JPH07224177A - Thermoplastic prepreg having tackiness and drapeability - Google Patents

Abstract

PURPOSE:To produce a prepreg having tackiness and drapeability in combination whereas the conventional prepreg composed of a thermoplastic resin matrix is lacking in both the properties, not requiring an impregnation treatment and having thermoplastic properties. CONSTITUTION:This thermoplastic prepreg having tackiness and drapeability is obtained by impregnating reinforcing filaments with a poly-alpha-olefin composition composed of 30 to 100wt.% amorphous alpha-olefin having (1) 100 to 170 deg.C softening point and (2) 10<-1> to 10 pascal.sec melting viscosity at 190 deg.C and 70 to 0wt.% crystalline poly a-olefin (provided that the total amount of the non-crystalline poly alpha-olefin and the crystalline poly alpha-olefin is 100wt.%).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic prepreg having tackiness and drapeability.
This prepreg can be easily laminated and attached to a base material, and since it is highly flexible, it has good handleability and can fit even on complicated curved surfaces. Therefore, it can be widely put to practical use as a construction material for site construction, an adhesive reinforcement material, and a composite material for structural materials.

[0002]

2. Description of the Related Art Conventionally, as a prepreg having tackiness and drapeability, a prepreg having a thermosetting resin represented by an epoxy resin as a matrix has been mainly used. However, toughness, prepreg shelf life,
The drawbacks of thermosetting resins such as molding time and recent recycling problems have been pointed out, and thermoplastic resin matrices have been attracting attention instead.

However, the prepreg of the thermoplastic resin matrix does not exhibit tackiness because it is not tacky, and lacks drapability because it is rigid. For this reason, the handling and laminating operation of the prepreg is significantly inferior to the case of the thermosetting resin matrix.

In order to solve such a drawback, for example, a method of imparting drape property to a prepreg by using a powdery or fibrous resin has been carried out (Japanese Patent Laid-Open No. 60-361).
39, JP 60-36156, JP 6
JP-A 1-146519, JP-A 2-112916, JP-A 2-130138, and JP-A 4-579.
No. 33, Japanese Patent Laid-Open No. 4-316633, Special Table Sho 5
No. 8-501943 and Japanese Patent Publication No. 63-502518), it is necessary to heat and melt the resin to impregnate it into the fiber. In addition, as a lamination method of thermoplastic prepreg with no tackiness, tape winding (C.Werd
ermann et al., J. Thermoplast.Comp.Mat., 2 (10), 293 (1
989)) and automatic laminating machine (GRGriffitho et al., S
AMPE J., 20 (5), 32 (1984), etc.) is also tried in the aerospace field, but the cost is high and it is used in general industrial fields such as construction, automobiles, and home appliances. The reality is that it is not suitable for certain general-purpose applications.

[0005]

Therefore, the present invention has a tackiness and a drape property, which are lacking in the conventional prepreg having a thermoplastic resin as a matrix, and has a thermoplasticity which does not require an impregnation operation. The purpose is to provide a prepreg.

[0006]

Means for Solving the Problems As a result of various studies for solving the above problems, the present inventors have found a prepreg obtained by impregnating continuous reinforcing fibers with a poly α-olefin composition having specific properties. By providing it, they found that the object could be achieved, and completed the present invention.

That is, according to the present invention, (1) the softening point is 10
Amorphous poly α having a temperature of 0 to 170 ° C. and (2) a melt viscosity at 190 ° C. of 10 ⁻¹ to 10 Pascal · sec.
-Poly α-comprising 30 to 100% by weight of olefin and 70 to 0% by weight of crystalline poly α-olefin (however, the total amount of amorphous poly α-olefin and crystalline poly α-olefin is 100% by weight). This can be achieved by providing a thermoplastic prepreg having tackiness and drapability, which is obtained by impregnating continuous reinforcing fibers with an olefin composition.

The present invention will be described in detail below. The amorphous poly α-olefin described in the present invention is a homopolymer of α-olefins or a copolymer thereof (for example,
Propylene homopolymer, propylene / ethylene copolymer, propylene / butene-1 copolymer, etc.) and mixtures thereof, which have relatively low molecular weight and are amorphous. Furthermore, those modified with well-known compounds such as unsaturated carboxylic acids and their esters are also included.

And in the present invention, those softening
Point (value measured by ring and ball method) and melt viscosity (circle)
Measured at 190 ° C with a cone / disk rheometer
Value) must fall within a certain range
It That is, the softening point must be in the range of 100 to 170 ° C.
I have to. If the softening point is lower than 100 ° C, the prep
The surface of the leg is sticky, difficult to handle, and higher than 170 ℃
And the tackiness is less likely to be expressed, both are not preferable.
Yes. In addition, the prevention of stickiness on the surface of the prepreg and the touch
In order to ensure the development of
The softening point of α-olefin is in the range of 105 to 155 ° C.
Is more preferable. The melt viscosity is 10^-1
Range of -10 Pascal-seconds (hereinafter abbreviated as "Pa-S")
It is required to be in the range of 1 to 8 Pa · S.
To be If the melt viscosity is lower than 1 Pa · S,
The deterioration of the physical properties of the prepreg that has come to be seen,
Especially 10 ^-1If the viscosity is lower than Pa · S, the
The physical properties of the preb are significantly reduced. And the melt viscosity
When the viscosity is higher than 8 Pa · S, the impregnating property for continuous reinforcing fibers is high.
It tends to worsen, especially for higher viscosity than 10 Pa · S.
In that case, the impregnation property into the continuous reinforcing fiber is adversely affected.

The crystalline poly α-olefin used in the present invention is a well-known compound such as a homopolymer of α-olefins or a copolymer thereof, and further these unsaturated carboxylic acids and their esters. It is a modified product of the above and has crystallinity such as having a definite melting point. Of course, a mixture of two or more of these may be used. Specific examples include high-density polyethylene,
Examples include isotactic polypropylene and crystalline ethylene / propylene copolymers (crystalline ethylene / propylene random copolymers, crystalline ethylene / propylene block copolymers, etc.). There are no particular restrictions on the molecular weight, chemical composition, melt viscosity, etc. of these crystalline poly-α-olefins, and the amorphous poly-α-olefins to be used are not limited.
It should be appropriately selected depending on the properties of the olefin and the mixing ratio of the two.

In the present invention, an α composed of two kinds of the amorphous poly α-olefin and the crystalline poly α-olefin.
-Using an olefin composition, which may be free of crystalline poly alpha-olefins. There is no particular limitation on the selection of both, but in general, a compatible combination is preferable because it is easy to form a uniform matrix. For example, amorphous polypropylene / crystalline polypropylene, amorphous propylene / ethylene copolymer / crystalline ethylene / propylene copolymer, amorphous polypropylene / crystalline ethylene / propylene copolymer, amorphous propylene -Butene-1 copolymer / crystalline ethylene-propylene copolymer, amorphous propylene-butene-1
Copolymer / crystalline polypropylene and the like.

Next, one of the important constituent features of the present invention is
These are the compounding ratios of both. That is, in the poly α-olefin composition of the present invention, the amorphous poly α-olefin is 30 to 100% by weight, preferably 50 to 100% by weight, and particularly preferably 60 to 100% by weight. Olefin 70 to 0% by weight, preferably 50 to
It is necessary to be composed of 0% by weight, particularly preferably 40 to 0% by weight (however, the total amount of the amorphous poly α-olefin and the crystalline poly α-olefin is 100% by weight). If the blending ratio of amorphous poly α-olefin is 30
If it is less than wt%, the tackiness and drapeability of the thermoplastic prepreg, which is the object of the present invention, cannot be expected sufficiently,
It cannot be put to practical use. In the present invention, various known additives, colorants, modifiers, fillers and the like may be added in addition to the above-mentioned two components as long as the effect is not impaired.

The poly α-olefin composition comprising the amorphous poly α-olefin and the crystalline poly α-olefin is produced by using a known method and apparatus. That is, it can be achieved by using a Banbury mixer, a super mixer, a mixing roll, a twin-screw continuous mixer, a Brabender plastograph, a kneader, a single-screw extruder, a twin-screw extruder, and the like, and melting and kneading both. The melt-kneading is performed at 180 to 250 ° C., preferably 1
It is performed at a temperature of 90 to 230 ° C. Melt kneading temperature is 18
If the temperature is lower than 0 ° C., the melt viscosity of the amorphous poly α-olefin and the crystalline poly α-olefin becomes too high in the kneading device, and a part of these poly α-olefin solidifies, The kneading of these poly α-olefins is not sufficiently performed. If it is higher than 250 ° C,
Thermal decomposition and thermal degradation of these poly α-olefins occur,
It is not preferable because it causes coloring and deterioration of physical properties.

In the present invention, the poly-α-olefin composition obtained as described above is impregnated into continuous reinforcing fibers. The continuous reinforcing fibers used in the present invention include well-known glass. In addition to fibers, carbon fibers and aramid fibers, various organic polymer fibers, inorganic fibers and metal fibers are included. These are usually used alone, but a combination of two or more of them may be used. There is no particular limitation on the diameter, the number of bundles and the count of these fibers,
Generally, the diameter is 4 to 20 μm, and the number of bundles is 1000 to
15,000 and count is 40-9000 tex (1
It is about the number of grams per 000 m). In the present invention, in addition to such tows, these woven fabrics and mats can also be preferably used. The fiber has improved wettability and adhesiveness with the poly-α-olefin composition serving as a matrix, and its reinforcing effect, that is, mechanical strength is further increased, and the fiber is not broken or damaged. In order to prevent it, it is usual to apply known treatment agents such as surface treatment agents (silane coupling agents, etc.) and sizing agents (modified polyolefin, urethane, epoxides, polymethylmethacrylate, polyvinyl acetate, etc.). is there. These are optimally selected depending on the above-mentioned poly α-olefin composition used.

The impregnation of the poly-α-olefin composition into the continuous reinforcing fiber can be performed by a known method. For example, an emulsion of poly-α-olefin composition, P-xylene, toluene,
Known methods such as a method of drying and removing water or a solvent after impregnating fibers into a solution of an organic solvent such as decalin, film or sheet extrusion molding of a poly α-olefin composition, calender roll processing, press sheet processing, etc. According to the method of forming into a film or sheet, and then heating and melting and pressurizing the fibers so as to impregnate them, the poly α-olefin composition is made into a powder or fibrous form and introduced into the continuous reinforcing fibers, and then heated and melted. Method of pressurizing and impregnating, method of superposing molten sheet of poly α-olefin composition and fiber, and method of pressurizing and impregnating, introducing fiber into melt of poly α-olefin composition, and pulling out through die Suitable methods include impregnation. In this case, it is also effective to appropriately perform operations such as preheating, deaeration, and fiber opening on the continuous reinforcing fiber in order to perform good impregnation.

The prepreg thus manufactured is
It is in the form of strands, tapes and sheets. Then, in consideration of ease of handling and drape when laminating the above prepreg, pasting on a base material, or molding, prepreg production productivity (impregnation). If put, the strand has a maximum diameter of about 1 to 3 mm and the tape has a width of 3 to 3
0 mm and a thickness of about 100 to 500 μm,
The sheet has a width of 200 to 1000 mm and a thickness of 100.
A typical shape is about 500 μm.

On the other hand, as the composition of the prepreg, the poly-α-olefin composition is 35 to 85% by volume, preferably 40 to 80% by volume, and the continuous reinforcing fiber is 65 to 65% by volume.
15% by volume, preferably 60 to 20% by volume (provided that the total amount of the poly α-olefin composition and continuous reinforcing fiber is 1
It is generally composed of 100% by volume). When the content of the continuous reinforcing fiber is less than 35% by volume, the mechanical strength and rigidity of the prepreg are not improved. When the content of the continuous reinforcing fibers exceeds 85% by volume, that is, when the content of the poly α-olefin composition is less than 15% by volume, the tack of the prepreg based on the amorphous poly α-olefin is used. And expression of drapeability are not sufficient, impregnation of the poly α-olefin composition into the continuous reinforcing fiber is insufficient, and operations such as laminating prepreg described below, attaching to a base material, and molding are difficult. Is not preferable. If the content of the continuous reinforcing fiber and the content of the poly α-olefin composition deviates from the preferable range described above, the above-mentioned undesirable phenomenon may appear in the obtained prepreg.

As described above, the prepreg obtained in the present invention has tackiness and drapeability at room temperature and is already impregnated with a thermoplastic resin. Therefore, there is no need for a new resin impregnation operation, and the prepreg itself can be laminated and overlapped without using special heat or large force, and metal, wood, paper, ceramic,
It can be easily attached to plastic and integrated. Of course, heating may be performed (40 to 80 ° C.) in order to efficiently perform the sticking to the base material and the stacking operation.
Further, since it has thermoplasticity, it can be used as a so-called moldable material that can be shaped into an arbitrary shape by applying force in a state of being heated and melted. As the molding method, a conventionally known method relating to a thermoplastic prepreg,
For example, molding methods such as hot pressing, stamping, thermoforming, and autoclave can be mentioned.

[0019]

The present invention will be described in more detail with reference to examples and comparative examples, but these do not limit the present invention.

In the following examples and comparative examples, the physical properties of the poly α-olefin composition and continuous reinforcing fiber used were measured by the following methods. (1) Softening Point of Amorphous Poly α-Olefin It was measured according to ASTM E28 using a ring and ball softening point tester.

(2) Melt Viscosity of Amorphous Poly .alpha.-Olefin A cone / disk type rheometer (Mechanical Spectrometer manufactured by Rheometrics Co., Ltd.) was used, and ASTM D3 was used.
Measured according to 236 at 190 ° C.

(3) Melt Flow Index of Crystalline Poly α-Olefin The melt flow index was measured at 230 ° C. according to ASTM D1238 using a melt indexer.

(4) Weight per unit area of continuous reinforcing fibers According to JIS R3420, the weight per 1 m ² was determined by weighing a 20 cm × 20 cm woven fabric.

(5) Diameter of continuous reinforcing fiber: Determined by using an optical microscope in accordance with JIS R3420.

(6) Thickness of continuous reinforcing fiber According to JIS R3420, the thickness of the woven fabric was measured using a dial gauge micrometer.

(7) Count of continuous reinforcing fiber: Measured according to JIS R3420, by measuring the weight of 10 m tow.

The evaluation method of the prepreg used in these examples and comparative examples is as follows. (A) Fiber volume fraction (V _f ) According to JIS K7052, it was determined by thermally decomposing the resin component.

(B) Impregnated state It was judged by visual observation.

(C) Drapeability 23 ° C., relative humidity 50% (hereinafter abbreviated as “50% RH”)
It was judged by the flexibility in the state.

(D) Tackiness The prepregs were lightly pressed together with a roller at 23 ° C. and 50% RH to bond them, and the adhesion of the obtained laminate was evaluated.

Example 1 Amorphous polypropylene (trade name: UBETAC APAO UT2180, manufactured by Ube Lexen Co., Ltd., softening point: 15)
2 ° C, melt viscosity: 1.5 Pa · S) 190 ° C, 1.5
A sheet having a thickness of 50 μm (measured with a dial gauge micrometer) was obtained by press molding for 1 minute at MPa (gauge pressure). Therefore, this sheet and a glass fiber woven fabric (trade name: glass cloth WF 110 P10, manufactured by Nitto Boseki Co., Ltd.)
4, areal weight: 100 g / m ² , thickness: 130 μm, texture: plain weave), 190 ° C., 1.5 MPa
Press molding with (gauge pressure) for 2 minutes, 20cm × 20c
A prepreg having a thickness of m and a thickness of 150 μm (note that the width and length of the prepreg are steel products and the thickness of the prepreg was measured with a digital micrometer. The same applies below). Table 1 shows the evaluation results of the prepreg.

Example 2 70 parts by weight of the amorphous polypropylene used in Example 1,
Crystalline ethylene / propylene random copolymer (manufactured by Ube Industries, Ltd., trade name UBE Polypro B301H, ethylene content (calculated from absorbance ratio of infrared absorption spectrum at 1155 cm ^-1 and 720 cm ^-1 ): 3% by weight Melt flow index: 1 g / 10 min) and 30 parts by weight were melt-kneaded at 200 ° C. using a twin-screw extruder to prepare pellets. Example 1 except that the above pellets were used instead of the amorphous polypropylene in Example 1.
Table 1 shows the evaluation results of the prepreg obtained by performing the same treatment as described above.

Example 3 Instead of the amorphous polypropylene of Example 1, an amorphous propylene / butene-1 copolymer (manufactured by Ube Lexen Co., Ltd.,
Table 1 shows the evaluation results of the prepreg obtained by treating in exactly the same manner as in Example 1 except that the product name UBETAC APAO UT2780, softening point: 110 ° C., melt viscosity: 8 Pa · S) was used.

Example 4 The same as Example 2 except that the amorphous polypropylene used in Example 2 was replaced with the amorphous propylene / butene-1 copolymer used in Example 3. Table 1 shows the evaluation results of the prepregs obtained by performing the above treatment.

Example 5 Instead of the glass fiber material in Example 3, a carbon fiber woven fabric (trade name: trading card fabric CO614 manufactured by Toray Industries, Inc.) is used.
2, weight per unit area: 119 g / m ² , thickness: 150 μm, texture: plain weave) were treated in exactly the same manner as in Example 3 to obtain a prepreg having a size of 20 cm × 20 cm and a thickness of 170 μm. Table 1 shows the evaluation results of the prepreg.

Example 6 Instead of the crystalline ethylene / propylene random copolymer in Example 4, maleic anhydride-modified crystalline polypropylene (trade name: UBE Polypro Z, manufactured by Ube Industries, Ltd.)
P1313, maleic anhydride amount (calculated from absorbance ratio of infrared absorption spectrum at 1785 cm ^-1 and 840 cm ^-1 ): 0.2% by weight, melt flow index: 35
Table 1 shows the evaluation results of the prepreg obtained by treating in exactly the same manner as in Example 4 except that (g / 10 min) was used.

Example 7 Instead of the amorphous propylene / butene-1 copolymer used in Example 6, another amorphous propylene / butene-1 copolymer (trade name: UBETAC A manufactured by Ube Lexen Co., Ltd.) was used.
PAO UT2715, softening point: 170 ° C, melt viscosity:
1.5 Pa · S) and the mixing ratio of maleic anhydride-modified crystalline polypropylene to 30/70
Table 1 shows the evaluation results of the prepreg obtained by performing the same treatment as in Example 6 except that the (weight ratio) was used.

Example 8 Instead of the amorphous propylene / butene-1 copolymer in Example 6, an amorphous propylene / ethylene copolymer (trade name: UBETAC APAO manufactured by Ube Lexen Co., Ltd.) was used.
UT2535, softening point: 129 ° C, melt viscosity: 3.5P
Table 1 shows the evaluation results of the prepregs obtained by treating in exactly the same manner as in Example 6 except that a.S) was used.
Shown in.

Comparative Example 1 Evaluation of a prepreg obtained by treating in exactly the same manner as in Example 6 except that the amorphous propylene / butene-1 copolymer used in Example 6 was not used. The results are shown in Table 1.
Shown in.

Comparative Example 2 The mixing ratio 30/70 (weight ratio) of the amorphous propylene / butene-1 copolymer and the maleic anhydride-modified crystalline polypropylene in Example 7 was changed to 20/80 (weight ratio). Table 1 shows the evaluation results of the prepreg obtained by performing the same treatment as in Example 7 except that the prepreg was changed.

Example 9 Using a 30 mmφ extruder, the pellet of Example 6 was fed to a crosshead die (heated to 190 ° C.) attached to the tip of the extruder, through which a glass fiber tow (Nippon Electric Glass Co., Ltd. ), Fiber diameter: 17 μm, count: 2300 tex) 30 pieces are drawn out at a speed of 1 m / min, width 20 cm,
A unidirectional prepreg sheet having a thickness of 400 μm was obtained. Table 1 shows the evaluation results of the prepreg.

[0042]

[Table 1]

[0043]

As is clear from the examples and comparative examples described above, the thermoplastic prepreg obtained in the present invention has the resin well impregnated in the fiber, and has excellent tack at room temperature. It has sex and drape. Such a feature is not obtained by a conventionally known technique, and the thermoplastic prepreg of the present invention is
It can be widely used as a composite material for structural materials in addition to construction materials and adhesive reinforcement materials for on-site construction, where it was difficult to use conventional thermoplastic prepregs.

Claims (1)

[Claims] 1. A softening point of 100 to 170 ° C.,
And (2) the melt viscosity at 190 ° C. is 10 ⁻¹ to 10
Amorphous poly α-olefin 30 to 1 which is Pascal · second
00% by weight and 70 to 0% by weight of crystalline poly α-olefin (provided that amorphous poly α-olefin and crystalline poly α-olefin
-A total of 100% by weight of olefin)
A thermoplastic prepreg having tackiness and drapeability, which is obtained by impregnating continuous reinforcing fibers with an olefin composition.