JP2705793B2 - Non-woven fabric consisting of three-dimensional network fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]   The present invention can be used as a special material for various surface materials
A useful reticulated fiber nonwoven fabric. For more information, see High
Highly fibrillated continuation of high density polyethylene
Highly opaque coating made of fibers with a reticulated morphology
For flexible, high-strength nonwoven fabrics
You. [Conventional technology]   Conventionally, three-dimensional reticulated fibers and non-woven fabrics made of these fibers
Known from. In other words, the technology for obtaining three-dimensional reticulated fibers
The polymer and solvent from high temperature and high pressure
Discharge to low temperature / low pressure area, flush solvent and remove fibers
Flash spinning technology is known. And this fiber
For example, as shown in Japanese Patent Publication No. 40-28125,
3D fibrous continuous, single, longitudinal pull
Stretched and essentially free of free ends, each fibril
A network of fibrils with a thickness of less than 2μ
You.   A non-woven sheet made of this fiber is also known.
As shown in Japanese Patent Publication No.
Or as shown in JP-B-42-19520
Non-woven fabric sheeted from filaments is well known.
You. Particularly disturbs the flash-spun fibers shown in the latter
Non-woven sheet made by spreading net-like fibers against a board
Is the preferred method. That is, flash spinning is
It uses the flushing power of the solvent,
Yarn speed is over 4,900m / min, reaching 9,000-13,500m / min
To obtain a nonwoven sheet with good productivity
Is extremely useful.   The non-woven sheet is kept in a non-woven form.
Heat bonding, depending on the durability, strength and other purposes.
Can be. Various types of heat-bonded non-woven fabric
It is known that it can take a state. That is, the surface
Paper-like non-woven fabric, non-woven with embossed pattern on the surface
Cloth, flexible finished cross-like non-woven fabric,
With light heat bonding only on the surface or no heat bonding
Non-woven fabric etc. And these are fine
Consists of fibril mesh fibers for high covering power, whiteness,
It is used for various purposes by taking advantage of its strength.   Various polymers can be used as the network fiber nonwoven fabric.
Are shown, but polyolefins, especially
High-density polyethylene is a reticulated fiber from flash spinning.
Many studies have been conducted as suitable for textile nonwovens.
You. [Problems to be solved by the invention]   Flash spun fiber with three-dimensional network structure
The non-woven fabric used takes advantage of its unique fiber structure
Thus, it is used for various purposes. And the nonwoven
Was spun as known from the aforementioned JP-B-42-19520.
Raw fibers are used. That is, the fibers spun by flash spinning
It is made of continuous fiber made by spreading the fiber with a baffle plate into a sheet.
Used as non-woven fabric.   This non-woven sheet retains shape, develops strength, and
Various types of thermal bonding are performed for the purpose of feathering and the like. Usually these
Is a multi-layered sheet with three-dimensional mesh fibers spread and deposited
It is different for each layer in the cross section direction of the sheet
It can be in the state of adhesion between fibers.   The nonwoven fabric targeted by the present invention is a multilayer
At least a part of the fiber layer has loose adhesion
It relates to a nonwoven fabric containing a kana layer. That is, the non-woven fabric
Surface or inner layer when non-woven fabric is peeled off in layers
With partially unfused, independent mesh-form fibers inside
Related to nonwoven fabric. Therefore, a nonwoven having such a structure
The fabric is bulky, flexible, has high covering power, and
The tear strength can be high.   For example, as such a nonwoven fabric, high-density polyethylene
Heat-bonds the three-dimensional mesh fiber sheet
Tyvek  14 types (E.I.du Pont) are known
You. This non-woven fabric has a relatively strong heat-bonded surface layer
And an inner layer that is relatively loosely bonded by heat.
It has an embossed pattern partially crimped. Soshi
When the non-woven fabric is peeled off as a layer,
Independent continuous net of 20 mm or more from the inner layer that is thermally bonded to the crab
It is possible to take out the fibers.   However, this conventionally known non-woven fabric has a three-dimensional mesh shape.
Opaque and covering, the most basic physical properties of fiber non-woven fabric
Practical satisfaction in force, tensile strength and tear strength
No ability.   As is well known, the same non-bonded fiber
When heat bonding is performed using a sheet, tensile strength and tear strength
The degrees are roughly inversely correlated. That is, these two strengths
In order to satisfy one strength, the other must be sacrificed
There is a problem that must be. Generally, unconnected
Although the fiber sheet of the wear has a large tear strength,
The tensile strength is weak, and the fuzz on the surface is not stopped at all.
Heat-bonding this to increase the tensile strength and improve the surface hair
Feathers can be good, but tear strength decreases.
To go. And the stronger the degree of thermal bonding, the stronger this tendency
Round.   On the other hand, in the case of a non-woven fabric composed of reticulated fibers,
Many applications make use of the unique high covering power, and the opacity is also important.
Important physical properties. As described above, for example, increase in tensile strength
The aim of increasing the degree of thermal bonding is this uncertainty
It will spoil the nature. And be too hot
Is transparent and film-like
U.   Use an embossing roll, etc. to spread over the surface of the nonwoven sheet.
The same applies to the case of partially thermocompression
Has a relationship between strength and tear strength and has excellent opacity
There is a demand for reticulated fiber non-woven fabrics.
There is no appearance of nonwoven fabric.   The present invention is highly opaque, has excellent covering power, and is flexible.
And high-strength, high-density polyethylene fibrillation
To provide a nonwoven fabric composed of three-dimensional reticulated fibers.
Target. [Means for solving the problem]   The present inventors have solved the aforementioned problems of the conventional nonwoven fabric.
As a result of intensive research, the present invention was completed.   That is, the object of the present invention is to provide a high-density polyethylene
The fibrillated three-dimensional reticulated fibers of the system
Arranged in different directions, deposited in layers, in a separate net-like form
A nonwoven fabric comprising a layer from which fibers can be taken out,
Ratio of the long-period scattering intensity by small-angle X-ray scattering
The three-dimensional network fiber is characterized by the following:
Achieved by woven fabric. And more preferably,
A nonwoven fabric having a long period of 150 ° or more in the reticulated fiber.
You.   The nonwoven fabric of the present invention will be described below in detail with reference to the drawings.
explain.   The nonwoven fabric of the present invention is a high-density polyethylene three-dimensional net.
Made of fibrous fibers, which are randomly arranged,
Has been deposited. That is, the flash spun substantially
Three-dimensional reticulated fibers that do not contain edges are spread
Are arranged so that they are generally uniform in all directions,
Continuous fibers are deposited in layers to form a nonwoven fabric
I have.   And the nonwoven fabric of the present invention has many fibers
At least some of the layers are loose enough to adhere
Layers. In other words, on the surface of the nonwoven fabric or on the inner layer
Has this layer and is partially unfused independent from this layer
The obtained reticulated fiber can be taken out. Independence here
For example, when the interlayer is peeled off,
Hold a bundle of fibrous material and pull it carefully.
And can be separated from other fibrous materials and pulled continuously.
Wei. Therefore, in this layer, the film
Not adhered to, not adhered at all, or loose
Adhered to.   Such independent mesh fibers retain the fiber form
It is a continuous fiber of 20mm or more.
Measurement of small angle scattering can be performed.   And the long circumference by small angle X-ray scattering of independent mesh fibers
Initial scattering intensity is 40 or less.
The characteristics of the microstructure of the resulting reticulated fiber appear. this child
Means that the characteristics of the reticulated fibers constituting the nonwoven fabric of the present invention are independent
This indicates that the reticulated fibers appear as they are. Soshi
The other part of the fiber has been subjected to a strong heat bonding process
The long-period scattering intensity ratio where the fiber shape remains
Shows little change compared to immediately after threading
doing.   On the other hand, independent
The reticulated fiber has a long-period size that tends to increase,
It is preferably 0 ° or more, and usually up to about 300 °
sell.   Usually, when manufacturing heat-bonded non-woven fabric,
The physical properties basically depend on the properties of the fibers that compose it.
It is clear that In other words, spread the fiber and make a sheet
Or how to heat bond the sheet
The physical properties of the non-woven fabric that can be obtained by
For the mechanical, thermal, and optical properties of the constituent fibers
Depends. For example, the mechanical properties of heat bonded nonwoven
The quality depends on the mechanical and thermal properties of the constituent fibers.
And the optical properties of the nonwoven
It is easy to understand that
Will be.   There are various methods for thermally bonding flash spun fiber sheets.
A known method is employed. And with high density polyethylene
Is the appearance of strength and shape retention as a nonwoven fabric, and the surface
Bonding is performed at a temperature close to the crystal melting point for fuzzing.
Therefore, when considering a heat-bonded nonwoven fabric, the heat-bonding property between fibers
Is strong and does not easily shrink during thermal bonding.
High mechanical strength of the fiber at high temperature near the bonding temperature
Is required as a fiber.   In this sense, conventionally known tertiary spun as-spun
The purpose of the present invention is achieved when a non-woven fabric is
The resulting nonwoven fabric cannot be obtained. That is, the conventionally known fiber is
Poor mechanical strength and large deterioration near the bonding temperature
And the mechanical strength (tensile
・ Tear etc.) is poor, whiteness and covering power are insufficient,
It had problems such as being noticeable.   Therefore, the same applicant as the present invention has
X-ray small angle as three-dimensional mesh fiber suitable for use in manufacturing
That the ratio of long-period scattering intensity due to scattering is below a predetermined value
Characterized by fibrillated high density polyethylene
A three-dimensional reticulated fiber was proposed (see Japanese Patent Application No. 62-169682).
The present inventors demonstrated the present invention using the three-dimensional reticulated fiber.
New three-dimensional reticulated fiber non-woven fabric
You.   The fiber for obtaining the nonwoven fabric of the present invention is a high-density polyethylene-based fiber.
Is a fiber composed of the polymer of And many
Consists of fine fibrils, essentially free of free ends
It is a continuous three-dimensional network fiber.   As described above, such three-dimensional reticulated fibers are formed by flashing.
It is known to be obtained from spinning. However, the present invention
Three-dimensional reticulated fibers are used in the microstructure of the fiber and
Conventionally, the fineness and mechanical strength of
It is a three-dimensional reticulated fiber different from known fibers. Therefore,
Good mechanical strength, high temperature properties and adhesion
It is.   This fiber has a long-period structure in the fiber axis direction due to its microstructure.
Has features. And this means X-ray small angle scattering
Clarified by measuring.   FIG. 1 schematically shows a small-angle scattering photograph of this fiber.
You.   Fibrils and voids on the equator near direct beam 1
And a scattered image 2 indicating the existence of
A scatter image 3 is provided. Generally, a long-period X-ray
Angular scattering image, circular scattering, layer linear scattering, layer line-like two points
Scattering, layered linear four-point scattering, etc. are known.
Similar to the long-period structure of drawn yarn that goes through normal spinning and drawing
It turns out that there is.   And a position sensitive proportional counter in the meridian direction (PSPC)
According to the analysis of the scattering peak in the measurement by
Wei has a long period of 150-200Å. Furthermore, long period
The unexpected feature that the scattering intensity due to
I came out. That is, it is considered from the meaning of long-period scattering intensity.
For example, low scattering intensity means that the long-period structure is uneven.
One. Or it is not clear, the fineness of the fiber
Unfavorable structure due to mechanical properties and thermal characteristics
Was expected. However, surprisingly, the melting point
Excellent high-temperature properties in the vicinity, suitable for heat-bonded nonwoven fabric
It is a three-dimensional network fiber.   The long period and its scattering intensity ratio are quantified as follows.
Measured scattered intensity versus angle plot by PSPC in the meridian direction
Of the peak or shoulder of the scattering intensity curve shown in FIG.
The position showing the maximum scattering intensity of the portion is the long-period scattering angle (2
θ), and this value is M. When this value is difficult to find
Is the Lorentz factor L = (2 sin θ / λ)^TwoTo
Invariant intensity plot obtained by multiplying
It was determined from the plot.   And the long-period scattering peak or shoulder in FIG.
Draw the common tangent P of the inflections at both ends of the curve. Actual measurement of angle M
Let the disturbance intensity value be A and the value on line P be B. One angle
(2θ) The value of the measured scattering intensity (blank) of 2.5 ° is C
Then, the scattering intensity ratio D is obtained as D = (AB) / C.   Long period is Bragg's formula Is obtained by putting 2θ = M in   The three-dimensional reticulated fiber of the present invention has a long cycle of 15
0 to 200 °, and the long-period scattering intensity is 40 or less.   This small-angle X-ray scattering is measured using the following apparatus and method.
Was decided. X-ray diffractometer is RV-200-PL, X
Wire is Cu-Kα 1.54mm, 1st pinhole slit
SLIT 0.5 mmφ and 2nd SLIT 0.3 mmφ were used. Measurement voltage
Is 45kV, current is 140mA and irradiation time is 2 × 10^Threesec.
The sample for measurement is a sample of the irradiated part with reticulated fibers aligned.
It was made so that the pull width was about 2.5 mm.   This fiber has a special fine fiber structure and has a melting point
Excellent thermomechanical properties and adhesion in the vicinity. Fiber heat
Characteristic can be known by various methods of measurement. Soshi
This thermophysical measurement measures its use as a nonwoven
It is performed without twist.   This reticulated fiber has good thermomechanical properties near the thermal bonding temperature
And is characterized by a low elongation rate during heating. Immediately
In the test of thermomechanical testing machine (TMA), denier 1/1
The elongation at 130 ° C when the temperature is raised under a constant load of 0 is preferred.
At most 3%, more preferably at most 2%.
You. The measurement was performed at 2 ° C using a “TM-3000” manufactured by Vacuum Riko Co., Ltd.
It was measured at a heating rate of minutes.   In addition, thermal and dynamic
You can know the characteristic. That is, the reticulated fiber of the present invention
Indicates a high dynamic modulus even at high temperatures, for example, the dynamic modulus
Is 10^Tendyn / cm^TwoIs preferably 115 ° C. or higher.   Furthermore, the stability of the crystal at high temperature is
Evaluated at the starting temperature. And this fiber is crystal dispersed
Is preferably 123 ° C. or higher, more preferably 1 ° C.
High value of 25 ° C or higher, crystal stability near the bonding temperature
It turns out that it is excellent in sex. These measurements are
Implemented using an elasticity measuring device, the present invention
Using RHEOVIB RON DDV-II-EA manufactured by DWIN,
The test was performed at several 110 Hz at a temperature rise of 1 ° C./min.   This reticulated fiber is also a highly oriented fiber,
That is, by measuring the crystal orientation angle by X-ray diffraction.
It becomes clear. That is, the orientation angle by X-ray is 30 ° or less.
preferable. More preferably, it is 20 ° or less.   Also, from the infrared absorption dichroism, the crystalline part and the amorphous part of the polymer
It is known that the orientation of
Number F_D ²⁰Is evaluated in. Polyethylene parallel dichroic van
2017cm^-1Dichroic orientation coefficient of fibers at 0.3
It is preferred that Here, "JIR-
Using 100 "FT-IR equipment and KRS-5 as ATR crystal
Was measured by the following method.   In addition, birefringence measurement of fiber by microwave
It can be used to indicate the degree of orientation. God
According to MOA-2001A "Microwave molecular orientation meter" manufactured by Saki Paper
At 4 GHz birefringence, the reticulated fiber is preferably 0.3.
Shows a birefringence value of 13 or more.   Three-dimensional reticulated fibers have extremely high mechanical strength.
You. The three-dimensional reticulated fiber is branched in a reticulated form,
When measuring the elongation of yarn with
And the variation in the values increases. Therefore, the tensile test
Then, measurement was performed with twisting of 4 times / cm. like this
The fiber used in the present invention in the measurement is the initial modular
15 to 50 g / d, preferably 20 to 50 g / d, and the breaking strength is
It is 4.0 g / d or more, preferably 7.0 g / d.   This three-dimensional network fiber is in its fibrillated form.
And preferably consist of extremely fine fibrils.
Good. And the specific surface area of this three-dimensional network fiber is 30m^Two
/ g or more.   The present inventors have proposed a three-dimensional network fiber as follows.
It was obtained from a mash spinning mechanism. In other words, instantaneous
Between two liquid phases from one liquid phase known in the art
Activation structure different from phase separation structure due to change
After spinning from the spinning nozzle, the fibers based on the activated structure
To form a fiber structure. "Activation" here
Is to increase the pressure loss when passing through the decompression orifice
At least 80kg / cm^Two, More preferably
Is 120kg / cm^TwoWith the above pressure loss, the activity is
Is to carry out the conversion. This activation is not
It is caused by fluctuations and is extremely fine
To give a temporary structure as if phase separated.   Then, by discharging from the spinning nozzle in this state,
Thus, the three-dimensional reticulated fiber is obtained. That is, this fine
Solvent released from activation structure to low pressure / low temperature range rapidly
The flash force that is going to evaporate and expand begins to solidify
Gives the polymer a high degree of orientation.
Form three-dimensional network fibers.   This activation is instantaneous and measured at static equilibrium.
Three-dimensional that is preferable for spinning from within one liquid region of the defined phase diagram
A reticulated fiber can be obtained. Therefore, this activation structure
The fiber obtained from is different from the conventionally known fiber in the ratio table
Area is 30m^Two/ g of extremely fine fibrils
I have. And a high-strength tertiary with a unique long-period structure
Original reticulated fiber.   And the activation of the solution consisting of this polymer and solvent is
For polymers with high degree of polymerization and narrow molecular weight distribution
Therefore, it is effective to increase the above pressure loss
This has been clarified in the study of the present inventors.   Dissolution process used in the flash mechanism
The dissolution process is not particularly limited, and is a conventionally known dissolution process.
Can be used. The fiber constituting the nonwoven fabric of the present invention
Wei is a high-density polyethylene with a high molecular weight and a narrow molecular weight distribution
Dissolves raw polymer in solvent in a short time
And spun to prevent polymer degradation.
No. Also, the dissolution rate at high pressure and the spinning mechanism of the present invention
Is preferred. (The features already filed by the inventors
(See Japanese Patent Application No. 61-91254 and Japanese Patent Application No. 61-96826)   The solvent used for that purpose will be used for flash spinning.
There is no particular limitation as long as it is a known solution.
Agents may be used. Preferably, trichlorofluoro
Methane, methylene chloride, trichlorotrifluoro
Halogenated hydrocarbons such as ethane, and charcoals such as cyclohexane
Hydrogen or a mixture thereof is used.   The spinning assembly for obtaining this fiber is the same as the spinning assembly described above.
There is no limitation as long as it can take a thread mechanism.
That is, a decompression orifice for activating a homogeneous solution,
The decompression chamber, the nozzle, etc. may be of any conventionally known shape.
May be.   As described above, it is composed of extremely fine fibrils and has a long circumference
Fiber with a unique structure and excellent high-temperature characteristics
The heat-bonded nonwoven fabric made of fiber is the nonwoven fabric of the present invention,
It has high mechanical strength and high temperature properties near the melting point.   And, the nonwoven fabric of the present invention has excellent opacity.
Both are its features.   In other words, even if a conventionally known heat bonding method is used,
Fibers have a large specific surface area, which may cause irregular reflection of light.
Excellent opacity. Higher mechanical strength
And high-temperature properties, so that the fibers
Less damage, machine without high adhesion
Excellent opacity, coupled with the development of the target strength
It becomes a nonwoven fabric.   The opacity of this non-woven fabric depends on the coating of packaging materials, protective clothing, clothing, etc.
It is a very important property as a covering material, and the result of observation with the naked eye
Measure the amount of transmitted He-Ne laser as a method that matches
Is recommended. This measurement was performed in a dark room with an output of 5 mW.
Irradiate a non-woven fabric with a laser beam with a
Measure the amount of light transmitted through the cloth with a laser power meter, and
By averaging the positions of
Was.   Naturally, the amount of transmitted light changes depending on the basis weight of the nonwoven fabric,
If it increases, the amount of light decreases. In the nonwoven fabric of the present invention
Has a basis weight of 25 g / m^TwoIs less than 25μW and 40g / m^Two
Less than 20μW, 50g / m^TwoLess than 18μW, 60g / m^TwoThen 16
μW or less, even at relatively low basis weights
It shows good covering power.   The nonwoven fabric of the present invention takes out an independent reticulated fiber form
And other layers are similar layers,
May be more firmly adhered to a film.   That is, any conventionally known sheet for heat bonding the sheet
A method may be adopted, such as pressing and calendering between rolls.
ー, Partial heat bonding felt calendar with embossing roll
Adhesive, or in an oven or forced hot air flow
An adhesion method or the like may be employed. Naturally, both sides are processed simultaneously,
Various types of processing, such as processing only one side, sequentially processing one side at a time
A law may be adopted. Then, after heat bonding, kneading, etc.
And peel off some of the constituent fiber layers to make them softer, etc.
May be a nonwoven fabric treated.   On the other hand, heat treatment that contributes to the adhesion of the sheet
In short, the whole is in a non-adhesive state or pressed with pressure
Nonwoven fabric may be used. Needle punch and
Non-woven fabric with entangled fibers
In addition, nonwoven fabrics in which heat bonding is used in combination are also included.   The fibers used in the nonwoven fabric of the present invention have a high
Made of high density polyethylene. Mainly used
There is no particular restriction on the high-density polyethylene
High-density polyethyne may be used. Also, from 100% ethylene units
Besides, within 10 mol% of monomers other than ethylene
Is a polymer with random or block copolymerized components
There may be. Additives may be included in the polymer
The heat stabilizer, ultraviolet stabilizer, lubricant and pigment
It may be contained in an amount that does not impair the invention.   Also, this high-density polyethylene and other polymer
Of course, it is also possible to use according to the purpose
I can do it. In particular, this three-dimensional network fiber has a special structure.
Due to its high strength, it has a high strength.
Blending rimers causes a drop in strength, making them impractical
It is possible to blend different types of polymers.
You. Polymer blended with high density polyethylene
Low-density polyethylene, ethylene-vinyl acetate copolymer
Coalescing, ionomer, polypropylene, polystyrene,
And polymethyl methacrylate.   The high-density fibers forming the network fibers used in the nonwoven fabric of the present invention.
Preferably, ethylene has a high degree of polymerization. Spun
Melt index (MI) of non-woven fiber is 1 or more
It is preferably below. More preferably 0.5 or less
Yes (MI is measured according to ASTM D-1238-57T condition E). So
The molecular weight distribution of the polymer of the fibers that make up the nonwoven fabric
It is also important to be narrow. That is, even if the MI is the same,
If the amount distribution is wide, the performance is inferior to the nonwoven fabric of the present invention
Become something. The molecular weight distribution of the fibers of the nonwoven fabric of the present invention is Mw / M
n is 15 or less, more preferably 10 or less. Of course
MI of the raw material polymer used to obtain the fiber of the present invention.
Is a polymer equal to or less than MI of the fiber of the present invention.
Is used.   The nonwoven fabric of the present invention has a tertiary as-spun
Spread the original reticulated fiber to arrange the fiber elements in random directions.
The deposited non-adhesive sheet is heat-sealed as described above if desired.
It is what I wore. Professional to get this non-adhesive sheet
As the process, any conventionally known process may be selected.   In addition, this three-dimensional network fiber is expanded to form a non-adhesive non-woven sheet.
Any known method and apparatus can be used as the
May be used. Basically spread the spun reticulated fiber
Collision device determines the direction of fiber propagation
Device, device for charging spread fibers, receiving fibers
It consists of a device for depositing. That is, Tokiko 42-195
No. 20, No. 44-21817, USP 3,456,156,
Numerous methods, such as improvement thereof, are known.
Can be used without any restrictions. 〔Example〕   Hereinafter, the present invention will be described specifically with reference to examples. Example 1.   Extruder that continuously melts and supplies polymer, solvent continuously
Metering pumps to inject, and to mix them continuously
Solution adjustment equipment consisting of a device for
A decompression chamber with a volume of about 2 cc and a spinning nozzle consisting of a spinning nozzle
Perform continuous flash spinning from the assembly.   High density polyethylene (MI = 0.31, Mw / Mn = 4.8, density 0.9
60) and trichlorofluoromethane and polymer concentration 9.
Prepare a 2wt% homogeneous solution and use a 0.55mmφ-5mmL vacuum
Fiss, 0.55mmφ-0.55mmL hole followed by 3mmφ-3m
Spindle consisting of spinning nozzle with mL tunnel flares
Flash spinning was performed using the assembly.   At a polymer flow rate of 7.5 kg / Hr, the solution was
25kg / cm^TwoG, temperature 191 ° C, pressure 110kg in decompression chamber
/cm^TwoG, the fineness of the spinning nozzle is 101d and pure white
A continuous three-dimensional reticulated fiber was obtained.   This fiber has a specific surface area of 41m^Two/ g.   And the long period by X-ray small angle scattering is 162 °
Was 8.4.   In the tensile test with a twist frequency of 4 turns / cm, the initial
The glass had a viscosity of 38.5 g / d and the breaking strength was 9.3 g / d.   The elongation at 130 ° C with TMA is 1.5%,
Has a dynamic modulus of 10^Tendyn / cm^TwoIs 122 ° C, tanδ
Was at 126 ° C.   And the orientation angle by X-ray diffraction is 18 °, the wave number 2017cm
^-1Coefficient by infrared absorption dichroism at ▲ F²⁰ _D▼ is 0.43
The value of was shown. The microwave birefringence is 0.147.
You.   This fiber had MI = 0.34 and Mw / Mn = 4.8.   This fiber is then used as described in USP 3,456,156.
Using a dispersion device with a rotating deflection plate and a corona discharge device
And collected on a moving net conveyor. This time,
The three-dimensional reticulated fiber discharged from the spinneret has a width of 30 to 60 mm.
It is shaken continuously left and right on the net conveyor in a crooked state
While deposited.   This non-adhesive non-woven sheet is embossed with a rubber
And partially adhered. That is, with the embossing roll
And each protrusion is 0.7mm x 0.7mm square and
Emboss depth of 1.25mm in both the circumferential and circumferential pitch
Used a 0.3 mm roll.   Heat the embossing roll to 132 ° C and
Process both sides of the front and back by pressing
Was obtained. This non-woven fabric has abrasion resistance on the surface
Although it was an excellent non-woven fabric, the texture was a little hard,
Extremely flexible non-woven fabric after rubbing by hand
It became.   Cut this non-woven fabric and forcibly tear it
Rigidly heat-bonded surface layer and retains reticulated fiber form
It was peeled off to the inner layer portion made of the fiber. Reticulated fiber of inner layer
Grasping one end of the fiber and carefully separating it from other reticulated fibers
A large number of continuous mesh fibers of about 30 to 100 cm
Issued. Measure small-angle X-ray scattering using these reticulated fibers
As a result, the long-period scattering intensity ratio was 9.0. on the other hand,
The long period increased slightly and showed a value of 181Å.   This nonwoven is extremely flexible and has abrasion resistant surface
It has excellent properties, and even if you rub the surface with your fingers
Non-woven fabric, very high covering power, protective clothing, simple
Clothes, desiccants, breathable packaging materials such as deoxidizing materials, and other soft materials
It was suitable as a soft packaging material.   This nonwoven fabric has a basis weight of 50 g / m^TwoAnd the average amount of transmitted laser light
Was 14 μW. And the physical properties of nonwoven fabric vertical / horizontal
Has a tensile strength of 9.5 / 10.3 (kg / 3cm width), single tongue
Tear strength is 1.9 / 2.0 (kg) and cantilever method
The flexibility was 5.2 / 5.6 (cm). Example 2.   The non-adhesive nonwoven sheet obtained in Example 1 was fully pressed with a pressure roll.
Treated between rubber rolls. In this case, only the surface treatment
Roll temperature is 135 ° C Roll linear pressure 10kg / cm and speed 10m /
Minutes.   One surface of the obtained nonwoven fabric is firmly heat-bonded,
Non-woven fabric that is not thermally bonded to the surface and inner layer
Is a fiber that retains its reticulated form from the surface that has not been heated.
The fibers were removed independently.   In the measurement of small angle X-ray scattering of this fiber,
The power ratio was 8.5 and the long cycle was 180 °.   This non-woven fabric can be used for applications that take advantage of the difference between the two surfaces.
Adsorbent or deodorant to the non-adhered surface
Wearing filter, deodorizing filter, or other surface
Bonding materials (films, woven fabrics, etc.) for high covering power
It is used as a composite material having high tear strength.   This non-woven fabric has a basis weight of 50 g / m^TwoThe average laser transmission
The excess light amount is 5 μW, indicating an extremely high covering power.
The physical properties of the nonwoven fabric length / width are as follows: Tensile strength: 11.2 / 11.
8 (kg / 3cm width), with a tear strength of 1.6 /
The value was extremely high at 1.6 (kg). Example 3.   The non-adhesive nonwoven sheet obtained in Example 1 was used as a felt calendar.
And both sides were treated. Contact with drum heated to 132 ° C
The surface layer is thermally bonded by processing at a high speed of 1 second.
Thus, a nonwoven fabric having a reticulated fiber form in the inner layer was obtained.   X-ray small angle scattering of fiber taken out from inner layer of this non-woven fabric
The disturbance has a long-period scattering intensity ratio of 7.0 and a long-period of 230Å.
there were.   This non-woven fabric has a basis weight of 40 g / m.^TwoWith the laser average transmitted light
Is 8μW and has excellent covering power and is a bulky paper-like nonwoven fabric.
Can be used for envelopes, labels, and a variety of other paper uses.
Things.   And the physical properties of the length / width of this nonwoven fabric are
At 10.8 / 12.0 (kg / 3cm width), the Elmendorf tear strength is 1.4
/1.4 (kg). Example 4.   Using the same dissolution apparatus and spinneret assembly as in Example 1.
High density polyethylene with MI = 0.78, Mw / Mn = 8.0, density 0.
Changed to 962, 12.4wt% of trichlorofluoromethane
A solution was prepared and spun.   Solution pressure 210kg / cm at polymer flow rate 9.7kg / Hr^TwoReduced from G
Compression chamber pressure 83kg / cm^TwoG (decompression chamber temperature 190 ℃)
The fineness discharged from the spinning nozzle is 145d and continuous pure white
A three-dimensional network fiber was obtained.   This fiber has a specific surface area of 33m^Two/ g.   And the long period in X-ray small angle scattering is 173Å
Was 19.2.   This fiber was subjected to a tensile test with 4 twists / cm
The initial modulus was 23.6 g / d and the breaking strength was 7.4 g / d.
Was.   The elongation at 130 ° C measured by TMA was 1.7%.
Dynamic modulus of elasticity at ibron is 10^Tendyn / cm^TwoBecomes 116
℃, tanδ divergence onset temperature is 124 ℃
You.   The crystal orientation angle by X-ray diffraction is 27 °
Number 2017cm^-1Infrared Orientation Coefficient ▲ F²⁰ _D▼ is 0.51.
The microwave birefringence showed a value of 0.133.   The spun fiber has MI = 0.94 and Mw / Mn = 6.0.
Measured.   This fiber is used as a non-adhesive non-woven sheet as in Example 1.
After collection, a soft non-woven with just the same embossed pattern
Cloth.   Measurement of small angle X-ray scattering of fiber similarly taken out from inner layer
The long-period scattering intensity ratio is 20 and the long-period is 210 °.
Was.   This nonwoven fabric has a basis weight of 50 g / m^TwoWith an average laser transmission of 15
μW. In addition, the physical properties of the length / width of the nonwoven fabric are
Strength is 9.3 / 9.0 (kg / 3cm width), single tongue tearing strength
Is 1.7 / 1.8 (kg), flexible by the cantilever method
The degree was 5.0 / 5.0 (cm). Example 5.   The same spinning was performed using the same dissolving apparatus as in Example 1.
Was. At this time, high density polyethylene with MI = 0.78, Mw / Mn = 8.0
60/40 of high-density polyethylene with an MI and MI = 5.0, Mw / Mn = 5.0
Trichlorofluoromethane using a blend polymer of
12.0 wt% solution. The spout assembly is
The diameter of the fiss / spinning nozzle was 0.6 mmφ / 0.55 mmφ.   At a polymer flow rate of 10.2 kg / Hr, the solution pressure is 230 kg / cm^Two
The decompression chamber pressure is 90kg / cm at G^TwoG (temperature 190 ° C)
A continuous three-dimensional reticulated fiber was obtained from the wool.   This fiber has a long period of 170 when measured by small-angle X-ray scattering.
Å, the scattering intensity ratio was 36.8.   The specific surface area is 39m^Two/ g, with 4 twists / cm
Initial modulus 21.3 g / d, breaking strength 5.7 g / d in tensile test
d.   The elongation at 130 ° C by TMA is 3.0%.
The crystal dispersion start temperature of tan δ at this time was 123 ° C.   This fiber was embossed as a sheet in the same manner as in Example 1.
Both sides were adhered using a tool and a rubber roll. Further massage
To obtain a heat-bonded flexible nonwoven fabric.   This nonwoven fabric has a basis weight of 50 g / m^TwoThe average transmitted light amount of the laser beam
15 μW, and the nonwoven fabric has a tensile strength of 8.
3 / 9.7 (kg / 3cm width), single tongue tear strength is 1.7 /
It was 1.7. The flexibility by the cantilever method is 4.8 / 5.0
It was a very flexible nonwoven fabric. Comparative Example 1.   Using the dissolution apparatus of Example 1, high-density polyethylene
(MI = 5.0, Mw / Mn = 7.0, density 0.969) trichlorofluor
A 10 wt% solution of dichloromethane was prepared and spun. At this time,
0.7mmφ-5mmL for pressure orifice, 0.7mmφ− for spinning nozzle
0.7mmL hole followed by 4mmφ-4mmL tunnel flare
A spinning assembly with a hole was used.   At a polymer flow rate of 8.8 kg / Hr, the solution pressure is 130 kg / cm^Two
G is the decompression chamber pressure 53kg / cm^TwoSpins down to G (temperature 173 ° C)
A continuous three-dimensional reticulated fiber with a fineness of 157d is obtained from the nozzle
Was.   This fiber has a specific surface area of 18m^Two/ g, 4 twists
Initial modulus in tensile test of 10.8 g / d, tensile strength at break / cm
Was only 3.8 g / d.   In the measurement of small-angle X-ray scattering, the long period is 133 °
The turbulence intensity ratio was 52.4.   And the elongation at 130 ° C by TMA is 3.6%,
The crystal dispersion onset temperature of tanδ in Vibron is 113 ° C.
The physical properties were also inferior.   Using this fiber, non-adhesion
A woven sheet was prepared and a flexible nonwoven fabric was produced in exactly the same manner.   Similarly, take out fibers in the form of a reticulated fiber from the inner layer,
X-ray small angle scattering was measured. This long-period scattering intensity ratio is
At 60, the long cycle was 240Å.   This non-woven fabric has a basis weight of 50 g / m.^TwoWith the laser average transmitted light
At 20 μW was inferior to the example.   And the nonwoven fabric's vertical / horizontal properties are 6.5 / 6 in tensile strength.
4 (kg / 3cm width), single tank tear strength is 0.8 / 0.8 (k
g), and the strength was inferior to the examples. Comparative Example 2.   Commercial Tyvek manufactured by E.I.duPont  Dissolve 1443R nonwoven fabric
Folded.   This nonwoven fabric is a flexible nonwoven fabric with an embossed pattern
As shown in the present invention, the reticulated fiber form is preserved in the inner layer.
I have   According to the present invention, independent reticulated fibers are converted to small-angle X-ray scattering
As a result of measurement, the long-period scattering intensity ratio was 50,
Was 172Å.   Also, the basis weight of non-woven fabric is 44g / m^TwoAnd the laser average transmitted light
The amount was 22μW, and the coverage was inferior and the spot coverage was poor.
It is.   The vertical / horizontal properties of the nonwoven fabric are 7.9 / tensile strength.
9.0 (kg / 3cm width), single tongue tear strength is 1.4 / 1.6
(Kg) and the flexibility by the cantilever method is 6.2 / 6.3
(Cm). 〔The invention's effect〕   The nonwoven fabric comprising the three-dimensional network fibers according to the present invention is as described above.
So that the nonwoven fabric is extremely fine
Consistent of fibrils, uniform whiteness
It has covering power, opacity, and extremely high mechanical strength.
It will get loose.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a small-angle X-ray scattering image of the present invention. FIG. 2 is a drawing for explaining a method of obtaining a long-period scattering intensity ratio in PSPC of small-angle X-ray scattering.

Claims (1)

(57) [Claims] High-density polyethylene fibrillated three-dimensional reticulated fibers are arranged in random directions, deposited in layers, and in a nonwoven fabric including a layer from which independent reticulated fibers can be taken out, the X-rays of the independent reticulated fibers A nonwoven fabric made of three-dimensional network fibers, wherein a long-period scattering intensity ratio by small-angle scattering is 40 or less. 2. 2. The nonwoven fabric comprising three-dimensional mesh fibers according to claim 1, wherein the independent mesh fibers have a long period of 150 ° or more.