JPH0847992A - Three-dimensional composite reinforcing element using reticulated web of high modulus of elasticity, and production thereof - Google Patents

Abstract

PURPOSE:To inexpensively obtain a molded product of excellent quality by embedding a reinforcing element composed of a wide reticulated web produced from an oriented tape with tensile strength of a specific value or more and the tensile modulus of elasticity of a specific value or more composed of ultra-high molecular polyolefin with intrinsic viscosity of a specific value or more in a resin and/or inorg. structure. CONSTITUTION:An ultra-high mol.wt. polyolefin powder with intrinsic viscosity (measured in a decalin soln. at 135 deg.C) of 5dl/g or more is subjected to compression molding in a solid phase state and formed into a sheet by a rolling molding method to obtain an oriented material with tensile strength of 12g/denier or more, and the tensile modulus of elasticity of 200g/denier or more. This oriented material is split or slitted to be formed into a reticulated web which is, in turn, expanded in width and, if necessary, thermally fixed. A number of the reticulated webs thus formed are laminated in longitudinal and lateral directions to obtain a reticulated nonwoven fabric which is, in turn, embedded in a matrix of a polyester resin as a reinforcing element to mold, for example, the single side part of a trunk.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a three-dimensional composite reinforcing body composed of a resin or an inorganic structure in which a reinforcing body of an ultra-high molecular weight polyolefin is buried, and a method for producing the same, more specifically, an oriented film or sheet of an ultra-high molecular weight polyolefin. And a three-dimensional composite reinforcing body in which a split (split fiber) or slitted reticulated web is widened, and the reinforcing body thus obtained is embedded in a matrix of a thermoplastic resin, a curable resin or an inorganic material, and a method for producing the same. Is.

[0002]

2. Description of the Related Art Conventionally, as a three-dimensional composite structure of a resin or an inorganic material, there is a three-dimensional composite manufactured from SMC or BMC made of prepreg of glass fiber, carbon fiber, etc., but these SMC and BMC are molded. Although excellent in nature,
Since the fibers used for these are chopped strands (short fibers), they have the drawbacks that the reinforcing effect per fiber used is low and that the chopped strands after drawing are unevenly distributed. In addition, there are woven fabrics, unidirectional prepregs, etc. that use long fibers, but it is difficult to mold along a three-dimensional shape, and not only is the cost high, but there is the problem that drawing processing is not possible. is there. Furthermore, three-dimensional woven fabrics have been proposed, but there are problems that not only free-form fabrics cannot be formed, but also cost is high and large-sized products cannot be produced.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of extensive studies to solve the above-mentioned problems, and has a complicated three-dimensional composite reinforcement using a widened reticulated web produced from an oriented tape. As it provides a body, it is easy to adapt to complex three-dimensional shapes, and there is no uneven distribution of the constituent materials,
It is an object of the present invention to provide a low-cost manufacturing method that is excellent in the quality of molded products and is a rational molding method.

[0004]

That is, the present invention provides a resin and / or an inorganic structure having an intrinsic viscosity (135 ° C.).
Reinforcement consisting of a widened reticulated web made from an oriented tape having a tensile strength of 12 g / denier or more composed of an ultra high molecular weight polyolefin of 5 dl / g or more and a tensile modulus of 200 g / denier or more, as measured by a decalin solution. A second aspect of the present invention is a three-dimensional composite reinforcing body characterized by being buried in a body. The second invention comprises 12 g / denier or more of an ultrahigh molecular weight polyolefin having an intrinsic viscosity of 5 dl / g or more (measured with a decalin solution at 135 ° C.). A three-dimensional composite reinforcement body which has tensile strength and has a tensile elastic modulus of 200 g / denier or more and is formed by accumulating widened reticulated webs along a three-dimensional shape and then solidifying with a resin and / or an inorganic matrix. The third invention is a method for producing an ultrahigh molecular weight polymer having an intrinsic viscosity of 5 dl / g or more (measured with a decalin solution at 135 ° C.). After widening a reticulated web made of an oriented tape having a tensile strength of 12 g / denier or more and having a tensile modulus of 200 g / denier or more, which is made of a reffin, is flatly integrated, and then, a resin and / or an inorganic matrix is used. The fourth invention is a method for producing a three-dimensional composite reinforcing body, which is formed into a sheet and then processed into a three-dimensional structure.
A fifth aspect of the present invention is a method for producing a three-dimensional composite reinforcing body in which the reticulated web is electrified as a means for widening the reticulated web. The fifth invention is a method for producing a three-dimensional composite reinforcing body having an adhesive layer on the surface of which the web has a compatibility with a matrix. Is.

The present invention will be described in detail below. The ultra-high molecular weight polyolefin of the present invention has an intrinsic viscosity of 5 dl / g or more (measured with a decalin solution at 135 ° C.) and an intrinsic viscosity of 5 to 50 dl.
/ G, preferably 5 to 40 dl / g, more preferably 10 to 30 dl / g, and having a viscosity average molecular weight of 500,000 to 12,000,000, preferably 900,000 to 9,000,000,
More preferably, it corresponds to 1.2 million to 6 million.

When the intrinsic viscosity is less than 5 dl / g, the mechanical properties of the stretched product deteriorate, and when it exceeds 50 dl / g, the workability is deteriorated, which is not preferable.

The shape of the above-mentioned ultra-high molecular weight polyolefin is not particularly limited, but in order to obtain a homogeneous sheet by post-processing, a granular or powdery one is usually preferably used.

The particle size of these particles is 2000 μm or less, preferably 1 to 2000 μm, more preferably 10 to 100 μm.
0 μm is desirable. Further, it is preferable that the particle size distribution is narrow, because there are few defects when compression-molding to form a sheet.

The ultrahigh molecular weight polyolefin of the present invention comprises at least one compound selected from compounds containing a transition metal of Group IV to VI of the periodic table such as titanium compounds, vanadium compounds, chromium compounds, zirconium compounds and hafnium compounds. It is produced by homopolymerizing or copolymerizing an α-olefin in the presence of a catalyst formed by combining the contained catalyst component and, if necessary, an organometallic compound.

The α-olefin has 2 to 1 carbon atoms.
2, preferably 2 to 8 are preferably used. Specific examples include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and 1-dodecene.

Among these, especially ethylene, propylene,
1-butene, 4-methyl-1-pentene and 1-hexene are preferred. Further, as other comonomers, dienes such as butadiene, 1,4-hexadiene, vinyl norbornene, and ethylidene-norbornene may be further used in combination.

The comonomer content of the α-olefin copolymer is 0.001 to 10 mol%, preferably 0.0
It is used in the range of 1 to 5 mol%, more preferably 0.1 to 1 mol%.

The widened reticulated web of ultra-high molecular weight polyolefin of the present invention means that the oriented material of the ultra-high molecular weight polyolefin is split or slit into a reticulated web as shown in FIGS. 1a and 1b, and then the reticulated web is widened. Then, if necessary, it is heat-fixed and laminated as a weft and weft as shown in FIG. 1c and FIG. In order to enhance the physical properties of the reinforcing body, it is desirable to stack them together with an adhesive such as hot melt or emulsion, if necessary, to obtain an integrated body.

As the method for producing the oriented product of the ultra-high molecular weight polyolefin of the present invention, a method for producing and orienting a film by an inflation method by melt extrusion, a T-die method film formation, a skive method or the like, a method of dissolving with a solvent to form a film And a method in which ultra-high molecular weight polyolefin powder is compression-molded in a solid state and then rolled into a sheet for orientation. The compression method may be a batch method, a continuous method, or the like. Examples of the batch method include a slide method and a rotary method.As a continuous compression method, for example, an ultrahigh molecular weight polyolefin powder is sandwiched between a pair of vertically facing endless belts, while moving the endless belts, A method of compression molding and the like can be mentioned.

The above-mentioned orientation method is not particularly limited, but hot air drawing, cylinder drawing, roll drawing,
Examples include hot plate stretching. Since stretching of the ultrahigh molecular weight polyolefin material is slippery, it is desirable to stretch by applying stretching tension between nip rolls, clover rolls, multi-stage rolls, Nelson rolls and the like.

The orientation temperature is in the range below the melting point of the orientation material, usually 20 to 160 ° C., preferably 60 to 150 ° C.
More preferably, it is 90 to 145 ° C. Orientation process is 1
It is preferable to carry out not only stages but also multiple stages. In this case, it is desirable to raise the temperature sequentially to perform the alignment.

The orientation speed can be appropriately selected depending on the orientation method, the molecular weight of the polymer, the composition ratio, etc., but is usually 1 mm.
˜500 m / min. More specifically, in the case of batch type orientation, it is 1 to 500 mm / min, preferably 1 to 500 mm / min.
The range is 100 mm / min, more preferably 5 to 50 mm / min. On the other hand, in the case of continuous stretching, it is usually 0.1
˜500 m / min, preferably 1 to 200 m / min. Note that the high speed setting is more preferable in consideration of economy.

The higher the draw ratio, the higher the strength of the oriented material. Therefore, it is desirable to increase the draw ratio as much as possible. In order to stretch at a high ratio, it is desirable to perform stretching in a solid state, and examples of these methods include a method in which rolling and tensile stretching are used in combination, a gel stretching method, and the like.

In the present invention, the total draw ratio, which is the total draw ratio of rolling and drawing, is 20 times or more, preferably 30 times or more, more preferably 50 times or more, and further preferably 60 to 200 times. desirable.

In the present invention, the oriented material after stretching has a strength of 12 g / denier or more, preferably 50 g.
/ Denier or more, more preferably 100 g / denier or more, and the tensile elastic modulus is 200 g / denier or more, preferably 500 g / denier or more, more preferably 1000 g / denier or more, further preferably 150.
It is 0 g / denier or more.

In the reticulated web of the present invention, depending on the method of slitting or splitting, the constituent filament itself has sufficient strength, but there are cases in which sufficient strength cannot be obtained if measured directly. Therefore, the tensile strength of the web forming the reticulated web must be 12 g / denier or more when measured by twisting. The strength after twisting depends on the number of twists, and the indicated strength is indicated by the optimum number of twists. The optimum twist number varies depending on the denier used for measurement, and generally, the optimum twist number for a 1000 denier filament is around 100 turns / m.

The reticulated web of the present invention is disclosed in JP-A-3-130.
According to the method of 116, it can also be manufactured by an ultra-stretched reticulated web having an adhesive layer on the surface, and in that case, the adhesive layer is preferably a layer having an affinity with the matrix of the three-dimensional structure. Specifically, it is a case where an unsaturated polyester or epoxy resin is used as a matrix in a super-stretched reticulated web having a layer in which a powder of unsaturated polyester or epoxy resin is mixed. In this case, the strength of the super-stretched web,
As the elastic modulus, a numerical value calculated by excluding the thickness of the adhesive layer is used.

As a method of obtaining the oriented tape of the present invention,
The film or sheet (hereinafter collectively referred to as a sheet) may be cut into a tape shape in advance and used for orientation, or may be cut into a tape shape after orientation.

The reinforcing body composed of an aggregate of widened reticulated webs of ultra-high molecular weight polyolefin can be obtained by reticulating and widening the orienting material. As a reticulation method, a method of tapping the orientation material, a method of twisting,
It is to form innumerable fine cuts by any one of mechanical methods such as sliding rubbing (rubbing), brushing, etc., air jet method, ultrasonic method, laser method, etc. The use of rotary mechanical methods is preferred.
As such a rotary mechanical method, it is possible to adopt various types of splitters such as a tap screw splitter, a file-like rough surface splitter, and a needle roll splitter. For example, the tap screw type splitter shown in FIG. 2 is usually a pentagonal or hexagonal prism having 10 to 40, preferably 15 to 35, threads per inch. Moreover, as the file-like rough surface splitter shown in FIG.
Those disclosed in the publication are suitable. This file-like rough surface splitter is a round file for ironwork or a rough surface similar to this with the surface of the circular cross-section axis having two spiral grooves cut at equal pitches on the surface.

It is particularly desirable that the reticulated web employed in the present invention be a wide web. With a wide width, not only a large molded product can be molded in a short time, but also widening during lamination is easy, and since there are few laminated lap portions, a uniform product can be obtained.

The reticulation method in the present invention is not particularly limited, but as a typical example, a splitter 4 is arranged between the nip rolls 2 and 2'and the nip rolls 3 and 3'as shown in FIG. 4 moves along with tension while sliding and making a sliding contact with a splitter rotating at a high speed to form a mesh.

As shown in FIG. 3, the splitter 4 has a surface 6 of a circular cross-section shaft 5 of the splitter 4 formed into a roughened surface having a file-like shape by cutting two spiral grooves 7 and 7'at equal pitches. The grooves 7 and 7'are formed by square grooves having a depth equal to or higher than the height of the surface blade. FIG. 5 and FIG. 6 show A when the film 1 is bent by the splitter of FIG.
-A 'cross section and a part of the axial cross section are shown.
The film 1 that fits into the file 7'and contacts the filed of the surface 6 is concentrated in tension and receives a large pressing force, and is also split by receiving the force of being pulled in the width direction, as shown in FIG. 1a or 1b. Be converted.

The moving speed of the film is usually 1 to 1000.
m / min, preferably 10 to 500 m / min. Also,
The rotational speed (peripheral speed) of the splitter can be appropriately selected depending on the physical properties of the film, the moving speed, and the properties of the target reticulated film, but is usually 10 to 3000.
m / min, preferably 50 to 1000 m / min. The contact angle between the film and the splitter is 30 to 180.
It is desirable that the angle is 40 to 160 degrees.
Since the film is slippery, it may be difficult to hold the film at a predetermined speed in the nip rolls installed before and after the splitter.
It is desirable to prevent slippage by using a nip roll and a clover roll together, or by using a Nelson roll, or by combining these.

In the brushing method and the method using a rotary splitter, the operation is preferably performed by applying tension to the alignment material. The tension is preferably such that the film is deformed by 0.1 to 3%, preferably 0.5 to 2% as elongation. Further, a controller such as a dancer roll may be installed to keep the tension of the film constant during the split.

The temperature during splitting is usually -20 to +1.
00 ° C., preferably −5 to + 50 ° C., more preferably 0 to 20 ° C. is desirable, and the splitting process may be performed not only in one step but also in multiple steps, and for a material having a large thickness. Alternatively, split processing may be performed from the front and back.

It is also possible to press the film with a rotary baking blade heated above the melting point of the resin and form slits in a zigzag pattern to form a net.

The resin and / or inorganic substance forming the matrix of the present invention means polyolefin resin such as polyolefin and polypropylene, polyester resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin, thermoplastic resin such as ABS resin and phenol resin. Resin, urea resin, melamine resin, epoxy resin,
Thermosetting resins such as polyurethane resin, unsaturated polyester, diallyl phthalate resin and silicon resin, and inorganic substances such as gypsum, concrete and plaster.

[0033]

In the present invention, since not a single fiber of ultra-high molecular weight polyolefin but a wide wide expanded mesh web is used, deformation in the width direction is free, and accordingly, deformation in the longitudinal direction is also possible. Therefore, the web can be freely arranged along the three-dimensional surface. Further, even in the draw forming, the constituent fibers are composed of continuous continuous fibers, so that the amount of the fibers used per amount of the fibers is small, the fibers are not unevenly distributed, and the three-dimensional formability is remarkably facilitated. Since the reticulated web of the present invention can be widened and deformed freely, specific portions of three-dimensional reinforcement can be integrated so as to increase the strength in a specific direction, and effective reinforcement can be achieved with a small amount of web.

[0034]

EXAMPLES The present invention will be described in detail below with reference to examples.

Production of Film: (Compression Roll Forming Apparatus) 1. Roll: Diameter 500mmφ Face length 300mm 2. Steel belt: wall thickness 0.6mm width 200mm 3. Small diameter roller: Diameter 12mmφ Face length 250mm 4. Pressure plate: length 1000 mm width 200 mm 5. Hydraulic cylinder: Diameter 125 mmφ Using the above device, 1 ultra high molecular weight polyethylene powder having an intrinsic viscosity of 14 dl / g (viscosity average molecular weight of about 2,000,000) was used.
Heated to 30 ℃, the average pressure on the material is about 6kg / c
A sheet having a thickness of 1.1 mm and a width of 100 mm was continuously compression-molded at a speed of 1 mm / min by pressurizing at m ³ . Next, this sheet is supplied between a pair of rolls having a diameter of 150 mm, a face length of 300 mm, and a roll distance of 30 μm which rotate in the opposite direction at the same peripheral speed of 1 m / min whose surface temperature is adjusted to 140 ° C. A film having a draw ratio of 7 times was obtained.

Production of Oriented Film: (Stretching device) 1. Heater: 3 preheating metal rolls, diameter 250mmφ, face length 200mm 1 drawing metal roll, diameter 125mmφ, face length 200mm Circulating the heat medium oil inside the roll. 2. Cooling metal rolls: 3 rolls, diameter 250mmφ, face length 200mm Water circulates inside the rolls. 3. Nip roll Inlet side: 200mmφ Silicon rubber roll nips with two metal rolls for preheating.

Outlet side: 200 mmφ silicon rubber roll is nipped between two cooling metal rolls.

The rolled sheet was stretch-stretched using the stretching device. The tensile stretching was repeated 3 times under the following conditions. The obtained tape had a width of 32 mm and a thickness of 60 μm, and the total draw ratio of pressure and drawing was 105 times. Number of times of drawing Metal roll temperature (° C) Nip roll peripheral speed (m / min) Drawing ratio For preheating For drawing Inlet side Outlet side (times) 1 135 140 140 4 4 2 140 145 4 10 2.5 3 3 140 150 10 15 1. 5 15 times in total Manufacture of reticulated web: The stretched tape of Example 1 described below was split by a splitting method shown in FIG. 3 under a tension with a speed difference of 1.2% between nip rolls. Was split to prepare a reticulated web. The conditions are as follows.

Film speed: Inlet side roll 20 m / min Outlet side roll 20.24 m / min Splitter: Hexagonal bar edge provided with 32 thread / inch tap screw-like protrusions (maximum diameter 25 mmφ) Contact angle: 90 Degree Rotational speed: 800 rpm (Surface speed 62.8 m / min) Sliding ratio: 3.14 (Splitter rotation speed / Film speed) The reticulated web was prepared and wound into a roll. The physical properties of this reticulated web are shown below.

Tensile Strength (g / d) Tensile Elastic Modulus (g / d) 18 800 Example 1 The reticulated webs are accumulated as shown in FIG. 7 to form a reinforcing body, which is embedded in a matrix of polyester resin, and then, as shown in FIG. A part of one side of the trunk shown in was molded. This molded product had no uneven distribution of the web and had good physical properties.

Example 2 A prepreg sheet was prepared by accumulating a reticulated web into a reinforcing body and using a polycarbonate resin as a matrix. Then, the sheet was drawn to form a helmet shown in FIG. This molded product had no uneven distribution of the web and had good physical properties. Example 3 As shown in FIG. 10, a reticulated web was unwound from an original roll of a reticulated web, brought into sliding contact with a charged roll, and the epoxy resin was used as a matrix while widening the web to form a three-dimensional shape directly in a boat shape. Molded.

[0042]

EFFECTS OF THE INVENTION Since the three-dimensional composite body of the present invention uses not a single fiber of an ultrahigh molecular weight polyolefin but a wide wide reticulated web, it can be freely deformed in the width direction. Since it can be deformed in the longitudinal direction, the web can be freely arranged along the three-dimensional surface, and the productivity and workability are remarkably superior to those of the conventional method using the woven fabric and the uniaxially oriented prepreg. Further, even in draw forming, since the constituent fibers are composed of continuous long fibers in the form of a mesh, the amount of fibers used per amount of fiber is small, the fibers are not unevenly distributed, and the three-dimensional formability is remarkably good. The reinforcement effect of is also remarkable. Further, since the manufacturing process is simple, there is a merit in cost.

[Brief description of drawings]

FIG. 1 (a) is a schematic view of an ultra-high molecular weight polyolefin oriented reticulated web. (B) Schematic of another ultra high molecular weight polyolefin oriented reticulated web. (C) A schematic view of a nonwoven fabric composed of an ultra-high molecular weight polyolefin oriented reticulated web. (D) A schematic view of a non-woven fabric composed of another ultra-high molecular weight polyolefin oriented reticulated web.

FIG. 2 is a schematic diagram of a tap screw splitter.

FIG. 3 is a schematic diagram of a file-like rough surface splitter.

FIG. 4 is a main schematic diagram of a reticulation process.

5 is an AA ′ of the file-like rough surface splitter of FIG.
Sectional sectional view.

6 is a cross-sectional view of the file-like rough surface splitter of FIG.

FIG. 7 is a schematic view of manufacturing a widened reticulated web.

FIG. 8 is a perspective view of a trunk component according to an embodiment of the present invention.

FIG. 9 is a process cross-sectional view of a helmet formed by drawing according to an embodiment of the present invention.

FIG. 10 is a molding schematic diagram of a direct three-dimensional composite molded product of a boat according to an embodiment of the present invention.

[Explanation of symbols]

 1 film 2,2 'inlet side nip roll 3,3' outlet side nip roll 4 splitter 5 shaft 6 surface 7,7 'groove 8 wide net web 9 belt conveyor

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B32B 27/32 Z 8413-4F 31/12 7148-4F // B29K 105: 10 (72) Inventor Kazuhiko Kurihara 3-11-5-1002 Takashimadaira, Itabashi-ku, Tokyo

Claims (5)

[Claims] 1. A resin and / or an inorganic structure having a tensile strength of 12 g / denier or more and an tensile modulus of elasticity of an ultrahigh molecular weight polyolefin having an intrinsic viscosity of 5 dl / g or more (measured in a decalin solution at 135 ° C.). A three-dimensional composite reinforcing body, wherein a reinforcing body made of a widened reticulated web manufactured from an oriented tape having an amount of 200 g / denier or more is embedded. 2. An oriented tape having an intrinsic viscosity (measured in a decalin solution at 135 ° C.) of 5 dl / g or more and an ultrahigh molecular weight polyolefin having a tensile strength of 12 g / denier or more and a tensile elastic modulus of 200 g / denier or more. A method for producing a three-dimensional composite reinforcing body, comprising: accumulating widened reticulated webs produced from, along a three-dimensional shape, and then solidifying with a resin and / or inorganic matrix. 3. An oriented tape having an intrinsic viscosity (measured in a decalin solution at 135 ° C.) of 5 dl / g or more and having an ultrahigh molecular weight polyolefin of 12 g / denier or more and a tensile modulus of 200 g / denier or more. A method for producing a three-dimensional composite reinforcing body, comprising the steps of accumulating a widened reticulated web produced from (1) into a plane, hardening it into a sheet with a matrix of a resin and / or an inorganic material, and then processing it into a three-dimensional structure. 4. The method for producing a three-dimensional composite reinforcing body according to claim 2, wherein the reticulated web is charged as a means for widening the reticulated web. 5. The method for producing a three-dimensional composite reinforcing body according to claim 1, wherein the reticulated web has an adhesive layer having an affinity for the matrix on the surface.