JPH08174682A - Continuous manufacture of high strength and high elastic-modulus polyethylene material - Google Patents

Abstract

PURPOSE: To improve the coloring properties, the weatherability, the antistaticity of a molded form without impairing the high strength and the high elastic modulus by laminating and compression molding powders or films of thermoplastic resin mixed with additive such as colorant, hydrophilic property imparting agent dyeability imparting agent, etc. CONSTITUTION: A method for continuously manufacturing a high strength and high molecular weight polyethylene material comprises the step of compression molding ultrahigh molecular weight polyethylene powder having critical viscosity of 5 to 50dl/g in 135 deg.C decalin, then rolling and orienting it. The method further comprises the steps of laminating and processing the powder or film of thermoplastic resin mixed with at least one type of additive selected from the group consisting of colorant, weathering agent, antistatic agent, hydrophilic property imparting agent, adhesiveness imparting agent and dyeability imparting agent in the steps of continuously pressurizing at a temperature of the melting point or lower of the polyethylene powder while holding by opposed rotary media 1 and moving, and compression molding it by a press 7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for continuously producing a surface-modified high-strength, high-modulus polyethylene material, and more particularly to an ultra-high molecular weight polyethylene tape yarn having high strength and high modulus. It relates to a continuous process for the production of polyethylene materials suitable for the production of split yarns.

[0002]

2. Description of the Related Art Polyolefins of so-called ultra-high molecular weight, which have a remarkably high molecular weight, are used in various fields as engineering plastics which are characterized by excellent impact resistance, abrasion resistance and self-lubrication. This ultra-high molecular weight polyolefin has a much higher molecular weight than general-purpose polyolefins, so that highly oriented materials can be stably formed into slit yarns or split yarns, and their molded products can be colored efficiently, resulting in light resistance. If it can be imparted with or subjected to an antistatic treatment, it is expected to have a wide range of usefulness as a rope, net or sports / leisure goods for outdoor industry having high strength and high elastic modulus.

However, compared with general-purpose polyethylene, ultrahigh molecular weight polyethylene has a high melt viscosity and is extremely poor in moldability, and under the present circumstances, it cannot be stretched and highly oriented in a state where an additive is added. is there.

As such an example, for example, Japanese Unexamined Patent Publication No. 1-
In No. 168980, since the polyolefin fiber is highly hydrophobic and has no dyeing seat, it is practically used as a seat for dyeing with an undiluted solution or a metal salt is mixed and dyed with a specific dye. Shows that high-strength polyolefin fibers cannot be obtained, and provides a method of dyeing with a specific dye.

Further, Japanese Patent Laid-Open No. 3-227464 also provides a method for dyeing with a specific dye having a specific inorganic value / organic value ratio for the same purpose. Furthermore, in JP-A-4-289213, a dye is applied to a gel-state fiber containing a solvent after spinning, and then the fiber is stretched.
A method for producing colored high strength and high modulus ultra high molecular weight polyethylene fibers is also provided.

Further, JP-A-4-77232 also provides a method of compression-molding a mixture of ultra-high molecular weight polyethylene and a dye and / or pigment at a temperature lower than the melting point of polyethylene, and then stretching.

Further, in Japanese Unexamined Patent Publication No. 4-122746,
Surface properties were modified by at least stretching the main component consisting of ultra-high molecular weight polyethylene and the component containing polyvinyl chloride at a temperature below the melting point of polyethylene,
That is, there is provided a method for producing a polyethylene material with improved adhesion, which method also shows compression molding, rolling and stretching of ultra-high molecular weight polyethylene in powder form on an endless belt.

On the other hand, as a continuous method for producing a high-strength, high-modulus polyethylene material, Japanese Unexamined Patent Publication (Kokai) No. 3-130116 discloses a method of compression-molding ultra-high-molecular-weight polyethylene powder, rolling it, and then stretching it. / Or laminating with a laminated plate or other material by mixing or interposing an olefin polymer of a lower molecular weight than ultra-high molecular weight polyethylene powder, rod, fiber, sheet, film or nonwoven fabric in the rolling process Alternatively, a method for facilitating complexation is disclosed.

Also, ultra-high molecular weight polyethylene is stretched,
Then, a split polyethylene stretched material obtained by splitting is also useful as a rope for sports / leisure and the like.
Known by No. 57.

However, the above-mentioned Japanese Patent Laid-Open No. 1-168.
The method of 980 and JP-A-3-22746 requires a special dyeing material and cannot satisfy a wide range of requirements, and the method of JP-A-4-77232 makes it possible to stably produce a high-strength, high-modulus polyethylene material. In addition, the method of JP-A-4-122746 is a method of molding from a mixture, so that the characteristics as a high-strength / high-modulus polyethylene material are significantly reduced.
Although the method of No. 130116 solves the problem to some extent, it is necessary to further fully exhibit the characteristics of the ultrahigh molecular weight polyolefin material itself, and there is a demand for a material suitable for a multifunctional slit yarn or split yarn. Furthermore, even if a method for splitting an ultrahigh molecular weight polyethylene stretch material is known from JP-A-5-214657, it is possible to immediately predict the constitution of the present invention and the effects of the present invention which will be described later and which are brought about by adopting the constitution. is not.

[0011]

That is, the present invention is
It is easy to meet various requirements without impairing the original high strength and high modulus characteristics of the ultrahigh molecular weight polyethylene material in the above-mentioned conventional method, and it is possible to improve the coloring, weather resistance and antistatic property of molded products. Along with the improvements, there is provided an improved method for producing polyethylene materials having excellent high strength and high elastic modulus, particularly tape yarns or split yarns having stable properties.

[0012]

That is, the present invention is as follows.
Intrinsic viscosity in decalin solution at 35 ° C is 5 to 50 dl
In a method for producing a high-strength, high-modulus polyethylene material by compression-molding ultra high-molecular-weight polyethylene powder of 1 g / g, rolling and stretching, the melting point of the polyethylene powder while moving while being sandwiched between opposed rotating media. At least one selected from the group consisting of a colorant, a weather resistance agent, an antistatic agent, a hydrophilicity-imparting agent, an adhesion-imparting agent and a dyeability-imparting agent in a compression molding step of continuously compression-molding at the following temperature. It is intended to provide a continuous production method of a high-strength, high-modulus polyethylene material, which comprises treating a thermoplastic resin powder or a film in which an agent is mixed while laminating it.

In the present invention described above, by further slitting after the drawing step to obtain a tape yarn or a split yarn, it is possible to obtain a more excellent high-strength / high-modulus polyethylene material. The material is useful as an industrial or sports / leisure material such as a rope, a golf net, a long rope, a safety net, a 2-4 axis riff, a high-strength binding band, etc. containing a weathering agent and a coloring agent.

The present invention will be described in detail below.

The ultra high molecular weight polyethylene powder used in the present invention has an intrinsic viscosity [η] in decalin of 5 to 50 dl / g, preferably 8 to 40 dl /, at 135 ° C.
g, more preferably 10 to 30 dl / g, having a viscosity average molecular weight of 500,000 to 12,000,000, preferably 900,000 to 9,000,000, and more preferably 1,200,000 to 600.
It is equivalent to ten thousand. When [η] is less than 5 dl / g, the mechanical properties of the stretched sheet, film and the like are deteriorated, which is not preferable. Further, if it exceeds 50 dl / g, the workability such as tensile stretching is deteriorated, which is not preferable.

The density of the ultra-high molecular weight polyethylene powder is usually 0.920 to 0.970 g / cm ³ , preferably 0.935 to 0.960 g / cm ³ .

The ultrahigh molecular weight polyethylene having the above-mentioned specific properties used in the present invention is required to have a catalyst component containing at least one compound selected from compounds containing transition metal elements of Groups IV to VI of the periodic table. Accordingly, in the presence of a catalyst that is combined with an organometallic compound, homopolymerization of ethylene,
Alternatively, it can be obtained by copolymerizing ethylene and α-olefin.

The α-olefin has 3 to 1 carbon atoms.
2, preferably 3 to 6 can be used. Specifically, propylene, butene-1,4-methylpentene-
1, hexene-1, octene-1, decene-1, dodecene-1 and the like. Of these, propylene, butene-1, 4-methylpentene-1, and hexene-1 are particularly preferable. Further, as the comonomer, dienes such as butadiene, 1,4-hexadiene, vinyl norbornene, ethylidene-norbornene and the like may be used in combination. The α-olefin content in the ethylene / α-olefin copolymer is usually 0.001 to 10 mol%, preferably 0.01 to 5 mol%, more preferably 0.1 to 1 mol%.

The ultra-high molecular weight polyethylene of the present invention is a transition metal of Group IV to VI of the periodic table such as titanium compound, vanadium compound, chromium compound, zirconium compound and hafnium compound as described above and, if necessary, an organometallic compound. However, since the method for adjusting these catalyst components is described in detail in the above-mentioned JP-A-3-130116, the description thereof is omitted here. The amount of the organometallic compound used at this time is not particularly limited,
Ordinarily 0.1 to 1,000 mol relative to the transition metal compound
It can be used in a double range.

The polymerization reaction is carried out in a gas phase in a state where oxygen, water, etc. are substantially cut off, or a solvent inert to the catalyst,
For example, butane, isobutane, pentane, hexane, octane, decane, dodecane and other aliphatic hydrocarbons, cyclopentane, cyclohexane and other alicyclic hydrocarbons,
It is carried out in the presence of an aromatic hydrocarbon such as benzene or toluene, a petroleum fraction, or the monomer itself as a solvent. The polymerization temperature is lower than the melting point of the ultra high molecular weight polyethylene to be produced, usually -20 to + 110 ° C, preferably 0 to 90.
° C. In the case where the polymerization temperature is not lower than the melting point of the obtained ultra high molecular weight polyethylene, in the stretching step which is a subsequent step
It is not preferable because it cannot be stretched more than 20 times. The polymerization pressure is usually 0 to 70 kg / cm ² G, preferably 0 to 60
It is desirable to set it to kg / cm ² G.

The molecular weight can be adjusted by changing the polymerization conditions such as the polymerization temperature, the polymerization pressure, the type of catalyst, the molar ratio of the catalyst components, hydrogenation in the polymerization system, and the method is not particularly limited. . Of course, it is possible to carry out a two-step or multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature without any trouble.

The shape of the ultra high molecular weight polyethylene thus obtained is not particularly limited, but normally, granular or powdery one is preferably used. The particle size is 2000 μm or less, preferably 1000 μm or less. Further, a narrower particle size distribution will give a better sheet.

The thermoplastic resin powder or film laminated in the compression molding step of the continuous production method of the high-strength, high-modulus polyethylene material of the present invention includes an olefin polymer (ethylene / vinyl acetate copolymer, modified Preferable examples thereof include ethylene polymers), polyamide-based polymers, polyester-based polymers and polyvinyl chloride-based polymer powders, or films or sheet-like products obtained by film formation. The shape of the powder, sheet-like material, and film-like material in the present invention is not particularly limited,
Generally, in the case of powder, a particle size range of usually 10 to 1000 μm, preferably 20 to 300 μm is desirable.
In the case of sheet and film, it is usually 10-2
It is desirable that the thickness is 00 μm, preferably 20 to 100 μm.

As the olefin polymer used for producing a preferable thermoplastic resin film, (1) an ethylene polymer produced by using a Ziegler catalyst, ethylene-
Ethylene (co) polymers such as α-olefin copolymers, ethylene polymers produced by high-pressure radical polymerization, copolymers, and mixtures thereof, and (2) these ethylene copolymers with unsaturated carboxylic acids. And / or a derivative thereof, and a polymer arbitrarily selected from the group consisting of a modified ethylene (co) polymer obtained by a graft reaction in the presence of an organic peroxide. These ethylene (co) polymers have a lower molecular weight than the above-mentioned ultra high molecular weight polyethylene powder, and usually have an [η] of 0.5 to 3 dl / g, preferably 0.8 to 2 dl / g. , Melt index (ASTM-D1238-6
5T, 190 ° C., 2.16 kg load) 0.1 to 100 g / 10 min, preferably 0.5 to 1
It is 0 g / 10 min.

As the α-olefin in the ethylene-α-olefin copolymer produced by using the above Ziegler catalyst, various α-olefins can be used, preferably having 3 to 12 carbon atoms, and more preferably carbon. Number 3-8
Α-olefin is desirable, specifically propylene,
Butene-1, pentene-1, 4-methylpentene-1,
Hexene-1, octene-1, decene-1, dodecene-
1 or a mixture thereof, and the α-olefin content in the ethylene-α-olefin copolymer is 20 mol% or less, preferably 15 mol% or less.

In the high pressure radical polymer, the comonomer concentration is 30% by weight or less, preferably 25% by weight.
The following ethylene-vinyl ester copolymers or ethylene / acrylic acid ester copolymers are included. If the comonomer concentration exceeds 30% by weight, the tackiness increases, and compression molding or rolling tends to be difficult.

These ethylene (co) polymers used in the present invention usually have a density of 0.935 g / cm ³ or less, preferably 0.930 to 0.860 g / cm ³ , and more preferably 0.930 to 0. It is 910 g / cm ³ . If the density exceeds 0.935 g / cm ³ , the difference between the melting points of the adhesive layer and the stretched polyethylene layer is small, the range of temperature conditions during heat lamination is narrow, and sufficient adhesive strength cannot be obtained, which is not preferable in some cases.

It should be noted that ethylene (co) polymers other than those described above may be added to these ethylene (co) polymers within a range not impairing the object of the present invention.
Propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, etc. homopolymers or interpolymers, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, poly Isobutylene and a mixture thereof may be appropriately blended.

The unsaturated carboxylic acid used for modifying the ethylene (co) polymer is preferably a monobasic acid or a dibasic acid, specifically acrylic acid, propionic acid, methacrylic acid, crotonic acid. , Isocrotonic acid,
Examples thereof include oleic acid, elaidic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and mixtures thereof. Examples of the unsaturated carboxylic acid derivative include metal salts, amides, esters, and anhydrides of the above unsaturated carboxylic acids. Among these, maleic anhydride is most preferable.

Examples of organic peroxides include benzoyl peroxide, lauryl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-
Butylhydroperoxide, α, α′-bis (t-butylperoxydiisopropyl) benzene, di-t-butylperoxide, 2,5-di (t-butylperoxy) hexyne and the like are preferably used.

As a method for modifying the ethylene (co) polymer with an unsaturated carboxylic acid and / or a derivative thereof, an unsaturated carboxylic acid and / or a derivative thereof is added to the ethylene (co) polymer and an organic peroxide is added. And react in the presence of. At that time, the amount of the unsaturated carboxylic acid or its derivative added to the ethylene (co) polymer is 0.05 to 10% by weight, preferably 0.1 to 7% by weight.

The amount of the organic peroxide used is 0.005 to 2 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the total amount of the ethylene (co) polymer and the unsaturated carboxylic acid.
Used in the range of 1.0 parts by weight. When the amount of the organic peroxide added is less than 0.005 parts by weight, the modifying effect is not substantially exerted, and even when it is added in excess of 2.0 parts by weight, it is difficult to obtain further effects. However, it may cause excessive decomposition or crosslinking reaction.

The modification reaction is carried out by melting and mixing in an extruder or a kneading machine such as a Banbury mixer in the absence of a solvent to cause a reaction, and aromatic hydrocarbons such as benzene, xylene and toluene, and fats such as hexane, heptane and octane. There is a method of heating and mixing in a solvent such as a group hydrocarbon, and the method is not particularly limited, but in the extruder because of its easy operation, excellent economical efficiency, continuity with subsequent steps, etc. It is preferable to carry out.

These olefin-based polymers have a wall thickness of 10 to 200 μm, preferably 20 to 10 by a known method.
A film formed into a 0 μm film is preferably used.

The polyvinyl chloride-based polymer includes all homopolymers of vinyl chloride and copolymers or terpolymers of vinyl chloride monomer and various comonomers. Such comonomers are not particularly limited, for example, vinyl alkyl esters such as vinyl acetate, acrylic acid or methacrylic acid and its esters, maleic acid and its esters, acrylonitrile, α-olefins such as ethylene or propylene,
Examples thereof include vinyl ether and vinylidene chloride. The content of the comonomer is not particularly limited, but is usually 50 mol% or less, preferably 20 mol% or less, and more preferably 0.1 to 15 mol%.

The method for producing these polyvinyl chloride polymers is not particularly limited, and examples thereof include bulk polymerization and
Those obtained by any known method such as suspension polymerization, emulsion polymerization, solution polymerization and precipitation polymerization can be used.

These polyvinyl chloride polymers have an average degree of polymerization of usually 50 to 10000, preferably 100 to 5
000, more preferably 500 to 5000 is desirable. The form of use of the molded product from these polymers is not particularly limited as long as the object of the present invention is not impaired, and may be a sheet or a film. The thickness of the coalescence is generally 10 to 200 μm, preferably 20 to 100 μm by a known method.
It may be formed into a film of m and may be further stretched and used.

As the nylon type polymer, 6 nylon, 11 nylon, 12 nylon type, or 6-6 nylon, 6-10 nylon, 6-66 nylon, and copolymerized nylon and blended nylon having a low melting point are used. Can be used, and can be used after forming a film or sheet into a film by a generally known method. The preferable molecular weight range of the above-mentioned nylon polymer is usually about 1000 to 30,000.

Polyethylene terephthalate (PE
A thermoplastic polyester polymer represented by T) can also be used. For the purpose of the present invention, by adopting the processing temperature in consideration of the glass transition temperature of PET, the ultrahigh molecular weight polyethylene layer is formed in the compression molding step of the ultrahigh molecular weight polyethylene powder, and further in the rolling step and the stretching step if necessary. It is possible to stack,
By replacing a part of terephthalic acid with isophthalic acid, it is possible to laminate more easily. Specific examples thereof include polyethylene terephthalate, polyethylene 2,6-naphthalate and the like, and the molecular weight is not particularly limited as long as it is various film grades and fiber grades.

Examples of the coloring agent, weather resistance agent, antistatic agent, hydrophilicity-imparting agent, adhesiveness-imparting agent and dyeability-imparting agent which are blended in the above-mentioned thermoplastic resin powder or film. The colorant used in the present invention is not particularly limited, and a wide variety of colorants, which are generally referred to as pigments when coloring resins or fibers, can be exemplified. The colorants are roughly classified into organic pigments and inorganic pigments.The organic pigments include nitroso-based, nitro-based, azo-based, phthalocyanine-based, basic dye-based, acid dye-based, textile dye-based, mordant dye-based, etc. And specifically, Hansa Yellow, Benzidine Yellow, Benzidine Orange, C.I. P. Toluidine Red M
ed, C.I. P. Para Pred Lt, Chlorinated Para Red, Ba Litol Toner, Litol Rubin, Permanent Red 28, Bon Red OK, Bon Maroon Lt, Pigment Scarlet Lake, Mader Lake,
Thioindigo Red, Pyrazolone Red, Dibenzanthilone Violet, Heliofast Ruby, Diazo Green, Diazo Yellow, Cyanine Flue, Cyanine Green, Phthalocyanine Blue, Phthalocyanine Green, Induslen Blue, Quinacridone, First Yellow, Brilliant Carmine 68, Examples include azo red, lake, lake bordeaux, fast sky blue, and the like, and examples of the inorganic pigment include chromic acid, ferrocyanide, sulfide, sulfate, oxide, hydroxide, silicate, carbon black. And the like.Specifically, cobalt pigments such as aureoline, cobalt green, cerulean blue, cobalt blue, and cobalt violet, iron pigments such as ocher, shenar, red iron oxide, and Prussian blue, Chromium, chrome yellow, chrome pigments such as viridian, manganese pigments such as mineral violet, copper pigments such as emerald green, vanadium yellow,
Examples thereof include vanadium pigments such as vanadium blue, mercury pigments such as chrysanthemum, lead pigments such as red lead, sulfide pigments such as cadmium yellow and ultramarine, selenide pigments such as cadmium red, and fine aluminum powder. The particle size of these pigments is several μm to several tens mμ, and their shapes are various such as spherical, lumpy, rod-shaped, needle-shaped, and flaky.
Any particle size and shape can be used in the present invention. These pigments may be used alone or in combination.

In the present invention, examples of the weather resistance agent that can be blended with the thermoplastic resin film include antioxidants such as radical chain inhibitors, peroxide decomposers and ultraviolet absorbers. It can be illustrated. -Antioxidant radical chain inhibitor: phenyl-α-naphthylamine, phenyl-β-naphthylamine, diphenylamine, N, N'-diphenyl-p-phenylenediamine,
N, N′-di-β-naphthyl-p-phenylenediamine, p-hydroxydiphenylamine, p-hydroxyphenyl-β-naphthylamine, 2,2,4-trimethyldihydroquinoline, di-β-naphthyl-p- Amine compounds such as phenylenediamine, N-phenyl-N'-cyclohexylparaphenylene-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, aldol-α-naphthylamine, p
-Hydroxyphenyl cyclohexane, di-p-hydroxyphenyl cyclohexane, 2,6-di-t-butylphenol, styrenated phenol, 1,1'-methylenebis (4-hydroxy-3,5-t-butylphenol), 2,2 '-Methylenebis (4-methyl-6-t-
Butylphenol), 2,6- (2-t-butyl-4-)
Methyl-6-methylphenol) p-cresol, 2,
2'-thiobis- (4-methyl-6-t-butylphenol), 4,4'-thiobis- (4-methyl-6-t-
Butylphenol), 4,4'butylidene bis- (4-
Methyl-6-t-butylphenol), di-β-naphthyl-p-phenylenediamine, N-phenyl-N′-cyclohexylparaphenylene-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, Phenolic compounds such as aldol-α-naphthylamine, etc. Peroxide decomposer: 4,4′-thiobis- (3-methyl-6-t-butylphenol), thiobis- (β-naphthol), thiobis (N-phenyl) -Β-naphthylamine), mercaptobenzothiazole, mercaptobenzimidazole, dodecyl mercaptan, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, trinonylphenyl phosphite, dilauryl thiodipropionate, distearyl thiodipropione. UV absorbers 2-hydroxy-4-methoxybenzophenone, 2,
2'-dihydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-methoxy-4'-chlorobenzophenone, 2,2'-dihydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone,
2,4-dibenzoyl-resorcinol, resorcinol monobenzoate, 5-chloro-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyl-2-hydroxybenzophenone, 2,2,4 Benzophenone-based such as'-tetrahydroxybenzophenone, 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, alkylated hydroxyphenylbenzotriazole,

[0042]

Embedded image Benzotriazols such as, phenyl salicylates, 4
It is also possible to use salicylates such as -t-butylphenyl salicylate and p-octylphenyl salicylate, and dicyanoacrylates. Also a light stabilizer,
For example, a hindered piperidine-based hindered amine-based compound can also be used.

As other materials, carbon black,
Aluminum powder, metal powder such as copper powder, aluminum oxide, iron oxide, metal oxide powder such as titanium oxide, alumina, silicon carbide, barium carbonate, or fine ceramics, new ceramics, advanced ceramics, modern ceramics, Al ₂ O ₃ , BeO, SiC (+ BeO) for giving an electromagnetic function such as insulation, which is called high-tech ceramics.
Y ₂ O for imparting optical functions such as composition and fluorescence
S (Eu added) and the like can also be used.

Further, examples of the antistatic agent that can be blended with the thermoplastic resin include nonionic, anionic, cationic and amphoteric agents, and the following can be exemplified.・ Nonionic polyoxyethylene-alkylamine, polyoxyethylene-alkylamide,

[0045]

Embedded image Polyoxyethylene glycol alkyl ether, polyoxyethylene glycol alkyl phenyl ether,
Glycerin fatty acid ester, sorbitan fatty acid ester, glycerin monoester of stearic acid, searyldiethanolamine, etc.-Anionic alkyl sulfonate, alkyl benzene sulfonate, RSO ₃ Na, alkyl sulphate, ROSO
₃ Na, alkyl phosphate, ROPO ₃ K ₂ , polyphosphate, pentaalkyl tripolyphosphate, etc.-Cationic ammonium chloride, ammonium sulfate,
Quaternary ammonium salts such as ammonium nitrate, alkyl amine salts, higher amine ethylene oxide adducts, etc. Amphoteric alkyl betainine

[0046]

Embedded image

[0047]

[Chemical 4]

[0048]

Embedded image Such as aminocarboxylic acid derivatives, alanine-type amphoteric surfactant metal salts, imidazoline-type amphoteric surfactant metal salts, diamine-type amphoteric surfactant metal salts, EO-group-containing amphoteric surfactant metal salts, etc. , Carbon, etc., and polyvinyl benzyl type kaolin, polyacrylic acid type cation and the like.

Further, as an adhesiveness-imparting agent which can be blended with the thermoplastic resin, an uncured epoxy resin (granule,
Powdery), uncured unsaturated polyester (granular, powdery), modified polyamide and the like. Examples of the above-mentioned epoxy resin include bisphenol A type epoxy resin which is a glycidyl derivative of epichlorohydrin of bisphenol A, for example, manufactured by Nippon Pernox KK, trade name Perpowder PE-05, P.
Examples thereof include E-10 and PCE-273 °.
Further, as the above-mentioned unsaturated polyester, for example, so-called N type which uses isophthalic acid type, hydrogenated bisphenol type and the like as a main raw material is preferably used.

As the dyeability-imparting agent which can be similarly blended, polyvinyl alcohol powder having a saponification degree of 80% or more, preferably 95% or more, for example, K Kuraray, trade name K Kuraray Poval PVA-117, PVA- CS, P
Cellulose powders such as VA-217 and PVA-205, for example, MFR (190 ° C.): 0.1 to 2 g / min acetate powder, polyamide powder and the like can be mentioned.

As the hydrophilicity-imparting agent which can be similarly compounded, the same polyvinyl alcohol powder as described above,
Examples thereof include chitosan and acrylic acid having antibacterial properties and chelating properties.

In the present invention, the above-mentioned olefin polymer, nylon polymer, polyester polymer or polyvinyl chloride polymer is added to the above-mentioned coloring agent, weathering agent antistatic agent, hydrophilicity-imparting agent, adhesive agent. At least one additive selected from the group consisting of a property-imparting agent and a dyeability-imparting agent is blended, and preferably, a film is formed on these thermoplastic resin films, but the additive is blended into the polymer powder or pellets. As a masterbatch, a method of melt-blending a component contained in a high concentration with a base polymer is adopted, and a film forming method on a film or a sheet is not particularly limited. -Die or round-Extruded from a die can be used as it is.

The ratio of various additives contained in the above-mentioned thermoplastic resin powder or film is usually 0.01 to 50% by weight, preferably 0.05 to 50% by weight based on the thermoplastic resin.
It is 40 wt%. Specifically, in the case of an adhesive, it is usually 0.
5 to 30 wt%, preferably 1 to 25 wt%, and in the case of a weathering agent, usually 0.01 to 10 wt%, preferably 0.
05-5 wt%, in the case of an antistatic agent, usually 0.01-
10 wt%, preferably 0.05 to 5 wt% is desirable. In the case of a hydrophilicity-imparting agent, an adhesion-imparting agent or a dyeability-imparting agent, it is usually 1 to 20 wt%, preferably 2 to 15 w.
t% is desirable.

The form of the thermoplastic resin powder or film obtained by blending the above-mentioned various additives is not particularly limited in thickness, but it may be a compression molded product (or a rolled product, a stretched product) or the like. There is no particular limitation as long as it does not exceed the thickness of the core raw material, and the ratio of core agent / film thickness is 60/40 to 98/2, preferably 70/30.
It is desirable that the thickness is in the range of from 95 to 95/5. Further, the width is preferably the same as that of the core raw material, but the width can be slightly wide or narrow without any problem.

The thermoplastic resin film to be laminated in the compression molding step, if necessary, further in the rolling step and the stretching step may be, for example, an olefin polymer film or a nylon polymer film, which may be laminated alone. It is also possible to laminate in multiple layers sandwiching an ultra high molecular weight polyethylene layer, and it is also possible to use in a state where an olefin polymer film layer and a nylon polymer film layer or a polyester polymer film layer are laminated. At this time, a desired additive may be blended only in a part of the film layers.

That is, in consideration of the purpose and the product form, for example, coloring of the product, imparting weather resistance, imparting electrostatic property, or lamination use of a high-strength / high-modulus polyethylene material, that is, considering adhesiveness during lamination. It can be changed appropriately.

Next, the method for producing the high-strength, high-modulus polyethylene material will be described in detail. In the present invention, as described above, the ultra high molecular weight polyethylene powder is compression molded at a temperature lower than the melting point of the polyethylene by a specific pressurizing means, then rolled and stretched, and in the compression molding step, the heat treatment is performed. A high-strength, high-modulus polyethylene material is manufactured by laminating plastic resin powders or films. The term "lamination" in the present invention means to disperse the thermoplastic resin powder or film inside and / or on the surface of the ultrahigh molecular weight polyethylene layer. In this case, the core material essentially contains an ultrahigh molecular weight polyethylene layer.

The following methods can be given as typical examples of these.

1. In the compression molding step, a method in which a powdery or film-like thermoplastic resin is interposed on one side or both sides of the surface layer of ultra-high molecular weight polyethylene powder to perform compression lamination molding.

2. Further, in the rolling step, the thermoplastic resin film is coated with the above 1. The method for laminating and molding one side or both sides of the compression molded product of the ultra high molecular weight polyethylene of 1.

3. Further, in the stretching step, the thermoplastic resin film is treated with the above 1. Or 2. The method of laminating and molding one side or both sides of the ultra-high molecular weight polyethylene molded article of 1.

In the above-mentioned molding method, as described above, the laminating method can be appropriately changed in relation to the desired characteristics of the molded product and the variety of the thermoplastic resin film. For example, the compression molding process and the rolling process can be performed. It is also possible to stack different thermoplastic resin films in each step, and the mode is not limited.

Next, a method of continuously compression-laminating and molding the thermoplastic resin powder or film in the compression molding step of ultra-high molecular weight polyethylene powder will be described.

In the present invention, the compression molding step is carried out at a temperature lower than the melting point of the polyethylene powder which is the object to be compressed, so that the high strength and high elastic modulus can be obtained by the subsequent rolling and stretching steps. It is extremely important in obtaining a polyethylene material. However, in order to obtain a good compression-molded sheet, the temperature is lower than the melting point but is within an acceptable range, that is, usually 20 ° C. or higher and lower than the melting point, preferably 50 ° C. or higher and lower than the melting point, and further preferably 90 to 140 ° C., particularly preferably 110 to 1
It is desirable to be within the range of 35 ° C. The pressure during compression molding is not particularly limited, but is usually 1000 kg / c.
It is less than m ² , and preferably within the range of 0.1 to 1000 kg / cm ² .

Further, the compression molding device is not particularly limited as long as it is a device which can continuously perform compression molding with the opposed rotating medium, and the rotating medium is a pair or two or more pairs of opposed rolls or a pair of endless or more endless media. Examples include a combination of a belt or an endless belt and a roll. Hereinafter, a brief description will be given based on FIG. 1 showing one specific example of the preferable molding apparatus.

This apparatus is basically a pair of endless belts 5 and 6 vertically opposed to each other, which are tensioned by rolls 1 to 4, and pressurization for pressurizing a powder sample through the endless belts. It has a pressurizing means consisting of a plate 7 and a chain roller group 8 rotatably connected to each other between the pressurizing plate and the endless belt.

The pressing means is composed of a pressing plate provided inside the endless belt and a group of rollers which are rotatably connected to each other between the pressing plate and the endless belt. As a chain roller group that is rotatably connected to each other and interposed between the pressure plate and the endless belt, the rotation axes of the rollers in the roller group are arranged substantially perpendicular to the traveling direction of the endless belt and contact each other. It is suitable to arrange a large number of them in close contact with each other to the extent that they do not occur.

The center axes of both ends of each of these rollers are fixed by a chain, and the chain is meshed with sprockets 9 and 10 arranged in front of and behind the pressure plate, so that the roller group can be moved at the running speed of the endless belt. It is good to drive at about 1/2 speed.

This roller group may be fixedly interposed between the endless belt and the pressure plate. In this case, however, the frictional force due to the slip is respectively generated between the roller group and the endless belt and the pressure plate. As a result, there is a problem in the durability of the device.

The pressure plate is not particularly limited as long as the surface in contact with the roller group is smooth and the pressure can be transmitted uniformly.

The length of the pressure plate in the running direction of the endless belt is not particularly limited, but is usually 30 to 400 c.
m, preferably about 50 to 200 cm. The average pressure applied to the endless belt by the pressure plate is appropriately selected, but is usually less than 200 kg / cm ² , preferably 1
Less than 00 kg / cm ² , preferably 0.1-50 kg /
cm ² , more preferably 0.1 to 20 kg / cm ² ,
The pressure is particularly preferably 0.5 to 10 kg / cm ² , and particularly preferably 1.0 to 8.0 kg / cm ² .
The pressing plate has a primary role of pressing the polyethylene powder through the endless belt, but can also be used as a heating means for the object to be compressed at the same time.

In the present invention, it is extremely important that the compression molding step is carried out at a temperature lower than the melting point of the polyethylene powder which is the object to be compressed as described above. More preferably 50 ° C
It is desirable that the temperature is not lower than the melting point, particularly preferably in the range of 90 to 140 ° C, and particularly preferably in the range of 110 to 135 ° C.

As means for heating the object to be compressed for that purpose,
Although it is optimal to directly heat the endless belt in the pressure section, a heating means is provided in the pressure plate to heat the object to be compressed from the pressure plate through the roller group and the endless belt. It is practically convenient to dispose the preheater 11 close to the endless belt as shown in FIG.

As a mode of arranging the heating means on the pressurizing plate, an electric heater may be embedded in the pressurizing plate after providing a heat insulating portion, or a circulation channel for the heat medium may be arranged in the pressurizing plate. It may be provided and heated using a heat medium.

In order to carry out the continuous production method of the high-strength and high-modulus polyethylene material using this exemplified apparatus, first, the ultra-high molecular weight polyethylene powder charged in the hopper 12 'is put into the lower endless form. It is dropped onto the belt 6.

A specific method for laminating a thermoplastic resin powder or a film containing an additive in this compression molding step is, for example, in the case of laminating a film, the thermoplastic resin film is previously prepared. A method of supplying ultra-high molecular weight polyethylene powder from the lower supply roll 13 onto the endless belt 6 and then dropping the ultra-high molecular weight polyethylene powder from the hopper 12 onto the endless belt 6 for compression molding. Examples of the method include a method in which the thermoplastic resin film is supplied from above and then the thermoplastic resin film is supplied from the supply roll 14 to perform compression molding, and a method in which the thermoplastic resin film is simultaneously supplied from the supply rolls 13 and 14 to perform compression molding.

When laminating the powders,
Although not shown in FIG. 1, the thermoplastic resin powder containing the additive is dropped onto the endless belt 6 or the ultra high molecular weight polyethylene powder from the hopper 12 provided before or after the hopper 12. A compression molding method is adopted. Further, a method of laminating and forming a composite with the method of laminating the thermoplastic resin film is adopted.

The running speed of the endless belt depends on the length of the pressure plate and the compression conditions, but is usually 10 to 5.
00 cm / min, preferably 50-200 cm / mi
It is about n. The polyethylene powder on the endless belt is formed into a predetermined cross-sectional shape by the doctor knife 16, and if necessary preheated by the heater 11,
The upper and lower endless belts are moved to a pressing unit, and then transferred to a compression unit in which a roller group and a pressure plate are arranged. Here, the pressure from the hydraulic cylinder 15 is transmitted to the pressure plate, and the compression force is applied to the object to be compressed via the roller group and the endless belt. At this time, heat from the heating body is also transferred to the object to be compressed through the roller group and the endless belt, and the temperature of the object to be compressed is maintained at a predetermined temperature.

In this way, the intermediate step product as the high-strength and high-modulus polyethylene material of the present invention, in which the sheet obtained by compression-molding the ultrahigh molecular weight polyethylene powder and the thermoplastic resin film are laminated, is the sheet winding. It is wound up on the machine 17.

Next, the step of laminating the thermoplastic resin films in the compression molding step of the ultra high molecular weight polyethylene powder and then rolling will be described.

A known method such as roll rolling can be used as a rolling method for the sheet obtained by compression molding, but the same direction or rotation is carried out while the compression molded sheet is held in a solid state without being melted. A rolled sheet or film can be obtained by pressing with rolling rolls having different directions. At this time, the deformation ratio of the material can be widely selected depending on the rolling operation, and the rolling efficiency (length after rolling / length before rolling) is usually 1.2 to 20, preferably 1.5 to 10. It is desirable to do. The temperature at this time is usually 20 ° C or higher and lower than the melting point of the ultrahigh molecular weight polyethylene powder used in the present invention, preferably 50 ° C or higher and lower than melting point, more preferably 90 to 140 ° C, and particularly preferably 110 to 135 ° C. It is carried out in a temperature range. Of course, the above-described rolling operation can be performed in one or more multi-stage rolling steps.

When a thermoplastic resin film is interposed in this rolling process as needed, as in the case of interposing it in the compression molding process, the ultra roll fed from the feeding roll 20 of FIG. A high-molecular-weight polyethylene powder compression molded sheet is placed on the sheet,
After being preheated on the roll surface of the preheating roll group 22 by being brought into contact with the thermoplastic resin film fed from the feeding rolls 21, 21 ′ installed below or above and below, it is further repreheated by the infrared preheating heater 23 if necessary. The rolled sheet obtained by rolling with the rolling roll 24 is a winding machine 25.
The method of winding up is generally adopted.

Various methods can be adopted also in the stretching step performed after rolling. Examples of the stretching means include hot air stretching, cylinder stretching, roll stretching, and hot plate stretching. However, it is common to perform stretching with a speed difference between a pair of nip rolls or clover rolls.

As a typical drawing apparatus, an example in which a thermoplastic resin film is interposed on a rolled sheet of ultrahigh molecular weight polyethylene by a drawing apparatus adopting a hot platen system is shown in FIG. 3 (a), and an example of using a hot roll method is shown. Is shown in FIG. Although details are omitted, in FIG. 3A, the rolled ultrahigh molecular weight polyethylene sheet delivered from the delivery roll and, if necessary, the delivery roll installed above, below, or above and below, as in the case of FIG. The thermoplastic resin film that has been fed from and contact with a feeding pinch roll,
It is drawn on a hot plate for drawing while being drawn by a take-up pinch roll, and is wound on a take-up roll.Before winding on the take-up roll, the drawn product may be split into a tape yarn if desired. Alternatively, the split yarn may be formed by slitting and then splitting. 3 (b) is a drawing of the drawing hot plate for drawing 3 shown in FIG. 3 (a).
The drawing illustrates a method of stretching by changing the roll rotation speed according to need with a hot roll for stretching.

The stretching temperature in the above stretching operation is within the range of less than the melting point of the stretched material, usually 20 to 160 ° C., preferably 60 to 150 ° C., more preferably 90 to 145.
C., particularly preferably 90 to 140.degree. Further, the stretching process can be performed not only in one stage but also in multiple stages. In this case, it is preferable to carry out the second step at a higher temperature than the first step.

The stretching speed varies depending on the method of tensile stretching, the molecular weight of the polymer, and the composition ratio, and can be appropriately selected, but it is usually 1 mm / min to 500 m / min, and particularly,
In the case of batch type stretching, usually 1 to 500 mm / min,
The range is preferably 1 to 100 mm / min, more preferably 5 to 50 mm / min. In the case of continuous stretching, it is usually 0.1 to 500 m / min, preferably 1 to 500 m / min.
200 m / min, more preferably 10-200 m /
It is within the range of min, and it is more preferable to set the high speed in consideration of economical efficiency.

The higher the draw ratio, the higher the strength and the high elastic modulus that can be achieved. Therefore, it is desirable to increase the draw ratio as much as possible. In the present invention, the total draw ratio which is the total draw ratio of rolling and tensile drawing is Usually 20 times or more, preferably 60 times or more, more preferably 80 to 2
It is possible to set the stretching ratio to 00, and it is possible to stretch at an extremely high stretching ratio.

The tensile elastic modulus of a stretched product obtained by subjecting only the ultrahigh molecular weight polyethylene powder to the compression molding process, rolling process and stretching process by the above-mentioned method is usually 60 GPa.
As described above, the range is more generally 80 GPa to 180 GPa, and more generally 120 to 150 GPa. The tensile strength is usually 0.7 GPa or more, more generally 1.0 GPa to 5.0 GPa, and more generally 1.5 GPa.
It has an extremely high physical property value of GPa to 3.0 GPa.

In the present invention, as described above, the thermoplastic resin powder or film to be laminated is appropriately selected according to the desired characteristics, and the physical characteristics of the stretched product are slightly different depending on the characteristics, but in general, Tensile elastic modulus is from 40 GPa
180 GPa range, more typically 100 GPa to 1
It is in the range of 50 GPa and the tensile strength is 0.7 GPa.
~ 5.0 GPa range, more typically 1.0 GPa ~
It is in the range of 3.0 GPa.

The present invention has the great advantage of obtaining a stretched product having physical properties that are substantially the same or do not significantly deteriorate even if a thermoplastic resin powder or film is interposed.

The high-strength, high-modulus polyethylene material of the present invention can be used for any purpose. However, by using it as a yarn, it can be used as a high-strength, high-modulus polyethylene material having more excellent properties. can do.
This will be further described below.

The yarn includes tape yarns such as multifilament yarns, monofilament yarns, tape-shaped filament yarns, and split yarns. Of these, the case of post-processing as a split yarn, which is particularly characteristic as a high-strength, high-modulus polyethylene material, will be described in detail first.

The split yarn, which is one of the objective products symbolizing the characteristics of the high-strength and high-modulus polyethylene material of the present invention, is produced by splitting the above-mentioned ultrahigh molecular weight polyethylene stretched product. The method for splitting is not particularly limited, and a known method can be used. For example, a stretched material in the shape of a film or a sheet, a method of beating, a method of twisting, a method of rubbing, a mechanical method such as a method of brushing, a method by an air jet, a method of making a crack by ultrasonic waves, An explosive method of treating with an explosive wind can be mentioned.

In the present invention, a mechanical method is preferably used, and a rotary mechanical method is particularly preferable. Such mechanical methods include tap screw splitters,
A method of using various shapes of splitters such as a file-like rough surface splitter and a needle roll splitter can be exemplified. The tap screw splitter is generally a pentagonal or hexagonal prism (FIG. 4) and has 10 to 40, preferably 15 to 35, threads per inch. Further, as a file-shaped splitter, the inventors of the present invention devised (Jitsuko 51-38980).
No.) shown in FIG. 5 is preferable. In FIG. 5, the surface 27 of the circular cross-section shaft 26 is a round file for ironwork or a rough surface similar to this, and the surface thereof has two helical grooves 2
8 and 28 'are cut into equal pitches.

The splitting device used is not particularly limited, but as shown in FIG. 6, basically, a rotary splitter 31 is arranged between the nip rolls 29, 29 'and the nip rolls 30, 30'. A typical example is a method of bringing the stretched product into contact with a moving rotary splitter while applying tension. The moving speed of the stretched material at this time is not particularly limited, but is usually 1 to 1000 m /
min, preferably 20 to 300 m / min. The rotation speed (peripheral speed) of the splitter is appropriately selected depending on the physical properties of the stretched product, the moving speed, and the properties of the target split yarn, but is usually 10 to 3000 m / mi.
n, preferably 50 to 1000 m / min. The contact angle between the stretched product and the splitter is usually 30-18.
It is desirable that the angle is 0 degrees, preferably 60 to 90 degrees.
Since the stretched tape is slippery, it may be difficult to hold the tape at a predetermined speed in the nip rolls installed before and after the splitter. It is desirable to take anti-slip measures such as using them or combining them.

In the method of brushing or the method of using a rotary splitter, the operation is preferably carried out by applying tension to the stretched product, and in relation to the high tensile elastic modulus of the stretched product described above, the stretching product is usually 0. Deformation of 0.1 to 3%, preferably 0.5 to 2% In this case, it is also an effective means to install a tension controller such as a dancer roll in the split device in order to keep the tension of the tape constant.

The temperature during splitting is usually −
The range of 20 to + 100 ° C, preferably -5 to + 50 ° C, more preferably 0 to 20 ° C is adopted. Splitting may be performed not only in one stage but also in multiple stages, and for a material having a large thickness, splitting can be performed from both front and back sides. Incidentally, as these methods, specifically, US Patent Publication No. 2185789.
No. 3214899, No. 2954587, No. 36
No. 62935, No. 3693851, Japanese Patent Publication No. 36-13
No. 116 and Japanese Patent Publication No. 43-16909.

In the split yarn obtained by these methods, the thickness of the split yarn is usually 1
It is 0 to 200 μm, preferably 30 to 100 μm.
If the thickness is less than 10 μm, the film-like or sheet-like stretched product may tear in the longitudinal direction, and the fibrils that are split may become fluff or wind around the splitter, resulting in unstable quality and process. is there. On the other hand, if it exceeds 200 μm, the splitting property tends to deteriorate. The split width is usually in the range of 10 to 500 μm, preferably 50 to 200 μm.

The split yarn obtained by the present invention is characterized in that it has excellent flexibility and high strength as well as the effects of the addition of pigments, weather resistance agents, antistatic agents and the like. The strength after splitting is usually 0.4
It is at least GPa, and the strength can be further increased by applying twist, and the strength can be made almost equal to the strength before splitting. The maximum value of the tensile strength when twisted in the range of 50 to 500 times / m is at least 0.
7 GPa or higher, generally 1 GPa or higher, and more generally 1.5 GPa or higher.
This corresponds to a high strength of about 8 g / d or more, generally about 11.5 g / d or more, and more generally about 17 g / d or more.

The stretched polyethylene material used in the present invention has no polar groups and the surface is not active, so that it is generally difficult to print or adhere to the surface. Therefore, if necessary, it is also preferable to perform a surface treatment such as a corona discharge treatment, a plasma treatment, a chemical oxidation treatment, or a flame treatment on the stretched product before the split treatment or preferably after the split treatment.

Obtained by the above method, that is,
A high-strength and high-modulus polyethylene material obtained by laminating thermoplastic resin powder or film containing additives in at least the step of compression-molding ultra-high molecular weight polyethylene powder, then rolling and stretching, and further slit treatment Or, the properties of the polyethylene material obtained by the split treatment are significantly different depending on the kind of the thermoplastic resin powder or film in which the additive is mixed, the amount of lamination, the lamination method, etc., but the additive is mixed. The properties of the slit body or split body obtained without laminating the thermoplastic resin can be explained as follows.

That is, in the case of the slit body, it is generally a plurality of independent long rectangular tapes, while in the case of the split body, they are not dispersed with each other, and conversely form a mesh-like body connected to each other. . For example, the limit value of the slit width of a film having a thickness of 60 μm is about 1.6 mm, and the fineness of the slit body in this case is approximately 800 to 900.
It is about d. In contrast, the split width of the split body is generally in the range of 10 to 500 μm, the logarithmic average value of this value is 70 μm, and the split thickness is 10 to 10.
The range of 200 μm, the logarithmic average value of this value is 45 μm, and the fineness of such a split body is about 30 d.

Incidentally, the above-mentioned 1.6 mm slit body has a flexibility of about 2660 mg · cm, and the split body has a flexibility of about 980 mg · cm.

[0104]

[Equation 1] However, since the degree of flexibility of the polyethylene material before slitting is about 3500 mg · cm, a high strength / high elastic modulus polyethylene material is further slitted or more preferably measured by applying a twist of 250 t / m. It is possible to obtain a more preferable high strength / high elastic modulus / high flexibility polyethylene material by performing split processing.

The split polyethylene stretch material of the present invention may be used as it is or in a twisted state. The number of times to twist is not particularly limited,
It is usually about 50 to 500 times / m, preferably 100.
Approximately 300 times / m is preferable because it exhibits high strength. The conditions in that case are not particularly limited, but are usually in the range of 0 to 100 ° C, preferably 10 to 60 ° C.

[0106]

【Example】

Example 1 (1) Production of thermoplastic resin film High-density polyethylene (trade name: Stafrene E-710
(Nippon Petrochemical Co., Ltd., M1: 1.0)) was used as a base polymer, and 15% by weight of azo red was mixed and processed into a master batch by using a melt extruder. Next, 20 parts by weight of this masterbatch and high-density polyethylene (trade name:
Stafrene E-710 (manufactured by Nippon Petrochemical Co., Ltd., M1:
1.0)) is kneaded at 230 ° C. and then the thickness is 0.02 m.
The film was continuously extruded into a film having a thickness of m. (2) Manufacture of high-strength materials (compression molding) Equipment specifications: 1. Roll diameter 500mm Face length 300mm 2. Steel belt, thickness 0.6mm, width 200mm 3. 3. Small diameter roller, diameter 12 mm, surface length 250 mm 4. Pressure plate length 1000 mm width 200 mm 5. Hydraulic cylinder diameter 125 mm Using a compression molding apparatus having the above specifications, insert a pair of the azo-based red compounded thermoplastic resin film (width of about 100 mm) between a pair of steel belts, and insert an ultra-high pressure film between the pair of films. Molecular weight polyethylene powder (Intrinsic viscosity [η] in 135 ° C decalin = 14dl / g, viscosity average molecular weight 2,000,000, melting point 142 ° C) was sandwiched and heated to 130 ° C, and the average pressure to the material was about 6kg / cm ² . Pressure was applied (pressure was transmitted in the order of hydraulic cylinder, pressure plate, small diameter roller, steel belt), and compression molding was continuously performed at a speed of 1 m / min.

As a result, the thickness is 1.1 mm and the width is 100 mm.
Got a sheet of.

(Rolling) Between the pair of rolls (diameter 250 mm, face length 300 mm, roll gap 0.07 mm) arranged above and below and rotating in the opposite directions at the same speed and the surface temperature was adjusted to 140 ° C. A compression-molded sheet was supplied, and the speed was 1 m / min at the inlet and 7 m / min at the outlet to obtain a rolled sheet having a rolling ratio of 7 times.

(Stretching) Device Specifications 1. Three preheating rolls Diameter 250 mm Face length 200 mm 2. Roll for drawing Diameter 125 mm Surface length 200 mm Oil for heat medium is circulated inside the roll. Distance between rolls is 30 mm. 3. Cooling rolls 3 diameter 250mm face length 200mm Cooling water circulates inside the roll 4. Nip roll Inlet side: φ200mm silicon rubber roll is nip to two preheating rolls Outlet side: φ200mm silicon rubber roll is nip to two cooling rolls The obtained rolled sheet is slit into a width of 6mm and the above specifications are applied. Tensile stretching was performed using a stretching device. The tensile stretching was repeated 3 times under the conditions shown in the following table.

As a result of the stretching, a polyethylene stretched material uniformly colored red was obtained.

When the physical properties of this material were measured,
The tensile strength was 24.4 g / d and the elongation was 1.8%.

[0112]

[Table 1] (Split process) Equipment specifications 1. Entrance pinch roll: φ160mm, surface length 200m
m metal roll and urethane rubber roll 2. Exit pinch roll: φ160mm, surface length 200m
m metal roll and urethane rubber roll 3. Splitter: A splitting tool with a regular hexagonal cross section and a tapped blade with a side length of 20 mm and a blade pitch of 0.6 mm Split condition 1. Nip roll speed: 30 m / min on the inlet side → 3 on the outlet side
0.3 m / min 2. Contact angle of splitter and peripheral speed ratio: 90 degrees,
2.3 times The red stretched tape (width of about 2 mm) was split under the above-mentioned apparatus and operating conditions to obtain a diamond-shaped reticulated split yarn having a single yarn width of 0.6 mm and a side length of 12 mm. . Physical properties of this split yarn (100 per 1 m
The tensile strength was 20.1 g / d and the elongation was 1.6% in 100 t / m, which was measured over time.

Example 2 In the production of (1) thermoplastic resin film of Example 1, the same procedure as in Example 1 was carried out except that cyanine blue was used instead of azo red.

As a result, a stretched polyethylene colored uniformly in blue was obtained, and its physical properties were a tensile strength of 24.3 g.
/ D, and the elongation was 1.8%. When this stretched polyethylene was split, a diamond-shaped blue reticulated split yarn was obtained. Regarding the physical properties (100 t / m) of this split yarn, the tensile strength was 20.0 g / d and the elongation was 1.6%.

Example 3 (1) The production of the thermoplastic resin film of Example 1 was repeated except that ultrafine carbon black was used in place of azo red.

As a result, a stretched polyethylene colored uniformly in black was obtained, and its physical properties were a tensile strength of 24.4 g.
/ D, and the elongation was 1.8%. When this drawn polyethylene was split, a diamond-shaped black-grey reticulated split yarn was obtained. Regarding the physical properties of this split yarn, the tensile strength was 20.1 g / d and the elongation was 1.6%.

Example 4 (1) Production of the thermoplastic resin film was carried out in the same manner as in Example 1 except that 0.5 wt% of stearyldiethanolamine was used instead of azo red.

As a result, stretched polyethylene was obtained, and the physical properties thereof were a tensile strength of 24.2 g / d and an elongation of 1.8%. When this drawn polyethylene was split, a diamond-shaped reticulated split yarn was obtained.
The physical properties of this split yarn are that the tensile strength is 19.9g.
/ D, and the elongation was 1.6%.

When the drawn product and the split yarn were brought close to the upper part of the dispersed ash, sufficient antistatic performance was recognized because the ash did not adhere even at a distance of several cm.

Example 5 In Example 4, stearyldiethanolamine 0.
Instead of 5 wt%, fatty acid monoglyceride 0.5 wt
The same procedure as in Example 4 was carried out except that% was used. As a result, stretched polyethylene was obtained, and its physical properties were a tensile strength of 24.0 g / d and an elongation of 1.8%. When this drawn polyethylene was split, a diamond-shaped reticulated split yarn was obtained. The physical properties of this split yarn are that tensile strength is 19.8 g / d and elongation is 1.6.
%Met.

When the drawn product and the split yarn were brought close to the upper part of the dispersed ash, sufficient antistatic performance was observed because the ash did not adhere even at a distance of several cm.

Example 6 In Example 4, stearyldiethanolamine 0.
Instead of 5 wt%, HALS (trade name, Tinuvin 62
2, manufactured by Ciba-Geigy) was performed in the same manner as in Example 4 except that 0.1 wt% was used.

As a result, stretched polyethylene was obtained, and its physical properties were a tensile strength of 24.0 g / d and an elongation of 1.8%. When this drawn polyethylene was split, a diamond-shaped reticulated split yarn was obtained.
The physical properties of this split yarn are that the tensile strength is 20.0g.
/ D, and the elongation was 1.6%.

When the light stability performance of this stretched product and split yarn was tested, it showed good properties.

Example 7 In Example 4, stearyldiethanolamine 0.
Instead of 5 wt%, HALS (trade name SANOL LS26
26, manufactured by Sankyo) except that 0.1 wt% was used.
I went the same way.

As a result, stretched polyethylene was obtained, and its physical properties were a tensile strength of 24.5 g / d and an elongation of 1.8%. When this drawn polyethylene was split, a diamond-shaped reticulated split yarn was obtained.
The physical properties of this split yarn are that the tensile strength is 20.1g.
/ D, and the elongation was 1.6%.

Further, when the light stability performances of the stretched product and the split yarn were tested, good properties were shown.

Example 8 (1) Production of thermoplastic resin film High density polyethylene (trade name: Staflen E-710 (manufactured by Nippon Petrochemical Co., Ltd., M1: 1.0)) was used as a base polymer, and 30 parts by weight of polyvinyl alcohol was used. %, Mix 2
After kneading at 30 ° C., continuous extrusion was performed to form a film having a thickness of 0.02 mm.

(2) Production of high-strength material The same procedure as in Example 1 was carried out except that the above thermoplastic resin film was used.

As a result, stretched polyethylene was obtained, and its physical properties were a tensile strength of 25.0 g / d and an elongation of 1.8%. When this drawn polyethylene was split, a diamond-shaped reticulated split yarn was obtained.
The physical properties of this split yarn are that the tensile strength is 20.3g.
/ D, and the elongation was 1.6%.

The hydrophilicity of this stretched product was measured by measuring the contact angle, and it showed good characteristics.

Example 9 (1) In the production of the thermoplastic resin film of Example 8, 30% by weight of chitosan was used instead of polyvinyl alcohol.
The same procedure as in Example 1 was carried out except that was used.

As a result, stretched polyethylene was obtained, and its physical properties were a tensile strength of 24.0 g / d and an elongation of 1.8%. When this drawn polyethylene was split, a diamond-shaped reticulated split yarn was obtained.
The physical properties of this split yarn are that the tensile strength is 20.0g.
/ D, and the elongation was 1.6%.

When the hydrophilicity of this stretched product was measured by measuring the contact angle, good properties were exhibited.

Example 10 Example 1 (1) was carried out in the same manner as in Example 1 except that 30% by weight of acrylic acid was used instead of polyvinyl alcohol in the production of the thermoplastic resin film.

As a result, stretched polyethylene was obtained, and its physical properties were a tensile strength of 24.2 g / d and an elongation of 1.8%. When this drawn polyethylene was split, a diamond-shaped reticulated split yarn was obtained.
The physical properties of this split yarn are that the tensile strength is 20.1g.
/ D, and the elongation was 1.6%.

When the hydrophilicity of this stretched product was measured by measuring the contact angle, good properties were exhibited.

[0138]

Industrial Applicability According to the present invention, a thermoplastic resin film obtained by blending at least one of a colorant, a weather resistance agent, an antistatic agent, a fresh water imparting agent, an adhesive agent and a dyeability imparting agent When processing while laminating on one side or both sides in the compression molding process of high molecular weight polyethylene powder,
The obtained high-strength, high-modulus polyethylene material can be easily colored, and properties such as weather resistance and antistatic property can be easily imparted. Workability can also be easily imparted.

[Brief description of drawings]

FIG. 1 is an apparatus suitable for carrying out the compression molding process of the present invention.
Here is an example.

FIG. 2 shows an example of an apparatus suitable for carrying out a rolling process.

FIG. 3 shows two examples of suitable devices for carrying out the stretching process.

FIG. 4 shows an example of a tap screw splitter suitable for implementation.

FIG. 5: One of file-like splitters suitable for implementation
Here is an example.

FIG. 6 shows an example of an apparatus suitable for performing a splitting step.

[Explanation of symbols]

 1 to 4 rolls 5 to 6 endless belt 7 pressure plate 8 chain roller group 9 to 10 sprocket 11 heater 12 hopper 13 to 14 supply roll 15 hydraulic cylinder 16 doctor knife 17 sheet winder 20 to 21 feeding roll 22 preheating roll 23 Infrared Preheater 24 Rolling Roll 25 Winder 26 Circular Cross Section Shaft 27 Surface 28, 28 'Helical Groove 29, 29' 30, 30 'Nip Roll 31 Splitter

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 27/18 Z 27/20 A // B29K 23:00 101: 12 B29L 9:00 (72) Inventor Kazuhiko Kurihara 3-11-5-1102 Takashimadaira, Itabashi-ku, Tokyo (72) Inventor Hiroshi Yazawa 2-25-15 Higashi, Kunitachi, Tokyo

Claims (3)

[Claims] 1. A method for producing a high-strength, high-modulus polyethylene material by compression-molding ultra-high-molecular-weight polyethylene powder having an intrinsic viscosity of 5 to 50 dl / g in a 135 ° C. decalin solution, rolling and then stretching. , A colorant, a weathering agent, an antistatic agent, in a compression molding step of continuously compression molding at a temperature equal to or lower than the melting point of the polyethylene powder while moving while being sandwiched between opposed rotating media.
High strength characterized by processing while laminating a thermoplastic resin powder or film containing at least one additive selected from the group consisting of a hydrophilicity-imparting agent, an adhesion-imparting agent and a dyeability-imparting agent -Continuous manufacturing method for high modulus polyethylene material. 2. The continuous production method of a high-strength, high-modulus polyethylene material according to claim 1, wherein the tape yarn is further slit after the drawing step. 3. The continuous method for producing a high-strength, high-modulus polyethylene material according to claim 1, wherein split processing is further performed after the drawing step to obtain a split yarn.