JPH01280077A - Drawn article of ultrahigh molecular weight polyolefin and production thereof - Google Patents

Abstract

PURPOSE:To provide the subject drawn article having improved adhesivity to other polymers by coating the surface of the drawn article with an active energy ray-curable composition comprising an epoxy resin as a main component. CONSTITUTION:After preliminarily subjected to a plasma discharge treatment or electron beam treatment (or coated with an active energy ray-curable composition), the surface of an ultrahigh mol.wt. polyolefin drawn article is coated with a composition comprising (A) an epoxy resin, preferably bisphernol A glycidyl ether, (B) a sulfonium salt or cyclopentadienyl iron compound (preferably triphenyl sulfonium salt or cyclopentadienyl compound having cyclopentadienyl group and isopropylphenyl group), (C) a compound selected from acrylates, methacrylates and oligomers thereof and (D) an organic peroxide and subsequently cured with the irradiation of active energy rays to improve the adhesivity of the drawn article to other polymers. When used for the production of sport goods, etc., the treated drawn article provides the goods having highly improved mechanical strengths such as flexural strength.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stretched ultra-high molecular weight polyolefin product and a method for producing the same. More specifically, the present invention relates to a stretched ultra-high molecular weight polyolefin product whose surface is coated with an active energy ray-curable composition containing an epoxy resin as a main component to improve adhesion, and a method for producing the same.

Fiber-reinforced plastics have excellent strength and rigidity, so they can be used for automobile parts, appliance parts housings, industrial materials, small ships, sporting goods, medical materials, and civil engineering materials. It is widely used in construction materials, etc. However, since most of the fiber reinforcing materials used in fiber reinforced plastics are glass fibers, there is a problem in that fiber reinforced plastics (composite materials) are heavier than unreinforced plastics. Therefore, there is a desire for a composite material that is lightweight and has good mechanical strength.

On the other hand, ultra-high molecular weight polyolefin filaments obtained by drawing ultra-high molecular weight polyolefin to a high ratio have high elasticity, high strength, and light weight, and are therefore expected to be a fiber reinforcing material suitable for reducing the weight of composite materials. However, as is well known, ultra-high molecular weight polyolefins have poor adhesion to polar materials, so it is necessary to improve their adhesion in order to use them as reinforcing materials for plastics and the like.

Generally, in order to improve the adhesiveness of polyolefin, a method of plasma discharge treatment of a polyolefin molded product to improve the adhesiveness with the base material (Japanese Patent Publication No. 53-794, Japanese Patent Application Laid-open No. 53-794,
No. 7-177032) has been proposed, and US Pat. No. 3,440,418 discloses a method of subjecting polyolefin to electrical discharge treatment to improve adhesiveness. Among these, JP-A-57-177032 proposes treating polyolefin molded articles with a potassium dichromate solution before plasma discharge treatment.

By adopting such a method, the adhesion between the polyolefin reinforcing material and the base resin is considerably improved, but for example, structural materials such as building materials, carriers, tanks, vehicles, aircraft, etc. or leisure goods, sports equipment,
Depending on the application, such as medical materials or acoustic materials, the adhesion between the polyolefin reinforcing material and the base material is still insufficient, and further improvements are desired.

In addition, after plasma discharge treatment or electron beam irradiation treatment is applied to the drawn ultra-high molecular weight polyolefin, an unsaturated carboxylic acid or a derivative thereof is graft-polymerized on the surface of the drawn ultra-high molecular weight polyolefin. Method for improving adhesion (Japanese Patent Application Laid-Open No. 62-59
, No. 637) has also been proposed, but further improvements are desired.

The inventors conducted extensive studies to solve the above-mentioned problems, and found that an active energy ray-curable composition mainly composed of an epoxy resin containing specific components was applied to the surface of a stretched ultra-high molecular weight polyolefin. They discovered that it is sufficient to provide a hardened coating, and have completed the present invention.

The present invention aims to solve the problems associated with the prior art as described above, and provides a stretched ultra-high molecular weight polyolefin product with excellent adhesion to other polymers and its production. The purpose is to provide a method.

1. The ultra-high molecular weight polyolefin stretched product according to the present invention has a surface comprising (A) an epoxy resin, (B) a compound selected from the group consisting of a sulfonium salt and a cyclopentadienyl iron compound, (C) It is characterized by being coated with a cured product of an active energy ray-curable composition containing a compound selected from the group consisting of acrylates, methacrylates, and oligomers thereof, and (D) an organic peroxide.

Further, the method for producing a drawn ultra-high molecular weight polyolefin product according to the present invention includes coating the surface of the drawn ultra-high molecular weight polyolefin product with an active energy ray-curable composition containing the components (A) to (D) above, and then It is characterized by curing the composition by irradiating it with energy rays.

■LII+<TE [I Hereinafter, the drawn ultra-high molecular weight polyolefin product and the method for producing the same according to the present invention will be specifically explained.

In the present invention, a stretched product of ultra-high molecular weight polyolefin or ultra-high molecular weight ethylene/α-olefin copolymer is used.

Specifically, such ultra-high molecular weight polyolefins include ultra-high molecular weight polyethylene, ultra-high molecular weight polypropylene, ultra-high molecular weight poly-1-butene, and two or more types of α-
Examples include ultra-high molecular weight copolymers of olefins. The drawn product of this ultra-high molecular weight polyolefin is lightweight, has high strength, and has excellent water resistance and salt water resistance.

In addition, the ultra-high molecular weight ethylene that constitutes the drawn product of the present invention
Examples of α-olefin copolymers include ultra-high molecular weight ethylene/propylene copolymer, ultra-high molecular weight ethylene/1-butene copolymer, ultra-high molecular weight ethylene/4-methyl-1-pentene copolymer, and ultra-high molecular weight ethylene/1-butene copolymer. Ethylene/1-hexene copolymer, ultra-high molecular weight ethylene/1-octene copolymer,
Ethylene such as ultra-high molecular weight ethylene/1-decene copolymer and α- having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms.
Examples include ultra-high molecular weight ethylene/α-olefin copolymers with olefins. This ultra-high molecular weight ethylene/α-olefin copolymer has 3 or more carbon atoms.
The olefin is 0.1 per 1000 carbon atoms in the polymer.
~20 pieces, preferably 0.5 to 10 pieces, more preferably 1 piece
It is contained in an amount of ~7.

A drawn product obtained from such an ultra-high molecular weight ethylene/α-olefin copolymer is particularly excellent in FR impact resistance and creep resistance compared to a drawn product obtained from ultra-high molecular weight polyethylene. This ultra-high molecular weight ethylene/α-olefin copolymer is lightweight and has high strength, and has excellent abrasion resistance, impact resistance, and creep resistance, as well as weather resistance, water resistance, and salt water resistance.

The ultra-high molecular weight polyolefin or ultra-high molecular weight ethylene/α-olefin copolymer constituting the stretched product of the present invention is
Its intrinsic viscosity [η] is 5d, Q/g or more, preferably 7~
306j/g, and the stretched product obtained from this copolymer has excellent mechanical properties or heat resistance. In other words, the molecular terminals do not contribute to fiber strength, and the number of molecular terminals is the reciprocal of the molecular weight (viscosity), so the intrinsic viscosity [
η] gives high strength.

The density of the stretched product of the present invention is 0.940 to 0.990sr
/- preferably 0.960 to 0.985 g/13A. Here, the density was measured by the density gradient tube method according to a conventional method (^STHD 1505). The density gradient tube at this time was prepared by using carbon tetrachloride and toluene, and the measurement was performed at room temperature (23° C.).

The dielectric constant (IKHz, 23°C) of the stretched product of the present invention is 1.
4 to 3.0, preferably 1.8 to 2.4, and the positive electric dissipation tangent (IKHz, 80°C) is 0.05 to 0,00%, preferably 0.040 to 0,000%. Here, the dielectric constant and the positive electric dissipation tangent were measured using an 8STHD 150 using a film-like sample made by closely arranging fibers and tape-shaped molecular white wood in one direction.

The stretching ratio of the stretched product of the present invention is 5 to 80 times, preferably 1
0 to 50 times.

The degree of molecular orientation in the stretched product of the present invention can be determined by X-ray diffraction, birefringence, fluorescence polarization, etc. When the ultra-high molecular weight polymer of the present invention is a stretched filament, for example, Yukichi Go, Teru Kubo: Industrial Chemistry Magazine Vol. 39, 992
(1939), the degree of orientation in terms of the half-width, that is, the formula (formula ``[H'') is the half-width (°) of the intensity distribution curve along the Debye ring of the strongest paratropic surface on the equator. The degree of orientation (F) defined by ) is 0.90 or more, especially 0.9
From the viewpoint of mechanical properties, it is desirable that the molecules be oriented so that the number of particles is 5 or more.

Furthermore, the drawn product of the present invention has excellent mechanical properties, such as 20 GPa or more in the form of a drawn filament,
In particular, it has an elastic modulus of 30 GPa or more and a tensile strength of 1.2 GPa or more, especially 1.5 GPa or more.

The impulse voltage breakdown value of the stretched product of the present invention is 110 to 2
50 K V/am preferably 150-220 K
V/l1lI. The impulse voltage breakdown value is
Using the same sample as in the case of dielectric constant, brass (25
2 impulses of negative polarity are generated by the JIS type electrode of
The pressure was increased while adding KV/3 times and the measurement was made.

When the stretched product of the present invention is a stretched product of an ultra-high molecular weight ethylene/α-olefin copolymer, this stretched product has the characteristics of extremely excellent impact resistance, breaking energy, and creep resistance. ing. The characteristics of drawn products of these ultra-high molecular weight ethylene/α-olefin copolymers are expressed by the following physical properties.

The breaking energy of the stretched ultra-high molecular weight ethylene/α-olefin copolymer used in the present invention is 8 kg-m/
or more, preferably 10 kg-m/2 or more.

Further, the drawn product of the ultra-high molecular weight ethylene/α-olefin copolymer of the present invention has excellent creep resistance. In particular, it has outstanding creep resistance at high temperatures, which corresponds to the conditions that promote creep at room temperature.
%) is 7% or less, especially 5% or less, and the creep rate after 90 seconds to 180 seconds (ε
, sac) is less than 4 x 10'5ec-1, especially less than 5x10'sec-'.

Among the stretched products of the present invention, the stretched products of ultra-high molecular weight ethylene/α-olefin copolymers have the above-mentioned room temperature physical properties, but in addition to these room temperature properties, they also have the following thermal properties: If it has both, the above-mentioned room temperature properties will be further improved,
It is preferred because it also has excellent heat resistance.

The drawn product of the ultra-high molecular weight ethylene/α-olefin copolymer used in the present invention has at least one crystal melting peak (' The heat of fusion based on I'p) is 15% or more, preferably 20% or more, particularly 30% or more.

Ultra-high molecular weight ethylene copolymer original crystal melting temperature (T1
1) is by completely melting this molded body and then cooling it.
A method of raising the temperature again after relaxing the molecular orientation in the compact, the so-called second heating method in a differential scanning calorimeter.
It can be found by running.

To explain further, in the stretched product of the present invention, there is no crystal melting peak at all in the above-mentioned crystal melting temperature range inherent to the copolymer, or even if it exists, it exists only as a slight tailing.

The crystal melting peak (Tp) is generally in the temperature range Tn+20
℃~TI+50℃, especially Tn+20℃~T11+100
It is usually expressed in the region of °C, and this peak (T
o) often appears as multiple peaks within the above temperature range, i.e., this crystal melting peak (To)
are the high-temperature side melting peak ('rp1) in the temperature range T1m +35°C to TIl+100°C, and the temperature range TI+
It often appears as two separate peaks, the low-temperature side melting peak (TI2) at 20°C to T" rm + 35°C, and depending on the manufacturing conditions of the drawn product, T11. and TI2 may further consist of multiple peaks. There is also.

These high crystal melting peaks ('rp +"r'p2
) is thought to significantly improve the heat resistance of drawn products of ultra-high molecular weight ethylene/α-olefin copolymers and contribute to strength retention or elastic modulus retention after high-temperature thermal FF history. It will be done.

Also, high temperature f in the temperature range TIl+35℃~Tn+100℃
The total heat of fusion based on the fl1 melting peak ('rp 1) is desirably 1.5% or more, particularly 3.0% or more, based on the total heat of fusion.

In addition, in the interval where the sum of the heat of fusion based on the high temperature side melting peak ('rp 1) satisfies the above-mentioned value, if the high temperature side melting peak ('rp 1) does not appear prominently as the main peak, that is, Even if it becomes a collection of small peaks or a broad peak, heat resistance may be slightly lost, but creep resistance is excellent.

The melting point and heat of crystal fusion in the present invention were measured by the following method.

The melting point was determined using a differential scanning calorimeter as follows.

Differential scanning calorimeter is DSCn type (manufactured by PerkinElmer)
was used. The sample was restrained in the orientation direction by wrapping approximately 3 cm around an aluminum plate of 4 rm x 4 rm, thickness 0.2+n+.The sample was then wrapped around the aluminum plate and sealed in an aluminum pan for measurement. It was used as a sample. Also, the empty aluminum pan that is usually placed in the reference holder contains
The same aluminum plate used for the sample was enclosed to maintain heat balance. First, the sample was held at 30°C for about 1 minute, and then
The temperature was raised to 250°C at a heating rate of °C/min, and the melting point measurement at the first temperature rise was completed. 1 at 250℃
held for 0 minutes, then lowered the temperature at a rate of 20°C/min,
The sample was further held at 30°C for 10 minutes.

Then, the second heating was carried out to 250″ at a heating rate of 10°C/min.
The temperature was raised to C, and at this time, the melting point measurement at the second temperature increase (second run) was completed. At this time, the maximum value of the melting peak was taken as the melting point. When it appears as a shoulder, a tangent is drawn at the inflection point immediately on the low-temperature side and the inflection point immediately on the high-temperature side of the shoulder, and the intersection is taken as the melting point.

In addition, from the straight line (baseline) connecting the endothermic curve at 60°C and 240'C and the original crystal melting temperature (T11) of the ultra-high molecular weight ethylene copolymer, which is determined as the main melting peak at the second temperature increase, Draw a perpendicular line to the point with a high temperature, and assume that the part on the low temperature side surrounded by these is based on the crystal melting (T11) inherent to the ultra-high molecular weight ethylene copolymer,
In addition, the high-temperature side part undergoes crystal melting (
Tp), and the heat of fusion of each crystal is
Calculated from these areas. Also, Tp and Tl
]2, the heat of fusion based on the melting of Tn
The area surrounded by the perpendicular line from ÷20°C and the perpendicular line from TI+35°C was taken as the heat of fusion based on the melting of Tp2, and the high temperature side part was calculated in the same way as the heat of fusion based on the melting of 1゛p1.

The drawn filament of the ultra-high molecular weight ethylene/α-olefin copolymer of the present invention has a strength retention rate of 95% or more and an elastic modulus retention rate of 90% or more after being subjected to a heat history of 5 minutes at 170°C. In particular, it has an excellent heat resistance of 95% or more, which is completely unrecognizable in conventional drawn polyethylene filaments.

A method for producing a drawn product of ultra-high molecular weight polyolefin A method for producing a drawn product of ultra-high molecular weight polyolefin having the above-mentioned cavity elasticity and high tensile strength is, for example, disclosed in JP-A No. 5
6-15408 Publication 1, JP-A-58-5228, JP-A-59-130313, JP-A-59-18
The stretchability of ultra-high molecular weight polyolefin can be improved by making ultra-high molecular weight polyolefin into a dilute solution, or by adding a low molecular weight compound such as paraffin wax to ultra-high molecular weight polyolefin, as described in detail in Publication No. 7614. An example of an improved method for stretching to a high magnification can be given.

Ultra-high molecular weight ethylene/α-olefin copolymer 8-
♂-2. Next, the present invention will be explained below in order of raw materials, manufacturing method, and purpose so that it can be easily understood.

L-1 Above: The ultra-high molecular weight ethylene/α-olefin copolymer used in the present invention is obtained by slurry polymerizing ethylene and an α-olefin having 3 or more carbon atoms in an organic solvent using a Ziegler type catalyst. It can be obtained by

As the α-olefin having 3 or more carbon atoms, propylene,
butene-1, pentene-1,4-methylpentene-1,
Hexene-1, heptene-1, octene-1, etc. are used, but among these, butene-1,4-methylpentene-1, hexene-1, octene-1, etc. are particularly preferred.
Such α-olefins are copolymerized with ethylene in the amount stated above per 1000 carbon atoms of the resulting copolymer. Further, the ultrahigh-molecular ethylene/α-olefin copolymer used as a base in producing the molecularly oriented body in the present invention should have a molecular weight corresponding to the above-mentioned intrinsic viscosity [η].

The α-olefin component in the ultra-high molecular weight ethylene/α-olefin copolymer used in the present invention is determined using an infrared spectrophotometer (manufactured by JASCO Corporation). Specifically, the absorbance of 1378cz-1, which represents the bending vibration of the methyl group of the α-olefin incorporated into the ethylene complex, was measured using an infrared spectrophotometer, and this value was determined in advance by 13C nuclear magnetic resonance. Using the device, quantify the α-olefin precipitate in the ultra-high molecular weight ethylene/α-olefin copolymer by converting it into the number of methyl branches per 1000 carbon atoms using a calibration curve created using a model compound. .

In the basic invention, when producing a stretched product from the ultra-high molecular weight ethylene/α-olefin copolymer, a diluent is blended into the copolymer. As such a diluent, a solvent for the ultra-high molecular weight ethylene copolymer or various wax-like substances having compatibility with the ultra-high molecular weight ethylene copolymer can be used.

Such a solvent has a boiling point higher than the melting point of the copolymer, more preferably 20" higher than the melting point of the copolymer.
A solvent having a boiling point higher than C or higher is used.

Specifically, such solvents include n-nonane, n-
- Decane, n-undecane, n-dodecane, n-tetradecane, n-octadecane or liquid paraffin, aliphatic hydrocarbon compounds such as kerosene, xylene, naphthalene,
Tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene,
Aromatic hydrocarbon solvents such as dodecylbenzene, bicyclohexyl, decalin, methylnaphthalene, ethylnaphthalene or hydrogenated derivatives thereof, 1,1,2.2-tetrachloroethane, pentachloroethane, hexachloroethane, 1.2.3- Examples include halogenated hydrocarbon solvents such as trichloropropane, dichlorobenzene, 1.2.4-)dichlorobenzene, and bromobenzene, and poor oils such as paraffinic process oil, naphthenic process oil, and aromatic process oil.

Further, as the wax as a diluent, specifically, an aliphatic hydrocarbon compound or a derivative thereof is used.

Such aliphatic hydrocarbon compounds are mainly composed of saturated aliphatic hydrocarbon compounds, and are usually compounds called paraffin waxes having a molecular weight of 2,000 or less, preferably 1,000 or less, more preferably 800 or less.

Examples of such aliphatic hydrocarbon compounds include n-alkanes having 22 or more carbon atoms such as tocosan, tricosane, tetracosane, and triacontane, mixtures of these with lower n-alkanes as main components, petroleum So-called paraffin wax separated and purified from ethylene or low molecular weight polymer obtained by copolymerizing ethylene with other α-olefins, medium/low pressure polyethylene wax, high pressure polyethylene wax, ethylene copolymer wax or medium・Waxes obtained by reducing the molecular weight of polyethylene such as low-pressure polyethylene and high-pressure polyethylene by thermal degradation, oxides of these waxes, oxidized waxes modified with maleic acid, waxes modified with maleic acid, etc. are used.

Examples of aliphatic hydrocarbon compound derivatives include, for example, one or more carboxyl groups, preferably one to two carboxyl groups, particularly preferably one carboxyl group, at the terminal or inside of an aliphatic hydrocarbon group (alkyl group, alkenyl group), A compound having a functional group such as a hydroxyl group, a carbamoyl group, an ester group, a meltcapto group, or a carbonyl group, with a carbon number of 8 or more, preferably a carbon number of 12 to 50'J, and a molecular weight of 130 to 20
00 to 800, preferably fatty acids, aliphatic alcohols, fatty acid amides, fatty acid esters, aliphatic mercaptans, aliphatic aldehydes, aliphatic ketones, etc. are used.

Examples of such aliphatic hydrocarbon compound derivatives include fatty acids such as capric acid, lauric acid, myristic acid, valmitic acid, stearic acid, and oleic acid, lauric alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol. Fatty acid amides such as caprinamide, lauramide, palmitinamide, and stearylamide, fatty acid esters such as stearyl acetate, and the like are used.

The super molecular weight ethylene/α-olefin copolymer and diluent differ depending on their type, but - 3 for boat fishing.
=97~80:20, especially 15:85~60:
A weight ratio of 40 is used. If the amount of the diluent is lower than the above range, the melt viscosity will become too high, making melt kneading and melt molding difficult, and the resulting molded product will have a markedly rough surface and is prone to stretch breakage, etc. If the amount of the diluent is larger than the above range, melt-kneading will become difficult, and the resulting molded product will have poor stretchability.

Melt kneading is generally carried out at 150 to 300°C5, particularly at 170 to 300°C.
It is carried out at a temperature of 270°C. If the temperature is lower than the above range, the melt viscosity will be too high and melt molding will be difficult, and if the temperature is higher than the above range, the molecular weight of the ultra-high molecular weight ethylene/α-olefin copolymer will decrease due to thermal degradation. However, it becomes difficult to obtain a molded article having excellent high elastic modulus and high strength. The formulation is made using a Henschel mixer, V
It may be carried out by dry blending using a mold blender or the like, or it may be carried out using a single screw extruder or a multi-screw extruder.

Melt molding of a dope (spinning stock solution) comprising an ultra-high molecular weight ethylene/α-olefin copolymer and a diluent is generally performed by melt extrusion molding. Specifically, filaments for drawing are obtained by melt extruding the dope through a spinneret.

At this time, the molten material extruded from the spinneret may be drafted, that is, drawn in the molten state. Molten Q1t + Extrusion speed of fat in Gui orifice■. The draft ratio can be defined by the following formula:

Draft ratio -V/vo (2) This draft ratio varies depending on the temperature of the mixture, the molecular weight of the ultra-high molecular weight ethylene copolymer, etc., but is usually 3 or more, preferably 6 or more. can.

Next, the ultra-high molecular weight ethylene α obtained in this way
- Stretching the unstretched molded olefin copolymer. Stretching is carried out so as to effectively impart at least uniaxial molecular orientation to the unstretched molded article obtained from the ultra-high molecular weight ethylene/α-olefin copolymer.

Stretching of an unstretched molded article obtained from an ultra-high molecular weight ethylene/α-olefin copolymer is generally carried out at a temperature of 40 to 160°C, particularly 80 to 145°C. Air,
Either water vapor or liquid medium can be used. However, as a heat medium, a liquid medium that is a solvent capable of eluting and removing the diluent described above and whose boiling point is higher than the melting point of the molded article composition, specifically, decalin, decane, kerosene, etc., is used. It is preferable to carry out the stretching operation in such a manner that the diluent described above can be removed, uneven stretching will not occur during stretching, and a high stretching ratio can be achieved.

The means for removing the diluent from the ultra-high molecular weight ethylene/α-olefin copolymer is not limited to the above-mentioned method, but may include a method of treating an unstretched material with a solvent such as hexane, heptane, hot ethanol, chloroform, or benzene, and then stretching it; A stretched product with high elastic modulus and high strength can also be obtained by removing the diluent in the molded product by treating the stretched product with a solvent such as hexane, heptane, hot ethanol, chloroform, or benzene.

The stretching operation can be performed in one stage or in multiple stages of two or more stages. The stretching ratio depends on the desired molecular orientation and the associated effect of increasing the melting temperature, but is generally between 5 and 5.
80 times, preferably 10 to 50 times.

In general, it is preferable to carry out the stretching operation by two or more stages of stretching, in which the diluent in the extrudate is extracted at a relatively low temperature of 80 to 120°C before the stretching operation is carried out, and the stretching operation is performed in the second stage. In the subsequent stages, it is preferable to stretch the molded body at a temperature of 120 to 160'C and at a temperature higher than the first stage stretching temperature.

In the case of a uniaxial stretching operation, tension stretching may be performed between rollers having different circumferential speeds.

The drawn product thus obtained can be heat-treated under constrained conditions, if desired. This heat treatment is generally 1
at a temperature of 40-180°C, preferably 150-175°C,
It can be carried out for 1 to 20 minutes, preferably 3 to 10 minutes. By heat treatment, the crystallization of the oriented crystal part further progresses,
This results in a shift of the crystal melting temperature to a higher temperature side, an improvement in strength and elastic modulus, as well as an improvement in creep resistance at high temperatures.

In the present invention, the ultra-high molecular weight polyolefin drawn product thus obtained may be used in the form of a filament, or the drawn product may be used in the form of a lobe, a net, a cloth, a sheet, a non-woven fabric, etc. Good too.

In the present invention, the surface of the above-mentioned ultra-high molecular weight polyolefin stretched product is coated with a cured product of an active energy ray-curable composition containing the following components (A) to (D).

In the present invention, an active energy ray-curable composition (hereinafter also simply referred to as a composition) containing an epoxy resin as a main component is used, but the epoxy resin (A) contained in the active energy ray-curable composition is For example, compounds containing two or more epoxy groups in one molecule are preferred, and aliphatic or alicyclic epoxy compounds are particularly preferred.

Specifically, such epoxy resins (A) include bisphenol A, bisphenol F, 1.1, 2.2-
Glycidyl ether-based epoxy resins of polyphenol compounds such as tetrakis(4-hydroxyphenyl)ethane; glycidyl ether-based epoxy resins of polyhydric phenols such as catechol, resorcinol, hydroquinone, and phloroglucin; ethylene glycol, butanediol, glycerol, erythritol, Glycidyl ether type epoxy resin with polyhydric alcohol head such as polyoxyalkylene glycol; Novolak type epoxy resin; Cycloaliphatic type epoxy resin such as vinyl cyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide; phthalic acid, cyclohexane A polyglycidyl ester-based epoxy resin of an ester condensate of a polycarboxylic acid such as -1,2-dicarboxylic acid: a polyglycidylamine-based epoxy resin, etc. are used. Among these epoxy resins, glycidyl ether-based epoxy resins or novolak-type epoxy resins of polyphenol-like compounds are preferred, and glycidyl ether-based epoxy resins of bisphenol A or bisphenol F are more preferred, and among these, glycidyl ether-based epoxy resins of bisphenol A are particularly preferred. Resins are particularly preferred.

Furthermore, the active energy ray-curable composition contains a sulfonium salt or a cyclopentadienyl iron compound (B).

As such a sulfonium salt, a triarylsulfonium salt is preferable, and a triphenylsulfonium salt is especially preferable.As an anion of this sulfonium salt, for example, AsF6- or BFi, -
etc. are preferred.

Specifically, such sulfonium salts include triphenylsulfonium salt tri(4-methylphenyl)sulfonium salt tri(
4-methoxyphenyl)sulponium salt is used.

In addition, cyclopentadienyl iron compounds include compounds containing two cyclopentagenyl groups in the molecule, or one cyclopentagenyl group and one aromatic compound such as phenyl or isopropylphenyl. Compounds containing group groups are used. Among these, the latter compound is more preferable, and furthermore, cyclopentadienyl iron compounds as shown below having a cyclopentadienyl group and an isopropylphenyl group are particularly preferable, and such sulfonium salts and cyclopentadienyl iron compounds are particularly preferable. Each of the compounds can be used alone, or both can be used in combination.

Component (C) contained in the active energy ray-curable composition is selected from the group consisting of acrylates, methacrylates, and oligomers thereof.

As such acrylates and methacrylates, esters of hydroxy compounds or di or more polyhydroxy compounds and acrylic acid or methacrylic acid are used. Such esters include, for example, monohydric aliphatic alcohols having 1 to 20 carbon atoms;
-30 alicyclic alcohol, C1-20 divalent aliphatic alcohol, C1-20 divalent alicyclic alcohol, C1-2 trivalent aliphatic alcohol, hydroxyl terminal Examples include esters of hydroxy compounds such as polyesters, and acrylic acid or methacrylic acid.

Specifically, the following compounds are used as such esters.

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate; cyclohexyl acrylate, norbornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, 3.6 10.13 Hexacyclo[6,6,1,1,1,02°7
,09°14]heptadecyl-4-acrylate 3.6
10.13 12-methylhexacyclo[6,6,1,1,12,7
9,14 ,0,0]]Heptadecyl-4-acrylate 3.6
10.13 11-Methylhexacyclo[6,6,1,1,12,7
9,14,O,O]]heptadecyl-4-acrylate 3.6
10.13 12-ethylhexacyclo[6,6,1,1,12,7
9,14,O,O]]hegetadecyl-4-acrylate 3゜6
10.13 11-ethylhexacyclo[6,6,1,1,12,7
9,14, O, O]] 1 Tadecyl-4-acrylate 2.9
4.7 Octacyclo[8,8,1,111,181
3,163,812,17,1,1,0,G,O
] Tocosyl-5-acrylate 2.9 4.7 15-methyloctacyclo[8,8,1,111,18
13,163,812,17,1,1,0,0,O]
] Tocosyl-5-acrylate 2.5 7.10 2.7-dimethyltetracyclo[4,4,0,1,1]
] Dodecyl-3-acrylate 2.10-dimethyltetracyclo[4,4,0,12°
5.17°10] Dodecyl-3-acrylate, 11
．． 12-dimethyltetracyclo[4,4,0,12°5
．． 17°10] Dodecyl-3-acrylate, 2.5
7.10 Tetracyclo[4,4,0,1,1]dodecyl-3-acrylate 2.5 7.10 9-substituted tetracyclo[4,4,0,1,1]]dodecyl-3-acrylate formula shown below The substituents at the middle 9th position are methyl, ethyl, propyl, isobutyl, hexyl, cyclohexyl, stearyl, bromo, full 2.5 7.10), 8-substituted tetrash [4,4,0,1,1 ]
] Dodecyl-3-acrylate The substituent at position 8 in the formula is methyl, ethyl, propyl, isobutyl, hexyl, cyclohexyl, stearyl, bromo or fluoro)
, 8.9-disubstituted tetracyclo[4°2.5 7.10 4.0,1 . 1] ] dodecyl-3-acrylate The substituents at the 8th and 9th positions are methyl, ethyl, propyl, isobutyl, hexyl, cyclohexyl, stearyl, bromo or fluoro), 3.6 10
．． 13 2.7 Hexacyclo[6,6,1,1,1,0,09°14]
Heptadecyl-4-methacrylate, 3.6 10.
13 12-methylhexacyclo[6,6,1,1,12,7
9,14,O,O]]heptadecyl-4-methacrylate 3.6
10.13 11-Methylhexacyclo[6,6,1,1,12,7
9,14, O, O]]1 Tadecyl-4-methacrylate 3.6
10.13 12-ethylhexacyclo[6,6,1,1,12,7
9,14 ,0,0]]Heptadecyl-4-methacrylate 3.6
10.13 11-ethylhexacyclo[6,6,1,1,12,7
9,14 ,0,0]]Heptadecyl-4-methacrylate 2.9
4.7 11.18 13.16 octacyclo[8,
8,1,1,1,13,812,17 ,O,O,O]]Tocosyl-5-methacrylate2.
9 4.7 15-methyloctacyclo[8,8,1,111,18
13,163,812,17,1,1,0,O,O codocosyl-5-methacrylate, 2.5 7.10 2.7-dimethyltetracyclo[4,4,0,1,1]
] Dodecyl-3-methacrylate 2.5 7.10 2.10-dimethyltetracyclo[4,4,0,1,1
]]Dodecyl-3-methacrylate 2.5 7.10 11,12-dimethyltetracyclo[4,4,0,1,
1]]Dodecyl-3-methacrylate 2.5 7.10 Tetracyclo[4,4,0,1,1]]Dodecyl-3-
Methacrylate 2.5 7.10 9-substituted tetracyclo[4,4,0,1,1]]dodecyl-3-acrylate In the formula, the substituent at position 9 is methyl, ethyl, propyl, isobutyl, hexyl, cyclohexyl, stearyl, bromo or fluoro), 2.57゜10 8-substituted tetracyclo[4,4,0,1,1]]dodecyl-3-methacrylate In the formula, the substituent at position 8 is methyl, ethyl, propyl, isobutyl, hexyl, cyclohexyl , stearyl, bromo or fluoro) and 8,9-disubstituted tetracyclo[4,42,57,10,0,1,1]]dodecyl-3-methacrylate in which the substituents at the 8th and 9th positions are methyl, ethyl, propyl, isobutyl, hexyl, cyclohexyl, stearyl, bromo or fluoro), the following formula (I) A-f-M-N-')-M-A ... (I)
(wherein A is an acrylic acid residue, M is a divalent aliphatic or alicyclic alcohol residue, N is a dibasic acid residue, and n is a positive number) A polyester whose both ends are controlled with acrylic acid represented by the following formula (II) AA A +X -Y (X -A...(II)
(In the formula, the definition of A is the same as above, X is a trivalent or higher polyvalent aliphatic or alicyclic alcohol residue, and N
is a divalent or higher polybasic acid, and m is a positive number), and the hydroxyl groups at both ends and in the chain are blocked with acrylic acid.

Some of these acrylate or methacrylate compounds are disclosed in JP-A-61-136529.

Furthermore, these acrylates or methacrylates can also be used as oligomers produced by pre-(MM) synthesis according to methods known per se.

Among the components (C) as described above, the component (C) contained in the active energy ray-curable composition is an alkyl ester of acrylic acid or methacrylic acid, an alkyl ester of the above formula (I
) and a mixture of the compound represented by the above formula (n) are preferred. Furthermore, monomers having a carboxyl group, hydroxyl group, or epoxy group or oligomers thereof are added to the alkyl ester moieties of the acrylates and methacrylates described above. The resulting compounds are preferred, and further include methacryloxyethyl phosphate, bismethacryloxyethyl phosphate, diphenyl-2-(
It is also preferable to add a phosphate-containing (meth)acrylate such as meth)acryloyloxyethyl phosphate in order to improve the adhesion between the active energy ray-curable composition and the drawn ultra-high molecular weight polyolefin.

Examples of the organic peroxide (D) contained in the active energy ray-curable composition include benzoyl peroxide,
Dichlorobenzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, di-tart-butyl peroxide, 2,5-dimethyl-2,5-di(peroxide benzoate) hexyne-3,1,4-bis(
tert-butylperoxyisopropyl)benzene,
lauroyl peroxide, tart-butylberacetate, 2,5-dimethyl-2,5-di(tart-butylperoxy)hexyne-3,2,5-dimethyl-2,
5-di(tart-butylperoxy)hexane, te
rt-butylberbenzoate, tart-butylberphenylacetate, tert-butylberisobutyrate, tart-butylber-5ac-octoate,
Tart-butylbelpivalate, cumylbelpivalate, tart-butylbeldiethyl acetate, etc. are used.

Among these, dicumyl peroxide, di-tar
t-Butyl peroxide, 2,5-dimethyl-2,5-
di(tart-butylperoxy)hexyne-3,2,
Dialkyl peroxides such as 5-dimethyl-2,5-di(tart-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred.

In the composition used as an active energy ray-curable composition in the present invention, component (B) is used in an amount of 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of component (A). Component (C) is used in an amount of 1 to 35 parts by weight, preferably 20 to 30 parts by weight, per 100 parts by weight of component (A), and component (D) is used in an amount of 1 to 35 parts by weight, preferably 20 to 30 parts by weight, per 100 parts by weight of component (A).
It is used in an amount of ~10 parts by weight, preferably 2 to 5 parts by weight.

In the ultra-high molecular weight polyolefin stretched product according to the present invention, the composition used as the active energy ray-curable composition does not necessarily need to contain a photopolymerization initiation aid, but when curing the active energy ray-curable composition, When a relatively low-energy active energy ray such as ultraviolet rays is used, the composition preferably contains a photopolymerization initiation auxiliary agent. Various known copolymerization initiation aids can be used, such as a decomposition type compound that decomposes to generate radicals or a hydrogen abstraction type compound that generates radicals by abstracting hydrogen. Specifically, such photopolymerization initiation aids include benzoin or its ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether; benzophenone, p-thalolbenzophenone, p-methoxy Benzophenone compounds such as benzophenone: benzyl, benzyl compounds such as penzyldimethylgetal; 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 1-phenyl-2-hydroxy-2 -Methyl-
Hydroxyalkylphenylgetone compounds such as 1-propanone and 1-(4-tert-butylphenyl)-2-hydroxy-2-methyl-1-propane are used.

Furthermore, the active energy ray-curable composition may contain a sensitizer, if necessary.

Examples of such sensitizers include hydrocarbon compounds such as anthracene, naphthalene, chrysene, and phenanthrene: p-dinitrobenzene, p-nitroaniline, 1,3.5-trinitrobenzene, p- Nitro compounds such as nitrodiphenyl; n-butylamine, di-n
- Amino compounds such as butylamine, triethylamine, diethylaminoethyl methacrylate, p-nitroaniline, doacetyl-4-nitro-1-naphthylamine; phenol, p-ditrophenol, 2,4-dinitrophenol, 2,4゜6-tri Phenol compounds such as nitrophenol; ketones such as benzaldehyde, 9-anthraldehyde, acetophenone, benzophenone, dibenzalacetone, benzyl, p, p'-diaminobenzophenone, p, p-tetramethyldiaminobenzophenone; anthraquinone, 1. 2-Benzanthraquinone, benzoquinone, 1.2-naphthoquinone, 1
．． Quinones such as 4-naphthoquinone: anthrone, 1.
9-Benzanthrone, 6-phenyl-1,9-benzanthrone, 3-phenyl-1,9-benzanthrone, 2-keto-3-aza-1,9-benzanthrone, 3
Anthrones such as -methyl-1,3-diaza-1,9-benzaanthrone are used.

Moreover, a solvent can be added to the active energy ray-curable composition as needed.

By adding a solvent to the composition in this way, the composition can be easily applied onto the drawn ultra-high molecular weight polyolefin. The solvent added to the composition is preferably an organic ketone solvent, particularly acetone, methyl ethyl ketone, methyl isobutyl ketone, or diisobutyl ketone.
It is used in an amount of 0 to 20% by weight, or 70 to 30% by weight.

Furthermore, components that can be added to ordinary adhesives, such as reactive diluents, sensitizers, thickeners, anti-sagging agents, storage stabilizers, and plasticizers, can be added.

In the present invention, the surface of the drawn ultra-high molecular weight polyolefin product is coated with the active energy ray-curable composition as described above, but before the surface of the drawn ultra-high molecular weight polyolefin product is coated with the composition described above, The surface of the stretched ultra-high molecular weight polyolefin product may be subjected to plasma discharge treatment, electron beam irradiation treatment, corona discharge treatment, etc. in advance, or acid treatment with an unsaturated carboxylic acid or a derivative solution thereof, etc. Alternatively, by performing such a pretreatment, the adhesion between the active energy ray-curable composition and the stretched ultra-high molecular weight polyolefin product can be further improved.

Note that plasma discharge treatment is specifically performed as high-frequency discharge treatment, microwave discharge treatment, or glow discharge treatment, and such treatment is performed in an atmosphere of air, nitrogen, oxygen, argon, helium, etc. It is done. These gases may be used alone or in a mixture at any ratio.

The plasma discharge treatment conditions include a discharge output of 20 to 100 Watts, more preferably 50 to 100 Watts, and a degree of vacuum of 10-4 to 10 Torr, more preferably 10-2 to 10 Torr.
5 TOrr, and the processing gases are nitrogen, air, oxygen,
It is desirable to carry out the treatment using argon or the like for a treatment time of 1 to 1800 seconds, preferably 10 to 300 seconds.

In addition, in the electron beam irradiation treatment, the acceleration voltage is 100 to 1000K.
V, preferably 200-400KV, and the electron current is 1-400KV.
10 mA, preferably 2 to 8 mA, particularly preferably 3
-7 mA, and the irradiation dose is desirably 0.1 to 10 megarats, preferably 0.5 to 5 megarats.

In the present invention, the surface of a stretched ultra-high molecular weight polyolefin product is coated with the active energy ray-curable composition. In this case, a dipping method is usually used, but other methods such as spraying may also be used.

After the surface of the stretched ultra-high molecular weight polyolefin product is coated with the composition in this manner, the composition is dried, using means such as air drying or an air oven.

The active energy ray-curable composition thus provided on the surface of the stretched ultra-high molecular weight polyolefin product is irradiated with active energy rays.

Active energy rays include ultraviolet rays, electron beams, radiation,
γ-rays etc. are used. By irradiating these active energy rays to the active energy ray-curable composition provided on the surface of the stretched ultra-high molecular weight polyolefin material, the composition is cured in a short time and has excellent initial adhesion and moisture-resistant adhesion. Moreover, a film with excellent transparency can be obtained.For example, when using ultraviolet rays, the cumulative amount of irradiation is 50 to 4000+1J.
/cd is preferred; if the amount of light is too small, the composition will not be cured, while if the amount of light is too large, the substrate may warp due to the heat accompanying irradiation.

The ultra-high molecular weight polyolefin stretched product whose surface is coated with a cured product of the active energy ray-curable composition obtained in this way is blended into a material 71 as described below and bonded to this material, or The following materials are impregnated.

Cement such as Portland cement, alumina cement, Aj O, 5102, B4C11゛1B Z, Z
R-free polar materials such as ceramics such as r82, phenolic resin, epoxy resin, unsaturated polyester resin, diallyl phthalate resin, urethane resin, melamine resin,
Thermosetting resins such as urea resin, nylon, polyester, polycarbonate, polyacetal, polyvinyl chloride, cellulose resin, polystyrene, thermoplastic resins such as acrylonitrile-styrene copolymer, and other polar materials.

When the curing temperature or molding temperature of these polar materials is below the softening point of the drawn ultra-high molecular weight polyolefin,
Both can be bonded by heating them to a temperature below the softening point of the stretched ultra-high molecular weight polyolefin. On the other hand, if the curing temperature or molding temperature of the polar material exceeds the softening point of the drawn ultra-high molecular weight polyolefin, the drawn material is immersed in a solution prepared by dissolving the polar material in an organic melt, etc. A method of dry heating to remove the solvent can be used.

The stretched ultra-high molecular weight polyolefin treated by the method of the present invention has high elasticity and high tensile strength as well as excellent adhesion to polar materials. Using stretched high molecular weight polyolefin as a reinforcing fiber, composites such as rackets, skis, fishing rods, golf clubs, sports equipment such as bamboo swords, leisure goods such as yachts, boats, surfing boards, artificial joints, medical materials such as denture stands, etc. When the material is produced, the a-mechanical strengths such as bending strength and flexural modulus are significantly improved compared to untreated products.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Shakukan ■ Ubisphenol A type epoxy resin (Mitsui Petrochemical Industries ■
(formerly EPO R-140), four types of acrylic monomers and oligomers (manufactured by Toagosei Chemical Co., Ltd., Aronix, H-5700, H-6100, H-6300, H
-8030), epoxy resin: H-5700+ 8
-6100: H-6300: M-8030 were mixed at a ratio of 80 near:5:3:5. To 100 parts by weight of the obtained mixture, 2 parts by weight of cyclopentadienyl isopropylphenyl iron <I [) salt (manufactured by Ciba Geigy), 0.25 parts by weight of anthracene (manufactured by Wako Pure Chemical Industries, Ltd.), and cumene hydroperoxide. (cumene hydroperoxide) (manufactured by Kayaku Nouri Co., Ltd., 70% product) 3.1
Parts by weight and 100 parts by weight of toluene were mixed to prepare a coating material. A cloth made of a stretched ultra-high molecular weight polyolefin (trade name: Techmilon) as described below was immersed in this coating material.

After pulling it up, it was dried in an air oven at 100°C for 5 minutes, and then ultraviolet rays were irradiated for 15 seconds at an illuminance of 160 mW/-. (The cumulative amount of light was 1100 nJ/-) The ultra-high molecular weight polyolefin stretched product (trade name: Techmilon Cross) obtained by ultraviolet irradiation treatment was treated with two types of epoxy resins (formerly known as EPO: R-30IH80 and R- 140, manufactured by Mitsui Petrochemical Industries ■), dicyanodiamide and 3-(p-
(chlorophenyl)-1,1-dimethylurea and dimethylformamide in this order at 87.5/30, respectively.
Immersed in resin mixed at a weight ratio of 1515/25,
A prepreg was prepared by dry lighting at 0° C. for 10 minutes. After laminating six sheets of this prepreg, press molding was performed at 100° C. for 1 hour to produce a laminate. Using this laminate as a sample, the bending strength and bending elastic modulus were measured according to JIS K691.

The results are shown in Table 1.

The same Tekmilon cloth as in Example 1 was heated using high-frequency plasma processing equipment 1RF manufactured by Samco International Laboratories.
G-400) was used to perform plasma discharge treatment. When performing plasma discharge treatment, air is used as the processing gas, the high frequency output is 50 W, and the degree of vacuum is 2.0 Torr.
r, and the processing time was 10 seconds.

The thus treated Techmilon cloth was subjected to the same coating treatment as in Example 1.

A 'MI laminate was prepared in the same manner as in Example 1 using the thus coated ultra-high molecular weight polyolefin stretched product (trade name: Techmilon cloth), and its bending strength and bending modulus were measured.

The results are shown in Table 1.

A laminate similar to that of Example 1 was prepared without any treatment on the Techmilon cloth of Example 1, and using this laminate as a sample, the bending strength and flexural modulus were measured according to JIS K 69.
Measured according to 1.

The results are shown in Table 1.

Table-”.

According to the results in Table 1, the laminates made of the drawn ultra-high molecular weight polyolefins obtained in Examples 1 and 2 had better bending strength and flexural modulus than the drawn ultra-high molecular weight polyolefins obtained in the comparative example. It can be seen that the increase is significantly greater than that of the laminate.

Agent: Patent Attorney: Shunbetsu Suzuki

Claims (1)

[Scope of Claims] 1) A stretched ultra-high molecular weight polyolefin product, the surface of which is coated with a cured product of an active energy ray-curable composition containing the following components (A) to (D): (A) Epoxy resin (B) Compound selected from the group consisting of sulfonium salts and cyclopentadienyl iron compounds (C) Compound selected from the group consisting of acrylates, methacrylates and oligomers thereof, and (D) Organic peroxide . 2) Claim 1, characterized in that an ultra-high molecular weight polyolefin stretched product whose surface has been previously subjected to plasma discharge treatment or electron beam irradiation treatment is coated with a cured product of an active energy ray-curable composition. The ultra-high molecular weight polyolefin stretched product described in . 3) After coating the surface of the stretched ultra-high molecular weight polyolefin product with an active energy ray-curable composition containing the following components (A) to (D), curing the composition by irradiating the composition with active energy rays. A method for producing a stretched ultra-high molecular weight polyolefin product characterized by: (A) an epoxy resin (B) a compound selected from the group consisting of sulfonium salts and cyclopentadienyl iron compounds (C) acrylates, methacrylates and oligomers thereof and (D) an organic peroxide. 4) After coating a stretched ultra-high molecular weight polyolefin whose surface has been previously subjected to plasma discharge treatment or electron beam irradiation treatment with an active energy ray-curable composition, the composition is cured by irradiation with active energy rays. The drawn ultra-high molecular weight polyolefin product according to claim 2, characterized by: