JPH0424285A - Polyolefin nonwoven sheet - Google Patents

Abstract

PURPOSE:To obtain a nonwoven sheet having excellent antistatic properties without impairing waterproofness by applying a specific phosphate salt compound to a polyolefin nonwoven sheet. CONSTITUTION:A polyolefinic polymer is formed into a three-dimensional netlike fiber by, e.g. a flash spinning method and the resultant nonwoven polyolefin sheet is presubjected to corona discharge treatment. A textile treating agent expressed by the formula (M is lithium, sodium potassium, H or ammonium; m and n are 1 or 2), e.g. a blend of a monomethoxy lower alkyl phosphate salt with a bismethoxy lower alkyl phosphate salt at 1:1 molar ratio in an amount of >=0.01wt.% owf is applied to the resultant nonwoven polyolefin sheet to afford the objective nonwoven polyolefin sheet, having waterproofness and simultaneously excellent in antistatic properties.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a sheet that is waterproof and has excellent antistatic properties. The present invention relates to a polyolefin nonwoven sheet that has excellent waterproof and antistatic properties and can be preferably used as a sheet for clothing and the like.

[Conventional technology]

Various types of polyolefin nonwoven sheets are conventionally known for use in the above-mentioned applications. For example, a non-woven sheet obtained by spinning fibers based on a conventional synthetic fiber spinning method and pulling them at high speed using a high-speed air stream, a non-woven sheet obtained by a melt-blowing method, and a polyolefin made into fibrillar three-dimensional network fibers by a so-called flash spinning method. A non-woven sheet made of carbon fibers is known. Nonwoven sheets produced by flash spinning are characterized by the fact that the constituent fibers are extremely fine and have a complicated cross-sectional shape, and these characteristics are used for various purposes.

When used in the above-mentioned applications, the nonwoven sheet is required to have waterproof properties and antistatic properties. In order to meet this demand, Japanese Patent Publication No. 55-51068 states:
If a fiber treatment agent that is a compound of the chemical formula MnRz-nPO4 (n is 1 or 2) and is a mixture of a compound with R of 1 and a compound with R of 2 in approximately equimolar amounts will impair waterproofness. It is disclosed that antistatic properties can be imparted without causing any damage.

[Problem to be solved by the invention] The structure disclosed in Japanese Patent Publication No. 55-51068 is
A fiber treatment agent consisting of a compound can impart waterproofness and antistatic properties to the nonwoven sheet, but it is necessary to use this fiber treatment agent in an amount of at least 0.19% by weight of the fiber. be. However, when applying these fiber treatment agents to non-woven sheets, it is often the case that the amount applied is as small as possible due to odor and printing characteristics, and the amount applied to the fibers in the first treatment requires at least 0.1%. Processing agents have a problem in that their range of practical applications is limited.

The present invention solves the problems of the previously known fiber treatment agents that can impart both waterproofness and antistatic properties, and provides practically sufficient waterproofness even when applied in a small amount. By discovering a fiber treatment agent that can impart antistatic properties to a nonwoven sheet, and by adding the fiber treatment valve, it has both waterproof and antistatic properties, and improves product characteristics such as odor, especially oil-based offset ink printing and UV rays. It is an object of the present invention to provide a polyolefin nonwoven sheet that has excellent usability properties such as printing properties such that the drying speed of ink becomes faster in offset printing.

[Means to solve the problem]

The object of the present invention is achieved by a polyolefin nonwoven sheet characterized by containing a fiber treatment agent consisting of a compound represented by the following chemical formula in a weight percent of fibers of 0.01 or more.

M is lithium, sodium, is ammonium m is an integer between 1 and 2 n is an integer of 1 to 2.

The polyolefin nonwoven sheet of the present invention can be produced by a known method. For example, JP-A-61-160
No. 469 provides an example of a method for manufacturing polypropylene continuous filament nonwoven fabric, and JP-A-63-6107 provides an example of a method for manufacturing ultrafine polypropylene fibers.
Japanese Patent No. 40618 discloses an example of a nonwoven sheet having a sheath-core structure, in which the core is made of polyethylene terephthalate or a copolymer thereof and the sheath is made of polyolefin such as polyethylene or polypropylene. In addition, as an example of the flash spinning method, for example, Japanese Patent Publication No. 62-172
Publication No. 073 includes an example of high-density polyethylene,
-192598 discloses an example of polypropylene.

For example, a polyolefin polymer is dissolved under high temperature and pressure with halogenated carbon such as trichlorofluoromethane or trichlorotrifluoroethane, halogenated hydrocarbon such as methylene chloride, hydrocarbon such as cyclohexane, or a mixture thereof. After that, by applying a sudden pressure drop, this liquid material that gives the solution a structure that looks like it has undergone extremely fine phase separation is discharged from a spinning nozzle, giving orientation to the polymer and forming a three-dimensional network fiber (
so-called flash spinning). After shaking this onto a conhair belt and making it into a web, it is partially or fully crimped using a roll (smooth roll, embossed roll, etc.) kept at room temperature or an appropriate temperature (below the melting point of the polyolefin polymer) or a felt calendar. and form it into a sheet. This nonwoven sheet is made of fibers with extremely fine and complex cross sections.

The basis weight of the nonwoven sheet of the present invention is 30 to 200 g/
It is preferably 40 to 100 g/bo. 30g
If it is smaller than /bo, sufficient waterproofness cannot be obtained. Moreover, if it is too thick, the flexibility will be impaired and it will wrinkle or break during manufacturing, which is unfavorable from a quality standpoint.

A fiber treatment agent consisting of a compound represented by the chemical formula is applied to the obtained nonwoven sheet.

When M is potassium, the fiber treatment agent of the present invention consists of potassium monooxacycloalkyl methyl phosphate and potassium bisoxacycloalkyl methyl phosphate, and the molar ratio of the two is between 3:1 and 1:3. Yes, usually about a 1:1 ratio.

The fiber treatment agent of the present invention can be produced by a conventional method. For example, 1 mole of phosphorus pentoxide is added little by little to 3 moles of commercially available tetrahydrofurfuryl alcohol and stirred to produce mono- and bis-tetrahydrofurfuryl phosphate. The resulting product is neutralized using caustic soda or caustic potash to reach a predetermined hydrogen ion concentration (pH).
Adjust to.

A conventional method can be used to apply the fiber treatment agent. Specific examples include dip-nip method, coating method, gravure roll method, kiss roll method, spray method, and the like. The applied fiber treatment agent is dried and finished by hot air heating using a tenter or contact heating using a hot drum. or,
By performing corona discharge treatment in advance before applying the fiber treatment agent, the wettability of the surface of the nonwoven sheet can be improved and the application of the fiber treatment agent can be facilitated.

If corona treatment is not performed, add approximately 1 to 10% by weight of alcohol (ethanol, propatool, etc.) or acetone to the fiber treatment agent aqueous solution, or add Triton
0 (nonylphenylethylene oxide 8 mol adduct)
A nonionic surfactant such as 0.05 to 1.0% by weight may be added to the treatment liquid. 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 anionic, cationic, nonionic, and amphoteric surfactants, and synthetic resin emulsions. There is no problem even if it is mixed with other materials such as or latex.

The fiber treatment agent used in the present invention may also contain other compounds such as phosphates and other inorganic salts, as long as the effects are not affected. To avoid problems, the monobismethoxy lower alkyl phosphate salt of the compound represented by the chemical formula has a pH of 4 to 10.
It is preferable to use it by adjusting it accordingly. p of fiber treatment agent solution
If H is too low, problems will occur, such as it being difficult to achieve an anti-static effect and the area around the machine being susceptible to rust. In addition, if the pH is too high, skin damage etc. may occur during handling.

The fiber treatment agent of the present invention exhibits an antistatic effect when applied to the nonwoven sheet in an amount of 0.01% by weight or more. Generally, the fiber treatment agent is 1
．． Although it has been practiced to apply 0% by weight, such a large amount is not economical, and depending on the type of fiber treatment agent, there may be an odor problem, and it is also unfavorable in terms of printing characteristics. In this regard, the nonwoven sheet of the present invention has a very small amount of 0.01% by weight or more, which is much smaller than the amount of fiber that is conventionally thought to be applied in order to obtain the required waterproof and antistatic properties. By giving, you can achieve your goals. However, depending on the intended use, it may be added in an amount of 0.2 to 0.3% by weight to provide even better antistatic properties, and may be softened or embossed on the surface for use in clothing, etc. In this case, the treatment liquid is less likely to form a film, and it may be necessary to increase the amount of the fiber treatment agent applied to about 0.5% by weight.

[Examples] The present invention will be explained in detail below using Examples. Prior to describing 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 charging a test piece in a corona discharge field, this charging voltage is 1
The antistatic properties were evaluated by measuring the time (half-life) until decay to /2 (JIS-L-1094).

This measurement method is suitable for evaluating the static electricity decay characteristics of woven or knitted materials. A half-life of 60 seconds or less is acceptable, and a half-life of 10 seconds or less is more preferable.

・Water resistance test Measured using the hydrostatic pressure method of method A and method B of the waterproof test method for textile products (JIS-L-1092). In the water resistance test, it is sufficient that the water pressure resistance (alHt O) of the treated nonwoven sheet is 70% or more of the water pressure resistance (ttrta Hz O) of the untreated nonwoven sheet.

- Glazing Charcoal Test (Spray Test) Measured using the waterproof test method for textile products (JIS-L~1092). In the deicing charcoal test (spray test), although there was moisture on the surface, there was no wetting of water droplets on the back surface, and a deicing charcoal of 70 or higher was considered to have passed.

・Moisture permeability test Method for testing moisture permeability of textile products (JIS-L-1099)
Method A-1 (calcium chloride method): This test method involves creating an air layer inside a moisture-permeable cup, using the test piece as a boundary, drying the inside of the moisture-permeable cup with calcium chloride, and keeping the outside of the moisture-permeable cup in a humid condition. During this period, water vapor is forcibly absorbed by the smoke pressure difference, and the amount of permeation is measured to evaluate moisture permeability. Therefore, this test method is suitable for measuring moisture permeability under wearing conditions where the inside of clothing is humid, and can be applied to all textile materials including moisture-permeable waterproof materials. This moisture permeability is the moisture permeability Cg/rd・day) of the treated nonwoven sheet.
Moisture permeability of untreated nonwoven sheet (g/n (day) 70
% or more is sufficient.

Application of the fiber treatment agent and preparation of measurement samples in each of the Examples described below were performed in the following manner.

The nonwoven sheet was immersed in a fiber treatment agent solution and nipped 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 mixture was kept in a prespecified constant temperature room at 20±2°C and 40±2% RH for 24 hours or more.

1-2, ・1-2 A polyolefin nonwoven sheet made 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 area through a nozzle, the solvent is flashed to form fibrillated reticular fibers, which are then deposited on a wire gauze and bonded under heat and pressure using a calendar roll at 130°C. A nonwoven polyethylene sheet having a basis weight of 63 g/rrr and a thickness of 0.2 m was obtained. This nonwoven sheet was subjected to corona discharge treatment, and various fiber treatment agents as shown in Table 1 were applied at 0.2
The treatment was performed with an aqueous solution of % by weight. All of these fiber treatment agents are shown in Table-1.

The compound was a mixture of potassium mono-, bis-oxacycloalkylmethylphosphate (1:1 molar ratio).

Each of these fiber treatment agents was applied to the nonwoven sheet in an amount of 0.05% by weight based on the weight of the fibers. Since the surface of the nonwoven sheet had been previously subjected to a corona discharge treatment, it was possible to easily attach it to the nonwoven sheet.

Table-1 All treated nonwoven sheets exhibited excellent antistatic properties.

3-6.3 A polypropylene deposit nonwoven sheet consisting of three-dimensional network fibers was obtained by the same method as in Example 1.

This sheet was partially crimped with an embossing roll at 155°C to obtain a nonwoven sheet with a basis weight of 69 g/n (and a thickness of 0.22 mm). The fiber treatment agent consisting of potassium furfuryl phosphate was applied to the nonwoven sheet in varying amounts.The results are shown in Table 2.

Table 2 The fiber treatment agent according to the present invention is added to the nonwoven sheet in an amount of 0.01% by weight.
It can be seen that sufficient antistatic properties can be imparted by applying the above.

11. A polyolefin nonwoven sheet made of polypropylene was obtained by a conventional melt spinning method and a melt blowing method. Each of these nonwoven sheets had a basis weight of 40 g/rd.

The sheet was previously subjected to a corona discharge treatment, and then the effects of antistatic properties and water repellency were investigated when the metal (M) of the compound was changed as a fiber treatment agent.

The fiber treatment agent used consisted of mono- and bis-tetrahydrofurfuryl phosphate salts, and the hydrogen ion concentration (pH) of the fiber treatment agent solution was adjusted to between 6 and 7 (between the first and second equivalence points). The nonwoven sheet was treated so that the amount of fiber treatment agent applied was 0.2% by weight.

It was found that the antistatic effect and waterproof property did not substantially change even if the metal (M) was changed.

! A nonwoven sheet consisting of fibers with a sheath-core structure consisting of polyethylene in the sheath and polyethylene terephthalate in the core was obtained by a two-component melt spinning method. The basis weight of this non-woven sheet is 40
g/rd. The sheet was treated with an aqueous solution containing 0.5% by weight of a fiber treatment agent consisting of potassium mono- and bis-tetrahydropyran 2-methyl phosphate and 5.0% by weight of isopropyl alcohol, and dried to finish. The amount of fiber treatment agent adhered to this nonwoven sheet was 0.1% by weight. Moreover, the half-life of the ostometer was 1.3 seconds, and the value of tree bark (spray method) was 80.

12-14, '''j5-7 The polyethylene nonwoven sheet obtained in Example 1 was antistatically treated with a fiber treatment agent consisting of 1 mole of monotetrahydrofurfuryl phosphate potassium monotetrahydrofurfuryl phosphate. After processing, for comparison,
Antistatic processing was performed using a fiber treatment agent consisting of 1 mol of potassium monobutyl phosphate and 1 mol of potassium dibutyl phosphate, and treated sheets were prepared in which the amount of adhesion was varied so that the honest meter half-life was 60 seconds or less.

The odor of the treated sheets and the drying properties of the printing ink were compared.

Table 3 Comparison of odor is shown in Examples 12, 13, 14 and Comparative Example 5
Approximately 5CIIX5 for each 100g sample of ゜6.7
Cut into pieces of CIl size, place in a 500 d Erlenmeyer flask, and seal the narrow neck with a silicone rubber stopper. After leaving this condition in a constant temperature room at 24°C for 24 hours, remove the silicone rubber stopper and smell the opening.
Judgment was made using the graded odor intensity display method, and an odor intensity of 2 or less was considered a pass.

Table 4 6-stage odor intensity display method Regarding the drying time of ink, oil-based offset ink (
Impermeable ink: Compared to the ingredients of ordinary oil-based offset inks, the pigments, resins, drying oils, auxiliary agents, metal soaps, etc. remain unchanged, while the petroleum-based high boiling point solvent is kept to about 1%. ) printed on the entire surface in a size of 15cm x 20cm, and
Leave in a room at °C. Press the Sellotape against the printed surface every hour and check the time until the ink no longer transfers to the Sellotape, which is considered the drying time. A case where the drying took place within 1 to 4 hours was judged as a pass (◯), a case where the drying took place within 5 to 8 hours was judged as a semi-pass (△), and a case where the drying took place over 8 hours was judged as a failure (x).

The tetrahydrofurfuryl phosphate salt of the present invention is
It is found to be useful in terms of odor and ink drying properties.

[Effects of the Invention] The present invention allows the polyolefin non-woven sheet of the present invention to contain a fiber treatment agent having the following chemical formula of 0.01 or more based on the weight of the fibers, without impairing waterproof properties. Woven sheets can have excellent antistatic properties. In addition, it was confirmed through actual experiments that this fiber treatment agent has little odor and does not cause any problems in printability.

M is lithium, sodium, potassium, hydrogen or ammonium; m is an integer of 1 to 2; n is an integer of 1 to 2;

Claims (1)

[Claims] A polyolefin nonwoven sheet characterized by containing a fiber treatment agent consisting of a compound represented by the following chemical formula at 0.01% or more by weight of the fiber ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ M is lithium , sodium, potassium, hydrogen or ammonium m is an integer of 1 to 2 n is an integer of 1 to 2.