JP2003138419A - Hot-melt monofilament or yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot-melt monofilament or a yarn capable of hot-melted at a low temperature by using a propylene polymer and a product using the same. SOLUTION: This hot-melt monofilament or yarn comprises a propylene/α- olefin random copolymer polymerized by using a metallocene catalyst, containing 1-18 mole% α-olefin and having 0.5-30 g/10 minute MRF (melt flow rate), 2-4 Q value, <=3 wt.% soluble part at 0 deg.C by TREF (temperature rising elution fractionation) measurement, <10 deg.C T80 -T20 by TREF measurement and 110-135 deg.C Tm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a monofilament or yarn excellent in low-temperature fusion property and a product using the same.

[0002]

2. Description of the Related Art Conventionally, synthetic resins such as polyester resins, polyamide resins, polyvinyl chloride resins, polyolefin resins, etc. have been used for various nets, insect repellent nets, carpet base cloths and laminated cloth bags. It is manufactured by weaving a monofilament or drawn yarn consisting of a single component of the above into a warp shape.

However, when a woven fabric composed of a single component of synthetic resin is used, a misalignment occurs due to the fact that the crossing portion is not blocked, and in particular, the misalignment from a cut portion such as a net cloth or a base cloth. Since it becomes remarkable, there is a problem that workability is significantly hindered and a bonding step using binder fibers is required.

Further, in the case of laminating a film of polyolefin or the like on both sides of a woven or knitted base cloth such as a cloth sheet to strengthen the strength of the base cloth, conventionally, a base material obtained by weaving a polyethylene-based stretched yarn is used. Although a method of laminating a low-density polyethylene film on a cloth is generally used, it is preferable to use a propylene-based polymer as a base cloth in a field where a cloth sheet having high strength is required. However, when a propylene-based polymer is used as the base fabric, the use of a polyethylene-based film as the laminate material causes a problem that the interfacial peeling becomes remarkable. On the other hand, when a propylene-based film is used as a laminating material, it is necessary to set the laminating temperature to a high temperature, which causes a problem that the shrinkage of the base fabric on the laminated side becomes remarkable. As a solution to such a problem, Japanese Patent Application Laid-Open No. 11-48418 has developed a technique of using polyethylene polymerized by a metallocene catalyst as a heat-fusible film, but in terms of adhesive strength, etc. It wasn't enough.

[0005]

In view of the above situation, the present invention provides a heat-fusible monofilament or yarn which can be fused at a low temperature by using a propylene-based polymer, and a product using them. That is the purpose.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that monofilaments or yarns using a specific propylene / α-olefin random copolymer polymerized with a metallocene catalyst, particularly When a composite yarn or core-sheath type composite monofilament in which a specific propylene / α-olefin random copolymer polymerized with a metallocene catalyst and a propylene homopolymer are laminated is used for a net fabric, etc. The present invention has been completed by finding that they can be fused at low temperature and have excellent adhesive strength.

That is, according to the first aspect of the present invention,
Polymerized by a metallocene catalyst, the following conditions (1) ~
A heat-fusible monofilament or yarn comprising a propylene-based resin containing at least one component of propylene / α-olefin random copolymer satisfying (6) is provided. (1): Content of α-olefin is 1 to 18 mol% (2): MFR is 0.5 to 30 g / 10 minutes (3): Q value is 2 to 4 (4): 0 ° C is acceptable by TREF measurement. extractable content is 3 wt% or less _{(5): TREF T 80 -T} 20 is less than 10 ° C. by measuring (6): Tm is 110 to 135 ° C. (however, MFR is 230 ° C. by JIS-K6921,
The melt flow rate at 21.18 N and the Q value are the ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC, and T ₈₀ is the temperature rising elution fractionation (TR
In the integrated elution curve obtained by EF), the temperature at which 80% by weight is eluted, T ₂₀ is the temperature at which 20% by weight is eluted, and Tm is the peak temperature of the melting curve obtained by a differential scanning calorimeter (DSC). )

According to the second aspect of the present invention, the polymerization is carried out by a metallocene catalyst and the following conditions (1) to (6) are satisfied.
A heat-fusible yarn comprising a laminate of a propylene / α-olefin random copolymer layer and a propylene homopolymer layer satisfying the above requirements. (1): α-olefin content of 1 to 18 mol% (2): MFR of 0.5 to 30 g / 10 minutes (3): Q value of 2 to 4 (4): Soluble at 0 ° C. by TREF measurement. Content is 3% by weight or less (5): T ₈₀ -T ₂₀ by TREF measurement is 10 ° C or less (6): Tm is 110 to 135 ° C (however, MFR is 230 ° C according to JIS-K6921,
The melt flow rate at 21.18 N and the Q value are the ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC, and T ₈₀ is the temperature rising elution fractionation (TR
In the integrated elution curve obtained by EF), the temperature at which 80% by weight is eluted, T ₂₀ is the temperature at which 20% by weight is eluted, and Tm is the peak temperature of the melting curve obtained by a differential scanning calorimeter (DSC). )

According to the third aspect of the present invention, the polymerization is carried out by a metallocene catalyst, and the following conditions (1) to (6) are satisfied.
A core-sheath type heat-fusible monofilament is provided, which comprises a propylene / α-olefin random copolymer satisfying the above as a sheath material and a propylene homopolymer as a core material. (1): α-olefin content of 1 to 18 mol% (2): MFR of 0.5 to 30 g / 10 minutes (3): Q value of 2 to 4 (4): Soluble at 0 ° C. by TREF measurement. Content is 3% by weight or less (5): T ₈₀ -T ₂₀ by TREF measurement is 10 ° C or less (6): Tm is 110 to 135 ° C (however, MFR is 230 ° C according to JIS-K6921,
The melt flow rate at 21.18 N and the Q value are the ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC, and T ₈₀ is the temperature rising elution fractionation (TR
In the integrated elution curve obtained by EF), the temperature at which 80% by weight is eluted, T ₂₀ is the temperature at which 20% by weight is eluted, and Tm is the peak temperature of the melting curve obtained by a differential scanning calorimeter (DSC). )

According to a fourth aspect of the present invention, the first aspect
Alternatively, there is provided a carpet base fabric using the heat-fusible yarn according to the second aspect of the invention.

According to the fifth aspect of the present invention, the first aspect
Alternatively, there is provided a cloth sheet or a laminated bag using the heat-fusible yarn according to the second invention.

According to a sixth aspect of the present invention, the first aspect
Alternatively, a net fabric using the heat-fusible monofilament according to the invention of 3 is provided.

According to a seventh aspect of the present invention, the first aspect
Or, an insect repellent net using the heat-fusible monofilament according to the invention of 3 is provided.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The propylene / α-olefin random copolymer used in the present invention is a copolymer obtained by using a metallocene catalyst. The metallocene catalyst is a catalyst that uses a complex of a transition metal of Groups 4 to 6 of the periodic table such as titanium, zirconium, and hafnium with a cyclopentadienyl group or a cyclopentadienyl derivative group.

In the metallocene catalyst, the cyclopentadienyl derivative group is an alkyl substituent such as pentamethylcyclopentadienyl, or two or more substituents are combined to form a saturated or unsaturated cyclic substituent. A group can be used, and typical examples thereof include an indenyl group, a fluorenyl group, an azulenyl group, and partial hydrogenated products thereof. Further, those in which a plurality of cyclopentadienyl groups are bound by an alkylene group, a silylene group, a germylene group or the like are also preferably used.

Specific examples of the metallocene complex preferably include the following compounds. (1) methylenebis (cyclopentadienyl) zirconium dichloride,
(2) Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (3) Isopropylidene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, (4) ethylene (cyclopentadienyl) (3,5-dimethylpentadienyl) zirconium dichloride, (5) methylenebis (indenyl) zirconium dichloride, (6) Ethylene bis (2-methylindenyl) zirconium dichloride, (7) ethylene 1,2-bis (4-phenylindenyl) zirconium dichloride, (8) ethylene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, (9) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (1
0) dimethylsilylenebis (indenyl) zirconium dichloride, (11) dimethylsilylenebis (4,5,5
6,7-Tetrahydroindenyl) zirconium dichloride, (12) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (1)
3) Dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (1
4) Methylphenylsilylenebis [1- (2-methyl-
4,5-Benzo (indenyl)] zirconium dichloride, (15) Dimethylsilylenebis [1- (2-methyl-4,5-benzoindenyl)] zirconium dichloride, (16) Dimethylsilylenebis [1- (2- Methyl-4H-azulenyl)] zirconium dichloride, (1
7) Dimethylsilylenebis [1- (2-methyl-4-
(4-Chlorophenyl) -4H-azurenyl)] zirconium dichloride, (18) dimethylsilylene bis [1
-(2-Ethyl-4- (4-chlorophenyl) -4H-
Azulenyl)] zirconium dichloride, (19) dimethylsilylenebis [1- (2-ethyl-4-naphthyl-
4H-azurenyl)] zirconium dichloride, (2
0) diphenylsilylene bis [1- (2-methyl-4-
(4-Chlorophenyl) -4H-azurenyl)] zirconium dichloride, (21) dimethylsilylene bis [1
-(2-Methyl-4- (phenylindenyl))] zirconium dichloride, (22) dimethylsilylene bis [1- (2-ethyl-4- (phenylindenyl))]]
Zirconium dichloride, (23) dimethylsilylene bis [1- (2-ethyl-4-naphthyl-4H-azulenyl)] zirconium dichloride, (24) dimethylgermylene bis (indenyl) zirconium dichloride,
(25) Dimethylgermylene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride.

The same compounds as those mentioned above can be used for other Group 4, 5 and 6 transition metal compounds such as titanium compounds and hafnium compounds. These compounds may be used in combination with the catalyst component and catalyst of the present invention.

Further, compounds in which one or both of the chlorides of these compounds are replaced by bromine, iodine, hydrogen, methylphenyl, benzyl, alkoxy, dimethylamide, diethylamide and the like can be exemplified. further,
Instead of the above zirconium, compounds in which titanium, hafnium, etc. are replaced can be exemplified.

The cocatalyst is composed of an ionic compound capable of reacting with an aluminum oxy compound or a metallocene compound to convert the metallocene compound component into a cation, a Lewis acid, a solid acid, or an ion-exchange layered silicate. At least one compound selected from the group is used. Moreover, an organoaluminum compound can be added together with these compounds as needed.

Examples of the aluminumoxy compound include methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane, methylethylalumoxane, methylbutylalumoxane, methylisobutylalumoxane and the like.
It is also possible to use a reaction product of a trialkylaluminum and an alkylboronic acid. For example, a 2: 1 reaction product of trimethylaluminum and methylboronic acid, a 2: 1 reaction product of triisobutylaluminum and methylboronic acid, a 1: 1: 1 reaction product of trimethylaluminum and triisobutylaluminum and methylboronic acid, triethylaluminum and butylboron. 2: 1 reaction of acid and the like.

As the ion-exchange layered silicate, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite,
A silicate such as a smectite group such as bentonite or teniolite, a vermiculite group, or a mica group is used.
It is preferable that these silicates have been chemically treated. Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure and chemical composition of the layered silicate can be used. Specifically, (a) acid treatment, (b) alkali treatment, (c) salt treatment, (d) organic substance treatment and the like can be mentioned. These treatments remove impurities on the surface, exchange cations between layers, and elute cations such as Al, Fe, and Mg in the crystal structure, resulting in ionic complexes, molecular complexes, organic derivatives, etc. Can be formed to change the surface area, interlayer distance, solid acidity, and the like. These treatments may be performed alone or two or more treatments may be combined.

If necessary, triethylaluminum, triisobutylaluminum,
Organoaluminum compounds such as diethyl aluminum chloride may also be used.

In the present invention, a propylene / α-olefin random copolymer is obtained by using the above metallocene catalyst. Examples of the α-olefin include α-olefins having 2 to 20 carbon atoms excluding propylene, and examples thereof include ethylene, butene-1, pentene-1,3-methyl-1-butene, hexene-1,3-methyl-1. -Penten, 4-
Methyl-1-pentene, heptene-1, octene-1,
Examples include nonene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1, octadecene-1, eicosene-1. Α-copolymerized with propylene
The olefins may be used alone or in combination of two or more. Of these, ethylene and butene-1 are preferable.

As the polymerization method, in the presence of these catalysts,
Examples thereof include a slurry method using an inert solvent, a gas phase method or a solution method substantially using no solvent, and a bulk polymerization method using a polymerization monomer as a solvent.

The propylene / α-olefin random copolymer used in the present invention is a copolymer polymerized by the above-mentioned metallocene catalyst and must have the following properties (1) to (6). is there.

(1) α-Olefin Content The content of α-olefin (comonomer) in the propylene / α-olefin random copolymer used in the present invention is 1
It is necessary to adjust to -18 mol%. The comonomer content is preferably 2.5-10 mol%, more preferably 3-8 mol%. Particularly when the comonomer is ethylene, 1 to 12 mol% is preferable. If the comonomer content is less than the above range, the melting point will be high, and the sheath and outer layer parts will not function as fusion. On the other hand, if the amount is too large, the fabric becomes too soft, which adversely affects the woven processability. The α-olefin content in the polymer can be easily adjusted by controlling the amount of α-olefin supplied to the polymerization reaction system. In the present invention, the α-olefin content is quantified by a Fourier transform infrared spectrophotometer.

(2): MFR MFR is 230 ° C. according to JIS-K6921, 21.
It represents the melt flow rate at 18N. MF of propylene / α-olefin random copolymer used in the present invention
R is 0.5 to 30 g / 10 minutes, and preferably 0.
8 to 25 g / 10 minutes, more preferably 1.0 to 2
It is 0 g / 10 minutes. When the MFR is less than 0.5 g / 10 minutes, the spinning pressure becomes too high, which causes adverse effects such as operability, fiber diameter, and uneven film thickness. Conversely, 30 g /
If it exceeds 10 minutes, the melt viscosity is low, so that the yarn sway becomes noticeable just below the nozzle during monofilament molding,
Thread breakage occurs due to contact between adjacent threads,
In the case of yarn molding, the inflation film becomes unstable, which causes a problem of impairing productivity.
To control the MFR of a polymer, for example, the polymerization temperature,
There is a method of appropriately adjusting the catalyst amount, the supply amount of hydrogen as a molecular weight modifier, or a method of adjusting by adding a peroxide after completion of the polymerization.

(3): Q value The Q value represents the ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC. The propylene / α-olefin random copolymer used in the present invention has a Q value of 2 to 4, preferably 2.2 to 3.7, and more preferably 2.3 to 3.5. When the Q value exceeds 4, there is a problem that the stretchability is impaired due to the presence of the high molecular weight component. On the other hand, when it is less than 2, since the high molecular weight component is too small, in the case of monofilament molding, the viscosity of the molten monofilament immediately below the spinneret becomes low, and the yarn swaying accompanying it becomes remarkable, and the spinning stability is improved. Damaged and not preferable. In the yarn molding, there is a problem that bubbles are not stable due to the low viscosity during the inflation film molding. The method for adjusting the Q value of the propylene / α-olefin random copolymer is preferably carried out by using a catalyst system in which two or more metallocene catalyst components are used in combination or a catalyst system in which two or more metallocene complexes are used in combination. Alternatively, the Q value can be widely controlled by carrying out multi-stage polymerization of two or more stages during the polymerization. On the contrary, in order to adjust the Q value narrowly, it can be adjusted by polymerizing the propylene / α-olefin random copolymer and then melt-kneading it with an organic peroxide.

The Q value is specifically measured under the following conditions. Apparatus: Waters HLC / GPC 150C Column temperature: 135 ° C. Solvent: o-dichlorobenzene Flow rate: 1.0 ml / min Column: Tosoh Corporation GMH _HR- H (S) HT 60 cm × 1 Injection amount: 0.15 ml (No filtration treatment) Solution concentration: 5 mg / 3.4 ml Sample preparation: Using o-dichlorobenzene, adjust to a solution of 5 mg / 3.4 ml and dissolve at 140 ° C. for 1 to 3 hours. Calibration curve: A polystyrene standard sample was used. Calibration curve order: primary PP molecular weight: PS x 0.639

(4): 0 ° C. soluble content in TREF measurement is 3% by weight or less In the propylene / α-olefin random copolymer used in the present invention, 0 ° C. soluble content is 3% by weight or less,
It is preferably 1.0% by weight or less, more preferably 0.5% by weight or less, particularly preferably 0.3% by weight.
It is the following. The low molecular weight component occupies most of the 0 ° C soluble content, which causes stickiness of the woven fabric. When it exceeds 3% by weight, the woven fabric becomes significantly sticky, which causes a decrease in productivity in the weaving process, which is not preferable. Propylene / α-olefin random copolymer TREF 0 ° C
The amount of the soluble component is, when the metallocene catalyst component is loaded on the carrier, when the polymerization is carried out using a catalyst whose loading is non-uniform,
The low molecular weight increases, and the amount of TREF 0 ° C. solubles increases accordingly. Therefore, by polymerizing using a catalyst in which the metallocene catalyst component is uniformly supported on the carrier, T
The amount of the REF0 ° C soluble component can be adjusted to 3% by weight or less.

(5): T₈₀-T₂₀ T₈₀Is obtained by elevated temperature elution separation (TREF)
In the elution curve, the temperature at which 80% by weight elutes, T₂₀
Represents the temperature at which 20% by weight elutes. Used in the present invention
In propylene / α-olefin random copolymer
Is T₈₀-T ₂₀Is 10 ° C. or less, preferably 2
-9 ° C, more preferably 2-8 ° C. T₈₀
-T₂₀When the temperature exceeds 10 ° C, the low melting point component increases
Therefore, the deterioration of surface slip characteristics when using woven fabric
This causes adverse effects such as deterioration of filament spinning performance. polymer
Of T₈₀-T₂₀Is in a certain narrow range as above
This means that the molecular weight distribution of the polymer is more uniform.
I mean. Propylene / α-olefin random
Polymer T₈₀-T₂₀There are two or more ways to adjust
A catalyst system in which metallocene catalyst components are used in combination or two or more kinds of meta
By polymerizing using a catalyst system in combination with a rosene complex
, T₈₀-T₂₀Can be greatly adjusted. Well
In addition, when loading the metallocene catalyst component on the carrier,
Low molecular weight component when polymerized using a homogeneous catalyst
Is increasing, and T_{8 0}-T₂₀Will grow
U Therefore, the metallocene catalyst component is uniformly loaded on the carrier.
The technology to do is important.

Here, the temperature rising elution fractionation (TRE
F) means that the polymer is completely dissolved in the presence of an inert carrier at a constant high temperature and then cooled to form a thin polymer layer on the surface of the inert carrier, and then the temperature is continuously or gradually increased. This is a method in which the temperature is raised, the eluted components are recovered, the concentration thereof is continuously detected, and the composition distribution of the polymer is measured by a graph (integrated elution curve) drawn by the elution amount and the elution temperature. For more information on elevated temperature elution fractionation (TREF) measurements, see Journal of Appl.
ied Polymer Science Vol. 26, pp. 4217-4231 (1981), and the present invention is also carried out accordingly.

Note that T ₈₀ -T ₂₀ is specifically a value measured under the following conditions. As a measuring device, CFC T-102L manufactured by Dia Instruments is used. First, a sample to be measured is dissolved in a solvent (o-dichlorobenzene) at 140 ° C. so as to be 3 mg / ml, and this is dissolved in the measuring device. Inject into the sample loop of. The following measurements are automatically performed according to the set conditions. The sample solution held in the sample loop is separated into a TREF column (a stainless steel column with an inner diameter of 4 mm and a length of 150 mm, which is filled with an inert carrier, glass beads), which is separated by utilizing the difference in melting temperature. 0.4 ml is injected. The sample is then run from 140 ° C to 0 at a rate of 1 ° C / min.
Allow to cool to a temperature of ° C. After the TREF column was kept at 0 ° C. for another 30 minutes, 2 ml of the dissolved component at 0 ° C. was passed through the SEC from the TREF column at a flow rate of 1 ml / min.
It is injected into a column (3 AD806MS manufactured by Showa Denko). While molecular size separation is being performed by SEC, T
In the REF column, the temperature was raised to the next elution temperature (10 ° C),
Hold at that temperature for about 30 minutes. The measurement of each elution section by SEC is performed at intervals of 39 minutes. Elution temperature is 0 ℃ to 4
0 ° C every 10 ° C, 40 ° C to 90 ° C every 5 ° C,
From 90 ° C to 140 ° C, the temperature is raised stepwise at every 4 ° C. The solution separated by the molecular size in the SEC column is detected by an infrared spectrophotometer attached to the apparatus, and a chromatograph in each elution temperature section can be obtained. The infrared spectrophotometer performs detection using the absorbance at a detection wave number of 3.42 μm, and the following data processing is performed assuming that the amount of the polymer component in the solution is proportional to the absorbance. The chromatogram in each elution temperature segment is processed by the built-in data processing software, and the elution amount in each elution temperature segment is calculated based on the area of each chromatogram so that the integration is 100%. Furthermore, an integrated elution curve is created from the elution amount of each elution temperature segment obtained. The 0 ° C. soluble content indicates the amount (%) of the polymer component eluted at 0 ° C., and T ₂₀ is the cumulative elution amount of 20.
%, And T ₈₀ is the temperature at which the cumulative elution amount becomes 80%.

(6): Tm (melting peak temperature) Tm represents the peak temperature of the melting curve obtained by a differential scanning calorimeter (DSC). The Tm of the propylene / α-olefin random copolymer used in the present invention is 110-110.
It is 135 ° C. If the Tm exceeds 135 ° C., it is necessary to set the fusion temperature high when laminating the film between filaments or the yarn, which causes a problem that the shrinkage of the filament or the yarn itself becomes significant. On the other hand, when the temperature is lower than 110 ° C., the filament or yarn becomes too soft, which adversely affects the weavability. The Tm can be easily adjusted by controlling the amount of α-olefin supplied to the polymerization reaction system.

A specific measurement of Tm was made by using a differential scanning calorimeter (DSC) manufactured by Perkin Elmer Co., Ltd., a sample amount of 10 mg was taken, and the sample was kept at 200 ° C. for 5 minutes, and then 40
Crystallize up to 10 ° C at a rate of 10 ° C / min, then 10 ° C
The melting peak temperature Tm (° C.) is the peak position of the curve drawn when melting is performed at a heating rate of / min.

The propylene / α-olefin random copolymer of the present invention contains various additives such as a heat resistance stabilizer, an antioxidant, a weather resistance stabilizer and an ultraviolet absorber within a range not impairing the object of the present invention. , A crystal nucleating agent, a copper damage inhibitor, an antistatic agent, a slip agent, an anti-blocking agent, an antifogging agent, a colorant, a filler, an elastomer, a petroleum resin, and the like,
It can be a polypropylene resin composition.

The polypropylene resin composition, which is a molding material for monofilaments or yarns in the present invention, contains the above-mentioned propylene / α-olefin random copolymer and, if necessary, the above-mentioned various additives, and further other resin components. Using a dry blended state or a melt kneader,
It is preferably melt-kneaded by heating at 180 to 300 ° C. and provided in the form of pellets cut into particles.

The monofilament of the present invention is formed by a known method using the above polypropylene resin composition. The monofilament may have a single, core-sheath, or side-by-side composite monofilament shape. In the case of a composite monofilament, it is preferable to use a propylene homopolymer as the core material and the above propylene resin composition as the sheath material. The fineness of the polypropylene fiber is not particularly limited, but is 0.01 to 2000.
Decitex is preferable, and more preferably 0.1-10.
It is 00 decitex.

The yarn of the present invention is formed by forming a film by a known method using a propylene / α-olefin random copolymer, slitting and heating and stretching. Preferably, it is obtained by forming a laminated film with a propylene homopolymer, slitting and stretching. As the laminate, a three-layer structure in which a layer made of a propylene homopolymer is used as an inner layer and the above-mentioned propylene / α-olefin random copolymer composition is used as both outer layers is preferable. Demonstrate wearability.

The knitted woven fabric using the heat-fusible monofilament of the present invention, in particular, the core-sheath type composite monofilament, is excellent in insect repellent property and air-permeability, which is stopped by the heat-sealing by utilizing its low-temperature heat-sealing property. It can be used as a net material having properties and an insect repellent net obtained therefrom.
The heat-fusible yarn can be preferably used as a material for a carpet base cloth, a laminating bag, a cross sheet or a laminated bag, for example, a woven fabric using a drawn yarn having a three-layer structure as warp and weft. .

[0041]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. The measurement of physical properties and the like is as follows. In addition, a method for producing a resin constituting the resin composition used in Examples and Comparative Examples is shown in Polymerization Examples.

(1) MFR measuring method: JIS-K692
1-2 Measured according to Annex. (Condition: temperature / 230
℃, load 21.18N)

(2) Q value: The measurement was performed according to the method described above. Calibration curve: The polystyrene standard sample in Table 1 was used.

[0044]

[Table 1] Calibration curve order: Primary PP molecular weight: PS x 0.639

(3) Temperature rising elution fractionation (TREF) T ₈₀ -T ₂₀ , 0 ° C. Soluble content: measured by the above-mentioned method.

(4) Melting peak temperature (Tm): Measured by the method described above.

(5) Peel strength of composite monofilament:
Sealing temperature of 130 ° C and pressurizing condition of 2 kgf / cm with a heat seal tester manufactured by Yasuda Seiki Co., Ltd. in a state where two monofilaments having a length of 100 mm are cross-crossed.
^2. After fusing under the condition of 1 ^second , one side of each monofilament was sandwiched by a chuck by a Toyo Seiki Co., Ltd. strograph, and the tensile speed was measured at 50 mm / min. The peeling strength was defined as the strength at which the fusion-bonded portion peeled off.

(6) Peel strength between woven fabric made of laminated yarn and laminated film: The woven fabric and laminated film were applied with a heat seal tester manufactured by Yasuda Seiki Seisaku-sho, Ltd. at a sealing temperature of 150 ° C. and a sealing width of 15 mm. Pressure condition 2kgf
/ Cm ² , after fusing under the condition of 1 second, a pulling speed of 100 mm / by a Toyo Seiki Co., Ltd. strograph
Measured in minutes. The peeling strength was defined as the strength at which the fusion-bonded portion was peeled off.

Polymerization Example 1 (1) Preparation of catalyst Into a three-necked flask (volume: 1 L), 20 g of a smectite group silicate (Ben clay SL manufactured by Mizusawa Chemical Co., Ltd.) sequentially treated with sulfuric acid and 200 mL of heptane were charged. It was treated with 50 mmol of trinormal octylaluminum and then washed with heptane to obtain a slurry 1. In another flask (volume 200 mL), heptane 90 mL, [(r) -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}]
Zirconium] 0.3 mmol and triisobutylaluminum 1.5 mmol were prepared as a slurry 2. Slurry 2 was added to Slurry 1 and stirred at room temperature for 60 minutes. Thereafter, 210 mL of heptane was added, and this slurry was introduced into a 1 L autoclave. After the internal temperature of the autoclave was set to 40 ° C, propylene was fed at a rate of 10 g / hour to carry out preliminary polymerization while maintaining 40 ° C for 4 hours.
The residual polymerization was carried out for a period of time to obtain 83 g of a preliminary polymerization catalyst.

(2) Production of propylene / α-olefin random copolymer In a reactor having an internal volume of 270 L, liquid propylene, ethylene,
Hydrogen, and triisobutylaluminum (TIBA)
Was continuously supplied to maintain the internal temperature at 70 ° C. The supply amount of propylene was 38 kg / hr, the supply amount of ethylene was 0.65 kg / hr, the supply amount of hydrogen was 0.12 g / hr, and the supply amount of TIBA was 18.0 g / hr. It was The pre-polymerization catalyst was slurried with liquid paraffin to obtain 2.05 g / hr.
It was fed with. As a result, 14.5 kg / hr of propylene / ethylene random copolymer I was obtained. The resulting propylene / ethylene random copolymer I has MFR =
5.8 g / 10 minutes, ethylene content = 3.1 mol%, T
m = 134.2 ° C. and Q value = 2.8.

Polymerization Example 2 Liquid propylene, ethylene,
Hydrogen, and triisobutylaluminum (TIBA)
Was continuously fed to maintain the internal temperature at 62 ° C. The supply amount of propylene was 38 kg / hr, the supply amount of ethylene was 1.1 kg / hr, the supply amount of hydrogen was 0.11 g / hr, and the supply amount of TIBA was 18.0 g / hr. It was The preliminary polymerization catalyst was slurried with liquid paraffin and fed at 1.45 g / hr. As a result, 12.0 kg / hr of propylene / ethylene random copolymer II was obtained. The resulting propylene / ethylene random copolymer II has a MFR =
9.4 g / 10 minutes, ethylene content = 5.0 mol%, T
m = 124.9 ° C. and Q value = 2.7.

Polymerization Example 3 Using the solid catalyst prepared in Polymerization Example 1, the hydrogen supply amount was changed to 0.01 g / hr, and the feed amount of the prepolymerization catalyst made into a slurry with liquid paraffin was changed to 2.70 g / hr. Polymerization was performed in the same manner as in Polymerization Example 2 except for the above. As a result, 13.5 kg / hr of propylene / ethylene random copolymer III was obtained. The obtained propylene / ethylene random copolymer III has MFR = 1.5 g / 1.
0 minutes, ethylene content = 5.0 mol%, Tm = 124.
It was 7 ° C. and the Q value was 2.7.

Polymerization Example 4 Using the solid catalyst prepared in Polymerization Example 1, except that the hydrogen supply was stopped and the prepolymerization catalyst was slurried with liquid paraffin, the feed amount was changed to 4.10 g / hr.
Polymerization was carried out in the same manner as Polymerization Example 2. As a result, 1
3.7 kg / hr of propylene / ethylene random copolymer IV was obtained. The resulting propylene / ethylene random copolymer IV has MFR = 0.8 g / 10 minutes, ethylene content 5.0 mol%, Tm = 124.6 ° C., Q value =
It was 2.6.

With respect to 100 parts by weight of this polymer IV powder, 0.10 parts by weight of a master batch of 3-methylbutene polymer as a crystal nucleating agent as a crystal nucleating agent and 1, 3 as an antioxidant. 5-Tris [(4-tert-
Butyl-3-hydroxy-2,6-xylyl) methyl]
-1,3,5-triazine-2,4,6 (1H, 3H,
5H) -trione (manufactured by Cytec, trade name Sianox 1790) 0.04 parts by weight, tris- (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals, trade name Irgaphos 168) 0.05 part by weight, 0.05 part by weight of calcium stearate (manufactured by Nitto Kasei Kogyo, trade name Ca-St) as a neutralizing agent, and peroxide (Perhexa 25B: manufactured by NOF CORPORATION). After compounding 0.08 parts by weight and mixing at 500 rpm with a Henschel mixer for 3 minutes at high speed, φ50 m
m single screw extruder (made by Union Plastics Co., Ltd.)
Melting, kneading, cooling, and cutting were carried out under the conditions of an extrusion temperature of 230 ° C. to prepare a propylene copolymer composition IV ^* in the form of pellets. As a result, a polymer composition IV ^* having a modified MFR of 5 g / 10 min and a Q value of 1.7 was obtained.

Polymer composition I except that 0.05 part by weight of peroxide (Perhexa 25B, manufactured by NOF CORPORATION) was added to 100 parts by weight of the powder of polymer IV.
The composition was adjusted in the same manner as V ^* to obtain a polymer composition IV ^** . The modified polymer composition IV ^** has an MFR of 2 g / 10
The Q value was modified to 1.8.

Polymerization Example 5 After thoroughly replacing the stirring autoclave with an internal volume of 200 liters with propylene, 60 L of dehydrated and deoxygenated n-heptane was introduced, and 16 g of diethylaluminum chloride and a titanium trichloride catalyst (M and・ M company
4.1 g were introduced at 50 ° C. under a propylene atmosphere. Further, while maintaining the gas phase hydrogen concentration at 6.0% by volume, at a temperature of 50 ° C., 5.7 kg of propylene and 0.2 of ethylene.
After feeding for 4 hours at a rate of 8 kg / hour, the polymerization was continued for another hour. As a result, 12 kg of propylene / ethylene random copolymer V was obtained. The resulting propylene / ethylene random copolymer V had an MFR of 6.4 g /
10 minutes, ethylene content = 5.9 mol%, Tm = 140
C., Q value = 4.4.

Polymerization Example 6 Polymerization was carried out in the same manner as Polymerization Example 5 except that the gas phase hydrogen concentration was 0.8% by volume. As a result, 10 kg of propylene / ethylene random copolymer VI was obtained. The propylene / ethylene random copolymer VI thus obtained had MFR =
1.5 g / 10 minutes, ethylene content = 5.9 mol%, T
m = 140 ° C. and Q value = 4.6.

Table 1 shows the physical properties of the propylene / ethylene random copolymers I to VI produced in the above Polymerization Examples 1 to 6. As is clear from Table 1, the polymers I to III are
The propylene / ethylene copolymer of the present invention having the conditions (1) to (6), wherein the polymer composition IV ^* , IV ^** ,
And the polymers V and VI are copolymers outside the present invention.

[0059]

[Table 2]

Examples 1 to 2 0.10 parts by weight of a master batch of 3-methylbutene polymer as a crystal nucleating agent was added to 100 parts by weight of powders of polymers I to II shown in Table 2. Part, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,
6-xylyl) methyl] -1,3,5-triazine-
0.04 parts by weight of 2,4,6 (1H, 3H, 5H) -trione (manufactured by Cytec, trade name Sianox 1790), tris- (2,4-di-t-butylphenyl) phosphite (Ciba. 0.05 parts by weight of Specialty Chemicals, trade name Irgaphos 168) and 0.05 parts by weight of calcium stearate (Nitto Kasei Kogyo, trade name Ca-St) as a neutralizing agent were weighed. Blend the polymer and additives with a Henschel mixer at 500 rpm, 3
After high-speed mixing for a minute, a φ50 mm single-screw extruder (manufactured by Union Plastics Co., Ltd.) was used and melted, kneaded, cooled and cut under conditions of an extrusion temperature of 230 ° C. to prepare a pellet-shaped propylene copolymer composition. .

Next, the compositions of the polymers I and II thus obtained were used as a raw material for the sheath material, and a propylene homopolymer (FY4; manufactured by Nippon Polychem Co., Ltd.) was used as a raw material for the core material. The number of holes was 40 (pore diameter: 2). Monofilament molding was performed using a core-sheath type composite spinneret of 0.0 mm). The core / sheath ratio is 60/40, the extrusion temperature is 230 ° C., the discharge rate is 4.5 g / min / hole, the final speed is 100 m / min, the draw ratio is 7 times, and the fineness is 450.
A core-sheath type composite monofilament of Decitex was obtained. The peel strength of the obtained composite monofilament was measured. The results are shown in Table 3.

Comparative Example 1 A raw material was prepared and a composite monofilament was produced in the same manner as in Example 1 except that the polymer V was used as the raw material of the sheath material. The peel strength of the obtained composite monofilament was measured. The results are shown in Table 3.

Comparative Example 2 A composite monofilament was produced in the same manner as in Example 1 except that the raw material of the sheath material was high density polyethylene (HY430; manufactured by Nippon Polychem). The peel strength of the obtained composite monofilament was measured. The results are shown in Table 3.

Comparative Example 3 A composite monofilament was produced in the same manner as in Example 1 except that the polymer composition IV ^* was used as a sheath material, but the monofilament was melted just below the spinneret. Fusing occurred remarkably, and a composite monofilament could not be obtained.

[0065]

[Table 3]

As is clear from Table 3, according to each embodiment,
For example, all of these polypropylene-based monofilaments have excellent heat fusion properties.
You can get an filament. On the other hand, melting point, Q value, 0 ° C soluble content
Quantity, T ₈₀-T₂₀Of propylene resin out of range
The monofilament used for is the fusion of filaments
And the peel strength is low and the effect of the present invention is not exhibited.
(Comparative example 1). In addition, high density polyethylene resin is used as the sheath material.
The monofilament used was peeled between the core and the sheath
The strength is low and the effect of the present invention is not exhibited (Comparative Example 2).

Example 3 With respect to 100 parts by weight of Polymer III shown in Table 1, 0.10 part by weight of a master batch of 3-methylbutene polymer as a crystal nucleating agent and 1,3,5-tris as an antioxidant. [(4-Tert-butyl-3-hydroxy-2,6-
Xylyl) methyl] -1,3,5-triazine-2,
0.04 parts by weight of 4,6 (1H, 3H, 5H) -trione (manufactured by Cytec, trade name Syanox 1790), tris- (2,4-di-t-butylphenyl) phosphite (Ciba Specialty. 0.05 parts by weight of Chemicals, trade name Irgaphos 168) and 0.05 part by weight of calcium stearate (manufactured by Nitto Kasei Co., Ltd., trade name Ca-St) as a neutralizing agent are mixed at 500 rpm with a Henschel mixer. After mixing at high speed for 50 minutes, φ50
Using a mm single-screw extruder (manufactured by Union Plastics Co., Ltd.), the pelletized propylene copolymer composition was prepared by melting, kneading, cooling and cutting under the conditions of an extrusion temperature of 230 ° C. Next, the obtained composition was used as an outer layer, and a propylene homopolymer (FY6H; manufactured by Nippon Polychem Co., Ltd.) was used for the inner layer, and three-layer inflation molding was performed. The outer layer / inner layer ratio is 20/60/20, the film is formed under the conditions of the extrusion temperature of 230 ° C. and the discharge rate of 500 g / min, after slitting, the final speed is 100 m / min, the drawing temperature is 110 ° C., and the fineness is 1440 decitex. A three-layer drawn yarn of 11 yarns for both the warp and weft yarns of the yarn using a sruzer type loom
A woven fabric was formed at 2.54 cm.

Next, film formation was carried out using P40-25AB / M-F6 manufactured by Japan Steel Works as a raw material for the composition of polymer III prepared above as a laminating film. Molding was performed at an extrusion temperature of 230 ° C. and a take-up speed of 20 m / min to obtain a film having a thickness of 30 μm, which was used as a film for peel strength test.

Comparative Example 4 Preparation of a raw material, a three-layer drawn yarn and a woven fabric were carried out in the same manner as in Example 3 except that the polymer VI was used as a raw material for the outer layer material. The laminating film molded in Example 3 was used as a film for a peel strength test.

Comparative Example 5 A three-layer stretched yarn and a woven fabric were manufactured in the same manner as in Example 3 except that the outer layer material was high density polyethylene (HY430; manufactured by Nippon Polychem). Further, the laminating film is made of low density polyethylene (LC720;
A film for peel strength test was obtained in the same manner as in Example 3 except that it was manufactured by Nippon Polychem.

Comparative Example 6 Except that the polymer composition IV ^** was used as the outer layer material,
A three-layer stretched yarn was formed in the same manner as in Example 3, but during the formation of the blown film, the bubble of the film fluctuated and became unstable, and the stretched yarn could not be obtained.

[0072]

[Table 4]

As is clear from Table 4, according to each of the examples, polypropylene yarns having excellent heat fusion properties can be obtained. On the other hand, melting point, Q value, 0 ° C. soluble amount, T ₈₀
Yarn -T _{2 0} was used outside of the propylene-based resin outer layer has poor fusion of the film, a low peel strength (Comparative Example 3). Further, the yarn using the high-density polyethylene resin as the outer layer has a low peel strength due to peeling between the layers of the stretched yarn (Comparative Example 4).

[0074]

EFFECTS OF THE INVENTION The heat-fusible filament or yarn of the present invention is excellent in the fusing property between filaments and has a high peeling strength, so that the misalignment of the warp-and-cross intersections in the case of a woven fabric is prevented, Interfacial peeling and the like in the case of using a cloth sheet or the like is prevented, and it can be suitably used as a raw material for net cloth, insect screen, laminating bag, laminated cloth bag and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kenji Kobayashi             3-1, Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa             This Polychem Co., Ltd. Material Development Center F term (reference) 4L035 BB31 DD14 EE01 FF01 FF02                       LA02

Claims (7)

[Claims] 1. A heat-fusible monofilament or yarn which is polymerized by a metallocene catalyst and comprises at least one component of a propylene / α-olefin random copolymer satisfying the following conditions (1) to (6). (1): α-olefin content of 1 to 18 mol% (2): MFR of 0.5 to 30 g / 10 minutes (3): Q value of 2 to 4 (4): Soluble at 0 ° C. by TREF measurement. Content is 3% by weight or less (5): T ₈₀ -T ₂₀ by TREF measurement is 10 ° C or less (6): Tm is 110 to 135 ° C (however, MFR is 230 ° C according to JIS-K6921,
The melt flow rate at 21.18 N and the Q value are the ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC, and T ₈₀ is the temperature rising elution fractionation (TR
In the integrated elution curve obtained by EF), the temperature at which 80% by weight is eluted, T ₂₀ is the temperature at which 20% by weight is eluted, and Tm is the peak temperature of the melting curve obtained by a differential scanning calorimeter (DSC). ) 2. A heat comprising a laminate of a propylene / α-olefin random copolymer layer and a propylene homopolymer layer which are polymerized by a metallocene catalyst and satisfy the following conditions (1) to (6): Fusing yarn. (1): α-olefin content of 1 to 18 mol% (2): MFR of 0.5 to 30 g / 10 minutes (3): Q value of 2 to 4 (4): Soluble at 0 ° C. by TREF measurement. Content is 3% by weight or less (5): T ₈₀ -T ₂₀ by TREF measurement is 10 ° C or less (6): Tm is 110 to 135 ° C (however, MFR is 230 ° C according to JIS-K6921,
The melt flow rate at 21.18 N and the Q value are the ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC, and T ₈₀ is the temperature rising elution fractionation (TR
In the integrated elution curve obtained by EF), the temperature at which 80% by weight is eluted, T ₂₀ is the temperature at which 20% by weight is eluted, and Tm is the peak temperature of the melting curve obtained by a differential scanning calorimeter (DSC). ) 3. A propylene / α-olefin random copolymer polymerized by a metallocene catalyst and satisfying the following conditions (1) to (6) is used as a sheath material, and a propylene homopolymer is used as a core material. Core-sheath type heat-fusible monofilament. (1): α-olefin content of 1 to 18 mol% (2): MFR of 0.5 to 30 g / 10 minutes (3): Q value of 2 to 4 (4): Soluble at 0 ° C. by TREF measurement. Content is 3% by weight or less (5): T ₈₀ -T ₂₀ by TREF measurement is 10 ° C or less (6): Tm is 110 to 135 ° C (however, MFR is 230 ° C according to JIS-K6921,
The melt flow rate at 21.18 N and the Q value are the ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC, and T ₈₀ is the temperature rising elution fractionation (TR
In the integrated elution curve obtained by EF), the temperature at which 80% by weight is eluted, T ₂₀ is the temperature at which 20% by weight is eluted, and Tm is the peak temperature of the melting curve obtained by a differential scanning calorimeter (DSC). ) 4. A carpet base cloth using the heat-fusible yarn according to claim 1 or 2. 5. A cloth sheet or a laminated bag using the heat-fusible yarn according to claim 1. 6. A net fabric using the heat-fusible monofilament according to claim 1 or 3. 7. An insect repellent net using the heat-fusible monofilament according to claim 1.