeline construction to provide multi-layer pipe structures with longitudinal water impermeability.
8. Use of the water-swellable hot-melt adhesives as claimed in any one of claims 1 to 5 as binders for textile fabrics for the manufacture of personal hygiene products.
9. Use of the water-swellable hot-melt adhesives as claimed in any one of claims 1 to 5 for subsequently soluble (recyclable) bonded joints.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19859728A DE19859728A1 (en) | 1998-12-23 | 1998-12-23 | Water-swellable hot melt adhesive |
| DE19859728.2 | 1998-12-23 | ||
| PCT/EP1999/009909 WO2000039232A1 (en) | 1998-12-23 | 1999-12-14 | Water-swellable hot-melt-type adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2356925A1 CA2356925A1 (en) | 2000-07-06 |
| CA2356925C true CA2356925C (en) | 2010-03-09 |
Family
ID=7892437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002356925A Expired - Lifetime CA2356925C (en) | 1998-12-23 | 1999-12-14 | Water-swellable hot-melt-type adhesive |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6803400B1 (en) |
| EP (1) | EP1141160B1 (en) |
| JP (1) | JP4618893B2 (en) |
| AT (1) | ATE260961T1 (en) |
| BR (1) | BR9916581A (en) |
| CA (1) | CA2356925C (en) |
| DE (2) | DE19859728A1 (en) |
| ES (1) | ES2217883T3 (en) |
| WO (1) | WO2000039232A1 (en) |
Families Citing this family (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7259190B2 (en) * | 2001-02-21 | 2007-08-21 | Coloplast A/S | Adhesive composition |
| US6787579B2 (en) | 2001-05-02 | 2004-09-07 | L&L Products, Inc. | Two-component (epoxy/amine) structural foam-in-place material |
| US6887914B2 (en) | 2001-09-07 | 2005-05-03 | L&L Products, Inc. | Structural hot melt material and methods |
| US6793274B2 (en) * | 2001-11-14 | 2004-09-21 | L&L Products, Inc. | Automotive rail/frame energy management system |
| IES20020157A2 (en) * | 2002-03-01 | 2003-09-03 | Paltexa Ltd | A method and apparatus for detecting and prevention of water in cable joint closures |
| DE10224842A1 (en) * | 2002-06-05 | 2003-12-24 | Tesa Ag | Pressure-sensitive adhesive for single-sided or double-sided pressure-sensitive adhesive film strips and process for the production thereof |
| DE10234028B4 (en) * | 2002-07-26 | 2008-07-03 | Henkel Kgaa | Adhesive for water-soluble packaging |
| US8070994B2 (en) | 2004-06-18 | 2011-12-06 | Zephyros, Inc. | Panel structure |
| US20060257665A1 (en) | 2005-05-03 | 2006-11-16 | Bennett Ronald G | Barrier-coating layer application method |
| US7901750B2 (en) * | 2005-05-04 | 2011-03-08 | High Impact Technology, L.L.C. | Progressive thickness anti-leak barrier coating |
| US7220455B2 (en) * | 2005-05-24 | 2007-05-22 | High Impact Technology, Llc | Material-selectable, self-healing, anti-leak method for coating liquid container |
| US20060269680A1 (en) * | 2005-05-24 | 2006-11-30 | Bennett Ronald G | Method for creating and applying liquid-container barrier coating |
| US7381287B2 (en) * | 2005-05-24 | 2008-06-03 | High Impact Technologies, L.L.C. | Adhereable, pre-fabricated, self-healing, anti-puncture coating for liquid container and methodology |
| EP1858768A4 (en) * | 2005-05-24 | 2012-11-21 | High Impact Technology Llc | Material-selectable, self-healing, anti-leak method for coating liquid container |
| DE102005046771A1 (en) * | 2005-09-29 | 2007-04-05 | Mauss, Gert, Dr. | Making self-sealing sections in on-board power supply involves automatically coating individual wires with preferably super-absorbent polymers on their paths from meterware to on-board power supply in section(s) in longitudinal direction |
| DE202005022029U1 (en) | 2005-09-29 | 2012-07-05 | Gert Mauss | Self-sealing sealing arrangement of motor vehicles in on-board networks |
| EP1776966A1 (en) * | 2005-10-21 | 2007-04-25 | The Procter and Gamble Company | Absorbent article having improved absorption and retention capacity for proteinaceous or serous body fluids |
| DE102005050623A1 (en) * | 2005-10-21 | 2007-04-26 | CCS Technology, Inc., Wilmington | Optical cable and method of making an optical cable |
| EP1829563B1 (en) * | 2006-03-03 | 2013-05-01 | The Procter and Gamble Company | Thermoplastic absorbent material having increased absorption and retention capacity for proteinaceous or serous body fluid |
| US8043676B2 (en) * | 2007-08-17 | 2011-10-25 | High Impact Technology, L.L.C. | Sealing-reaction, layer-effective, stealth liner for synthetic fuel container |
| JP2009057476A (en) * | 2007-08-31 | 2009-03-19 | Nippon Kagaku Toryo Kk | Meltable water-swellable water-stopping composition and water-stopping method using the same |
| US8387548B2 (en) * | 2008-03-12 | 2013-03-05 | High Impact Technology, Inc. | Marine-vessel, anti-puncture, self-sealing, water-leak protection |
| GB0806434D0 (en) | 2008-04-09 | 2008-05-14 | Zephyros Inc | Improvements in or relating to structural adhesives |
| US8240036B2 (en) | 2008-04-30 | 2012-08-14 | Panasonic Corporation | Method of producing a circuit board |
| US20100285247A1 (en) * | 2008-07-22 | 2010-11-11 | High Impact Technology, L.L.C. | Combined self-sealing, and chemical and visual camouflage coating |
| US8050527B2 (en) * | 2008-11-10 | 2011-11-01 | The Boeing Company | Self healing optical fiber cable assembly and method of making the same |
| DE102009012667A1 (en) * | 2009-03-13 | 2010-09-30 | Henkel Ag & Co. Kgaa | Glue stick with superabsorbers |
| GB0916205D0 (en) | 2009-09-15 | 2009-10-28 | Zephyros Inc | Improvements in or relating to cavity filling |
| US20110162989A1 (en) * | 2010-01-06 | 2011-07-07 | Ducker Paul M | Ultra thin laminate with particulates in dense packages |
| US9549858B2 (en) * | 2010-01-06 | 2017-01-24 | Ching-Yun Morris Yang | Ultra-thin absorbent article |
| CN103153604B (en) | 2010-03-04 | 2016-04-13 | 泽菲罗斯公司 | Structural composite laminate |
| US9827347B2 (en) | 2011-08-09 | 2017-11-28 | Coloplast A/S | Pressure sensitive adhesive composition |
| US9370674B2 (en) | 2011-12-05 | 2016-06-21 | High Impact Technology, Llc | Plural layer, plural-action protective coating for liquid fuel container |
| WO2015011686A1 (en) | 2013-07-26 | 2015-01-29 | Zephyros Inc | Improvements in or relating to thermosetting adhesive films |
| CN103554333A (en) * | 2013-11-19 | 2014-02-05 | 宜兴丹森科技有限公司 | Preparation method of high strength super absorbent resin |
| ES2709726T3 (en) * | 2014-03-13 | 2019-04-17 | Flooring Technologies Ltd | Panel with a sealed chamfer by a superabsorbent and its manufacturing method |
| GB201417985D0 (en) | 2014-10-10 | 2014-11-26 | Zephyros Inc | Improvements in or relating to structural adhesives |
| CN105131887A (en) * | 2015-09-28 | 2015-12-09 | 京东方科技集团股份有限公司 | Box sealing adhesive, preparation method of box sealing adhesive, display panel mother board and manufacturing method of display panel mother board |
| DE102015121213A1 (en) * | 2015-12-07 | 2017-06-08 | Biolink Gesellschaft Für Verbindungstechnologien Mbh | Sealing element for building sealing |
| MX2019014127A (en) | 2017-05-31 | 2020-02-07 | Corning Res & Dev Corp | Super-absorbent swellable hot melt coated optical fibers, buffer tubes, cable designs thereof and manufacturing processes. |
| US20190157798A1 (en) * | 2017-11-22 | 2019-05-23 | Corning Research & Development Corporation | Telecommunications enclosure designs for improved sealing and reliability via superabsorbent polymers |
| FR3110592B1 (en) * | 2020-05-20 | 2022-09-30 | Lifco Ind | SUPER-ABSORBENT FUNCTIONAL POWDER WITH ADHESIVE PROPERTIES |
| CN113337239B (en) * | 2021-06-23 | 2023-04-28 | 广州市耐力环保科技有限公司 | Water-blocking sealant and preparation method thereof |
Family Cites Families (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345320A (en) | 1964-05-25 | 1967-10-03 | Gen Aniline & Film Corp | Remoistenable hot-melt adhesives containing plasticized copolymers of nvinyl lactams |
| US3972328A (en) | 1975-07-28 | 1976-08-03 | E. R. Squibb & Sons, Inc. | Surgical bandage |
| GB1576522A (en) | 1977-05-24 | 1980-10-08 | Colorplast International A S | Sealing material for ostomy devices |
| DK147035C (en) | 1980-12-05 | 1984-09-03 | Coloplast As | Skin Barrier |
| US4393080A (en) | 1981-12-24 | 1983-07-12 | E. R. Squibb & Sons, Inc. | Adhesive compositions |
| JPS58215334A (en) | 1982-06-09 | 1983-12-14 | Saitama Gomme Kogyo Kk | Manufactue of water swelling seal material |
| US4548845A (en) | 1983-04-21 | 1985-10-22 | Avery International Corp. | Reduced build-up pressure-sensitive adhesives |
| US4551490A (en) | 1983-06-27 | 1985-11-05 | E. R. Squibb & Sons, Inc. | Adhesive composition resistant to biological fluids |
| US4590227A (en) | 1984-10-24 | 1986-05-20 | Seitetsu Kagaku Co., Ltd. | Water-swellable elastomer composition |
| GB8502629D0 (en) | 1985-02-01 | 1985-03-06 | Shell Int Research | Polysaccharide aqueous solution |
| JP2831648B2 (en) * | 1988-03-31 | 1998-12-02 | 住友精化株式会社 | Water-absorbing water retention material |
| JP2574881B2 (en) | 1988-12-08 | 1997-01-22 | 株式会社日本触媒 | Salt resistant water swelling material |
| JP2684217B2 (en) * | 1989-06-15 | 1997-12-03 | 三洋化成工業株式会社 | Moldable water absorbent resin composition |
| JPH03176332A (en) | 1989-12-01 | 1991-07-31 | Fujikura Rubber Ltd | Water-stopping tape and manufacture therefor |
| CA2034211C (en) | 1990-01-23 | 1996-12-17 | Candido John Arroyo | Communications cable having microbial resistant water blocking provisions |
| US5138685A (en) | 1990-01-23 | 1992-08-11 | At&T Bell Laboratories | Communications cable having microbial resistant water blocking provisions |
| US5188883A (en) | 1990-03-22 | 1993-02-23 | Northern Telecom Limited | Composite tape structures |
| US5179611A (en) | 1990-07-17 | 1993-01-12 | Tokai Rubber Industries, Ltd. | Optical fiber cable having a water absorptive member |
| US5110605A (en) | 1990-08-21 | 1992-05-05 | Oramed, Inc. | Calcium polycarbophil-alginate controlled release composition and method |
| DE4206857C2 (en) | 1992-03-05 | 1996-08-29 | Stockhausen Chem Fab Gmbh | Polymer composition, absorbent material composition, their production and use |
| US5410629A (en) | 1992-12-22 | 1995-04-25 | At&T Corp. | Optical fiber cable which includes waterblocking and freeze preventing provisions |
| EP0701587B1 (en) | 1993-05-03 | 1997-08-06 | Stockhausen GmbH & Co. KG | Polymer compositions and their production, in particular absorbent materials, and their use |
| JP2843779B2 (en) * | 1994-05-13 | 1999-01-06 | 株式会社日本触媒 | Composition for water-swellable rubber and water-swellable rubber |
| DE4416927C1 (en) | 1994-05-13 | 1995-08-31 | Lohmann Therapie Syst Lts | Device for release of active agents from melt-type adhesive |
| GB9411028D0 (en) | 1994-06-02 | 1994-07-20 | Cookson Group Plc | Water blocking composites and their use in cable manufacture |
| EP0699800A2 (en) | 1994-08-31 | 1996-03-06 | National Starch and Chemical Investment Holding Corporation | Hot melt coatings for paper and paperboard |
| IT1272844B (en) | 1994-11-24 | 1997-06-30 | Pirelli Cavi Spa | OPTICAL CABLE PROTECTED AGAINST HUMIDITY |
| JPH08150690A (en) * | 1994-11-30 | 1996-06-11 | Kanebo Ltd | Food packaging sheet |
| JPH09137015A (en) * | 1995-11-15 | 1997-05-27 | Mitsubishi Chem Mkv Co | Water-swellable composition and molded product using the same |
| US6380292B1 (en) * | 1996-06-21 | 2002-04-30 | Bostik Findley, Inc. | Hydrophilic hot melt adhesive |
| DE19652762A1 (en) | 1996-12-18 | 1998-08-06 | Henkel Kgaa | Swellable hot melt adhesive |
| DE19744937A1 (en) | 1997-10-10 | 1999-04-15 | Cit Alcatel | Optical element with glued units |
| JP3176332B2 (en) | 1997-11-07 | 2001-06-18 | 固志 千代 | Anchored body used for foundation anchoring method of foundation pile |
-
1998
- 1998-12-23 DE DE19859728A patent/DE19859728A1/en not_active Ceased
-
1999
- 1999-12-14 EP EP99968796A patent/EP1141160B1/en not_active Expired - Lifetime
- 1999-12-14 JP JP2000591133A patent/JP4618893B2/en not_active Expired - Fee Related
- 1999-12-14 BR BR9916581-3A patent/BR9916581A/en not_active Application Discontinuation
- 1999-12-14 AT AT99968796T patent/ATE260961T1/en not_active IP Right Cessation
- 1999-12-14 DE DE59908777T patent/DE59908777D1/en not_active Expired - Lifetime
- 1999-12-14 CA CA002356925A patent/CA2356925C/en not_active Expired - Lifetime
- 1999-12-14 US US09/646,321 patent/US6803400B1/en not_active Expired - Lifetime
- 1999-12-14 ES ES99968796T patent/ES2217883T3/en not_active Expired - Lifetime
- 1999-12-14 WO PCT/EP1999/009909 patent/WO2000039232A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000039232A1 (en) | 2000-07-06 |
| EP1141160B1 (en) | 2004-03-03 |
| EP1141160A1 (en) | 2001-10-10 |
| CA2356925A1 (en) | 2000-07-06 |
| ES2217883T3 (en) | 2004-11-01 |
| DE59908777D1 (en) | 2004-04-08 |
| JP4618893B2 (en) | 2011-01-26 |
| JP2002533555A (en) | 2002-10-08 |
| ATE260961T1 (en) | 2004-03-15 |
| US6803400B1 (en) | 2004-10-12 |
| DE19859728A1 (en) | 2000-06-29 |
| BR9916581A (en) | 2001-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2356925C (en) | Water-swellable hot-melt-type adhesive | |
| US6534572B1 (en) | Compositions comprising a thermoplastic component and superabsorbent polymer | |
| CA2274649C (en) | A water-swellable hot-melt adhesive | |
| US6849672B2 (en) | Superabsorbent thermoplastic composition and article including same | |
| EP2390298B1 (en) | Hot melt pressure sensitive adhesive composition that includes vegetable wax and articles including the same | |
| US6608134B1 (en) | Adhesives and method for making same | |
| US5685758A (en) | Hot melt adhesive compositions with improved wicking properties | |
| JP3323232B2 (en) | Composite composition of superabsorbent resin particles | |
| AU2821600A (en) | Polymers that are cross-linkable to form superabsorbent polymers | |
| JP3086300B2 (en) | Waterproofing agent for cable | |
| CA2360523A1 (en) | Highly water-absorbing resin particle | |
| JPS6291577A (en) | Adhesive composition | |
| JP2606988B2 (en) | Water-absorbing agent composition and water-stopping material comprising the water-absorbing agent composition | |
| JPH10258229A (en) | Liquid absorptive composite | |
| JPH05346524A (en) | Production of water-shielding material | |
| JPH06118286A (en) | Water stop tape for optical cable and its manufacture | |
| AU5792601A (en) | Hot melt adhesive compositions with improved wicking properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20191216 |
|
| MKEX | Expiry |
Effective date: 20191216 |