JPS63277283A - Waterproof material - Google Patents

Abstract

PURPOSE:To obtain a waterproof material preventing metal ion-contg. water such as seawater from penetration, by forming a film of water-absorptive polymer from water-soluble polyalkylene oxide polyol, etc. on the surface of a substrate consisting of putrefaction-retardant polymer. CONSTITUTION:The objective waterproof material preventing optical fiber cables from water penetration can be obtained by forming on the surface of a substrate consisting of a putrefaction-retardant polymer, >=5wt.% of a film of water-insoluble and water-absorptive polymer made up of a reaction product from (A) a water-soluble polyalkylene oxide polyol having two or more hydroxyl groups with an average molecular weight >=4,000, (B) 1-20wt.% of a compound having two or more hydroxyl and/or amino groups (e.g., neopentyl glycol) and (C) 1-15wt.% of a polyisocyanate compound (based on the components A+B).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a material for preventing water running, and more specifically, to prevent water from entering into optical fiber cables, particularly water containing metal ions such as seawater. It concerns the material that prevents it.

[Conventional technology]

As shown in Fig. 2, the structure of a conventional optical fiber cable generally includes a tension member 1 as a core at the center 6, around which a plurality of optical fibers 2 are arranged at equal intervals. A filling material 3 is present in the gap and surrounding the entire area, and a tape 4 is placed around the outer periphery of the filling material 3.
is coated to form a circular cross section, and the whole is further wrapped in an outer covering l1f5.

As filler materials that have been used in optical fiber cables, hemp or polypropylene formed into thread or split yarn are known.

However, in recent years, optical fiber cables are increasingly being buried underground or on the seabed, and the characteristics required of conventional filling materials, such as cushioning performance and ease of filling, as well as the ability to prevent water run-in have become important. Ta.

For example, in an optical fiber cable as shown in Figure 2, if the outer sheath is somehow broken and water intrudes, water running prevention property instantly prevents the water from traveling in the longitudinal direction of the cable. It refers to the ability to absorb water, swell, and block water.

As a filling material for cables to prevent water running,
Vetram-based and polybutene-based jellies have been used.

However, these methods have drawbacks such as poor connection workability when connecting cables, poor cable productivity, and increased transmission loss due to microbending at extremely low temperatures.

In order to solve these problems, methods have been proposed that utilize water-absorbing polymers and fibrous materials such as cotton, strings, and tapes containing water-absorbing polymers. For example, U.S. Pat. No. 4,308,416 describes a method using a water-absorbing polymer made of a crosslinked product of unsaturated carboxylic acid containing an alkyl acrylate, and JP-A-58-207007 describes a method using a water-absorbing polymer made of a crosslinked product of an unsaturated carboxylic acid containing an alkyl acrylate; Method using string, tape, etc. containing water-absorbing polymer, JP-A-61-34
No. 810 discloses a method using carboxymethylcellulose-based, polyacrylic acid-based, poval-based, or polyoxyethylene-based water-absorbing polymers or string-like or cotton-like interpositions thereof; JP-A-59-157913 discloses JP-A-61-73113 discloses a method using a mixture of radiation-crosslinked polyacrylamide resin, polyethylene oxidized starch graft polymer, etc., and calcium carbonate surface-treated with a hydrophobic material. There are methods such as using methylcellulose fibers as strings or tapes.

[Problem that the invention seeks to solve]

If these water-absorbing polymers are used in powder form, the polymer powder tends to fall off when connecting cables, resulting in poor connection workability.The tilting and vibration of the cable can cause the powder to move within the cable, resulting in long-term damage. There is a problem in that it is difficult to keep it uniformly present in the cable. Furthermore, if the particle size is large, the optical fiber will be partially compressed, causing microbending and causing transmission loss.

On the other hand, when the cable is laid on the seabed, the water-absorbing polymer must also exhibit good water running prevention performance against seawater. Polyvinyl alcohol-based, carboxymethyl cellulose-based, and polyalkylene glycol-based water absorbers are examples of polymers that meet these conditions.

However, polyvinyl alcohol compounds are spoiled by bacteria that invade at the same time as water, resulting in a decrease in water absorption. Carboxymethyl cellulose compounds are also susceptible to decomposition due to water absorption, and this decomposition generates hydrogen gas.

Hydrogen gas penetrates into the quartz glass of the optical fiber and causes transmission loss.

The polyalkylene oxide water absorbent reported for optical fiber cables is a polymer type, but it is very difficult to reduce the particle size of this type of polymer, so large particle size is used as an intermediary for optical fibers. When used, there is a problem in that the optical fiber is partially compressed and microbending occurs. The particle size that causes microbending is 2°O microns or more in experiments conducted by the present inventors.

In order to prevent microbending, there are methods such as directly applying a liquid polyalkylene oxide water absorbent to the optical fiber, and using a string, tape, etc. treated with a liquid polyalkylene oxide water absorber. is possible. Liquid polyalkylene oxide-based water absorbers are disclosed in Japanese Patent Publication No. 50-36280 and Japanese Patent Application Laid-open No. 1983
No. 1-130324 has been reported. However, the conventionally reported liquid polyalkylene oxide water absorbers have the disadvantage that their films soften and become adhesive at temperatures of 60° C. or higher. Therefore, when this is used as an encapsulant, when the temperature inside the cable rises to 60°C or higher, polyalkylene oxide acts as an intermediary to bond the optical fibers together, and the optical fibers and the tension member or jacket. . As a result, when temperature changes occur, the difference in linear expansion coefficient between the optical fiber and other materials causes a contraction difference, causing distortion in the optical fiber and causing transmission loss.

The purpose of the present invention is to have good water running prevention properties even against water containing metal ions such as seawater, and to prevent adhesion from occurring even when the temperature inside the cable increases, and to prevent rot from occurring due to water absorption. It is an object of the present invention to provide a material for preventing water running of optical fiber cables.

[Means for solving problems]

The first aspect of the present invention is to coat (A) a water-soluble polyalkylene oxide polyol having hydroxyl groups of 2 (1? B) A reaction product of a compound having a melting point or softening point of 80°C or higher and having two or more hydroxyl groups and/or amino groups and (C) a polyisocyanate compound, which is insoluble in water. A water running prevention material for an optical fiber cable, characterized in that a film of a water-absorbing polymer compound is formed, and the adhesion ratio of the film to the support is 5ffi1% or more.

The second aspect of the present invention is a water running prevention material for optical fiber cables, which is the first aspect of the present invention, in which a film is formed by mixing an inorganic metal compound with a water-absorbing polymer compound.

Water running prevention material prevents water from entering the cable as soon as water enters the cable.
It is necessary to instantly absorb water and swell to prevent further water from entering.

An example of the use of the water running prevention material of the present invention will be described with reference to the drawings.

FIG. 1 is a sectional view of a layer-twisted type optical fiber cable showing an embodiment of the present invention. This cable consists of a tension member 1, a tape 6 for preventing water running according to the present invention provided sequentially on the outside thereof, an optical fiber core 2, a water-absorbing spun yarn 3A for preventing water running according to the present invention, and a water-absorbing pressure winding for preventing water running. It consists of tape 4A and jacket 5. In the optical fiber cable having such a structure, even if cracks occur in the jacket 5 and water infiltrates, the water-absorbing spun yarn 3A and the water-absorbing tape 4 remain intact.
．． 6 swells instantaneously, minimizing the intrusion of water and further preventing further intrusion for a long period of time.

Examples of the support used in the water running prevention material of the present invention include fibers, films, and the like. The fibers can be used in the form of long fibers or short fibers. It can also be used in the form of spun yarn, nonwoven fabric, immature material, etc. Nonwoven fabrics, knitted fabrics, and films are suitable for use in the form of tapes to cover optical fibers. Spun yarn is suitable for providing a buffering function and a water running prevention function.

The material of the support must be a non-perishable polymer compound. Cellulose and polyvinyl alcohol cannot withstand long-term use because they rot due to bacteria that invade when they absorb water.

Non-perishable means that the oxygen concentration is 15% by volume or more and no increase in hydrogen concentration is observed, as evaluated by the measurement method described below.

Examples of the non-perishable polymer compound include acrylic polymers, ester polymers, amide polymers, olefin polymers, and the like. These may be homopolymers or copolymers.

It is preferable that the non-perishable polymer compound has water absorption properties. An example of such a compound is an acrylic water-absorbing polymer. This polymer can be produced by a known method such as a method of hydrolyzing polyacrylonitrile, a method of copolymerizing an acrylic monomer having a carboxyl group, and having an active dim bond that can be copolymerized into acrylonitrile and acrylonitrile. It can be obtained by copolymerizing monomers having carboxyl groups. Such a copolymer may contain, for example, 65 to 90% by weight of acrylonitrile and preferably 0.5 to 4.5 mmo/g of a lithium, potassium, sodium or ammonia salt of a carboxylic acid, more preferably 1 to 3.5 mmo6. /g.

In addition to being used as a support, such a water-absorbing polymer can also be used by attaching such a water-absorbing polymer to a non-water-absorbing support in the form of powder, granules, or film.

The water-absorbing polymer compound applied to the surface of the support made of N-perishable polymer compound is (A) a water-soluble polyalkylene oxide polyol having two or more hydroxyl groups with an average molecular weight of 4000 or more, and (B) A compound having a melting point or softening point of 80°C or higher and having 2 (11 or more hydroxyl groups) and/or a compound having 2 or more amino groups is reacted with (C) a polyisocyanate compound in water. It is an insoluble polyalkylene oxide compound.The polyalkylene oxide polyol of component (A) may be a water-soluble resin having an average molecular weight of 14,000 or more and having a hydroxyl group having two or more functionalities.

Component (A) constitutes the main component of the water-absorbing polymer compound,
When the average molecular weight is 4000 or more, it exhibits good water absorption, particularly good water absorption for water containing total ion, such as seawater. If the average molecular weight is less than 4,000, only a fragile film is formed on the surface of the support, the water absorption and swelling properties are poor, and the water running prevention effect is insufficient.

In addition to ethylene oxide homopolymer, the polyalkylene oxide polyol may be a copolymer of ethylene oxide and propylene oxide or butylene oxide, and may contain other copolymerizable components as long as water solubility is not lost. You can leave it there. Further, the polyalkylene oxide polyol of the present invention may be bonded to a small amount of organic residue under the above conditions. These may be used alone, or in a mixed system of two or more, or in combination with some other polymer polyols.

Examples of the compound (B), which has a melting point or softening point of 80°C or higher and contains two or more hydroxyl groups and/or amino groups, include neopentyl glycol, pentaerythritol, 4.4f-bis(hydroxyethyl ) Bisphenol A, 4.4'-bis(hydroxyethyl)tetrabromobisphenol A, 3.9-bis(1゜1-dimethyl-2-hydroxyethyl)-2,
4゜8.10-tetraoxaspiro(5,5)undecane, dihydroxynaphthalene, 1.4-bis(β-hydroxyethoxy)benzene, bis(β-hydroxyethyl)terephthalate, 4.4'-bis(hydroxyethyl) )-2-bisphenol, ethylenediamine, diethylenetriamine, 1゜3-diaminopropane, tolylenediamine, 4゜4'-diaminodiphenylmethane, triethylenediamine, N-methyl-N, N-jetanolamine, aminophenol, hydroxyethylpiperazine and hydroxyalkylated polyethylene polyamines. (B) component is 1 to (A) component
It is preferable to use 20% by weight. These compounds are (
It reacts with the polyisocyanate compound that is component C) to form a water-absorbing polymer compound that forms a film in the present invention. By containing this component (B), the film of the water-absorbing polymer compound that forms the film in the present invention has a
It exhibits the effect of not adhering to the materials constituting the optical fiber cable even at temperatures of around 0°C. For example, if these films are laminated together or with a polyethylene film, a polyethylene terephthalate film, or a urethane-based ultraviolet curable film,
No adhesion occurs even when left at 70° C. for 24 hours under the weight of Il.

In the present invention, the polyisocyanate compound used as component (C) has an isocyanate group (-N
Compounds containing 2 ('a or more of Na-1-, phenyl isocyanate, p-chlorophenylisocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, stearoyl isocyanate, rl
-) Luolsulfonyl isocyanate, propane diisocyanate, hexane diisocyanate, decane diisocyanate, ω, ψ1-dipropyl ether diisocyanate, thiodiethyl diisocyanate, hexafluoropropane diisocyanate, i, 3 -dimethylbenzene-ω, ω1-diisocyanate, 1.4-dimethylnaphthalene-ω, ω1-diisocyanate, 2.4-1
-Lylene diisocyanate, 1,3-dimethylbenzene-2,4-diisocyanate, naphthalene-1,4-
Diisocyanate, biphenyl-4°4'-diisocyanate, 2-nitrobiphenyl-4,4°-diisocyanate, 3,31-dimethoxybiphenyl-4,4f-
Diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dichlorodiphenyldimethylmethane-4,4'-diisocyanate, 1-methylbenzene-2,4,6-1-liisocyanate-1 -, naphthalene-1,3,7-1-diisocyanate, biphenyl-
2,4,4'-)diisocyanate, triphenylmethane-4,4',4''-triisocyanate], also TD
Trimer of I (Desmodur IL), polymethylene polyphenylisocyanate (manufactured by Upjohn), trimethylolpropane, and other polyols are reacted with a diisocyanate in a number of moles corresponding to the number of active hydrogens thereof. There are urethane triisocyanate compounds (Desmodur) etc.

Furthermore, even if these polyisocyanate compounds are masked with a suitable masking agent, there is no problem as long as the temperature can be raised to above the regeneration temperature during the reaction. These isocyanate compounds can be used alone or in combination of two or more.

The amount of the polyisocyanate compound used in the present invention varies depending on the type of each reaction composition, but is usually preferably 1 to 1.5% by weight, more preferably 1 to 1.5% by weight based on the total amount of components (A) and (B). is 5 to 10% by weight.

The water-absorbing polymer compound consisting of components (A), (B) and (C) needs to be insoluble in water. If this compound is soluble in water, even if it is used in an optical fiber cable, it will dissolve when water enters, so it will not be effective in preventing water running.

It is necessary that this water-absorbing polymer compound forms a film on the surface of the support. If it is attached in powder form, the optical fiber will be compressed and microbending will occur as described above, causing transmission loss, as well as the water absorption rate will be slow and the ability to prevent water running will be poor. The adhesion ratio of the water-absorbing polymer compound to the support when forming a film varies depending on the usage form and usage conditions of the water running prevention material, but it is necessary that it adheres to the support at 5M% or more. Yes, preferably 5 to 80% by weight, more preferably 5 to 60% by weight.
% by weight, most preferably 10-50% by weight. If the amount of adhesion is less than 5M%, the anti-water running property will be insufficient and it cannot be put to practical use.

If the water-absorbing polymer compound contains an inorganic metal compound, the adhesion of the film will further decrease, and the films will not adhere to each other even if left at 90° C. for 24 hours using the method described above.

Preferably, the inorganic metal compound is insoluble in organic solvents. Such inorganic metal compounds include, for example, aluminum hydroxide, titanium dioxide, calcium carbonate, aluminum oxide, silicon dioxide, calcium silicate, and various total oxides such as clay minerals such as bentonite, montmorillonite, and clay. , fine particulate matter such as kinjoshio, etc.

An example of the method for producing the water-absorbing polymer compound of the present invention is as follows.

In an anhydrous state and in an inert gas atmosphere, a polyalkylene oxide polyol and a compound having two or more hydroxyl groups and/or amino groups are first mixed, and then the polyisocyanate is prepared in a solution using an appropriate solvent. Alternatively, a polyalkylene oxide polyol and a polyisocyanate may be reacted first, and then a compound having a hydroxyl group and/or an amino group of H[lI or more may be reacted. The reaction temperature is preferably 50°C to 150°C.

Triethylamine, triethanolamine,
Tertiary amines such as pentamethyldiethylenetriamine, dimethylbenzylamine, tetraethyldiamine, triethylenediamine, morpholine derivatives, piperazine derivatives, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, triphenyltin acetate, stannath octonite, etc. The reaction may proceed even better if a small amount of a promoter is added.

Depending on the purpose, various stabilizers such as hindered phenol-based, sulfur-based, and phosphorus-based antioxidants and light-resistant stabilizers are added to the water-absorbing polymer compound obtained in this way to greatly improve durability. It is also possible to improve.

The inorganic metal compound may be added before the reaction, during the reaction, or after the reaction.

Organic solvents used in the reaction or for dilution include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylenephosphoaramid, tetrahydrofuran, dioxane, Examples include methylene chloride, ethane dichloride, chloroform, I.lichloroethylene, perchloroethylene, 1,1.1-)lichloroethane, and toluene. These solvents can be used alone or in combination.

A method for forming a film by attaching a water-absorbing polymer compound to a support is to immerse a support made of n-perishable synthetic fibers in a solution of a water-absorbing polymer compound dissolved in a volatile organic solvent, and then squeeze the liquid with a mangle. If the support is filamentous,
Any method may be used, such as a method similar to gluing and warping of textiles, a method using single strand gluing, etc.

The method for measuring characteristics used in the present invention is as follows.

Water absorption; a) TB method A sample placed in a polyester net is immersed in water at 20°C for a certain period of time, suspended in the air for 10 minutes, and then taken out from the net and its weight is measured. Assuming the weight at this time as A, the water absorption capacity is determined by the following formula.

C: Weight after drying in a hot air drying layer adjusted to 80°C until there is no weight change.

CB method The sample whose weight was measured by the TB method is returned to the polyester net and matured for 1 minute with a force of 100 G in a centrifugal dehydrator, and then the sample is taken out from the net and its weight is measured.

The weight at this time is assumed to be B, and the water absorption capacity is determined by the following formula.

Water running prevention property: Water running prevention material was applied to a glass tube with an inner diameter of 5 mm and a length of 30mm (
Place this horizontally, connect the end of it to a vertically erected glass tube with an inner diameter of 1011φ using a rubber tube, and fill the vertically erected glass tube with water to a depth of 1 m from the horizontally placed glass tube. After 24 hours, the length of water penetration into the water running prevention material of the glass tube placed horizontally was measured, and the length was evaluated as water running performance. The shorter the water penetration length, the better the water running prevention property.

Bending hardness: The bending hardness of a filamentous material is shown as a substitute value for the hardness of the water running prevention material that affects micropending.

・Measuring device: Press bending flexibility tester (product name manufactured by Script Seisakusho Co., Ltd.) ・Sampling samples are arranged in parallel at 2 mm intervals and 10 cm wide. Next, at right angles to the length direction of the thread, the length of the thread is 3 c
Attach pieces of paper coated with adhesive to both ends of the thread so that the length is m.

・Attach the measurement sample and continue turning the handle at a constant speed until the value reaches its maximum value. Record the value as a measured value.

Place only the lower part of the sample on the stand and place it in the sample frame ff1l.
Read. The degree of bending flexibility is expressed in terms of maximum bending stress per denier (g/d).

= Measured value - Sample frame weight Td: Total denier putrefying property: Put 4g of the test sample 14 into the container 12 shown in Fig. 3, add 200cc of the soil extract 13 described below, mix it, and store it in the shade at 30°C. After 30 days, turn off the stopcock 1 of the container.
0 is opened, 2 to 4 cc of air is extracted from the air section, and the generated gas is analyzed using a gas chromatograph.
Check the color and condition of the solution with the naked eye.

The soil extract is prepared as follows.

(1) Collect soil from areas where there are fallen leaves and grass growing.

(2) Mix 500 g of soil with 2000 cc of pure water and stir.

(3) After leaving for 12 hours, filter the supernatant and 50c of the filtrate.
Add 150 cc of pure water to c to obtain a soil extract.

(4) Soil and soil extract should be freshly collected and extracted for each test batch.

Bulky property: a) Spun yarn A suitable amount of spun yarn is wrapped tightly and left in a constant temperature room (temperature 20°C ± 2°C, relative humidity 65 ± 2%) for more than 24 hours, and the length is 4c+
Cut it into a box (width 4 (2) x length 5 cI!l x height 4
cm) with a lid plate and a load cell of 14.4g /
After applying a pressure of cd for 1 minute, read the scale and calculate the bulkiness from the following formula.

Measuring Machine Ni-Maeda Compressive Elasticity Test Machine Cut the fabric, knitted fabric, or non-woven fabric sample into a rectangular size of 4CI1X5C11, and place it in a constant temperature room (
After being left at a temperature of 20±2℃ and a relative humidity of 65±2% for more than 24 hours, the height of 4. Stack them in a box (width 4 C1l x length 50 x height 4C11) with a lid plate and use a load cell to get 14.4 g/en! After applying pressure for 1 minute, read the scale and calculate bulkiness in the same manner as for spun yarn.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples. Note that all percentages in the examples are percentages by weight.

Example 1 Polyester spunbond E5030 (Asahi Kasei Kogyo)
30g of powdered Aqua Keep 10SH (manufactured by Steel Chemical Industry Co., Ltd., product name), which is an acrylic super water absorbent, was applied to a polyester long fiber nonwoven fabric (product name) coated with an acrylic adhesive. d After uniformly dispersing and maintaining, polyester spunbond E5030 coated with acrylic adhesive is layered on top of the polyester spunbond E5030 and bonded by applying pressure with a roller, each sheet is dehydrated by vacuum drying and used as a support. I got something like that. Next, the average molecular weight is 1
30 parts of polyethylene oxide with an average molecular weight of 10,000, 20 parts of a polyethylene oxide copolymer with an average molecular weight of 10,000 containing one molecule of bisphenol in the molecule, and 4.4'-bis(
85 parts of hydroxyethyl)bisphenol and 3 parts of silicon dioxide with an average particle size of 15 microns were added to 500 parts of tricrene, and the mixture was heated and stirred at 70°C in a nitrogen atmosphere to dissolve the polyol component and uniformly form the silicon dioxide powder. Further, 0.05 parts of dibutyltin diacetate and 4.5 parts of isophorone diisocyanate were added as catalysts, and the reaction was carried out at 70°C for 5 hours. A PAO)-based super absorbent material (film water absorption capacity: 20 times by TB method) was obtained.

The sheet material was immersed in this PAO-based high-handling super-absorbent liquid solution (PAO-based high-handling super-absorbent pure concentration 15%), squeezed with a mangle to a squeezing rate of 200%, and dried. Table 1 shows the results of measuring the water absorption capacity in artificial seawater (manufactured by Heshu Yakuhin Co., Ltd., trade name) of the obtained sheet-like material and, as a comparative example, the sheet-like material before PAO processing.

As shown in Table 1 (Table 1), it is clear that the water absorbing material of Example 1 of the present invention has a significantly improved water absorption capacity for artificial seawater compared to that of Comparative Example 1.

Further, when the water-absorbing material of Example 1 was examined for water running prevention properties in artificial seawater at a packing density of 015 g/d, it was found to be good at 80% sodium bicarbonate.

Examples 2 to 9 Cashmilon (trade name of acrylic synthetic single fiber produced by Asahi Kasei Industries, Ltd.) 3D tow of 650,000 denier was cut using a tow tension cutting machine, and 2. /
A yarn of 3ONm, α=0.6 to 65, and boiling water shrinkage rate of 26% was prepared. This yarn was steam-set at 15 minutes at 0.degree. C. to obtain a spun yarn having a bulkiness of 12 cJ/g.

Next, 50 parts of polyethylene oxide polymer with an average molecular weight of 10,000 and 4.4'-bis(hydroxyethyl)bisphenol A were thoroughly dehydrated by vacuum drying.
5 parts' to 1,500 parts of trichlene in a nitrogen atmosphere from 30 to 4
After completely dissolving at 0°C, 0.2 parts of triethylenediamine was added as a catalyst, and 3.5 parts of tolylene diisocyanate were further added, and the reaction was carried out at 70°C for 5 hours. Then, the average particle size was 15 μm. 3 parts of silicon dioxide was processed and further heated and stirred at the same temperature for 1 hour, resulting in a solid content of 10
To obtain a solution of a water-absorbing polymer composition uniformly dispersed at ) (trade name) to obtain various water-absorbing spun yarns with different amounts of polyethylene oxide attached.

Table 2 shows the results of evaluating the water-absorbing spun yarn thus obtained in terms of water absorbency and anti-water running properties.

In addition, water absorption evaluation was measured by TB method and CB method,
Commercially available purified water was used as pure water, and aquamarine was used as artificial seawater.

The evaluation of water running prevention property was 2 at a packing density of 0.5 g/cd.
It is shown as the length of water penetration after 4 hours.

Below is Table 2 in the margin * TB method immersion time 10 minutes Examples 10 to 21 Yarns with different bulkiness were created by changing the spinning method. Next, these spun yarns were treated in the same manner as in Example 2 using a luene solution of the polyalkylene oxide superabsorbent obtained in the same manner as in Example 2, and A water running prevention material having a water absorbent adhesion amount of 10-50% was obtained. Table 3 shows the results of evaluating the water absorption and water running properties of the water-absorbing spun yarn thus obtained.

Spinning method (1) Bulk height: 6 cnt/g Spinning method: Suffu spinning, 1152 Nm, K (number of twists) -95 Raw cotton: Calamilon 2dX51 (2) Bulk height: 8 c/g Spinning method: Worsted spinning, i/3ONm , K=65 Raw cotton: Cashmilon 3d 650,000 denier (4) Bulk height: 16cn!/g Spinning method: Worsted spinning, 2/3 ONm, K-65, k = 0.6 Raw cotton: Cashmilon high shrinkage raw cotton A25.4d x 840,000 denier tow is usually 30% raw cotton with boiling water shrinkage of 40% hot-stretched using the method of making high shrinkage cotton, and 70% raw cotton of Cashmilon 3dX70-127++m. Using raw cotton, the bulk height is 6 d/g and the thickness is 1.0 by carding and needle punching.
Created a dragon non-woven fabric. In addition, when needle bunching this nonwoven fabric, nylon 15d monofilament and cheesecloth having a basis weight of 30 g/rrf were used as reinforcing materials.

The thus obtained nonwoven fabric was immersed in a 30% trichlene solution of the polyalkylene oxide superabsorbent material used in Example 10, and then squeezed with a mangle to adhere 30% of the polyalkylene oxide superabsorbent material to a width of 4 cm. It was cut into a tape shape.

This tape was packed in the same manner as in Example 2 to a packing density of 0°5 g.
/ cta, the water running prevention property was 601 weight in artificial seawater, showing good water running prevention property.

Moreover, the workability during cable manufacturing and connection work using this tape was also good.

Example 23 A copolymer of 80% by weight of acrylonitrile and 20% by weight of acrylic acid was obtained by an aqueous suspension polymerization method using azobisisobutyronitrile as a polymerization catalyst. The obtained polymer was spun using 65% nitric acid, and the resultant polymer was spun in boiling water for 60 min.
Stretched twice. This drawn yarn was neutralized with a 0.4% aqueous sodium hydroxide solution containing 2% sodium chloride, thoroughly washed with ethanol, and dried to form acrylonitrile 7.
5゜4% by weight, sodium acrylate 24.6 positive ff1
A fibrous copolymer having a single fiber fineness of 3d was obtained.

Next, this fiber was cut into 76 pieces, passed through a card, and needle-bunched to produce a nonwoven fabric with a basis weight of 150 g/rrr. Next, 50 parts of polyethylene oxide polybutylene oxide copolymer with an average molecular weight of 20,000 and containing polybutylene oxide with a molecular weight of 2000 in the molecule, and 4.4'
- Thoroughly dehydrate 3 parts of bis(hydroxyethyl)bisphenol A, add them to 500 parts of tricrene, and dissolve them uniformly at 70°C, then uniformly disperse 3 parts of silicon dioxide with an average particle size of 15 microns, 0.05 part of dibutyltin diacetate was added as a catalyst, and further 4.3 parts of hexamethylene diisocyanate were added, and the reaction was carried out at 70°C for 5 hours. The nonwoven fabric was immersed in a toluene solution of the polyalkylene oxide superabsorbent material thus obtained, and then squeezed with a mangle and dried.

Table 4 shows the water absorption performance of the thus obtained acrylic fibrous superabsorbent material treated with a polyalkylene oxide-treated superabsorbent solution.

Table 4 * TB method Cleaning time 10 minutes As shown in Table 4, in the case of Comparative Example 4 without PEO treatment, the swelling degree of artificial seawater is significantly lower than that of pure water, but It can be seen that the degree of swelling of artificial seawater in the examples shown is significantly improved compared to the comparative examples.

In addition, the samples of Examples 22 and 23 shown in Table 4 showed excellent durability in the rot test, and the packing density was 0.4 g.
The water running prevention test conducted on /- was also good, with the length being 20 cm or less in 24 hours. Single fiber fineness: 3d, fiber length: 50 fins, intrinsic viscosity (1,3) in dimethylformamide (DMF) solution at 30°C 4 parts
The fibers were immersed in 96 parts of a 0% (7.5 mol/1000 g solution) aqueous caustic soda solution, boiled for 10 minutes while stirring, and then washed with water to remove the residual alkali in the fibers, and then dried to a white to slightly yellow color. A water-absorbing fiber exhibiting the following properties was obtained. Next, the fibers were passed through a card and needle bunched to create a nonwoven fabric with a basis weight of 150 g/rrr. This nonwoven fabric was immersed in a toluene solution of the PA6 water absorbent used in Example 1, and then squeezed with a mangle and dried.

Table 5 shows the water absorption performance of the acrylic fibrous superabsorbent material thus obtained.

Table 5 * TB method immersion time: 10 minutes The fibrous superabsorbent material of the present invention exhibits excellent water absorbency for metal ion-containing water; for example, the water absorbency for artificial seawater (aquamarine) is 10 times higher using the TB method. , P is added to acrylic super absorbent spun yarn (1/3 Nm) which has twice the water absorbency by the CB method.
The product of the present invention, in which 50% pure EO-based water absorbent is attached, has a water absorbency of 24 times the above artificial seawater by the TB method, and a C
Method B achieved a significant improvement of 11 times.

Furthermore, when the nonwoven fabric of Example 25 was evaluated for water running properties at a packing density of 0.5/cA in the same manner as in Example 2, the water running properties were 79+U in artificial seawater, indicating good water running properties.

Examples 26 to 33 30 parts of polyethylene oxide resin with an average molecular weight of 100,000 which was sufficiently dehydrated by vacuum drying method and 20 parts of polyethylene oxide cobolimer with an average molecular weight of 6,000 containing 80% polyethylene oxide. and 5 parts of silicon dioxide with an average particle size of 7 microns along with 5 parts of bis(β-hydroxyethyl) terephthalate.
After melting the polyol component at 70 to 80°C in a nitrogen atmosphere, add 0.2 parts of triethylenediamine as a catalyst, and further add 4 parts of xylylene diisocyanate, and react at 70°C for 5 hours. . The resin solution thus obtained was cast in a glass petri dish and vacuum dried at 40°C to obtain a film with a thickness of 0.1 nm. Note that this film is referred to as PE0-C.

In addition, PE film without the addition of colloidal silica fine powder
It is called 0-D. For these films, the adhesion with PET film, PE film, urethane-based UV curable film and the adhesion between these resin films was determined using 20 parts of polyalkylene oxide resin with an average molecular weight of 100,000,
and 0.05 parts of triethylenediamine with 5 parts of trichloride.
After completely dissolving it in a nitrogen atmosphere at 30-40''C, 0.1 part of 1-methylbenzo-2,5-diisocyanate was added and the reaction was carried out at 70℃ for 5 hours. The polyalkylene oxide superabsorbent material obtained by
Table 6 shows the results of a comparison with a film of PAO-E (referred to as PAO-E).

Adhesion evaluation conditions: Films cut to 2 crm width and 20 cm length were stacked on top of each other and placed on a Teflon film, a load of 100 g/c4 was applied to 5 cm from one end of the film, and the film was heated at 70°C for 24 hours and at 90°C. After processing for 24 hours at ℃, the film was left in a constant temperature room at 20℃ and 65% RH for 24 hours, and the resistance when peeling the film was measured using a Tensilon.
Adhesive strength.

Table 6 As shown in Table 6, the film of PE (1-E) shown in the comparative example adheres to other films, but as shown in this example, the film of PE0-C does not adhere to other films even at 90°C. The film of PE0-D does not adhere to the film of 7.
At 0°C, no adhesion with other films occurs, and even at 90°C, only weak adhesion of 100 g/cm occurs.

〔Effect of the invention〕

The water running prevention material of the present invention exhibits a good water running preventing effect on water containing metal ions such as seawater.

In addition, the film of the water-absorbing polymer compound used in the present invention is 7
Since it does not exhibit adhesive properties even at temperatures above 0°C, even if the temperature inside the optical fiber cable rises, the constituent materials of the cable do not adhere to each other, and therefore no transmission loss due to distortion of the optical fiber occurs. Furthermore, even if water enters the inside of the cable, it will not cause corrosion, so it can withstand long-term use.

[Brief explanation of the drawing]

Fig. 1 is a cross-sectional view showing an optical fiber cable filled with the water run-preventing material of the present invention, Fig. 2 is a cross-sectional view showing a conventional optical fiber cable, and Fig. 3 is a cross-sectional view of a conventional optical fiber cable. FIG. 1... Tension member, 2... Optical fiber core, 3... Filler, 3A... Water-absorbing spun yarn, 4...
- Pressure wrapping tape for preventing water running, 4A...Water absorbing pressure wrapping tape for preventing water running, 5...Outer cover, 6...Water absorbing tape for preventing water running. Agent Patent Attorney Takenaga Kawakita Figure 3

Claims (2)

[Claims] (1) On the surface of a support made of a non-perishable polymer compound,
(A) a water-soluble polyalkylene oxide polyol having two or more hydroxyl groups with an average molecular weight of 4,000 or more; and (B) a water-soluble polyalkylene oxide polyol having a melting point or softening point of 80°C or more and having two or more hydroxyl groups and/or amino groups. and (C) a polyisocyanate compound, a film of a water-insoluble water-absorbing polymer compound is formed, and the adhesion ratio of the film to the support is 5% by weight. % or more, a water running prevention material for optical fiber cables. (2) On the surface of a support made of a non-perishable polymer compound,
(A) a water-soluble polyalkylene oxide polyol having two or more hydroxyl groups with an average molecular weight of 4,000 or more; and (B) a water-soluble polyalkylene oxide polyol having a melting point or softening point of 80°C or more and having two or more hydroxyl groups and/or amino groups. and (C) the polyisocyanate compound, a film of a mixture of a water-insoluble water-absorbing polymer compound and an inorganic metal compound is formed, and A water running prevention material for optical fiber cables, characterized in that the adhesion ratio of the film is 5% by weight or more.