JPH0596635A - Forming material - Google Patents

Abstract

PURPOSE:To dispense with the separation of a carrier film by integrally forming a carrier film consisting of a polyethylene film as a forming material component on one or both surfaces of a sheet-like unsaturated polyester resin material. CONSTITUTION:Polyester resin 100 pts., polyethylene powder 3 pts., organic peroxide 1 pts., polymerization inhibitor 0.01 pts., pigment paste 4 pts. inner mold releasing agent 4 pts., and calcium carbonate 120 pts., are blended, and a thickener 1 pt is added thereto for adjusting a compound paste A. The compound paste A is supplied on a lower carrier film 23 consisting of a non-oriented polystylene film from resin baths 21, 21'. Simultaneously, glass roving B is cut by a cutter 24 and then supplied on the lower carrier film 23. Then, an upper carrier film 22 is so spread that the glass roving is held by the carrier films 22, 23 in order to form a sheet-like forming material 25, where it is then wound on a core pipe 29 via an accumulator 26 and a delivery control device 27.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material composed of a fiber reinforced resin using an unsaturated polyester resin, and in particular, a carrier film required at the time of production is integrated with a molding material to separate the carrier film during molding. Is unnecessary.

[0002]

2. Description of the Related Art Conventionally, a fiber-reinforced molding material using an unsaturated polyester resin of this kind has excellent mechanical strength, heat resistance, water resistance, chemical resistance and high productivity, and therefore has a high productivity. Widely used for engine parts such as engine hoods, spoilers, and trunk lids as well as water tank panels. The molding materials such as the unsaturated polyester sheet molding compound (hereinafter, abbreviated as SMC) and the thick molding compound (hereinafter, abbreviated as TMC) are paste-like substances mainly containing unsaturated polyester resin, glass fiber and A compound made of a reinforcing material such as carbon fiber is carried on both upper and lower sides by a carrier film, and the reinforcing material is impregnated with resin while being conveyed to a winding step or a folding step for continuous production.

As the above-mentioned carrier films used for both upper and lower surfaces, polyethylene films, polypropylene films, etc., which have good releasability from the molding material during molding, are used. In addition, the thickness (wall thickness) of the sheet-shaped molding material cannot be a thickness width due to the impregnation condition of the resin and the reinforcing material, etc., and is usually about 2 to 5 mm, and the maximum is about 10 mm. There is.

That is, in the conventional molding material, a molding material containing glass fiber reinforced unsaturated polyester resin as a main component is carried on both upper and lower sides by a carrier film made of polyethylene film, and the thickness thereof is about 2 to 5 mm. , Width is 1m
The sheet-shaped continuous molding material is manufactured in the form of a roll or a folded form for transportation and storage.

The molding material composed of the fiber-reinforced unsaturated polyester resin produced as described above is mainly molded by compression molding, transfer molding, injection molding or the like, and used in bathtubs, waterproof pans, water tank panels, automobile parts and the like. Used for purposes.

At the time of molding, the sheet-shaped molding material has a thin wall thickness of about 2 to 5 mm as described above. Therefore, when molding a molded article having a large wall thickness, the sheet-shaped molding material is laminated to form a sheet. It is necessary to perform the forming process in a thick state. Further, when used for injection molding, a laminated product having a thick wall is supplied to a hopper, and this is metered and injected by an injection molding machine to obtain a molded product.

[0007]

As described above, the molding material requires a carrier film that carries the molding material in order to evenly distribute the reinforcement material and to properly impregnate the reinforcement material with the resin during manufacturing. However, the carrier film must be peeled off and used at the time of molding. Therefore, it is necessary for a molding company to peel off the carrier film at the time of molding, which is very troublesome and has become a problem due to the recent lack of manpower.

Usually, a thin molding material is often used as a block having a large thickness by laminating as described above at the time of molding. In that case, the carrier film is peeled off to form the molding material. It is necessary to stack them into a block state, which requires a great deal of work.

To solve the above problems, the present inventors have developed a thick TMC in which the weight (unit amount) of the molding material per unit area of the carrier film is increased in order to reduce the labor of peeling the carrier film as much as possible. I've been However,
There is a limit to the required thickness or more due to molding problems, and the carrier film is indispensable on the upper and lower surfaces of the molding material during manufacturing for the above reasons, so there is still no need to remove the carrier film. There is a drawback that can not be said.

The present invention has been made in view of the above problems, and provides a molding material composed of a fiber-reinforced unsaturated polyester resin which can be used without peeling off a carrier film required at the time of manufacturing. The purpose is that.

[0011]

In order to achieve the above object, the present invention provides that a carrier film on one or both sides of a sheet-like unsaturated polyester resin molding material can be integrated with a polyester resin as a component of the molding material. The present invention provides a sheet-shaped molding material, which is a resin film.

The carrier film described above swells in the unsaturated polyester resin of the molding material by being left to stand at room temperature or in a specific state for a required time for swelling, and is integrated with the unsaturated polyester resin as a component of the molding material. However, a polystyrene film is preferable as such a film as long as it can be integrally molded.

More specifically, the polystyrene film used as the carrier film is a film made of styrene alone or a copolymer of styrene and butadiene, and a non-stretched, uniaxially stretched or biaxially stretched film is preferably used. The thickness of the film is 20 to 200 μm from the viewpoint of strength and handleability, and preferably 25 to 50 μm.
μm.

The molding material carried by the carrier film is usually an unsaturated polyester resin, a styrene copolymerizable monomer, a solution of a styrene copolymerizable monomer such as polystyrene or polyvinyl acetate, TBPB. (Tertiary butyl peroxybenzoate) and other organic peroxides,
Polymerization inhibitors such as HQ (hydroquinone) and PBQ (parabenzoquinone), metal soaps such as zinc stearate, toner pastes for coloring, fillers such as calcium carbonate, barium sulfate, clay and aluminum hydroxide, workability It is aged by impregnating a carbon fiber or glass fiber cut into 1/2 ", 1", or 2 "with a thickening agent such as magnesium oxide or magnesium hydroxide for improvement.

The unsaturated polyester is synthesized by condensation of an α, β-olefin-based unsaturated dicarboxylic acid and a divalent glycol, and has been widely used conventionally. In addition to these two components, a saturated dicarboxylic acid, an aromatic dicarboxylic acid, or dicyclopentadiene that reacts with a dicarboxylic acid can be used in combination in the synthesis of the polyester. Examples of α, β-olefin unsaturated dicarboxylic acids include, for example, maleic acid, fumaric acid, itaconic acid,
Examples include citraconic acid and anhydrides of these dicarboxylic acids. Examples of dicarboxylic acids used in combination with these α, β-olefin unsaturated dicarboxylic acids include, for example, adipic acid, sebacic acid, succinic acid, phthalic anhydride, o
-Phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid and the like.
As the divalent glycol, for example, alkane diol, oxa alkane diol, diol obtained by adding alkylenoxide such as ethylenoxide or propylenoxide to bisphenol A, and the like are used.
Monool or trivalent triol may be used. Examples of the alkanediol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 1,5-pentadiol. 1,6-hexanediol, cyclohexanediol and the like can be mentioned. Examples of the oxaalkane diol include diethylene glycol, dioxyethylene glycol, trioxyethylene glycol and the like. Examples of monohydric or trihydric alcohols used in combination with these glycols include octyl alcohol,
Examples include oleyl alcohol and trimethylolpropane. The synthesis of unsaturated polyester is generally carried out under heating, and the reaction proceeds while removing by-product water. In the present invention, an unsaturated polyester having a number average molecular weight of 800 to 4000 and an acid value of 5 to 60 is usually used.

The above styrene-based copolymerizable monomer includes
Examples thereof include styrene, tert-butylstyrene, vinyltoluene, chlorostyrene, α-methylstyrene and divinylbenzene. In addition, acrylic acid ester monomers such as methyl methacrylate, ethyl acrylate and glycidyl methacrylate, allyl monomers such as diallyl phthalate and triallyl cyanurate, vinyl acetate and dibutyl fumarate are copolymerized with styrene. It may be used in combination with a polymerizable monomer. The mixing ratio of these styrene-based copolymerized monomers and unsaturated polyester is not particularly limited.

A molding material continuously manufactured in a sheet shape in which the upper and lower surfaces of the above-mentioned molding material containing unsaturated polyester as a main component are carried by a carrier film made of a polystyrene film is continuously rolled into a cylindrical core tube. A carrier film made of a polystyrene film is wound around and wrapped in an exterior film such as a polyester film in this form, and then left to stand at room temperature or at a specific temperature for a long time to form a molding material integrated with an unsaturated polyester resin. Therefore, it is possible to perform molding processing without the need to peel off the carrier film. Also, the molding materials that are continuously manufactured in a sheet shape by integrating the polystyrene films that are laminated and contact with each other,
It is a very thick molding material with a cylindrical shape. Therefore,
As described above, when wound in a roll shape and aged in the state as it is, the carrier film carrying both surfaces of the sheet-shaped molding material, use polystyrene film which is a component of the molding material by aging both surfaces. Is preferred.

Further, immediately after the impregnation is completed, the sheet-shaped molding material which is continuously conveyed is cut into a predetermined width without being wound into a roll shape, and the cut sheet pieces are placed in a container made of corrugated cardboard or the like. By stacking it in the packaging material such as the nylon bag that has been set, and aging in this state,
Similarly to the above, the carrier film may be a component of the molding material.

When the cut sheet pieces are laminated to form a block-shaped molding material, there is an advantage that the thickness and area can be set to required dimensions. In addition, even when the number of laminated sheets is a thin block shape or when a large number of sheets are laminated to form a thick block shape, the carrier film of each sheet to be laminated is similarly unsaturated polyester on the upper side and the lower side. There is no problem due to the thickness because it swells and is aged to become a component of the molding material.

Except for the case of forming a thick molding material by laminating a large number of roll-shaped or block-shaped molding materials as described above, for example, a thick molding material obtained by laminating two continuously manufactured sheet-shaped molding materials is required. In this case, one of the carrier films may be a polystyrene film, the other may be a polyethylene film, and the polystyrene films may be laminated and aged in a state of being superposed.

[0021]

In the molding material according to the present invention, since the carrier film necessary for the production is aged to be a component of the molding material, the molding process can be performed without peeling the carrier film. Therefore, it is possible to completely eliminate the trouble of conventionally peeling the carrier film, and in particular,
It is effective when a block-shaped molding material is required.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the embodiments shown in the drawings. FIG. 1 shows a first embodiment of a molding material according to the present invention. A molding material 10 is obtained by rolling a sheet-shaped molding material 25 made of SMC and then integrally molding it into a cylindrical shape. .. The molding material 10 is housed in a pallet or container 12 in a state of being sealed with a packaging material 11 such as a polyester film.

The molding material 10 is manufactured by the manufacturing process shown in FIG. 2, and will be described in detail below. In the description of the examples, "part" means "part by weight". First, polyester resin (Polymer 640 manufactured by Takeda Pharmaceutical Co., Ltd.)
9) 100 parts, polyethylene powder (Sumitomo Seika Chemicals Co., Ltd. Flowsen UF-20) 3 parts, organic peroxide (NOF Corporation Perbutyl Z) 1 part, polymerization inhibitor (Seiko Chemical Co., Ltd.) pBQ)
0.01 parts, pigment paste (manufactured by Taitai Kako Co., Ltd.) 4 parts, internal mold release agent (Fco Chem ZNS-P manufactured by ADEKA CORPORATION), calcium carbonate (Super SS manufactured by Maruo Calcium Co., Ltd.) ) 12
After thoroughly mixing 0 part with a high-speed mixer, a thickener is further added.
(Kyowa Chemical Co., Ltd. Kyowamag # 40) 1 part is added to form a compound paste.

In the impregnation device 20 shown in the figure, the compound paste A is supplied from the resin tanks 21 and 21 'onto the lower carrier film 23 which is continuously fed out, and the glass robin B (manufactured by Nitto Boseki Co., Ltd.) is supplied. It is cut into 1 inch by a glass cutter 24, dropped on the lower carrier film 23, covered with the upper carrier film 22, and carried by both carrier films.

The ratio of the compound paste A and the chopped strand B obtained by cutting the glass robin is 70 parts to 30 parts.

As the carrier films 22 and 23 on both the upper and lower sides, an unstretched polystyrene film having a thickness of 30 μm (Brighton H-25 manufactured by Hokuetsu Chemical Co., Ltd.) is used. The mechanical strength of the polystyrene film is as shown in Table 1 below.

[0027]

[Table 1]

The compound paste A is carried in the horizontal direction while being impregnated in the glass chop strand B with the compound paste A while being carried by the carrier films 22 and 23. As shown in FIG. 3, the carrier film 2 is formed on the upper and lower surfaces of the molding material C composed of the compound paste A and the glass chop strand B.
The sheet-shaped molding material 25 carried by 2.23 has a thickness of about 3 mm and a width of about 1 m.

After passing through the accumulator 26 and the delivery control device 27, the sheet-shaped molding material 25 is wound into a roll on the cylindrical core tube 29 by the winding device 28. That is, as shown in FIG. 4, the sheet-shaped molding material 25 is laminated with the carrier films 22 and 23 on both upper and lower surfaces thereof being in contact with each other on the inner peripheral side and the outer peripheral side. The outer diameter of the cylindrical core tube 29 is 110 mm.
Then, the roll diameter of the sheet-shaped molding material 25 is usually 400 mm.
φ.

The sheet-shaped molding material 25 wound in the roll form as described above is detached from the winding device 28, and, as shown in the drawing, is supported by the support material 30 for holding the cylindrical core tube 29. It is wrapped with a film made of polyester or the like having barrier properties and aged at 40 ° C. for 24 hours. The aging temperature and time are not limited to 40 ° C. and 24 hours, and may be left at room temperature for a long time.

By the above aging, the carrier films 22 and 23 made of polystyrene film swell to the styrene monomer in the unsaturated polyester resin of the molding material C,
It becomes a component of the molding material C and is integrated with the unsaturated polyester resin. That is, when the sheet-shaped molding material 25 is molded, the carrier film 22 acting as a carrier film of the molding material C,
23 itself becomes a part of the molding material, and the sheet-shaped molding material 25 that has been wound in a laminated form has an inner diameter of 110 mm and an outer diameter of 400 mm.
It becomes one cylindrical molding material 10 of mm. Note that, in FIG. 1, the wound sheet-shaped molding material 25 is shown by a thin line for easy understanding, but it is integrated after aging.

The molding material that has been aged to form the cylindrical molding material 10 is enclosed in a packaging material 11 made of a polyester film or the like having a gas barrier property as shown in FIG.

The above molding material 10 was pressed by a hydraulic press 14
When molded by heating at 0 ° C, a molded product with a beautiful appearance is obtained.
No problem was found by using a carrier film made of a polystyrene film and using the carrier film itself as a part of the molding material.

Next, the second embodiment will be described. Figure 5
In the molding material of the second embodiment shown in Fig. 5, a sheet-shaped molding material made of TMC is cut into sheet pieces of a predetermined width, and the cut sheet pieces are aged in a laminated state to obtain a block-shaped molding material 10 '. It is a thing. The molding material 10 ′ is stored in a corrugated cardboard container 33 in a stacked state while being sealed with a nylon bag 32, aged in this state, and stored and transported after aging.

The molding material 10 'is manufactured by the manufacturing process shown in FIG. 6, and will be described in detail below. As a compound paste, 70 parts of a polyester resin (Polymer 6819 manufactured by Takeda Pharmaceutical Co., Ltd.), 30 parts of a resin in which polystyrene beads are dissolved in styrene (Polymer 9965 manufactured by Takeda Pharmaceutical Co., Ltd.), organic peroxide (NOF Corporation)
1 part of 3M manufactured by Co., Ltd., 0.005 part of polymerization inhibitor (HQ manufactured by Fuji Photo Film Co., Ltd.), internal release agent (SZ-2 manufactured by Sakai Chemical Co., Ltd.)
000) 4 parts, calcium carbonate (NS-1 manufactured by Nitto Koka Co., Ltd.)
After thoroughly mixing 130 parts of (00) with a high-speed mixer, 1 part of a thickener (Kyowamag # 40 manufactured by Kyowa Chemical Co., Ltd.) is further added to produce.

In the impregnating apparatus 20 'shown in the figure, above the pair of impregnating rollers 35, a glass robin B (Nittobo Co., Ltd.) is used.
(Made) is cut into 1 inch by a glass cutter 24 and dropped onto the impregnating roller 35, and the compound paste A is supplied onto the surface of the impregnating roller 35 by a supply pipe 36.
Therefore, the glass roving B cut when passing through the gap of the impregnating roller 35 is impregnated into the compound paste A, and the impregnated molding material C is dropped onto the lower surface carrier film 23. Then, the upper surface carrier film 22 supplied from above is covered on the molding material C and conveyed in the horizontal direction in a state where both upper and lower surfaces are supported. The ratio of the compound paste A and the chopped strand B obtained by cutting the glass robin is 72 parts to 28 parts.

The upper and lower carrier films 22 and 23 are made of the same unstretched polystyrene film having a thickness of 30 μm (Pryton H-25 manufactured by Hokuetsu Kasei Co., Ltd.) as in the first embodiment.

After passing through the accumulator 26 and the feeding control device 27, the sheet-shaped molding material 25 is cut into a predetermined length by a cutting device 38, and a sheet piece 25 'having a length of 1 m, a width of 1 m and a thickness of 10 mm. Are sequentially formed.

The sheet pieces 25 'are stacked in layers in a nylon bag 32 set in advance in a corrugated cardboard container 33 as shown in the figure. Any number of sheets can be stacked up to the required thickness, but in this embodiment, four sheet pieces 25 'are stacked to have a net weight of 50 kg.
After stacking, the nylon bag 32 is sealed and the cardboard container 33 is packed.

Then, it is aged at 40 ° C. for 24 hours. By the aging, the carrier film 2 was prepared in the same manner as in the first embodiment.
The polystyrene film used as 2,23 swells with the styrene monomer in the unsaturated polyester resin and becomes a part of the molding material, and the polystyrene films contacting each other are also integrated. Therefore, all the laminated sheet pieces 25 'are integrated into a block-shaped molding material 10' having a width of 1 m, a length of 1 m and a height of 40 mm.

When the molding material 10 'was molded into an automobile part by an injection molding machine, a molded product having a beautiful appearance was obtained. The carrier film itself was used as a molding material using a carrier film made of polystyrene film. No problems were found due to the inclusion of some of them.

Next, the molding material of the third embodiment of the present invention shown in FIG. 7 will be described. In the third embodiment, FIG.
As shown in (A), one side of the lower surface of the carrier film 2
A polyethylene film having a thickness of 40 μm is used as 3 ′, and the first and second carrier films 22 on the upper surface are used.
The same unstretched polystyrene film (Brighton H-25 manufactured by Hokuetsu Chemical Co., Ltd.) having a thickness of 30 μm as in the example is used. The same molding material C as in the second embodiment is used, and the sheet-shaped molding material 25 'is continuously manufactured by the same manufacturing method as in the second embodiment.

The sheet-shaped molding material 25 'of TMC obtained
Immediately after impregnation, the cut sheet piece 25 ″ is cut into 2 pieces.
As shown in FIG. 7 (B), the carrier films 22 made of polystyrene films are stacked in pairs so that they are housed and packed in a nylon bag set in advance in a cardboard container. The sheet piece 25 ″ has a length of 1 m and a width of 1 m, and when two sheets are stacked, the net weight is 25 kg.

Then, aging at 40 ° C. for 24 hours,
As in the first and second embodiments, the polystyrene film of the carrier film 22 swells with the styrene monomer in the unsaturated polyester resin of the molding material C to become a component of the molding material C, and is integrated. Therefore, as shown in FIG. 7 (C), the molding material 1 having a thickness twice that of the sheet-shaped molding material 25 'is used.
0 "is obtained.

The obtained molding material 10 "is provided with a carrier film 2 composed of polyethylene films on both sides thereof.
When 3 ′ was peeled off and heat-molded at 140 ° C. with a hydraulic press, a molded product with a beautiful appearance was obtained.

Although the above first, second and third examples are all aged by heating at 40 ° C., the polystyrene film can be used as a molding material by leaving it at room temperature for a long time. The polystyrene film can be made a part of a molding material by swelling it with a styrene monomer of a saturated polyester resin.

[0047]

As is apparent from the above description, in the molding material comprising the fiber-reinforced unsaturated polyester resin according to the present invention, a carrier film required for continuous molding as a sheet-shaped molding material is aged to form a molding material. Since it is made a part, it becomes possible to mold without peeling the carrier film during the molding process. Therefore, it is possible to eliminate the work of peeling the carrier film, especially when a block-shaped molding material is required, for example,
When it is used for injection molding, workability can be improved and labor can be greatly saved.

[Brief description of drawings]

FIG. 1 is a sectional view of a molding material according to a first embodiment of the present invention.

FIG. 2 is a schematic view showing a manufacturing process of the first embodiment.

FIG. 3 is a cross-sectional view of the sheet-shaped molding material of the first example.

FIG. 4 is a cross-sectional view showing a laminated state of the sheet-shaped molding material of the first example.

FIG. 5 is a sectional view of a molding material according to a second embodiment of the present invention.

FIG. 6 is a schematic view showing a manufacturing process of the second embodiment.

7 (A), (B), and (C) are cross-sectional views showing the manufacturing process of the molding material of the third embodiment.

[Explanation of symbols]

 A compound paste B cut glass roving C molding material 10,10 ', 10 "molding material 22,23 carrier film 25 sheet-shaped molding material 25' sheet piece

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location B29K 105: 06

Claims (5)

[Claims] 1. A molding material, wherein a carrier film on one or both sides of a sheet-shaped unsaturated polyester resin molding material is a resin film which can be integrated with an unsaturated polyester resin as a component of the molding material. 2. The molding material according to claim 1, wherein the carrier film is a polystyrene film, and the unsaturated polyester resin molding agent contains a styrene monomer. 3. A sheet-shaped molding material, both surfaces of which are supported by a carrier film made of the polystyrene film, is aged in a roll-wound state to form a cylindrical molding material. The molding material according to claim 2. 4. The sheet-shaped molding material, both surfaces of which are supported by a carrier film composed of the polystyrene film,
The molding material according to claim 2, wherein the molding material is a block-shaped integrated molding material that is aged in a block shape as a sheet having a predetermined width. 5. Of both sides of the carrier film carrying both sides of the sheet-like unsaturated polyester resin molding material,
2. The molding material according to claim 1, wherein one is a polystyrene film and the other is a polyethylene form, and the polystyrene form sides are laminated in a state of being overlapped and aged to be a component of the molding material.