JPH011524A - Manufacturing method of fiber reinforced resin tape - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for manufacturing a fiber-reinforced resin tape, particularly a fiber-reinforced resin tape useful as a thermoplastic resin molding material containing fibers aligned in a certain direction. The present invention relates to a manufacturing method.

[Prior Art] Various types of molded wood made of fiber-reinforced resin are known. Typical examples of such molding materials include FRP pellets made of thermosetting resin containing glass fibers, and prepregs such as BMC and SMC.

Various forms of FRTP, such as pellets, sheets, and tapes made of thermoplastic resin containing glass fibers, are in practical use.

The fibers contained in the above-mentioned molded materials made of fiber-reinforced resin are sometimes woven fabrics, but most are fibers, that is, multiple filaments with a diameter of about 2 μm, for example, thousands of water bundles. Chopped strands are used, which are obtained by cutting roving fibers with a diameter of about 2 mm. Then, the chopped strands are processed into any desired form by being randomly sprinkled, mixed, or mixed with a liquid or powdered synthetic resin. Therefore, there is a problem that the fibers are not continuous and tend to be non-uniform, so that the molded product obtained by molding cannot be expected to have sufficient strength. Furthermore, the random inclusion of fibers in the molded article makes it opaque even if the synthetic resin is transparent.

Therefore, as a means to solve this problem, for example, a roving fiber made of a plurality of fibers bundled together as a continuous fiber as described above is impregnated with an emulsion containing a synthetic resin polymer, and then dried. A fiber-reinforced resin molded material in the form of a thin sheet or tape with a thickness of 0.3 to 1 mm, in which the fibers are aligned in a certain direction by compression processing while heating, has been put into practical use.

[Problems to be Solved by the Invention] It is possible to obtain a molded product with increased strength by specifying the direction of the fibers during molding of the fiber-reinforced resin material in which the fibers are aligned in a certain direction. Can be done.

As a method for manufacturing such a material, a sheet manufacturing method is disclosed in which glass fiber roving is impregnated with an emulsion containing a vinyl chloride resin polymer, dried, and then heated and compressed into a thin plate shape (Japanese Patent Publication No. 47-13218). Reference) is publicly known. However, in this method, the emulsion impregnated into the glass fiber roving becomes powder by drying and is simply attached to the surface of the roving fiber, so that during the next heating and compression process, It easily peels off and falls off, resulting in areas where the resin is not attached.

Originally, the larger the amount of resin attached to the roving fibers, the better the material is, and measures are taken to increase so-called ignition loss (Ig 1oss), but the peeling and falling off of the resin as described above is not at all desirable. It's giving the opposite result. Furthermore, vinyl chloride resin has poor wettability with glass fibers, and vinyl chloride resin has a high melt viscosity, so even if the roving fibers are expanded in the Kanto region during the heat compression process, resin impregnation is not sufficient. However, due to the fact that the amount of resin deposited is originally small and the amount of resin deposited is non-uniform, it has been difficult to obtain fiber-reinforced resin molded wood in the form of thin plates or tapes on which a homogeneous resin layer is formed. In addition, the compression process essentially involves crushing the roving fibers under pressure between compression rolls, which can cause single fibers to break or become fluffy, resulting in a decrease in the strength of the molded product, so this should be avoided. Therefore, the thickness of the fiber-reinforced resin molded material in the form of a thin plate or tape is naturally limited, and for example, it has not been possible to obtain a material with a thickness of 0.2 mm or less.

As another example, roving fibers are impregnated with a solvent solution in which a thermoplastic synthetic resin polymer is dissolved, and after drying, the fibers are heated and compressed to spread the fibers in a certain direction to form a thin plate or tape-shaped fiber-reinforced resin. The method of manufacturing molded wood also has the same problems as in the above example, and it is difficult to obtain a homogeneous material.

The problems in the above representative examples cannot be solved even if the type of thermoplastic resin or the form of the obtained material is changed. It has also been considered to arrange the fibers in a Y-shaped direction and impregnate them with resin, but the process of obtaining such fibers, the winding means, etc. are extremely complicated.
It's not an advantageous method.

In view of the above-mentioned problems, the inventors of the present invention have developed a molded product that is made of fibers aligned in a certain direction, a large amount of thermoplastic resin is uniformly adhered, and that is thin and used as a material. We conducted extensive research and investigation into a method for producing fiber-reinforced resin molded materials, which are characterized by transparency and high strength. As a result, the fiber-reinforced resin tape obtained by immersing roving fibers in an emulsion or solvent solution containing a thermoplastic resin polymer and then rolling out the fibers has uniform resin adhesion, with many spots. In addition, they discovered that the molded product obtained by using the material as a material has excellent transparency despite containing fibers, and completed the present invention. This is what we have come to.

Therefore, an object of the present invention is to provide an improved method for manufacturing a fiber-reinforced resin tape in which fibers are aligned in a certain direction as a fiber-reinforced resin molded material having excellent properties that have not been possible before. .

[Means for Solving the Problems] First, the present invention impregnates a roving fiber, which is a bundle of a plurality of fibers, in an emulsion containing a thermoplastic resin polymer or a solvent solution in which the polymer is dissolved. The present invention provides a method for manufacturing a fiber-reinforced resin tape in which the fibers are aligned in a certain direction, which comprises expanding the roving fibers in Kanto region, drying and heating the roving fibers.

The roving fibers used in the present invention are inorganic fibers such as glass fibers, carbon fibers, ceramic fibers, and metal fibers, or organic fibers such as polyamide fibers, polyimide fibers, and polyamide-imide fibers (filament fibers). ) are focused by a focusing agent. Therefore, since the fiber-reinforced resin tape produced by the production method of the present invention has the characteristic that a transparent molded product can be obtained by using it as a molding material, it is appropriate to use glass fiber roving. be.

Roving fibers are usually made up of a plurality of microscopic fibers (filaments) bundled together using a binding agent. For example, a glass fiber roving with a diameter of approximately 2 mm has a diameter of approximately 2 mm! It is made up of about 3000 fibers of 2 μm, and is easily available commercially. Such roving fibers have a surface that is

For example, there are those that have been treated with a surface treatment agent such as a silane coupling agent, and those that have not been surface-treated. This is preferable in that the adhesion of the material is improved.

The thermoplastic resin polymer used in the present invention is easily handled in the form of an emulsion, and many are solvent-soluble. Moreover, as mentioned above, the fiber-reinforced resin tape produced by the production method of the present invention has characteristics as a molding material that can yield transparent molded products.
In order to take advantage of this feature, it is preferable to use transparent materials. Therefore, homopolymers such as vinyl chloride, vinylidene chloride, vinyl acetate, acrylic esters, methacrylic esters, styrene, acrylonitrile, ethylene, fluoropyrene, fluorine-containing electrolytes, etc., as well as other monomers that can be used, Copolymers obtained by polymerization are preferred.

Of these, vinyl chloride may be used alone, or 11 to an extent that does not reduce the properties of vinyl chloride.
vinyl acetate, vinylidene chloride, acrylic ester,
Vinyl chloride-based copolymers obtained by combining with methacrylic esters, acrylonitrile, maleic anhydride, maleic esters, etc. are known to be difficult to impregnate into fibers, but they can also be used in the present invention. . When using a thermoplastic resin as an emulsion in the present invention, emulsions prepared by dispersing the latex of the above-mentioned polymer or fine polymer powder in water are commercially available and can be easily prepared by hand. The particle size of the polymer is 0.1 to 50 μm, preferably O,S to 5 μm.

Incidentally, as a matter of course, it is a thermoplastic resin polymer,
Of course, it is also possible to use materials that are opaque or easily colored.

The use of thermoplastic polymers as emulsions,
In the use of the polymer as a dissolved solvent solution,
Depending on the type of polymer, the emulsion may contain a small amount of a solvent capable of dissolving or swelling the polymer, and for preparation as a solvent solution, a solvent capable of dissolving the polymer may be added. used. Examples of these solvents include hydrocarbons such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, and heptane, halogenated hydrocarbons such as carbon tetrachloride, ethane dichloride, perchloroethylene, and chlorobenzene, acetone, methyl ethyl ketone, and diethyl These include ketones such as ketones and cyclohexanone, esters such as butyl acetate and dimethyl phthalate, and esters such as dioxane and tetrahydrofuran. Furthermore, polymers such as styrene, divinylbenzene, methyl acrylate, methyl methacrylate, vinyl acetate, acrylonitrile, glycidyl methacrylate, and ethylene glycol dimethacrylate can be partially dissolved or swollen in the emulsion. Moreover, a compound which itself has polymerizability can also be used as a solvent. The amount of solvent used varies depending on the type of polymer and solvent, but in emulsions, a small amount is sufficient, and it is 1 to 1 % relative to the amount of resin in the emulsion.
In the case of a solvent solution, it is selected from 30 to 70% by weight in the solution. Therefore, in an emulsion, an excessive amount generally causes the emulsion to break, while a small amount does not provide the intended effect. In addition, if the solvent solution is in an excessive amount, the solution becomes dilute and cannot adhere enough resin to the roving fibers, and if the solvent solution is in a small amount, the viscosity of the solvent solution reaches its upper limit and impregnation cannot be performed sufficiently.

When used as emulsions or solvent solutions, their viscosity affects the amount of resin deposited on the roving fibers and the workability of each step in the manufacturing process.
Viscosity: 1 to 100 cps, preferably 20 to 50
cps and must be taken into account in setting the amount of medium in the emulsion or solvent in the solvent solution. In addition, the emulsion or solvent solution contains plasticizers, lubricants, stabilizers, colorants, ultraviolet absorbers, flame retardants, antistatic agents, surfactants, etc. Furthermore, when the polymerizable monomer is used as a solvent, a polymerization catalyst, It is also possible to add other compounding agents, auxiliary agents, etc. in appropriate amounts, taking into consideration the viscosity as described above.

The roving fibers are impregnated with the thus prepared emulsion containing the thermoplastic resin polymer or the solvent solution of the polymer. During impregnation, the roving fibers are continuously passed through an emulsion or solvent solution in an impregnation tank.

What is important in the production method of the present invention is to Kanto develop the impregnated roving fibers by passing them through an emulsion or a solvent solution. Kanto development may be carried out either inside the impregnation tank or outside the impregnation tank, but Kanto development is carried out in a wet state while the impregnated emulsion or solvent solution is not dried. It has no effect from scratch.

Kanto development, which is usually referred to as "shigoki", is a process in which roving fibers with a specific diameter are spread out in a flat shape, and continuous fibers are pulled in a certain direction, that is, in the length direction. It's about aligning. Such Kanto expansion is carried out by passing a roving fiber impregnated with an emulsion or solvent solution over a suitably curved surface of a fixed "straining member" having a slidable surface. Although it is sufficient to carry out Kanto expansion by passing over the second "stretching member" once, it is preferable to pass over the second and third "stretching members" subsequently. Therefore, it is not necessary to pressurize the roving fibers during Kanto expansion, but the degree of Kanto expansion is adjusted by applying a suitable, but not excessive, tensile stress in the length direction of the fibers. For example, by appropriately adjusting the tensile stress, the fibers are aligned in the thickness direction to about 5 fibers and the width direction to about 600 fibers, which is about 0.1 m thick.
A tape-like product with a width of about 10 mm can be obtained. Such Kanto expansion is achieved by the appropriate surface shape of the "ironing member" and appropriate tensile stress, which together with the Kanto expansion action of the roving fibers allows the emulsion or solvent solution to sufficiently penetrate into the center of the roving fibers, resulting in uniform impregnation. Ru.

It is necessary to maintain a specific interval until the next drying after Kanto expansion, and if this interval is long, the unfolded tape will shrink in the width direction, making it difficult to obtain the desired tape. . Drying involves evaporating the water in the emulsion, the solvent, or the solvent in the solvent solution, and is carried out at an appropriate temperature depending on the type of resin and solvent. For drying, any means such as passing through heated air or infrared irradiation may be employed, but a method of passing between heated rolls is preferred.

The dried resin-attached tape is thus heated to soften the resin attached to the fibers. The heating temperature at this time differs depending on the type of resin, but if it is too high, the resin may soften too much or decompose and come off, while if it is too low, it may not soften sufficiently. None of these methods are suitable because they cannot be expected to stick. Further, when the solvent is a compatible compound, the polymerization curing is accelerated and completed here. Therefore, generally about 150
A temperature of about 200°C is sufficient. The heating means is not particularly limited, and for example, heating means such as passing between metal plates such as aluminum plates heated by an appropriate means, or heating means such as infrared irradiation can be adopted as appropriate, but a method of passing between heating rolls is preferable. It is.

The tape is completely made into a fiber-reinforced resin tape by heating, and after cooling, it is wound up by an appropriate means.

Practical Example 5 An example of advantageous means for carrying out the manufacturing method of the present invention will be specifically explained with reference to the drawings.

FIG. 1 is a schematic diagram showing an example of the manufacturing method of the present invention, where l is a continuous roving fiber bundled into a suitable thickness, and the roving fiber is passed through a suitable gaitoronil 2 and then made into a thermoplastic resin. It is led to the impregnation tank 3. The tank 3 is filled with an emulsion containing a thermoplastic resin polymer or a solvent solution 4 in which the polymer is dissolved, and an impregnation roll 5 is disposed, and the roll 5 controls the amount of impregnation of the roving fibers. Impregnating and moving the roving fibers with some control.

Note that the rolls 5 are not limited to one location, but may be arranged in an appropriate number or may be arranged so as to be repeatedly impregnated. Thus, when the roving fiber impregnated with the emulsion or solvent solution leaves the impregnating bath, it is moved into the Kanto spreading member for Kanto spreading in a wet state, i.e., the first "
The roving fibers are guided to the upper surface of the "ironing member" 6 and are expanded when passing over this surface.The roving fibers are spread out in the width direction of the tape on the surface of the "ironing member" 6, and as a result, the roving fibers are spread out in the width direction of the tape. , are drawn with a constant width in the width direction. Fig. 2 is a schematic diagram showing the Kanto expansion of the roving fibers l on the upper surface of the "Igoring member" 6, and the situation of the Kanto expansion is made clear. 6 is fixed and does not rotate itself.Therefore, the conventional problem of cutting the fibers and winding them around the rotating body does not occur.

A "straining member" 6 may be provided above the impregnating tank 3 to remove excess impregnated emulsion or solvent solution and to allow recovery into the tank. The "ironating member" 6 is preferably molded from a material with sliding properties, and the portion on the upper surface through which the roving fibers pass and is expanded can be flat, but has a radius of curvature of 3 to 20 mmR, In particular, it is preferable that the convex surface has a curvature of 5 to IO mmR and has a shape that is almost inversely tangent.

The roving fibers are rolled out into a tape shape by a first "straining member" 6. It is sufficient for Kanto expansion with only the first "straining member", but in order to make it more reliable, the second "straining member" 7 and the third "striking member" 8 are sent.

Next, it is guided to a drying roll 9 installed at a specific distance from the "ironating member", and water, solvent, etc. are evaporated while moving slowly. Furthermore, the first heating roll 10
While passing through the second heating roll 11, the resin adhering to the tape-shaped fibers is softened and completely integrated with the fibers to form a fiber-reinforced resin tape, which is then wound onto a suitable winding roll. . In addition, in the drawing, “shidoki member”
, a plurality of heating rolls are provided and the process is repeated, but such repetition is not necessarily necessary. In addition, the roving fibers are not limited to one bundle, but can be used in multiple bundles, or they can be uniformly distributed in advance to almost match the width of the tape to be obtained, and then rolled out in parallel and simultaneously, and then placed on a heated roll. The desired tape width can also be obtained by integrating the tape.

[Function] In the production method of the present invention, the roving fibers are impregnated with latex or a solvent solution and then expanded into a Kanto region. Although the mechanism of action of obtaining a fiber-reinforced resin tape with excellent properties is not necessarily clear, the roving fibers are This is thought to be due to the fact that the tensile stress applied to the fibers is uniformized by sliding on the surface of the "ironating member" used for Kanto expansion. In other words, the roving fibers that have reached the surface of the "ironing member" initially have a mountain-shaped cross section, but by applying tensile stress to this, a greater stress is applied to the center of the mountain shape, and as a result, the center It is thought that the fibers in the area migrate toward the end, continue migrating until the stress becomes uniform, and eventually the cross section becomes flat.

The above-mentioned stress uniformity is most remarkable especially immediately after the roving fibers are impregnated with latex or a solvent solution, and the present invention was completed after discovering this phenomenon.

Next, the present invention will be specifically explained with reference to examples, all of which were carried out by the method shown in the drawings.

[Example] Example 1 Polymerization degree: 1150, particle size: approximately 1 μm, solid content: 45
% (weight %, same below) of polyvinyl chloride latex
An emulsion was prepared by adding and mixing 10 parts of xylene, 10 parts of an ester plasticizer, and 6 parts of a tin stabilizer to 174 parts (parts by weight, same hereinafter).

Next, a glass fiber roving made of about 4,500 bundles of long glass fibers with a diameter of about 13 μm is immersed in the above emulsion, sufficiently impregnated with an impregnated rod, pulled out of the emulsion, and immediately made into a synthetic resin round 20 mmφ diameter. A roving with a diameter of about 2 mmφ is passed over a first "iron member" which is made of a rod and is machined in a reverse contact type so that the upper surface has a curvature of 10 mm H, while applying a slight tensile stress. The Kanto region was developed in the form of a tape, and the Kanto region was further introduced into the second and third "stretching members". Next, the fibers were immediately passed continuously at a speed of 0.5 m/min between a drying roll heated to about 120°C and two heating rolls heated to about 180°C, so that the fibers were separated in the length direction. The aligned thickness is approximately 0. l5mm, width approx. 10
A transparent tape was obtained in which the fibers and the resin were closely adhered to each other. The ignition loss of the resin layer of this tape was determined to be 40%, and the tensile strength in the longitudinal direction was 50 to 60 kg/mm2. In addition, the conventional method (after impregnating the roving fiber with the emulsion and drying it,
The ignition loss of the tape obtained by heating and compressing (Kanto development) is up to 35%, bubbles remain, and the tape is opaque.

Use this tape as a molding material and align the direction for 10 m.
They are arranged in parallel with a spacing of m, and a vinyl chloride resin sheet is laminated on top of the sheets, and a pressure of 15 kg/m is applied by compression molding.
m”, thickness 0.1mm, 3QX 30c
A transparent laminate having a glass fiber content of about 25% was obtained and its physical properties were measured. The tensile strength of the fiber in the longitudinal direction is 25-35
kg/mm", bending strength is 40 to 60 kg/mm", and bending modulus is 1260 to 1320 kg/mm", 5 to 6 times that of hard PVC board, and 2 to 2 times that of fiber-reinforced PVC board made by conventional methods.
It has been strengthened up to 3 times.

Example 2 452 parts of vinyl chloride-acrylic acid ester copolymer resin with a uniform polymerization degree of 1350 and a solid content of 55% (vinyl chloride/acrylic acid ester = 9515), 43 parts of toluene, 5 parts of a tin-based stabilizer, and 1 part of an emulsifier. .8 parts and 36.2 parts of water were emulsified and mixed to prepare an emulsicon.

Next, a glass fiber roving similar to that used in Example 1 was immersed in the above emulsion, impregnated and Kanto-developed in the same manner as in Example 1, and dried on a drying roll heated to about 120°C and heated to about 190°C. 2 heated to 200℃
By continuously passing between base heating rolls, a transparent tape with a thickness of about 0.2 mm and a width of about 10 mm in which the fibers were aligned in the length direction and the resin was closely adhered to the fibers was obtained. . The ignition loss of this tape is 5
3%, and its longitudinal tensile strength is 27-3
It was 1 kg/mm2.

Using this tape as a molding material, knit it alternately vertically and horizontally, then laminate the knitted fabric by 1n compression molding to a thickness of 2 mm with almost no directionality, 30 x 30 cm, glass fiber content of about 50% M. A laminate having a transparency of 1 was obtained and its physical properties were measured. The tensile strength of this plate is 50kg/mm", the bending strength is 110kg/mm", and the bending modulus is 2800.
kg/mm2.

Example 3 Solid content obtained by emulsion polymerization of methyl methacrylate: 48
Latex containing % polymethyl methacrylate 200%
20 parts of toluene, 20 parts of water, and 2 parts of emulsifier are mixed in
An emulsion was prepared.

Next, a glass fiber roving similar to that used in Example 1 is immersed in the above emulsion, impregnated and Kanto-developed in the same manner as in Example 1, and continuously passed between a drying roll and a heating roll. The fibers are aligned in the length direction with a thickness of about 0.18 mm and a width of about 10 mm.
A transparent tape with good adhesion between the fibers and the resin was obtained. The ignition loss of this tape is 48%, and its longitudinal tensile strength is 24-29 kg/
It was mm2.

Use this tape as a molding material and align the direction for 10 m.
They are arranged in a line with an interval of m, and then arranged in parallel on top of them in the same way so that the directions cross, and this is repeated in sequence to form 6 layers and compression molded, resulting in a thickness with almost no directionality. A transparent laminate having a size of about 1 mm, 30×30 cm, and a glass fiber content of 45% was obtained, and its physical properties were measured. This plate had a tensile strength of 48 kg/mm", a bending strength of 90 kg/mm", and a bending modulus of 2400 kg/mm2.

Example 4 A solvent solution was prepared by dissolving 60 parts of general purpose polystyrene beads in 240 parts of toluene.

Next, the glass fiber roving used in Example 1 was impregnated in the above solvent solution, impregnated and Kanto-developed in the same manner as in Example 1, and continuously passed between drying rolls and heating rolls. A transparent tape was obtained in which the fibers were aligned in the length direction, the fibers were approximately 0.2 mm thick and the resin was closely adhered to the resin. The ignition loss of this tape is 42%.

Its longitudinal tensile strength was 22 kg/mm''.

Using this tape as a molding material, compression molding was performed in the same manner as in Example 3 to give a thickness of about 1 mm with almost no directionality, 3
A transparent laminate measuring 0.times.30 cm and containing about 42% glass fiber was obtained and its physical properties were measured. The tensile strength of this plate is 45k
g/mm2, bending strength was 93 kg/mm2, and bending elastic modulus was 3500 kg/mm''.

[Advantageous Effects of the Invention 1] The manufacturing method of the present invention makes it easy to manufacture a fiber-reinforced resin tape as a molding material suitable for obtaining fiber-reinforced molded products, and is superior to fiber-reinforced resin tapes manufactured by conventional methods. However, it has the characteristics that the resin adheres uniformly and in a large amount, and there is no fluffing at all, and these characteristics are manifested as an excellent effect of imparting transparency to the tape.

Therefore, a molded article formed using the fiber-reinforced resin tape obtained by the manufacturing method of the present invention as a molding material has excellent mechanical strength and transparency.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing the manufacturing method of the present invention, and FIG.
The figure is a schematic view showing the Kanto development of the roving fibers on the upper surface of the "ironing member" in FIG. 1. 1: Roving fiber 2: Gytro roll 3: Impregnating tank 4: Emulsion or solvent solution 5: Impregnating roll 6: 1st "ironing member" 7: 2nd "ironing member" 8: 3rd "ironing member" 9: Drying roll 10, II: Heating roll

Claims (2)

[Claims] (1) After impregnating a roving fiber consisting of a plurality of bundled fibers in an emulsion containing a thermoplastic resin polymer or a solvent solution in which the polymer is dissolved, the roving fiber is opened and expanded, and then drying,
A method for manufacturing a fiber-reinforced resin tape in which fibers are aligned in a certain direction, which comprises heating. (2) The manufacturing method according to claim 1, wherein the roving fiber is a glass fiber roving made of a bundle of glass fibers.