JPH03227454A - Polyolefin nonwoven sheet - Google Patents

Abstract

PURPOSE:To obtain a polyolefin-based nonwoven sheet excellent in waterproofness and antistatic properties by applying a specific amount of a textile treating agent composed of a specified compound thereto. CONSTITUTION:A polyolefin-based nonwoven sheet having 30-200g/m<2>, preferably 40-100g/cm<2> basis weight is treated in an aqueous solution of a textile treating agent composed of a compound expressed by the formula [R is 1-7C alkyl; M is lithium, sodium, potassium, hydrogen or ammonium; n is an integer of 1 or 2; AO is alkylene oxides, expressed by CH2CH2O or CH(CH3)CH2O alone or linked through block or random bonds; m is an integer of 1-10] to apply the aforementioned treating agent in an amount of >=0.01wt.% based on the fiber weight thereto.

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. More specifically, the present invention relates to a polyolefin nonwoven sheet having excellent waterproof and antistatic properties that can be preferably used as a sheet for packaging materials, protective clothing, windbreaker-1 raincoats, bedding, etc.

[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 MaRs-aPOa (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 any

[Problem to be solved by the invention]

A fiber treatment agent made of a compound having the structure disclosed in Japanese Patent Publication No. 55-51068 can impart waterproofness and antistatic properties to a nonwoven sheet, but this fiber treatment agent has a It is necessary to use at least 0.1%. However, when applying these fiber treatment agents to a nonwoven sheet, it is desired that the amount applied be as small as possible from the viewpoint of odor and printing characteristics, and the above-mentioned fiber treatment requires an application amount of at least 0.1%. The problem with these agents is that their range of practical use is limited.

The present invention solves the problems of the previously known fiber treatment agents that can impart both waterproofness and antistatic properties, and achieves practically sufficient waterproofness even when applied in an extremely small amount. We have discovered a fiber treatment agent that can impart antistatic properties to nonwoven sheets, and by applying this fiber treatment agent, we have both waterproofness and antistatic properties, and we also improve product properties such as odor, especially oil-based offset ink printing and UV rays. An object of the present invention is to provide a polyolefin nonwoven sheet that has excellent usability properties such as printing properties such that ink dries quickly 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.

(R-0-fAO+-=→-ir P O+ OM)
,-.

R is a C1-C7 alkyl group M is lithium, sodium, potassium, hydrogen or ammonium n is an integer of 1-2 -AO- is -CllzCH,O- or -CHCH,0-
Indicated by CH.

m is an integer of 1 to 10.

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 continuous filament nonwoven fabric. An example of a method for producing polypropylene ultrafine fiber is disclosed in Japanese Patent Application Laid-open No. 64-406.
Publication No. 18 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. Further, as an example of the flash spinning method, for example, Japanese Patent Publication No. 62-172073
The publication includes an example of high-density polyethylene,
No. 2598 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, the solution is given a structure that looks like it has undergone extremely fine phase separation.

This liquid is discharged from a spinning nozzle to give orientation to the polymer and form three-dimensional network fibers (so-called flash spinning), which is shaken off onto a conveyor belt to form a web, and then heated at room temperature or at an appropriate temperature. temperature (
The roll was kept at a temperature below the melting point of the polyolefin polymer (
(smooth roll, embossed roll, etc.) or partially or completely pressed using a felt calendar to form 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/rr
? , preferably 40 to 100 g/nf. 30g/
If it is smaller than A, 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.

The fiber treatment agent of the present invention is a monoalkyl alkylene oxide phosphate salt having an alkyl group consisting of methyl, ethyl, propyl, butyl, amyl, hexyl, and heptyl (that is, it also includes various alkyl isomers from methyl to heptyl). , a bisalkyl alkylene oxide phosphate salt, the molar ratio of the two being between 3:1 and 1:3, usually approximately 1:1.

In the case of potassium octyl cellosolve phosphate, potassium decyl cellosolve phosphate, potassium lauryl cellosolve phosphate, etc., there is a sudden increase in water permeability due to improved oiliness, which impairs the waterproof properties of polyolefin nonwoven sheets made of polyethylene and polypropylene. . Therefore, potassium octyl carpitol phosphate, potassium triethylene glycol monooctyl ether phosphate, etc. in which the number of added moles of ethylene oxide is further increased, have further increased hydrophilicity, and the antistatic waterproofing effect targeted by the present invention is not obtained. I can't. Furthermore, when the m number of alkylene oxide (AO) is 10 or more, the hydrophilicity increases, and when it is attached to a polyolefin nonwoven sheet, the water permeability of the nonwoven sheet increases and waterproofness is lost. Even in this case, between polyethylene oxide alone and polypropylene oxide alone, the polypropylene oxide alone is less likely to lose its waterproof properties.

C1 to C? which are made by block or random polymerization of polyethylene oxide and polypropylene oxide. Regarding the alkyl ether, polyethylene oxide alone and phosphate salts of analogous properties can be obtained.

A conventional method can be applied 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.

Further, by performing a corona discharge treatment in advance 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. Further, at the same time, water repellents such as valmitic acid triglyceride, stearic acid triglyceride, and dimethylpolysiloxane, oil repellents such as perfluoroalkyl phosphate and perfluoropolyethylene, and surfactants may be used in combination.

The fiber treatment agent used in the present invention may also contain phosphates and other inorganic salts as long as the effects are not affected. The monobisalkyl alkylene oxide phosphate salt of the compound represented by the chemical formula (% formula %) has a pita to 9, preferably 5 to 8 so that there is no problem even when such other compounds are mixed and used.
It is preferable to use it by adjusting it accordingly. p of fiber treatment agent solution
If H is too low, there will be problems such as the antistatic effect being difficult to produce or the parts around the machine will rust easily, and if pi is too high, skin problems 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 is practiced to apply 0% overlay, applying such a large amount is uneconomical and unprofitable, and depending on the type of fiber treatment agent, there is an odor problem, and it is also unfavorable in terms of printing characteristics. In the non-woven sheet of the present invention, a very small amount of 0.01% by weight or more is added to the fibers, which is much smaller than the amount that is conventionally thought to be applied to fibers in order to obtain the required waterproof and antistatic properties. By doing so, you can achieve your goal. 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.

〔Example〕

The present invention will be explained in detail with reference to Examples below. Prior to describing Examples, the method of measuring various physical properties of the nonwoven sheet of the present invention will be explained.

・Antistatic property (half-life measurement method) After charging a test piece in a corona discharge field, this charging voltage is 1
The antistatic property was evaluated by a method of measuring the time (half-life) until it decays to 72% (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 methods A and B of the waterproof test method for textile products (JIS-L-1092). In the water resistance test, the water pressure resistance (saHzO) of the treated nonwoven sheet was It is sufficient to maintain 70% or more of the water pressure resistance (gemHzo) of the woven sheet.

- Wood bark test (spray test) Measured using the waterproof test method for textile products (JIS-L-1092). In the tree bark test (spray test), although there was moisture on the surface, there was no water droplet moisture on the back surface, and a tree bark 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 time, water vapor is forcibly absorbed due to the vapor 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. The moisture permeability (Cg/rtr・day) of the treated nonwoven sheet is 70% of the moisture permeability (g/n?・day) of the untreated nonwoven sheet.
It's fine if you keep the above.

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, and then conditioned in a prespecified constant temperature room at 20±2°C and 40±2% RH for over 24 hours.

1-3 1-3 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/nf and a thickness of 0.2 mm was obtained. This nonwoven sheet was subjected to corona discharge treatment and treated with a 0.2% aqueous solution of various fiber treatment agents as shown in Table 1. These fiber treatment agents were all mixtures (1:1 mole ratio) of potassium monoalkyl cellosolve phosphate and potassium bis-alkyl cellosolve phosphate having alkyl groups shown in Table 1.

Each of these fiber treatment agents was applied in an amount of 0.05% by weight to the nonwoven sheet. 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.

All of the treated non-porous sheets showed excellent antistatic properties, but
It can be seen that the good water resistance of the nonwoven sheet is lost when increasing above Cm (octyl).

4-8, '4 Antistatic property and water pressure resistance when the number of moles of ethylene oxide added to the butyl alcohol ethylene oxide adduct potassium phosphate as a fiber treatment agent to the polyethylene nonwoven sheet obtained in Example 1 was changed. We investigated the effects. In addition, the hydrogen ion concentration (pH) of the fiber treatment agent solution is between 5 and 8 (
(between the first and second equivalent points) and added 0.1% by weight of each to the nonwoven sheet.

Table 2 Even when the number of moles of ethylene oxide added to butyl alcohol increased from 1 to 10, good results were obtained in terms of spray bark and water pressure resistance. However, if the number of moles of ethylene oxide added is too large (too much), the spray coating tends to have poor bark and water pressure resistance.

9-14, 5 As a fiber treatment agent, a fiber treatment agent consisting of butyl cellosolve potassium phosphate was applied to the polyethylene nonwoven sheet obtained in Example 1 in varying amounts.

The results are shown in Table-3.

Table-3 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.

A polypropylene deposit nonwoven sheet consisting of three-dimensional network fibers was obtained in the same manner as in Example 1 for prong U construction.

This sheet was partially crimped using an embossing roll at 155° C. to obtain a nonwoven sheet having a basis weight of 69 g/rrf and a thickness of 0.22 m. The nonwoven sheet was previously subjected to a corona discharge treatment, and a fiber treatment agent consisting of potassium heptyl cellosolve phosphate and potassium propylene glycol monoheptyl ether phosphate was applied at 0.02% each.
% by weight, 0.03% by weight was applied. The honest meter half-life of the non-woven sheet is 1.2 seconds and 1.1 seconds, respectively, and the half-life of the non-woven sheet is 70 and 8 seconds, respectively.
0, and has sufficient antistatic effect and water repellency.

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 date of 40 g/rtf. The sheet is previously subjected to a corona discharge treatment, and then subjected to a fiber treatment consisting of a mixture of potassium monoethyl cellosolve phosphate and potassium bis(ethyl cellosolve) phosphate in a ratio of 3 to 1.1 to 1.1 to 3 moles. The agent was given.

The amount of fiber treatment agent attached to these nonwoven sheets was 0.
．． 1% by weight, 0.11% by weight and 0.08% by weight. The honest meter half-lives of the nonwoven sheet are 1.7 seconds, 1.2 seconds, and 1.4 seconds, respectively, and the creeping bark (spray method) is 80, 80, and 90, respectively, and has a sufficient antistatic effect. It has water repellency.

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/n? Met. The sheet was treated with an aqueous solution containing 0.5% by weight of a fiber treatment agent consisting of potassium methyl cellosolve 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. In addition, the half-life on the Honestometer was 1.3 seconds, and the value on tree bark (spray method) was 80.

21-24, 6 The antistatic and water-repellent effects of the polyethylene nonwoven sheet obtained in Example 1 were investigated when the compound metal (M) was changed as a fiber treatment agent.

The fiber treatment agent used was composed of butyl cellosolve phosphate salt, and the hydrogen ion concentration (p
H) was adjusted to between 5 and 8 (between the first and second equivalent points), and the nonwoven sheet was treated so that the amount of the fiber treatment agent attached 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.

25-27 7-10 The polyethylene nonwoven sheet obtained in Example 1 was subjected to antistatic treatment using a fiber treatment agent consisting of 1 mol of monobutyl cellosolve phosphate potassium and 1 mol of subbutyl cellosolve phosphate potassium, and then compared. As a result, antistatic treatment was performed using a fiber treatment agent consisting of 1 mole of potassium monobutyl phosphate and 1 mole of potassium dibutyl phosphate, and treated sheets were created with varying amounts of adhesion so that the half-life of the honest meter was 60 seconds or less. . The odor of the treated sheets and the drying properties of the printing ink were compared.

Comparisons in the back are Examples 25, 26, 27 and Comparative Example 7
100g of samples of ゜8, 9.10 each about 501
Cut into 51×51 pieces, place in a 500× Erlenmeyer flask, and seal the silk opening 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, sniff the inside of the opening, and use the normally used 6
Judgment was made using the graded odor intensity display method, and an odor intensity of 2 or less was considered a pass.

Table - 76-level odor intensity display method Regarding the drying time of ink, see the table below for 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%. ) to the size of 15C1lX20C11,
Leave it in a room at 24°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 (0), a case where the drying took place within 5 to 8 hours was judged as a semi-pass (Δ), and a case where the drying took place over 8 hours was judged as a failure (x).

It can be seen that the butyl cellosolve phosphate salts of the present invention are useful in odor and ink drying properties.

〔Effect of the invention〕

The present invention allows the polyolefin nonwoven sheet of the present invention to contain a fiber treatment agent having the following chemical formula in an amount of 0.01 or more based on the weight of the fiber, thereby providing excellent properties to the polyolefin nonwoven sheet without impairing waterproof properties. It can have antistatic properties. In addition, it has been confirmed through actual experiments that this fiber treatment agent has little odor and does not cause problems in printability.

(R-0-+AO), →GOPO-←o M) s-R is Cr"C't alkyl group M is lithium, sodium, potassium, hydrogen or ammonium n is an integer from 1 to 2 -AO- is -Clff1Cl (10- or -cucnt
CI denoted by o-.

m is an integer from 1 to 1O.

Claims (1)

[Scope of 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 fibers ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ R is C_1 ~C_7 alkyl group M is lithium, sodium, potassium, hydrogen, or ammonium n is an integer of 1 to 2 -AO- is -CH_2CH_2O- or ▲There are numerical formulas, chemical formulas, tables, etc. The alkylene oxides shown by ▼ are alone or blocks or randomly combined m is an integer from 1 to 10.