JP2879935B2 - Non-woven polyolefin sheet - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a sheet having waterproofness and excellent antistatic properties. More specifically, the present invention relates to a nonwoven polyolefin sheet having excellent waterproof and electrostatic properties, which can be preferably used as a sheet for packaging materials, envelopes, protective clothing, windbreakers, raincoats, sleeping bags, and the like.

[Conventional technology]

Conventionally, various sheets are known as a nonwoven polyolefin sheet used for the above-mentioned applications. For example, a nonwoven sheet obtained by drawing a fiber spun based on a normal synthetic fiber spinning method by a high-speed air flow at a high speed, a nonwoven sheet by a melt blow method, or a polyolefin into a fibril three-dimensional network fiber by a so-called flash spinning method. Known nonwoven sheets are known. The non-woven sheet formed by the flash spinning method is characterized in that the constituent fibers have an extremely fine and complicated cross-sectional shape, and is used for various purposes by utilizing the characteristics.

When used for the above-mentioned applications, it is required that the nonwoven sheet has waterproofness and antistatic properties. The Japanese Patent Publication No. Sho 55-51068 in order to meet such demands, (the n 1 or 2) the formula M _n R _3-n PO ₄ A compound of the compound and compounds wherein R is a 2 R 1 is It is disclosed that antistatic properties can be imparted without impairing waterproofness by using a fiber treatment agent mixed in an approximately equimolar amount.

[Problems to be solved by the invention]

The fiber treating agent comprising the compound having the constitution disclosed in Japanese Patent Publication No. 55-51068 can impart waterproofness and antistatic property to the nonwoven sheet together. It is necessary to use at least 0.1% in%. However, when applying these fiber treating agents to a non-woven sheet, it is desired that the amount given is as small as possible from the viewpoint of odor and printing characteristics, and in the above-mentioned fiber treating agent requiring an application amount of at least 0.1%, There is a problem that the range of use is practically limited.

The present invention solves the above-mentioned problems of the fiber treatment agent capable of imparting both the conventionally known waterproofness and antistatic properties, and has a sufficiently sufficient waterproofness for practical use even with a very small amount of application. We found a fiber treatment agent that can impart antistatic properties to nonwoven sheets, and by applying the fiber treatment agent, we have both water resistance and antistatic properties, as well as product characteristics such as odor and especially oil-based offset ink printing and UV It is an object of the present invention to provide a nonwoven polyolefin sheet having excellent use characteristics such as printing characteristics such as a high ink drying speed in offset printing.

[Means for solving the problem]

The object of the present invention is attained by a nonwoven polyolefin sheet containing a fiber treating agent comprising a compound represented by the following chemical formula in an amount of 0.01 or more in terms of fiber weight%.

R is hydrogen or a methyl group M is lithium, sodium, potassium, hydrogen or ammonium n is an integer of 1-2.

The nonwoven polyolefin sheet of the present invention can be produced by a known method. For example, JP-A-61-160469 discloses an example of a method for producing a polypropylene continuous filament nonwoven fabric, and JP-A-63-6107 discloses an example of a method for producing a polypropylene ultrafine fiber, which is disclosed in JP-A-64-40618. Discloses an example of a nonwoven sheet having a sheath-core structure, in which a core portion is made of polyethylene terephthalate or a copolymer thereof and a sheath portion is made of a polyolefin such as polyethylene or polypropylene. Also, as an example of the flash spinning method,
For example, Japanese Patent Publication No. 62-172073 discloses an example of high-density polyethylene, and Japanese Patent Publication No. 62-192598 discloses an example of polypropylene.

For example, after dissolving a polyolefin-based polymer under high temperature and high pressure with a halogenated carbon such as trichlorofluoromethane, trichlorotrifluoroethane, a halogenated hydrocarbon such as methylene chloride, a hydrocarbon such as cyclohexane or a mixture thereof. By giving a sudden pressure drop, the solution is given a structure as if it had very fine phase separation. This liquid is discharged from a spinning nozzle to give orientation to the polymer and to form a three-dimensional network fiber (so-called flash spinning). This is shaken down on a conveyor belt, formed into a web, and then partially or entirely pressed by a roll (smooth roll, embossing roll, etc.) maintained at room temperature or an appropriate temperature (below the melting point of the polyolefin polymer) or a felt calender. , Into a sheet. This nonwoven sheet consists of fibers having a very fine and complex cross section.

The basis weight of the nonwoven sheet of the present invention is 30 to 200 g / m ² , preferably 40 to 100 g / m ² . If it is less than 30 g / m ² , sufficient waterproofness cannot be obtained. On the other hand, if the thickness is too large, the flexibility is impaired, and wrinkles and breaks occur during production, which is not preferable in terms of quality.

Chemical formula on the obtained non-woven sheet Is applied to the nonwoven sheet.

The fiber treating agent of the present invention comprises potassium monomethoxy lower alkyl phosphate and potassium bismethoxy lower alkyl phosphate when M is potassium, and the molar ratio of both is between 3: 1 and 1: 3, Is approximately one to one.

 The fiber treating agent of the present invention can be produced by a usual method.
come. For example, commercially available 3-methoxybutanol (Daice
Do not take 1 mole of phosphorus pentoxide for 3 moles.
Stir in small amounts and stir in mono, bismethoxybutyl
Produces phosphate. The result is caustic soda or
Is neutralized with potassium hydroxide and adjusted to a predetermined pH. or,
3-methyl-3-methoxybutanol (Solfit ; Kula
Product of the present invention)
Sodium 3-methyl-3-methoxybutylphosphate or
Can produce potassium.

An ordinary method can be applied as a method for applying the fiber treatment agent. Specific examples include a dip-nip method, a coating method, a gravure roll method, a kiss roll method, and a spray method.
The applied fiber treatment agent is dried and finished by hot air heating such as a tenter or contact heating by a hot drum. In addition, by performing a corona discharge treatment before applying the fiber treatment agent, the wettability of the surface of the nonwoven sheet is improved and the application of the fiber treatment agent can be facilitated.

When corona treatment is not performed,
Alcohols (ethanol, propanol, etc.) and acetone are added in an amount of about 1 to 10% by weight, or Triton x 100
A nonionic surfactant such as (nonylphenylethylene oxide 8 mol adduct) may be used in the treatment liquid in an amount of 0.05 to 1.0% by weight. Also, at the same time, water repellents such as palmitic acid triglyceride, stearic acid triglyceride, and dimethylpolysiloxane; oil repellents such as perfluoroalkyl phosphate and perfluoropolyethylene; surfactants such as anions, cations, nonions, and amphoteric surfactants; and synthetic resin emulsions. Or latex or the like may be mixed and used.

The fiber treating agent used in the present invention may contain phosphates or other inorganic salts if the effect is not hindered. Chemical formula so that there is no problem even if such other compounds are mixed and used The monobismethoxy lower alkyl phosphate salt of the compound represented by the formula (1) is desirably adjusted to pH 4 to 10 before use. When the pH of the fiber treating agent solution is too low, problems such as a difficulty in obtaining an antistatic effect and a tendency to rust around the machine occur. If the pH is too high, it may cause skin damage during handling.

The fiber treating agent of the present invention exhibits an antistatic effect when applied to a nonwoven sheet in an amount of 0.01% by weight or more. Generally, fiber treatment agent is 1.0
However, such a large amount is uneconomical, has an odor problem depending on the type of the fiber treatment agent, and is not preferable in terms of printing characteristics.
In that regard, in the nonwoven sheet of the present invention, in order to obtain the required waterproofness and antistatic property, the amount given to the fiber is much smaller than 0.01% by weight, which is much smaller than the amount applied to the fiber which is conventionally considered as common sense. , Can achieve the purpose. However, depending on the intended use, more excellent antistatic properties may be imparted by adding 0.2 to 0.3% by weight. For products that have been subjected to softness treatment or embossed surface for use in clothing, etc. The liquid does not easily form into a film, and the amount of the fiber treatment agent applied is 0.5% by weight
To some extent may be required.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to examples. Prior to the description of the examples, methods for measuring various physical properties of the nonwoven sheet of the present invention will be described.

・ Antistatic property (half-life measurement method) After a test piece is charged in a corona discharge field,
The antistatic property was evaluated by a method of measuring the time (half-life) until decay to 1/2 (JIS-L-1094). This measurement method is suitable for evaluating the static decay characteristics of a woven or knitted fabric. A half-life of 60 seconds or less is a pass, and a half-life of 10 seconds or less is more preferable.

-Water resistance test Measured by the hydrostatic method of Method A and Method B of the waterproof test method (JIS-L-1092) for textile products. Water pressure treatment nonwoven sheet in water resistance test (mmH ₂ O) it is sufficient to hold 70% or more of water pressure resistance of the untreated nonwoven sheet (mmH ₂ O).

・ Water repellency test (spray test) Measured using the waterproof test method (JIS-L-1092) for textiles. In the water repellency test (spray test), the surface was wet but no water droplets were wet on the back, and a water repellency of 70 or more was judged as acceptable.

・ Moisture permeability test Method for testing moisture permeability of textile products (JIS-L-1099) A-1
Method (calcium chloride method), in this test method, an air layer is provided in the moisture-permeable cup, the inside of the moisture-permeable cup is dried with calcium chloride with the test piece as a boundary, and the outside of the moisture-permeable cup is made humid. The water vapor is forcibly absorbed by the generated vapor pressure difference, the amount of permeation is measured, and the moisture permeability is evaluated. Therefore, this test method is suitable for measuring moisture permeability under wearing conditions in which the inside of the garment is humid, and can be applied to any fiber material including moisture permeable waterproof material. The moisture permeability may be such that the treated nonwoven sheet has a moisture permeability (g / m ² · day) of 70% or more of the moisture permeability (g / m ² · day) of the untreated nonwoven sheet.

The application of the fiber treatment agent and the adjustment of the sample for measurement in each of the examples described below were performed by the following methods.

The nonwoven sheet was immersed in a fiber treatment agent solution and nip between rubber rolls having a hardness of 75 ± 5 to remove excess solution from the surface of the nonwoven sheet. The wet nonwoven sheet was air dried, followed by drying at 105 ° C for 3 minutes. Next, the temperature was adjusted for at least 24 hours in a constant temperature room of 40 ± 2% RH at 20 ± 2 ° C. designated in advance.

Examples 1 to 3 and Comparative Examples 1 and 2 A nonwoven polyolefin sheet composed of three-dimensional network fibers is used. That is, a polyethylene polymer and a solvent are discharged from a high-temperature and high-pressure condition to a low-temperature and low-pressure region from a nozzle, and the solvent is flushed to form a fibrillated reticulated fiber, which is then deposited on a wire mesh. A nonwoven polyethylene sheet having a thickness of 63 g / m ² and a thickness of 0.2 mm was obtained. This non-woven sheet is subjected to corona discharge treatment,
Each of the fibers was treated with an aqueous solution containing 0.2% by weight of a fiber treating agent as shown in Table 1. In addition, these fiber treatment agents were all shown in Table-1.

The compound was a mixture of potassium mono and bis methoxy lower alkyl phosphates (1: 1 molar ratio).

Each of these fiber treatment agents is 0.05% by weight based on the fiber weight.
Applied to non-woven sheet. Since the surface of the nonwoven sheet had been subjected to corona discharge treatment in advance, it could be easily attached to the nonwoven sheet.

All of the treated nonwoven sheets exhibited excellent antistatic properties.

Examples 4 to 7 and Comparative Example 3 In the same manner as in Example 1, a nonwoven sheet of deposited polypropylene made of three-dimensional network fibers was obtained. This sheet was partially pressure-bonded with an embossing roll at 155 ° C to give a basis weight of 6
A non-woven sheet having a thickness of 9 g / m ² and a thickness of 0.22 mm was obtained. The nonwoven sheet was subjected to a corona discharge treatment in advance, and was applied to the nonwoven sheet while changing the amount of the fiber treating agent composed of mono-potassium bis (3-methoxybutyl) phosphate. Table 2 shows the results.
Shown in

It can be seen that the fiber treating agent according to the present invention can impart sufficient antistatic properties by giving 0.01% by weight or more to the nonwoven sheet.

Examples 8 to 11, Comparative Example 4 A nonwoven polyolefin sheet made of polypropylene was obtained by a usual melt spinning method and melt blow method. Each of these nonwoven sheets had a basis weight of 40 g / m ² . The sheet is subjected to a corona discharge treatment in advance, and thereafter,
The antistatic and water-repellent effects when the metal (M) of the compound was changed as a fiber treatment agent were examined.

The fiber treating agent used was composed of a mono, bis 3-methyl-3-methoxybutyl phosphate salt, and the hydrogen ion concentration (pH) of the fiber treating agent solution was between 6 and 7 (between the first and second equivalent points). The nonwoven sheet was treated so that the amount of the fiber treatment agent applied was 0.2% by weight.

It was found that the antistatic effect and the waterproofness were not substantially changed by changing the metal (M).

Example 12 By a two-component melt spinning method, a nonwoven sheet comprising a sheath-core structure fiber comprising a sheath polyethylene and a core polyethylene terephthalate was obtained. The basis weight of this non-woven sheet is 40
g / m ² . 0.5% by weight of a fiber treating agent comprising potassium mono-bis (3-methoxybutylphosphate) in the sheet
And an aqueous solution containing 5.0% by weight of isopropyl alcohol and dried to finish. The amount of the fiber treatment agent attached to this nonwoven sheet was 0.1% by weight. The half-life of the honest meter is 1.8 seconds, and the water repellency (spray method) is 90.
Met.

Examples 13 to 15, Comparative Examples 5 to 8 The polyethylene nonwoven sheet obtained in Example 1 was subjected to antistatic treatment with a fiber treating agent comprising 1 mol of potassium mono-3methoxybutylphosphate and 1 mol of potassium potassium bis3methoxybutylphosphate. As a comparison, antistatic treatment was performed using a fiber treating agent consisting of 1 mol of potassium monobutyl phosphate and 1 mol of potassium dibutyl phosphate, and the amount of adhesion was changed so that the half-life of the honestometer was 60 seconds or less. Created a sheet. The odor of the treated sheet and the drying property of the printing ink were compared.

For comparison of odor, 100 g of each of the samples of Examples 13, 14, 15 and Comparative Examples 5, 6, 7, 8 were cut into a size of about 5 cm × 5 cm, and 50
Place in a 0 ml Erlenmeyer flask and seal the narrow mouth with a silicone rubber stopper. After leaving it in a constant temperature room at 24 ° C for 24 hours in this state, remove the silicone rubber stopper, smell the odor from the opening, and judge by the commonly used 6-step odor intensity display method,
An odor intensity of 2 or less was considered acceptable.

The drying time of the ink is as follows: Oil-based offset ink (impervious ink; 1% of petroleum-based high-boiling solvent without pigments, resins, drying oils, auxiliaries, metal soaps, etc. as compared to the components of ordinary oil-based offset inks) To a size of 15cm x 20cm and left in a room at 24 ° C. The cellophane tape is pressed against the printing surface every hour, and the time when the transfer of the ink to the cellophane tape is not observed is determined as the drying time. Passed when dried within 1-4 hours (o), Semi-passed during 5-8 hours (８), 8
The time or more was rejected (x).

It can be seen that the 3-methoxybutyl phosphate salt of the present invention is useful in odor and ink drying properties.

〔The invention's effect〕

The present invention provides the nonwoven polyolefin sheet of the present invention, which contains a fiber treating agent having the following chemical formula in an amount of 0.01% by weight or more with respect to the fiber weight, without impairing waterproofness, and thereby has an excellent antistatic effect on the nonwoven polyolefin sheet. You can give the sex. Further, it was confirmed by experiments that this fiber treating agent had little odor and did not cause any problem in printability.

R is hydrogen or a methyl group M is lithium, sodium, potassium, hydrogen or ammonium n is an integer of 1-2.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D06M 13/292

Claims (1)

(57) [Claims] 1. A nonwoven polyolefin sheet containing a fiber treating agent comprising a compound represented by the following chemical formula in an amount of 0.01% or more based on fiber weight: R is hydrogen or a methyl group M is lithium, sodium, potassium, hydrogen or ammonium n is an integer of 1-2.