JPS6279239A - Polyolefin drawn, processed material - Google Patents

Abstract

PURPOSE:To drawn, process material providing knitted net or woven, processed material having low rigidity and feeling of cotton or flax, obtained by adding a compound selected from a higher fatty acid ester, etc., to an inorganic filler- containing polyolefin and drawing the polyolefin. CONSTITUTION:(A) 200pts.wt. polyolefin containing 10-70wt% inorganic filler is blended with (B) 0.1-10pts.wt. one or more selected from a group consisting of a monohydric higher alcohol, its derivative (no ether compound is included), a higher fatty acid ester and a higher fatty acid amide, drawn and processed to give a drawn, processed material having 10-60% porosity. Lauryl alcohol, capric acid, oleic amide, etc., are used as the component B. Calcium carbonate having 0.01-30mu average particle diameter, etc., are used as the filler in the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stretched product of polyolefin containing an inorganic filler, which has improved properties over a wide range of mechanical, thermal, optical, etc. properties.

Polyolefins such as polyethylene and polypropylene are
It is well known that it is made into thread-like, tape-like, or string-like products with or without stretching processing, and that these products are processed with LlH netting and tA weaving to make various products. .

Examples of these products include various ropes, binding tape,
Tying cords or knitted nets, woven products include various knitted net products such as vegetable nets, windbreak nets, and fishing nets, various cloth bags such as fertilizer bags, wool bags, and rice grain bags, and industrial, civil engineering, and agricultural uses. , various types of cloth seats such as those for marine products and inch rear seats. Of course, it is used in many fields because of its many features, but if we are to expand its use even further, we will need to take advantage of its excellent moldability, mechanical, and thermal properties. Taking advantage of these features and further improving their functions, as well as characteristics that are relatively easy to cite as drawbacks,
For example, improving various properties such as a transparent and shiny appearance similar to plastic, high rigidity, and a stiff and hard texture, for example, improving the texture of natural materials such as linen, cotton, etc., or improving the texture of conventional polyolefins. It is necessary to add features that were not previously seen in the product.

The present inventors have repeatedly studied [If4 processed products and woven products using polyolefins from the above viewpoints, and have determined the physical properties of the threads, tapes, and films that serve as the raw yarns, and the knitted net processed products obtained from them. , has continued to research from all angles the relationship with the physical properties of woven products. Taking advantage of its mechanical strength and thermal properties, we have improved the two drawbacks of high rigidity, hard feel, poor texture, and shiny appearance with a plastic-like transparency. We have discovered a stretched product that has a feel similar to that of natural products such as cotton products and linen products, or a unique texture that plastics do not have, and have accomplished the present invention.

That is, in the present invention, monohydric higher alcohol, its derivative (not including ether compound),
A polyolefin composition containing 0.1 to 10 parts of one or more selected from the group of higher fatty acid esters and higher fatty acid amides is used as a base material, and the porosity after stretching is 10 to 60%. This invention relates to polyolefin stretched products.

The features of the present invention are listed below.

(2) The stretched product of the present invention has mechanical strength, thermal properties, etc. at the level of ordinary polyolefins, and does not impair the properties of the polyolefin used as the base polymer.

(2) The stretched product of the present invention has low rigidity and has a good feel to the touch.

■Compared to conventional stretched products made of polyolefin, the stretched products of the present invention do not have plastic-like transparency and have a high-class appearance.

(2) The stretched product of the present invention has secondary processability such as knitting processability and weaving processability that is equal to or higher than that of a stretched product made of ordinary polyolefin.

■The knitted net processed product and woven processed product made from the stretched processed product according to the present invention have mechanical properties such as tensile strength, elongation, tear strength, etc., and thermal properties such as heat resistance, which are the same as those of ordinary polyolefin 11×4 mesh. , which is equivalent to or better than woven products.

■V4 net processed product made from the stretched product according to the present invention,
The woven product does not have the transparent and shiny appearance of plastic, giving it an image of so-called luxury.

■Knitted net products and woven products made from the stretched products according to the present invention have low rigidity, do not have a stiff or hard feel, are pleasant to the touch, and have a unique texture.

■Knitted net products and woven products made from the stretched product according to the present invention are easy to bend and fold, and have excellent workability.

■The knitted net products and woven products made from the stretched products according to the present invention make almost no noise when bent or folded, and are not as unpleasant as the fJdM of conventional polyolefins or the melange of woven products. There's no sound.

[Phase] The knitted net products and woven products made from the stretched products according to the present invention have excellent surface properties such as printability, paintability, and adhesion, and can be easily printed, painted, and bonded, and have a high commercial value. can be made to a high level. Also, it can be laminated or coated with resin, and can also be used after being laminated or coated.

■The stretched product according to the present invention can be easily subjected to ordinary knitting and weaving processes, such as flat knitting, which is usually called flat knitting, rubber knitting, crow knitting, etc., and warp knitting. It is made into knitted net products using various types of warp knitting such as plain knitting, decorative knitting, etc., and it is also possible to use plain weave, diagonal weave, satin weave, and each of these weaving structures as prototypes, and to change or combine them. It is made into woven products of various weaving structures such as patterned weaving, layered weaving, and pile weaving.

Q &[Workpiece, M made from the drawn workpiece according to the present invention
l@workpiece is the shape of the stretched workpiece that constitutes the workpiece,
By variously changing the thickness, thickness, width, etc. of the tape-shaped workpiece, and the number of constituting tapes, the thickness, polyuminous feel, mechanical properties, etc. can be freely changed depending on the purpose.

The present invention will be explained in detail below.

The polyolefin in the present invention refers to one whose main component is a monoolefin copolymer or copolymer such as ethylene, propylene, butene, etc. For example, high density polyethylene,
Medium and low density polyethylene, crystalline polypropylene, crystalline ethylene-propylene block copolymer, polybutene, poly-3-methylbutene-1, polymethylpentene-
1. Refers to ethylene-vinyl acetate copolymers, etc., and mixtures thereof.

The inorganic filler in the present invention is a powdered inorganic substance, such as calcium carbonate, basic magnesium carbonate,
Sodium aluminosilicate, potassium aluminosilicate,
Powder of inorganic substances that can be dispersed in polyolefins such as lithium aluminosilicate, aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, silica, alumina, titanium oxide, clay, talc, bolastonite, barium sulfate, calcium sulfate, etc. These may be used alone or in a mixture of two or more.

In the present invention, the average particle size of the inorganic powder is 0.0
It is in the range of 1 to 30μ, more preferably 0.05 to 2
It is in the range of 0μ. If the average particle size exceeds 30μ, not only will the moldability deteriorate when producing the stretched product of the present invention, but it will also be difficult to produce the stretched product having the porosity of the present invention. Therefore, it is not possible to obtain a stretched product that satisfies various properties such as mechanical strength, bending resistance, and Young's modulus, which are the objectives of the present invention.

The concentration of the filler in the present invention ranges from 10 to 70% by weight, preferably from 15 to 60% by weight.

When the amount of the filler is less than 10% by weight, it is extremely difficult to obtain a stretched product having the porosity of the present invention, no matter how the stretching conditions are selected, and therefore the objects of the present invention cannot be achieved. It is very difficult to obtain stretched products, knitted net products, and woven products that satisfy the properties. On the other hand, the filler is 7O
If the amount of N exceeds %, the molding processability will deteriorate, making it difficult to obtain a stretched product having the porosity of the present invention, and the mechanical strength etc. of the obtained stretched product will be extremely low.
Excellent stretched products and knitted net products that are the object of the present invention,
It becomes difficult to obtain woven products.

Examples of higher alcohols, derivatives thereof (not including ether compounds), higher fatty acid esters, and higher fatty acid amides in the present invention include the following.

■Higher alcohols and their derivatives are straight, cored, saturated and unsaturated monohydric alcohols with 10 or more carbon atoms and their derivatives (not including ether compounds), such as lauryl alcohol, myristyl alcohol, Examples include alcohols such as heptyl alcohol, stearyl alcohol, n-eicosyl alcohol, isoeicosyl alcohol, seryl alcohol, and oleyl alcohol, and alcohol esters such as eicosanol acetate and isoeicosanol acetate.

■Higher fatty acid ester refers to a dehydrated condensate of a straight or branched saturated or unsaturated fatty acid having 10 or more carbon atoms and a monohydric alcohol. namely, fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, isopalmitic acid, margaric acid, stearic acid, araxic acid, behenic acid, oleic acid, erucic acid, ricinoleic acid, and methyl alcohol, ethyl alcohol, and propyl alcohol. By dehydration condensation with lower monohydric alcohols such as alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, anyl alcohol, crotyl alcohol, the above-mentioned higher alcohols, or their isomer alcohols. It is an ester obtained by oxidation, including those that are partially acetylated.

■Higher fatty acid amide is a compound in which the 10H group of the carboxyl group of a saturated or unsaturated fatty acid having 10 or more carbon atoms is substituted with an amino group, such as oleic acid amide, valmitic acid amide, stearic acid amide, Examples include methylene bis stearamide, ethylene bis stearamide, and their monomethylamide and ethyleneimine adducts.

In the present invention, these compounds can be used alone or as a mixture of two or more. The amount of the compound to be used is 0.1 parts by weight or more and 10ffi based on 100 parts by weight of the composition consisting of the polyolefin and the inorganic filler.
less than 1 part by weight, preferably in the range from 0.5 to 5 parts by weight.

If the amount is less than 0.1 part by weight, not only will the moldability deteriorate, but it will also be difficult to increase the porosity, making it extremely difficult to obtain a stretched product having the porosity of the present invention.

Therefore, it is very difficult to obtain stretched products, knitted net compounds, and woven products that satisfy the properties targeted by the present invention. On the other hand, if it exceeds 10 parts by weight, it is undesirable that the compound may cause smoke generation during extrusion molding or bleed onto the surface of the tape-shaped product when producing a stretched product, which is the object of the present invention.

Next, a method for producing a stretched product according to the present invention will be explained.

When producing the stretched product of the present invention, at least three components are used: a polyolefin (A), an inorganic filler (B), a higher alcohol, a higher fatty acid ester, and a compound (C) selected from the group of higher fatty acid amides. Composition containing (D
) is mandatory.

The method for producing the composition (D) includes the above (A) and (B).
) and (C) are heated and kneaded. The mixing order of each component is arbitrary. For example, (A), (B),
Examples include a method of heating and kneading the three components (A) and (C) at the same time, and a method of adding (C) to a composition consisting of the two components (A) and (B) and then heating and kneading the mixture.

As the heating kneading device, commonly used kneading machines such as various extruders, Banbury mixers, kneaders, mixing rolls, etc. can be used.

The temperature for heating and kneading is in the range of not less than the melting and softening temperature of the base polymer and not more than the thermal decomposition temperature, but is usually 180°C or more and 280°C.
It is in the range of C or below.

In addition to the above compositions, the composition used in the present invention includes heat stabilizers, lubricants, plasticizers, ultraviolet absorbers, colorants such as pigments and dyes, flame retardants, antistatic agents, thickeners, and blowing agents. Various additives such as the above may be added as appropriate depending on the purpose. Among these additives, lubricants such as higher fatty acids and their gold salts are often effective in achieving the purpose of the present invention. play a role. When adding a foaming agent, the concentration, foaming conditions, etc. must be selected so that the porosity of the resulting stretched product falls within the range of the present invention.

The inorganic filler-containing polyolefin composition obtained as described above is stretched to form monofilament, film, or tape-like products having a porosity of 10 to 60%.

Here, the porosity (V) is determined by the following method.

Theoretical specific gravity D of the composition used (calculated from the true specific gravity of the raw materials contained in the composition and the blended composition, or the specific gravity determined by measuring a test piece obtained by compression molding the composition after completely defoaming it) ), the appearance of a processed product such as a thread, film, or tape is determined by the specific gravity ρ, and V= ((D−ρ)
/D) xlOO(%) is called the porosity of the present invention.

In the present invention, the porosity is in the range of 10% to 60%, preferably 15% to 50%.

The object of the present invention is achieved by stretching the composition so that it has such a porosity. When the porosity is less than 10%, bending resistance, Young's modulus, etc. are not improved, transparency or appearance is not sufficiently improved, and bending recovery property is not sufficiently improved.

On the other hand, when the porosity is 60% or more, the weft strength and knitted network
Weaving processability etc. are greatly reduced, and the object of the present invention cannot be achieved.

Although ordinary uniaxial or biaxial stretching is used as the stretching method, the stretching conditions are a very important factor in the present invention. By appropriately selecting the stretching conditions, a stretched product having the excellent properties aimed at by the present invention can be obtained. That is,
■The stretching temperature is as follows, assuming that the melting point of the base polymer is Tp″C.
Tp-5 to Tp-80°C, preferably Tp
It is in the range of -10 to 'rp-50°C.

If the stretching temperature is higher than Tp-5°C, the porosity is low and it is difficult to obtain the porosity of the present invention, and if it is lower than Tp-80°C, the stretching processability is poor and the porosity of the present invention is substantially I can't do it.

■Stretching ratio is 1.5 times or more and 15 times or less, preferably 2
It is more than 13 times more than that. When the stretching ratio is less than 1.5 times, the porosity is low and it is difficult to obtain the porosity targeted by the present invention. On the other hand, when the stretching ratio exceeds 15 times, the porosity becomes too high and the welt crack strength etc. decrease, which is not preferable.

The term "monofilament" as used in the present invention refers to any filament, usually called a monofilament, which has a circular cross section, an elliptical shape, or various other shapes, a cross-sectional area of several square millimeters or less, and a length of less than a few square millimeters.

The shape of the film-like or tape-like product referred to in the present invention is free, but the cross section is generally rectangular and the width is larger than the thickness, and usually the thickness is several hundred microns or less and the width is about 1 m or less. It has an arbitrary length. In order to obtain the desired thickness and width, various conditions such as the thickness and width before stretching, stretching ratio, stretching conditions such as stretching temperature, and stretching method must be taken into consideration.

Further, in order to adjust the width, it is convenient to slit the film before or after stretching. The tape-shaped product thus obtained can also be slit by a conventional method to form a slit tape. The slit tape thus obtained has an increased volume and becomes a stretched product with even more features.

The stretched product obtained in the above manner is processed into various knitted mesh products by using a normal knitting machine or weaving machine.
If necessary, a twisting process may be added before the zero-knitted net or weaving process to be made into a woven product.

Further, it is preferable that the target product of the present invention satisfies the following conditions (1) to (4) as appropriate.

■The tensile strength of the stretched product is at least 7Kg/m at room temperature.
tt? , preferably 10 Kg/mm' or more.

■ The warp strength of the stretched product is 30 g/mm' or more at room temperature, more preferably 5 Qg/+am2 or more (
The warp strength was determined by cutting the obtained tape-shaped workpiece into a length of 10 mm in the direction perpendicular to the length direction, and pulling it in the length direction of the tape at 23°C, 50% humidity atmosphere, and a tensile speed of 50 mm/lll1n. , is the maximum strength at which the tape breaks)
.

(2) The bending resistance of the stretched product is 5% or more greater in l value according to JIS-L-1004 shown in FIG. 1 than the base material (polyolefin) to be modified (the larger the j7 value, the softer it is).

(2) The Young's modulus of the stretched product is 10% or more smaller than the base material (polyolefin) to be modified in terms of tensile Young's modulus.

(2) The tensile elongation of the stretched product is in the range of 3 to 100% at room temperature.

■Transparency of the stretched product, A for the object to be modified.
The degree of haze of StMD D-1003 is increased by at least 10%, and the absolute value of the degree of haze is 70% or more.

(2) The bending recovery property of the stretched product, as determined by JIS L-1004, is 10% or more smaller than the target object, expressed as the recovery angle after bending under a constant load over a certain period of time and then removing the weight.

In order to achieve these conditions (1) to (2), the physical properties of the base polymer, the composition of the inorganic filler, the composition of the polyhydric alcohol derivative, and the stretching conditions of the composition may be appropriately selected.

Among the above conditions, ■, ■, ■ are conditions such as knitted net processability, weaving processability, and mechanical strength of the obtained knitted net processed product and woven processed product, etc.
It is necessary because it is at the same level as normal polyolefin, and when SAMURAI lacks ■, the tape tends to warp and fluff during knitting or weaving, and &1! The efficiency of the net weaving process decreases, and the knitted net and woven products also become more fluffy, reducing not only the appearance but also the functionality itself. In addition, ■ and ■ are extremely effective in improving not only the bending properties of stretched products, but also the softness and texture when the knitted net products and woven products obtained from them are bent or stretched. This is a big factor. (2) is a very important factor in improving the plastic-like transparency and shine of not only yarns and drawn products, but also knitted net products and woven products obtained from them. Furthermore, when (1) is added to these properties, knitted net products and woven products exhibit a unique feel and texture not found in conventional polyolefins.

Below, in order to take advantage of the mechanical strength, thermal properties, etc. of conventional polyolefin IJA net processed products and woven processed products, improve the above-mentioned drawbacks, and bring out the features, we will satisfy the above conditions. I will show with a few examples that this is not so simple.

For example, taking conventional polyolefin monofilaments and stretched tapes as an example, in order to improve the stiffness and transparency of polypropylene monofilaments and tapes, it is possible to replace them with high-density polyethylene monofilaments and tapes. This goes toward satisfying the conditions to some extent, but on the other hand, it significantly impairs the thermal properties of polypropylene, which is not the intention of the present invention.Also, in order to improve the transparency of low-density polyethylene,
If this is replaced with high-density polyethylene, the above conditions (1) and (2) change in the opposite direction to the objective of the present invention, and the objective cannot be obtained.

As mentioned above, the knitted net and woven products made from the stretched products manufactured in the above manner have various excellent properties, but when folded or folded, Wel of polyolefin! , there is no unpleasant melange sound like woven products,
Significant accompanying effects such as improved surface properties for printing, painting, etc. can also be obtained.

It goes without saying that the stretched product produced as described above can be used as it is as a film, tape, thread, etc. without being knitted or woven.

EXAMPLES The present invention will be explained in detail below using examples, but the present invention is not limited to the scope of the examples.

Example 1 Melt index (hereinafter simply referred to as Ml, load 2.1
6Kg, temperature 190℃') 1.0, specific gravity 0.953
, 64.9% by weight of high-density polyethylene with a melting point of 130°C
, heavy calcium carbonate powder with an average particle size of 1.0μ 35.
To 100 parts by weight of a mixture consisting of 0% by weight and 0.1% by weight of 2,6-ditert-butyl-4-methylphenol, 2.5 parts by weight of stearyl alcohol was added and mixed for 30 minutes with a ribbon blender to form a mixture. was manufactured.

The mixture was heated and kneaded in a Banbury mixer at a temperature of 230° C. for 3 minutes to obtain a filling composition, which was then formed into a sheet with a roll and granulated with a sheet pelletizer to obtain a pellet-shaped filling composition.

A test piece obtained by compression molding this composition after completely defoaming it had a specific gravity of 1.228. In addition, is the specific gravity measured by AST? !
The method of D-1505 was followed.

This composition was processed using a 65IllIll extruder at a resin temperature of 19
Extruded at 5℃, blow ratio 1.5 using inflation method
A film with a thickness of about 60 μm was formed. This film was slit into medium 161 mm, and stretched with a roll stretching machine at a stretching temperature of 11 mm.
2°C, stretching ratio 8 times, winding speed 120 va/wi
A stretched tape was manufactured under the conditions of n. The stretching went smoothly and the stretched tape could be manufactured without any trouble. The obtained stretched tape has a thickness of about 28 μm and a width of about 61 μm.
1IIIll, and the apparent specific gravity was 0.82. Therefore,
The porosity of this tape was 33.2%.

In addition, the tensile strength, elongation, warp strength, bending resistance, Young's modulus, haze, and bending recovery properties of this tape were measured.

These measurement methods are as follows.

Tensile strength, elongation: 23°C, 50% humidity atmosphere, chamber/rib spacing 200mm, tensile speed 50++m/sin
.

Warp strength: 23℃, 50% humidity atmosphere, Chi+7
Attach 2mm cellophane tape to both edges of the tape at a tension distance of 50m+m and a tension speed of 50mm/5h.
Attach the Sellotape part to the chuck.

Bending resistance: 23℃, 50% humidity atmosphere, JIS L-
1004, and is indicated by l in FIG.

Young's modulus: In the above tensile test, it is determined as the initial tensile resistance.

Haze degree: According to the method of ASTM D-1003, a slit of 5 ma + width was provided in the sample mounting section, and a tape was pasted on this slit to measure it.

Bending recovery: 23°C, 50% humidity atmosphere, JISL
-1004 method, as shown in Figure 2, 5
After applying a load of g for 5 minutes, the weight is removed, and the recovery angle θ is measured 5 minutes after the weight is removed.

Reference Example 1-1 0.1% by weight of 2,6-di-tert-butyl-4-methylphenol was blended with the high-density polyethylene used in Example 1, and a film was produced under the same extrusion and film forming conditions as Example 1. A film was formed. However, the thickness of the film was approximately 65 μm. This film was slit to a width of 16a+m in the same manner as in Example 1, and the stretching temperature was 112°C, the stretching ratio was 7 times, and the winding speed was 120.
A stretched tape was manufactured under the condition of va/sin. The obtained stretched tape has a tape thickness of approximately 25 μm and a width of approximately 5.5 μm.
It was im. In addition, other physical properties were also measured in the same manner as in Example 1.

These results are shown in Table 1.

Reference Example 1-2 64.9% by weight of high-density polyethylene used in Example 1-1, 35.0% by weight of heavy calcium carbonate powder, and 2
, 0.1% by weight of 6-ditert-butyl-4-methylphenol to obtain a filling composition in the same manner as in Example 1,
A film was formed. An attempt was made to produce a stretched tape from this film under the same conditions as in Example 1-1. However, since the stretching breakage occurred frequently, the stretching ratio was lowered, the winding speed was also lowered, and conditions under which stretching was possible were searched for. As a result, stretching was possible under the following conditions. That is, the stretching temperature 112
It was possible to produce a stretched tape under the following stretching conditions: °C, a stretching ratio of 4 times, and a winding speed of 70 m/win.

Regarding the stretched tape thus obtained, Example 1
The apparent specific gravity measured in the same manner as above was 1.08, and the porosity was 12.3%. However, the thickness was about 35μ and the width was about 8111O1.

Since the thickness was too large compared to the tapes obtained in Example 1 and Reference Example 1-1, the physical properties were not compared.

Reference Example 1-3 In Reference Example 1-2, the thickness of the film was set to about 40 μm, and this was stretched in the same manner. However, in this case, the film could only be stretched at a stretching ratio of 3 times. The stretched tape produced in this way was measured. The apparent specific gravity is 1
．． 15, and the porosity was 6.7%. The thickness of the tape was approximately 25μ and the width was 9mm.

Various physical properties of this tape were measured in the same manner as in Example 1.

These results are shown in Table 1.

(Left below) Example 2 Using the stretched tape produced in Example 1, NCLm
A woven fabric with a width of 1800 nm was woven using the t& with a number of threads of 12/inch x 12/inch, and a woven fabric with a plain weave structure was woven at the highest weaving speed of this loom, 150 rpm. There were no troubles during weaving during the approximately 20 hours of operation, and a white fabric that was soft, opaque, and free of strings could be obtained.

It feels soft to the touch and does not feel sticky, and even when bent or folded, it does not produce the unpleasant clinking sound that occurs with conventional plastic stretched tape fabrics. It had an image of luxury that was not present in conventional plastic stretched tapes.

The tensile strength, elongation, bending resistance of the fabric made in this way,
Young's modulus and bending recovery properties were measured.

These measurement conditions are as follows.

Tensile strength and elongation: Cut the obtained fabric into 30 mm width,
℃, 50% humidity atmosphere, 200mm between chucks.

Measured at a tensile speed of 50 mm/ffl1n.

Bending resistance: The obtained fabric was cut into 25 mm width and heated at 23°C.
In an atmosphere of 50% humidity, it is indicated by l in Fig. 1 according to the method of JIS L-1004.

Young's modulus: In the above tensile test, it is determined as the initial tensile resistance. In this case, the cross-sectional area was not converted.

Bending recovery = 23°C, 50% humidity atmosphere, JISL
- According to the method of 1004, 2
After applying a load of 00 g for 5 minutes, the weight was removed, and the recovery angle θ was measured 5 minutes after the weight was removed.

These evaluation results are shown in Table 2.

Reference Example 2-1 Using the stretched tape produced in Reference Example 1-1, a woven fabric was produced under the same weaving conditions as in Example 2.

There were no problems during weaving, but the finished fabric was translucent, like plastic, and stiff and stiff.
It doesn't feel good to the touch, and when you bend or fold it,
There was an unpleasant clanking sound.

Various physical properties of this fabric were measured in the same manner as in Example 2.

These evaluation results are shown in Table 2.

Reference Example 2-2 Using the stretched tape produced in Reference Example 1-3, weaving was attempted under the same weaving conditions as in Example 2. Weaving was extremely difficult due to thread breakage and fuzziness during weaving. Therefore, the weaving speed was lowered to 50 rpm, one third of that in Example 2, and weaving was carried out. Even so, the tape still broke during weaving and fuzzing due to warping occurred, so weaving was stopped after about 1 hour.

The fabric thus obtained had a white appearance and no plastic-like transparency and met the purpose of the present invention, but it was stiff and stiff and had a poor feel, and in this respect it It wasn't fit for purpose. Moreover, the tensile strength was also low. This fabric was evaluated in the same manner as in Example 2, and the results are shown in Table 2.

(Left below) Example 3 Mll, 5, ratio ii 0.905, polypropylene with a melting point of 169°C, magnesium hydroxide powder with an average particle size of 2.5μ, 2,6-di-tert-butyl-4-methyl as a stabilizer A filling composition was prepared in the same manner as in Example 1-1 by blending phenol and butyl stearate as an additive in the composition shown in Table 3, and forming the film used in Example 1-1. Using a machine, extrude at a resin temperature of 215℃,
A film with a thickness of 80 μm was formed. This film is 3rd grade
Slit to 0mm, and use an oven stretching machine to stretch at a temperature of 12.
A stretched tape was produced under the conditions of 5° C., a stretching ratio of 7 times, and a winding speed of 120 m/min. This tape is approximately 33cm thick
μ, width was approximately 15 mm, and apparent specific gravity was 0.90.

The physical properties of this tape were evaluated in the same manner as in Example 1.

These evaluation results are shown in Table 3.

Reference Example 3 0.1% by weight of 2,6-di-tert-butyl-4-methylphenol was added to the polypropylene used in Example 3, and a film was formed in the same manner as in Example 2-1. The tape was stretched under the following conditions to produce a stretched tape. However, the stretching ratio was 6 times.

The stretched tape produced in this way has a thickness of about 28μ,
The width was approximately 16mra. Example 1 about this tape
Various physical properties were evaluated in the same manner.

These evaluation results are shown in Table 3.

(Left below) Example 4 Using the stretched tape manufactured in Example 3, Example 2
A woven fabric having a width of 1800 am was woven into a twill weave fabric using the loom used in Example 1 at a weaving speed of 150 rpw+ with a number of threads of 8 threads/inch x 8 threads/inch. During the weaving time of about 20 hours, there were no troubles at all during the weaving, and a fabric with a unique texture, soft (and without plastic-like luster) and bluish white in color, could be obtained.

It feels soft to the touch and doesn't have the sticky feel of plastic, and even when bent or folded, it doesn't make the unpleasant squeaking noise that traditional plastic stretched tape fabrics make. However, it had an image of luxury that was not found in conventional plastic stretched tape fabrics.

Various physical properties of the fabric thus produced were measured in the same manner as in Example 2.

These results are shown in Table 4.

Reference Example 4 Using the stretched tape manufactured in Reference Example 3, Example 4
A similar fabric was produced in the same manner as above.

There were no problems during weaving, but the finished fabric had a shiny, transparent plastic-like appearance, was hard and stiff to the touch, and made an unpleasant clanking sound when folded or folded. Also, the workability when folding was poor.

Various physical properties of this fabric were measured in the same manner as in Example 2. These results are shown in Table 4.

(Space below) Example 5 High-density polyethylene with Mlo of 8, specific gravity of 0.959, melting point of 135°C was used, barium sulfate powder with an average particle size of 3 μ was used, and 2.6-di-tert-butyl-4 was used as a stabilizer. - methylphenol, calcium stearate as additive,
The five methylene bisteramides were blended in the composition shown in Table 5, and a filling composition was produced in the same manner as in Example 1.
Next, a film having a thickness of about 120 μm was formed. This film was slit to a width of 50 mm, and stretched using an oven stretching machine at a stretching temperature of 100°C, a stretching ratio of 4 times, and a winding speed of 5 m/wi.
It was stretched at n.

The resulting tape had a thickness of approximately 54 μm, a width of 34 mm, and an apparent specific gravity of 0.92. This tape was opaque yellowish white, soft to the touch, pleasant to the touch, and had a unique texture.

The physical property values of this tape measured in the same manner as in Example 1 are shown in Table 5.

Reference Example 5-1 A stretched tape was produced using the high-density polyethylene used in Reference Example 5 under the same conditions as in Example 5.

The resulting tape had a thickness of approximately 50μ and a width of 3411III+.

This tape was transparent and had a stiff and hard texture.

The evaluation results for this tape are shown in Table 5.

Reference Example 5-2 A stretched tape was manufactured under the same conditions as in Example 5 except that the stretching temperature was 130°C. The obtained tape has a thickness of about 44μ, a medium diameter of 35mm, and an apparent ratio of ffi 1,092
Met. This tape was opaque, but felt hard to the touch.

The evaluation results for this tape are shown in Table 5.

(The following is a blank space) Example 6 The fabric produced in Example 2 was laminated and its lamination properties were examined.

The lamination method is extrusion lamination.
Using high-pressure polyethylene with an MI of 5 and a ratio of ff of 10.918, lamination was performed on one side at an extrusion temperature of 260° C. and an average lamination thickness of 30 μm.

Lamination properties were good, adhesion was good, and there was no peeling after lamination.

In the same manner as in Example 2 for the laminated fabric,
Tensile strength, elongation, bending resistance, and elastic recovery rate were measured.

These evaluation results are shown in Table 6.

(The following is a blank space) Example 7 A printing test was conducted on the fabric produced in Example 2 using a gravure printing machine to examine printability.

In this case printing was carried out using a printing ink for polyopins.

The printability was very good, and even when the printed parts were rubbed against each other, there was almost no peeling of the printed parts. We also pasted cellophane tape on the printed surface and rapidly peeled it off to see how much the printed surface peeled off.
0% remained without peeling.

Reference Example 7-1 The fabric produced in Reference Example 2-1 was tested for printability in the same manner as in Example 7.

When the printed parts were rubbed against each other, most of the printed parts came off. In addition, in a peel test using Sellotape, only about 5% of the printed surface remained in terms of area.

Reference Example 7-2 The woven fabric produced in Reference Example 2-2 was tested for printability in the same manner as in Example 7.

When the printed parts were rubbed against each other, a considerable portion of the printed parts came off. In addition, in a peel test using Sellotape, only about 20% of the printed surface remained in terms of area.

Example 8 High density polyethylene used in Example 1 44.9
% by weight, powder of ground calcium carbonate 55.0% by weight, and 0.1% by weight of 2,6-di-tert-butyl-4-methylphenol.
% lauryl alcohol per 100 parts by weight of the mixture. 1.0 parts by weight of oleic acid amide was added and mixed for 30 minutes using a ribbon blender to prepare a mixture.

The mixture was heated and kneaded in a Banbury mixer at a temperature of 220° C. for 3 minutes to obtain a filled composition.

This composition was extruded with a 401 extruder through a 1.0 φ spinneret at a resin temperature of 250°C, the strand was cooled with cooling water of 30°C, and then rolled up in hot water at 96°C with a stretching ratio of 10 times. A 500 denier monofilament was produced at a speed of 80 m/+ein.

The apparent specific gravity of this monofilament was 0.94. The appearance was white and opaque, and when a few meters of it were grasped and rubbed, it felt soft and felt like cotton thread. The tensile elongation, bending resistance, and Young's modulus of this monofilament were measured using the same method and conditions as in Example 1. Note that the tensile strength is expressed in grams per denier.

These evaluation results are shown in Table 7.

Reference Example 8 High density polyethylene used in Example 8 99.9% by weight
, 2,6-ditert-butyl - 4-methylphenol 0゜1
A monofilament of 500 denier was produced in the same manner as in Example 8 by blending the following amounts by weight%. However, in order to adjust to 500 denier, the extrusion amount was slightly different from Example 8.

This monofilament had a transparent appearance similar to that of plastic, and when several meters of it were grasped and rubbed in the hands, it felt hard and stiff and had a very bad feel.

The physical properties of this monofilament were measured in the same manner as in Example 8. The evaluation results are shown in Table 7.

Example 9 Using the monofilament produced in Example 8, a woven fabric with a basis weight of approximately 50 g/m was knitted using a warp knitting machine using a stockinette knitting machine.

This knitted fabric was white, opaque, and soft, as if it were made from cotton thread.

Regarding this knitted fabric, tensile strength and elongation were determined in the same manner as in Example 2.
Bending resistance and Young's modulus were measured.

The results are shown in Table 8.

Reference Example 9 Using the monofilament produced in Reference Example 8, Example 9
I made the knitted fabric in the same way.

This knitted fabric was transparent, shiny, stiff, and had a stiff feel.

Regarding this knitted fabric, tensile strength and elongation were determined in the same manner as in Example 8.
Bending resistance and Young's modulus were measured.

The results are shown in Table 8.

(Left below) Examples 9-1 to 9-3 62.9% by weight of high-density polyethylene used in Example 1
, heavy calcium carbonate powder 35.0% by weight, 2゜6-
A pellet-shaped filling composition was prepared in the same manner as in Example 1 using 0.1% by weight of di-tert-butyl-4-methylphenol and 2.0% by weight of the compounds shown in Table 9.

This composition was compression molded to form a sheet with a thickness of 1 mm.

Next, a test piece was cut out from this sheet and its stretchability was examined. The method of examining the stretchability is to pull the test piece at a temperature of 23° C. and determine the elongation at break according to the tensile test method of STM D-638. In this method, a large elongation at break, that is, a large elongation at break, basically indicates excellent stretchability. Therefore, a composition with a high elongation at break can be stably stretched, and is advantageous for industrial production of stretched products.

Reference Examples 9-1 to 9-2 The stretchability of the filled compositions was examined in the same manner as in Examples 9-1 to 9-3. The composition of the filling composition and the types of compounds in these cases are as shown in Table 9.

These results are shown in Table 9, and the following can be said.

That is, looking at the effects of adding the compounds and the types of compounds, higher alcohols, higher fatty acid esters, and higher fatty acid amide compounds (Examples 9-1 to 9-3) were better than higher amine compounds (for reference). Example 9-1) and a composition that does not contain these compounds (Reference Example 9-2), it has excellent stretchability,
Industrially advantageous.

(Left below) Example 10-1 High-density polyethylene used in Example 1, calcium carbonate powder, 236-di-tert-butyl-4-methylphenol, erucic acid amide, stearyl alcohol, and further low-density polyethylene (MI7.O1 A filling composition was prepared in the same manner as in Example 1 except that the specific gravity was 0.921 and the melting point was 108°C. This composition was then extruded using a 65IllIII extruder equipped with a T-die at a temperature of 200° C. to form a film having a width of 90 ca+ and a thickness of 50 μm. Next, this film was stretched on a uniaxial roll stretching machine at a roll temperature of 60°C.
, uniaxial stretching was carried out at a take-up speed of 20 m/min. Using this method, the maximum stretchable stretch ratio and porosity at that time for each filling composition were determined. In this method, the higher the maximum stretching ratio, the better the stretching property, the more stable the stretching, and the higher the porosity, which is industrially advantageous. The film after stretching has a width of about 85 cm and a thickness of about 35 μm, although this varies depending on the stretching.

The raw material composition on each side is as shown in Table 10.

Reference Example 10-1 Evaluation was performed in the same manner as in Example 10-1 except that only the type of compound was changed. The results are shown in Table 10.

From Table 10, the amide compound and alcohol compound are
It is recognized that the stretching improvement effect is greater than that of the amine compound, and the achieved porosity is greater.

Note that the maximum stretch ratio that can be stretched in Example 10-1 is lower than in other Examples, but this is because the base polymer uses low-density polyethylene produced by a high-pressure method, and the stretching method is different. The main cause is axial stretching during restraint.

As mentioned above, the stretched products of the present invention, as well as knitted net products and woven products made from the stretched products, have excellent features that are not found in conventional polyolefin products. , highly suitable for a wide range of applications.

(Margin below)

[Brief explanation of drawings]

The drawing is a schematic diagram of a measuring method used to quantitatively express the effects of the present invention. FIG. 1 relates to a method for measuring bending resistance, and is for a hole having a length of 250 mm. 1 is a sample. 2 to 4 show a method for measuring bending recovery properties, where 1 is the stand, 2 is the sample, 3 is the load, and θ is the angle after the load is removed.

Claims (1)

[Claims] (1) Based on 100 parts by weight of a polyolefin containing 10 to 70% by weight of an inorganic filler, selected from the group of monohydric higher alcohols, derivatives thereof (not including ether compounds), higher fatty acid esters, and higher fatty acid amides. The base material is a polyolefin composition containing 0.1 to 10 parts by weight of one or more types, and the porosity after stretching is 10 to 60.
% polyolefin stretched product.