WO1999032278A1

WO1999032278A1 - Thermoplastic resin sheet structure reinforced with continuous fibers

Info

Publication number: WO1999032278A1
Application number: PCT/JP1998/005146
Authority: WO
Inventors: Susumu Arase; Rikio Yonaiyama; Takao Nakamura; Masanori Ishikawa
Original assignee: Chisso Corporation
Priority date: 1997-12-19
Filing date: 1998-11-16
Publication date: 1999-07-01

Abstract

A thermoplastic resin sheet structure reinforced with continuous fibers, which is constituted of a sheet-form core layer consisting mainly of continuous reinforcement fibers arranged approximately in parallel to the machine direction and a thermoplastic resin bonding the fibers to each other, especially one having an affinity for the fibers and a skin layer made of a thermoplastic resin and laminated to at least one side of the core layer. Due to the constitution, the structure has various advantages that it is excellent in all of tensile strength, bending strength, safety, and workability and is suitable for use in producing products of high value, e.g., a band for packing weighty objects.

Description

Specification

Continuous fiber reinforced thermoplastic resin sheet-like structure

The present invention is mainly obtained by laminating a core material layer containing a thermoplastic resin and a continuous fiber reinforcement and a skin material layer made of thermoplastic resin (hereinafter referred to as a skin material layer). The present invention relates to a continuous fiber reinforced thermoplastic resin sheet-like structure (hereinafter, referred to as a structure or a laminated band).

INDUSTRIAL APPLICABILITY The structure of the present invention is particularly useful for a heavy-duty band, a transport band such as a conveyor belt, a driving belt such as a transmission belt, and the like. It has much better performance than the belt and belt. Background art

Resin bands are widely used for packaging various products because of their ease of handling, but have sufficient strength to be used for heavy packaging bands that require excellent mechanical strength. Absent. There are also methods of using resin bands as conveyor bands and transmission belts.However, such applications require more excellent mechanical strength, and are therefore difficult to use. It was extremely difficult to use this resin band.

Therefore, attempts have been made to use a continuous fiber reinforced resin having high mechanical strength for a resin band. The continuous fiber reinforced resin is formed by impregnating the resin with a continuous fiber reinforced material, and a resin band using such a continuous fiber reinforced resin is a resin band not using a continuous fiber reinforced resin. The mechanical strength, such as tensile strength, is extremely superior to that of metal.

However, a resin band using a continuous fiber reinforced resin is not connected to the band surface. In many cases, the end portion of the continuous fiber reinforcing material protrudes, so that the continuous fiber reinforcing material and the resin are easily separated, and the tensile strength of the band is significantly reduced, and the band is easily cut. It has the disadvantage of becoming

In addition, the protruding end portion of the continuous fiber reinforced material has a high risk of being pierced by an operator's hand or the like during packaging and injuring the operator or damaging the packaged object. There has been a problem that fluffing occurs on the surface of the belt, resulting in insufficient surface gloss and smoothness, thereby lowering the commercial value. Disclosure of the invention

An object of the present invention is to provide a structure that is excellent in mechanical strength represented by tensile strength and bending strength, handling safety, workability, and has high commercial value. The structure is particularly useful as a heavy packaging band, a transport band, and a drive belt.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic view showing an example of a series of apparatuses for manufacturing the structure of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

The manufacturing procedure of the structure of the present invention will be specifically described with reference to FIG. In the explanation of the figure, ΓUp, down, left, right, front or back J etc. are expressions for convenience of explanation.

In FIG. 1, a continuous fiber reinforcing material (2) using a long fiber bundle of glass roving is introduced into an opening and impregnating device (1) to which molten resin is supplied, and a continuous fiber reinforcing material (2) is used. After the molten resin adheres to and impregnates between the fibers and on the fiber surface (hereinafter collectively referred to as impregnation), it is drawn out and becomes the core layer (71), which is a narrow continuous fiber-reinforced thermoplastic resin. . For convenience, the upstream side is the upstream side and the downstream side is the downstream side. The open fiber impregnation tank (1) basically consists of a top plate (lwT), an upstream end wall (lw), a downstream end wall (lwR), a bottom plate (1wB) and two side plates (1wB). (Illustration omitted).

The molten resin is continuously supplied to the inside of the opening-impregnation tank (1) via a resin inlet (5) formed in the bottom plate (1 wB). As a method of supplying the molten resin, there is a method of supplying the molten resin melt-kneaded by an extruder or the like (not shown) through a pipe or the like connecting the extruder and the resin inlet (5). It is valid.

The continuous fiber reinforcing material (2) is introduced substantially horizontally into the opening and impregnating device (1) 內 through the fiber inlet (3) drilled in the upstream end wall (1 wL), and the continuous fiber reinforcing material ( The fabric is unwound by passing through the middle of the spread pin (4u) and the spread pin (4d), which sandwiches 2) from above and below, so as not to contact any of the spread pins (4). While the molten resin is impregnated in the continuous fiber reinforcing material (2), the continuous fiber reinforcing material (2) is drawn out of the opening and impregnating tank (1) through the shaping nozzle 6 formed in the downstream end wall (1 wR). The spreading pins (4) form a pair substantially horizontally toward the downstream side, or substantially vertically up and down. Each of the weaving pins (4 ul and 4 dl, 4 u2 and 4 d2, and 4u3 and 4 d3) is referred to as an opening pin pair.

The core layer (71) drawn out of the open fiber impregnation tank (1) has a skin layer (72u) on the upper surface and a skin layer (72d) on the lower surface. It becomes a structure (7).

In the lamination, the skin layer (72 u) located on the upper surface is laminated on the upper surface of the core layer (71) by the upper pressing roll (8u), and the skin layer (72 d) located on the lower surface. ) Is laminated on the lower surface of the core layer (71) by the lower pressing roll (8d). Finally, the structure (7) is wound by a take-up reel (10) located at the downstream end while being sandwiched between a pair of upper and lower nip rolls (9).

Further, the structure of the present invention preferably has one or more of the following.

(1) The thermoplastic resin, which is a constituent component of the core material layer, has at least a partial affinity for continuous fiber reinforcement.

(2) The thermoplastic resin that is a component of the core material layer is polypropylene. (3) The continuous fiber reinforcement is glass fiber. Glass fiber is useful because it has excellent mechanical strength and sufficient economical price. For applications where the balance between lightness and strength, that is, having a high specific strength, is the most important condition, replace glass fiber with carbon fiber.

熱 The thermoplastic resin that is a component of the core layer and the skin layer is of the same type.

合計 The total thickness of the skin material layer is usually in the range of 0.1 to 2ππη, preferably in the range of 0.2 to 1 mm.

Structure>

Next, the structure of the present invention will be specifically described.

The structure of the present invention comprises a sheet-like core layer formed of a continuous fiber reinforcement arranged substantially parallel to the longitudinal direction and a thermoplastic resin bonding (adhering) the continuous fiber reinforcement to each other. The core layer is made of a thermoplastic resin skin layer laminated on at least one side. In the present invention, a relatively narrow one is referred to as a sheet for convenience. First, the core material layer will be described below.

Core layer>

The core material layer constituting the structure of the present invention is mainly composed of a continuous fiber reinforcing material arranged substantially parallel to the longitudinal direction and a thermoplastic resin that bonds the continuous fiber reinforcing materials to each other. Any thermoplastic resin may be used as long as it can be impregnated into the continuous fiber reinforcement, but a thermoplastic resin modified to have an affinity for the continuous fiber reinforcement is preferable.

For example, when glass fiber is used as the continuous fiber reinforcing material, it is desirable to use a modified thermoplastic resin having a strong bond with glass fiber.

The thermoplastic resin, along with the modifier, organic peroxide, and other additives described below, is uniformly dispersed in a mixing device such as a Henschel mixer (trade name), and then melt-kneaded in an extruder and melted. It is impregnated into continuous fiber reinforcement as resin. <Thermoplastic resin>

The thermoplastic resin, which is a constituent component of the core material layer, includes polyolefin (PO), which is a homopolymer or copolymer of a 1-olefin monomer containing usually 2 to 10 carbon atoms,

{For example, at least one of polyethylene (PE), polypropylene (PP), propylene-ethylene copolymer, propylene-1-butene copolymer, and propylene-1-methyl-1-pentene copolymer And polyhalogenated vinyl, {preferably polychlorinated vinyl (PVC)}, polyamide resin (NL) {eg, 6-nylon, 6,6-nylon, 6 , 10-Nylon, 6,12-Nylon and Nylon MXD6 (co-condensate resin of m-xylylenediamine and adipic acid) etc.) and wholly aromatic polyamides, saturated polyesters {eg PET And PBT, etc.), wholly aromatic polyesters, AS (acrylonitrile-styrene copolymer) resin, ABS (acrylonitrile) resin, poly (methyl methacrylate) (PMMA), polyacetal, polyca One bone (PC), fluororesin, polyphenylene sulfide (PPS), polysulfone (PSO), polyether sulfone, polyether ketone, polyester ether ketone (PEEK), polyimide, polyarylate, etc. It is a thing.

Among these, crystalline polypropylene, particularly crystalline polypropylene, is preferable because of its excellent versatility and mechanical strength.

Further, it is desirable that the thermoplastic resin contains a force-modified thermoplastic resin which is a modified thermoplastic resin modified with a modifier or the like described later.

Modifier>

Examples of the modifier for giving the thermoplastic resin an affinity with the continuous fiber reinforcing material include an organic silane compound, an unsaturated carboxylic acid, and an unsaturated carboxylic anhydride. Among them, unsaturated carboxylic anhydrides (eg, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, and norbornene dicarboxylic anhydride) Is preferred, and maleic anhydride is most preferred.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, and itaconic acid. Examples of the unsaturated carboxylic acid effective in the present invention include derivatives such as acid halides of unsaturated carboxylic acids in which one OH of a carboxyl group (—COOH) contained in the unsaturated carboxylic acid is substituted with a halogen atom or the like.

These unsaturated carboxylic acids or unsaturated carboxylic anhydrides may be used alone or in combination of two or more.

Examples of the organic silane compound include aminosilane, epoxysilane, bursilane, and methacryloxysilane. These organic silane compounds may be used alone or in combination of a plurality of types.

Organic peroxide>

In the present invention, when the above-described modifier is used, an organic peroxide may be used in combination as necessary. Examples of organic peroxides that are effective in combination with organosilane compounds include 2,5-dimethyl (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, Dicumyl peroxide (DCP) and benzoyl peroxide (BPO).

Other additives>

Functional additives such as antioxidants, ultraviolet stabilizers, coloring agents, weathering agents, flame retardants, lubricants, antiblocking agents, copper anti-static agents and antistatic agents are appropriately added to the core material layer and the skin material layer. Can be blended.

Continuous fiber reinforcement>

The continuous fiber reinforcing material, which is a component of the core material layer, has a bundle of about 500 to 400 single fibers having an average diameter of 3 to 21 μιη, preferably 9 to 21 μm. Hereinafter, it may be referred to as roving). When the average diameter of a single fiber is 1 / zm or less, the fiber is easily broken at the time of forming the structure, and the impact strength of the structure is easily reduced. On the other hand, single fiber When the average diameter is 25 μm or more, the appearance of the structure tends to be deteriorated, and the mechanical strength of the structure tends to decrease.

The average length of the continuous fiber reinforcing material is preferably substantially equal to the average length of the structure. When the continuous fiber reinforcement continuously extends in the longitudinal direction of the structure, the structure has extremely improved tensile strength and bending resistance in the longitudinal direction. Examples of continuous fiber reinforcements include inorganic fibers and organic fibers. Examples of the inorganic fibers include artificial fibers such as glass fibers, carbon fibers, and metal fibers. Among them, glass fiber is preferably used because of its excellent physical properties and economy. Hard glass is preferable as the glass fiber, and E glass or borosilicate glass (porosilicate glass), which is non-alkali glass, is particularly preferable. Inorganic fiber is, for example, a silane coupling agent or a titanate coupling agent. It may be used after being surface-treated with a chemical agent, a boron-based coupling agent, an alumina-based coupling agent, a zirco-aluminate-based coupling agent, or the like. When surface treatment is applied to inorganic fibers, compatibility with hydrophobic thermoplastic resins such as polypropylene can be enhanced, and the thermoplastic resin is easily impregnated between the fibers of the continuous fiber reinforcement. Become.

Examples of the organic fibers include polyolefin fibers {eg, polyethylene fibers, polypropylene fibers and poly- ⁴ -methyl-1-pentene fibers}, polyamide fibers {eg, 6-polyamide (6-nylon), 7-polyamide. , 11-polyamide, 12-polyamide, 6,6-polyamide, 6,7-polyamide, 6,10-polyamide, 6,12-polyamide}, semi-aromatic polyamide fiber {e.g. Ron MXD 6 (co-condensate of m-xylylene diamine and adipic acid)}, wholly aromatic polyamide fiber [aramid fiber (trade name: Kepler)], thermoplastic polyester fiber {for example, PET (polyethylene terephthalate) Rate) fiber, PBT (poly-1,4-butylene terephthalate) fiber} and wholly aromatic polyester Fiber and the like. These are preferred in that they have a high melting point and excellent mechanical strength.

The inorganic fiber and the organic fiber may be used alone, or two or more kinds may be used in combination.

Preparation of core material layer>

The core layer is basically obtained by impregnating a continuous fiber reinforcement with a molten thermoplastic resin. It is desirable to spread the continuous fiber reinforcing material as evenly as possible in a planar shape and to impregnate the spreaded material uniformly with a thermoplastic resin. The core material layer obtained in this manner is used for the structure of the present invention. When used, the mechanical strength is significantly improved.

The method of impregnating the continuous fiber reinforcement with the thermoplastic resin may be any method as long as the continuous fiber reinforcement can be impregnated with the thermoplastic resin. The impregnation method disclosed in Japanese Patent Application Laid-Open Publication No. Hei 4-418886 and Japanese Patent Application Laid-Open No. Sho 61-229354 is desirable.

It is desirable that the continuous fiber reinforcing material, which is a component of the core material layer, is contained in the core material layer in an amount of 10 to 80% by weight, preferably 30 to 70% by weight. When the continuous fiber reinforcement is used at this content, the continuous fiber reinforcement is sufficiently impregnated with the thermoplastic resin, so that the continuous fiber reinforcement and the thermoplastic resin are excellent in mutual integration. If the content of the continuous fiber reinforcing material is 5% by weight or less, mechanical properties such as tensile strength may not be sufficiently exhibited. On the other hand, the content of continuous fiber reinforcement is 90% by weight. If the ratio is / ₀ or more, sufficient mechanical properties may not be exhibited. It is understood that the cause is that the thermoplastic resin does not sufficiently impregnate the continuous fiber reinforcement.

The skin material layer is a thermoplastic resin film or sheet layer laminated on at least one side of the core material layer. The thermoplastic resin that is a constituent component of the skin material layer may be different from the thermoplastic resin used for the core material layer, but is preferably the same. Is good. Preferable examples of the thermoplastic resin which is a component of the skin material layer include polyolefin (PO) (for example, polyethylene (PE), polypropylene (PP), propylene-ethylene copolymer, etc.), Ethylene vinyl monoxide copolymer (EVA), thermoplastic polyamide resin (NY) {For example, 6-polyamide (6-nylon), 7-polyamide, 1-polyamide, 12-polyamide, 6,6-polyamide, 6,7-polyamide, 6,10-polyamide, 6,12-polyamide}, semi-aromatic polyamide fiber {e.g., Nylon MXD 6 (m-xylylenediamine and Thermoplastic condensed polyester (eg PET (polyethylene terephthalate) fiber, PBT, etc.), wholly aromatic polyamide fiber [alamide fiber (trade name: Kepler)], etc. (Poly-1,4-butylene terephthalate) fiber} And wholly aromatic polyester fibers.

Among them, crystalline polyolefins, particularly crystalline polypropylene, are excellent in properties such as versatility, mechanical strength, surface gloss, and moderate heat resistance (thermal strain temperature). Due to these advantages, the use of crystalline polyolefin, especially crystalline polypropylene, makes it possible to obtain an inexpensive structure that is excellent in strength and commercial value.

Most preferably, a modified thermoplastic resin treated with a modifier or the like, particularly a modified thermoplastic resin obtained by blending an organic peroxide at the time of reforming, is desirable. The modifier, organic peroxide and other additives used for the skin layer may be of the same type as those used for the core layer.

Preparation of skin layer>

The skin material layer may be made of the thermoplastic resin alone or a composition of two or more types, but is preferably made of a modified thermoplastic resin alone or a composition containing an appropriate amount of the modified thermoplastic resin, It is particularly preferable to use a thermoplastic resin of the same type as the core material layer or a material having compatibility with the thermoplastic resin used for the core material layer. If the thermoplastic resins used for the skin material layer and the core material layer are the same type of resin or are compatible with each other, a high bonding force is generated at the interface between the skin material layer and the core material layer. Get It is.

The skin layer is usually formed on both sides of the core layer, and sometimes on one side, but the total thickness of the skin layer is usually 0.1 to 2 nun, preferably 0.2 to 1 mm. Set within.

If the total thickness of the skin layer is less than 0.05, the core layer cannot be satisfactorily reinforced, and the mechanical strength tends to decrease. On the other hand, if it is more than 1.5 ππη, the bending strength does not improve in accordance with the amount used, and the skin layer becomes too thick, which makes handling inconvenient. In other words, the bending rigidity (bending strength) of the obtained structure becomes too large, and it becomes difficult to perform secondary forming.

The skin material layer may be laminated on one surface of the core material layer, but is more preferably laminated on both surfaces of the core material layer. By laminating skin layers on both sides of the core layer, it is possible to maintain good bending resistance in the surface direction or the back side direction (perpendicular to the surface) of the structure, and also to provide the surface on both sides of the structure. Gloss and protection can be given to increase the commercial value.

Examples of the method for producing the skin material layer include a method in which a thermoplastic resin composition is formed into a film in advance, and then the film is laminated on the surface of the core material layer, or a thermoplastic resin in a molten state. Examples of the method include a method of tinting the composition on the surface of the core material layer.

In the laminating method, it is desirable to laminate the skin material layer while keeping the surface of the core material layer in a semi-molten (semi-softened) state, but it is not necessarily required to be in a semi-molten state, and the lamination is performed using an adhesive. May be.

In the coating method, it is desirable to laminate the melt-extruded skin layer on the surface of the core layer while maintaining the surface of the core layer in a semi-molten (semi-softened) state, but it is not necessary to be in a semi-molten state.

By laminating the skin material layer on the surface of the core material layer as described above, The structure can be manufactured with good procedure. By setting the outer shape of the structure manufactured in this way to, for example, a sheet having a width of 5 to 200 mm and a thickness of 0.1 to 2 mm, a heavy packing band, It can be used for transmission belts and the like.

When the structure of the present invention is used for a heavy packaging band or the like, tensile strength, bending strength, surface smoothness, safety, workability, and the like are good. The invention's effect

The structure of the present invention has the following effects.

(1) The structure of the present invention is excellent in all of tensile strength, bending strength, surface smoothness, safety and workability.

(2) The heavy packaging band obtained by using the structure of the present invention has high commercial value. Example

The present invention will be described more specifically based on the following examples, but the present invention is not limited to these examples.

The tensile strength, bending resistance and surface gloss of the structure (7) obtained by each of the following Examples and Comparative Examples were evaluated under the following conditions.

(1) Tensile strength: along a continuous fiber reinforcement direction of the resultant structure, taking the strip wide samples 3 3 mm, its tensile according to JISZ- 1 5 2 7- 1 9 7 6 Strength Was measured.

(2) Bending resistance: Take a rectangular sample with a width of 33 nun along the direction of the continuous fiber reinforcement of the obtained structure, and bend it at right angles to the longitudinal direction of the sample. The tensile strength of the returned sample was measured in accordance with TISZ-152-197-76. (3) Surface gloss: The obtained structure was used as a sample, and the surface of the sample was measured for gloss according to ASTM D523.

[Example 1]

<Manufacture of structures>,

Maleic anhydride-modified thermoplastic polypropylene (hereinafter referred to as “modified PP”) [Crystal melting point by DSC measurement: 160 ° C; MFR under conditions of 230 ° C and 21.18 N g / 1 Omin] is melted and kneaded in a melt kneading apparatus (not shown) set at 270 ° C, and the obtained molten resin is placed in the fiber impregnation tank (1) shown in Fig. 1 as described above. Provided in accordance with.

Next, 6 continuous fiber reinforcements (2), which are long glass fiber bundles, in which 40000 single fibers are bundled from the upstream side, are introduced into the open fiber impregnation tank (1) at the same time horizontally and in parallel. The fiber opening and impregnation in which the fiber is opened inside the fiber-opening impregnation tank (1) and the molten material is impregnated between the fiber-opened and impregnated tanks (1) shown in FIG. In a pair of upper and lower rod-shaped fixed opening bins (4) installed between the inner wall and the inner wall of the right plate (4) Two or more opening pins constituting each pair (4) The continuous fiber reinforcement (2) was opened without passing through any of the opening pins (4) without contact, and was impregnated with the molten resin.

Next, a slit-shaped shaping die (6) consisting of 3 Omiu width and 0.5 mm thickness, drilled in the downstream end wall (1 wR) of the opening impregnation tank (1), A core material layer (71) having a semi-molten surface was drawn out.

Both surfaces of the core material layer (71) are made of polypropylene [MFR under the conditions of a crystalline melting point of 160 ° C, 230 ° C and 21.18 N by DSC measurement is 2.0 min] After layering with a 0.3 mm thick skin layer (7 2) using Nippon, it is laminated between nipples (8 u and 8 d) sandwiched from both sides, with an average width of 33 average thickness 1 · 0 4 structures (7 were obtained. At this time, the two skin layers (72) are supplied from the respective webs. One of them is a web (72u) located above the core layer (71), and the other is a web (72d) located below the core layer (71).

The average thickness of the core layer (71) was 0.44 mm, and the average thickness of the skin layer (72) was 0.3 nun per side. Table 1 also shows the configurations of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

[Example 2]

According to Example 1, except that the average thickness of the skin layer (72) laminated on both surfaces of the core layer (71) is changed to 0.1 mm per one side, A structure (7) having an average width of 33 mm and an average thickness of 0.64 mm, in which the skin material layers (72) were laminated on both surfaces, was obtained.

The average thickness of the core layer (71) was 0.44 mm, and the average thickness of the skin layer (72) was 0.1 mm per side. Table 1 also shows the configurations of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

[Example 3]

According to Example 1, except that the average thickness of the skin layer (72) laminated on both surfaces of the core layer (71) was changed to 0.5 mm on each side. Thus, a structure (7) having a width of 33 mm and an average thickness of 1.44 was obtained, in which both surfaces were laminated with the skin material layer (72).

The average thickness of the core layer (7 1) is 0. 4 4m _m, the average thickness of the skin layer (7 2) on one surface was per 0. 5 mm. Table 1 also shows the configurations of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

[Comparative Example 1]

A structure having an average width of 33 mni and an average thickness of 0.44 ηπα according to Example 1 except that the skin material layer (7 2) is not laminated on any surface of the core material layer (71). A product (7) was obtained.

Table 1 also shows the configurations of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7). The obtained structure (7) was excellent in tensile strength, but inferior in bending resistance and surface gloss.

[Comparative Example 2]

Polypropylene [03. The melting point of the crystal was determined by melting and kneading a melt melting and kneading apparatus (not shown) with an MFR of 2.0 gZ 10 min under the conditions of a crystal melting point of 16.0; 2300 ° C, and 2.18 N. The melted resin is extruded at 250 ° C from a T-die mounted at the downstream end of the extrusion molding device to form a semi-molten (sintered) core layer (71) without continuous fiber reinforcement. did.

Then, both surfaces of the core layer (71) were polished with polypropylene [crystal melting point of 160 ° C. by DSC measurement; 230 ° C .; _< l O min], and then wrapped with a 0.3 mm skin layer (72) with an average thickness, then passed between nip rolls (8u and 8d) sandwiched from both sides to obtain an average width of 3mm. A structure (7) with a thickness of 3 mm and an average thickness of 1.0 mm was obtained.

The average thickness of the core material layer (71) was 0.4 mm, and the average thickness of the skin material layer (72) was 0.3 mm per side. Table 1 also shows the configurations of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

The obtained structure (7) was excellent in surface gloss, but was inferior in tensile strength and bending resistance.

[Example 4]

Modification? ? [The crystal melting point in the measurement at 05 ° 1600 °; 2300 ° 〇, MFR under the condition of 2.1.8 N is 13 Og / 10 min] is set to 270 ° C. The melted resin was melted and kneaded by a melt-kneading apparatus (not shown), and the obtained molten resin was supplied to the opening and impregnating tank (1) shown in FIG. 1 according to the above description.

Next, 36 continuous fiber reinforcements (2), which are long glass fiber bundles, in which 400 single fibers are bundled from the upstream side, are bored into the upstream wall inside the open fiber impregnation tank (1). Fiber guide The fiber was introduced through the inlet (3) and opened in the opening and impregnating tank (1), and the molten resin was impregnated between the opened products. Next, from a shaping die (6) with a width of 195 mm and a length of 0.5 mm drilled in the downstream end wall (1 wR) of the opening and impregnating tank (1), the surface is in a semi-molten state. The core material layer (71) was drawn out.

Both surfaces of the core layer (71) are made of polypropylene [crystal melting point of 160 ° C. by DSC measurement; MFR of 2.0 _g 10 under the condition of 230 ° C. and 2.1.18 N]. min] using a 0.3 mm thick skin material layer (72), and then passing between two nip rolls (8u and 8d) sandwiched from both sides to laminate, with an average width of 200mm The structure (7) having an average thickness of 1.04 mm was obtained. The average thickness of the core layer (71) was 0.44 ηιπ! The average thickness of the skin material layer (72) was 0.3 πιπι per side. Table 1 also shows the structures of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

[Comparative Example 3]

According to Example 4, except that the skin material layer (72) was not laminated on any surface of the core material layer (71), the width was 200 mm, and the average thickness was 0.44 mm. (7) was obtained.

Table 1 also shows the configurations of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

The obtained structure (7) was excellent in tensile strength, but inferior in bending resistance and surface gloss.

[Comparative Example 4]

Polypropylene [crystal melting point (DSC): 160 ° C; MFR under conditions of 230 ° C and 2.1.18 N was 2.0 gZ 10 min] was melted in a melt-kneading apparatus (not shown). The molten resin obtained by extrusion is extruded at 250 ° C from a T-die attached to the downstream end of the extrusion molding device, and the surface of the core material layer is not semi-molten and contains continuous fiber reinforcement (71). Was prepared. Next, both surfaces of the core material layer (71) were coated with polypropylene [crystal melting point by DSC measurement]. Skin layer with an average thickness of 0.3 mm using a temperature of 160 ° C; 230 ° C and 21.1 8 1 ^ After stacking in 7 2), the stack is passed between the nipples (8 u and 8 d) sandwiched from both sides and stacked to obtain a structure (7) with an average width of 200 min and an average thickness of 1. Omm .

The average thickness of the core layer (71) was 0.4 min, and the average thickness of the skin layer (72) was 0.3 mm per side. Table 1 also shows the configurations of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

The structure (7) was excellent in surface gloss, but was inferior in tensile strength and bending resistance.

[Example 5]

Modified PP [Crystal melting point 16.0 ° 〇 from 03〇 measurement; 230 ° 〇, MFR under conditions of 2.1.18 N is 130 g / 10 min] at 270 ° C The melted resin was melted and kneaded by a melt-kneading device (not shown) set in the above, and the obtained molten resin was supplied to the opening and impregnating tank (1) shown in FIG. 1 according to the above description.

Next, 36 continuous fiber reinforcing materials (2), which are glass long fiber bundles, in which 400 single fibers are bundled from the upstream side in the open fiber impregnation tank (1), are arranged in a horizontal line. Then, the fibers were simultaneously introduced through the fiber introduction holes (3) drilled in the upstream wall, opened in the opening and impregnating tank (1), and the molten resin was impregnated between the opened materials. Next, the surface was semi-molten from a shaping die (6>) with a width of 195 mm and a thickness of 0.5 mm drilled in the downstream end wall (1 wR) of the opening and impregnating tank (1). The core layer (71) was drawn out.

Next, on one surface of the core material layer (71), propylene [having a crystal melting point of 160 ° C by DSC measurement; 230 ° C; gZl Omin], a 0.3 mm thick skin material layer (72) is layered, and then passed between the nipples (8u and 8d) sandwiched from both sides to form an average width 2 A structure (7) having a thickness of 0.0 mm and an average thickness of 0.74 mm was obtained. The average thickness of the core layer (71) was 0.444 mm, and the average thickness of the skin layer (72) was 0.3 mm. Table 1 also shows the configurations of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

[Comparative Example 5]

Polypropylene [Crystal melting point (DSC): 160 ° C; MFR under the condition of 230 ° C and 21.18 N is 2.0 g / l 0 min] in a melt-kneading apparatus (not shown) The obtained molten resin is extruded at 250 ° C from a T-die attached to the downstream end of the extrusion molding device, and the continuous fiber reinforcement with a semi-molten surface is not blended. A core material layer (71) was produced.

Then, one side of the core material layer (71) was polished with polypropylene [crystal melting point of 160 ° C; DSC measurement, 230 ° C; 0 min] and a layer of skin material (72) with an average thickness of 0.3 mm, and then laminated between the nipples (8u and 8d) sandwiched from both sides to form an average width of 2 A structure (7) having a thickness of 0.0 mm and an average thickness of 0.7 mm was obtained.

The average thickness of the core layer (71) was 0.4 mm, and the average thickness of the skin layer (72) was 0.3 mm. Table 1 also shows the structures of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

[Example 6]

Melt kneader with modified PP [03 (crystal melting point 16.0; 2300, 21.1, 18 M NFR under measurement conditions of 130 gZl Omin) at 270 ° C] (Not shown), and the obtained molten resin was supplied to the opening and impregnating tank (1) shown in FIG. 1 according to the above description.

Next, 400 pieces of single fibers were bundled from the upstream side into the open fiber impregnation tank (1). Eighteen continuous fiber reinforcements (2), which are long glass fiber bundles, are introduced simultaneously through the fiber introduction holes (3) drilled in the upstream wall in a state where they are arranged horizontally in parallel, and they are impregnated. The fiber was opened inside the tank (1) and a molten resin was impregnated between the opened materials. Next, from a shaping die (6) with a width of 195 mm and a thickness of 0.25 nun drilled on the downstream end wall (1 wR) of the opening and impregnating tank (1), a semi-molten surface was obtained. The core material layer (71) was drawn out.

Next, both surfaces of the core material layer (71) were coated with polypropylene [crystal melting point of 160 ° C by DSC measurement; 230]. C, Nippers sandwiched from both sides after layering on a skin layer (72) with an average thickness of 0.2 mm using an MFR of 2.10 min] (8u and 8d) to obtain a structure (7) having an average width of 20 2πηιι and an average thickness of 0.62 mm.

The average thickness of the core layer (71) was 0.22nnn, and the average thickness of the skin layer (72) was 0.2ιηπι per side. Table 1 also shows the configurations of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

[Comparative Example 6]

Except that the skin material layer (72) was not laminated on any surface of the core material layer (71), the width was 200 mm and the average thickness was 0.22 mm according to Example 6. (7) was obtained.

[Comparative Example 7]

Polypropylene [Crystal melting point (DSC) of 160 ° C; MFR under conditions of 230 ° C and 21.18 N is 2.0 g / 1 Omin] in a melt-kneading apparatus (not shown) The obtained molten resin is extruded at 250 ° C from a T-die attached to the downstream end of the extrusion molding device, and the continuous fiber reinforcement with a semi-molten surface is not blended. Preparation of core material layer (7 1) did.

Then, both surfaces of the core material layer (71) were polished with polypropylene [having a crystal melting point of 160; 230 ° C by DSC measurement, and an MFR of -2.0 under the condition of 2.1.18N. g / 10 min] and a layer of skin material (72) with an average thickness of 0.2 mm, and then passed between the nipples (8 u and 8 d) sandwiched from both sides, and laminated. A structure (7) having an average width of 200 mm and an average thickness of 0.6 mm was obtained.

The average thickness of the core layer (71) was 0.2 mm, and the average thickness of the skin layer (72) was 0.2 mm per side. Table 1 also shows the configurations of the core layer (71) and the skin layer (72) and the evaluation results of the structure (7).

01

Claims

The scope of the claims

1. Consists of a core layer made of a continuous fiber reinforcement and a thermoplastic resin arranged substantially parallel to the longitudinal direction, and a skin layer made of a thermoplastic resin laminated on at least one side of the core material layer. A continuous fiber reinforced thermoplastic resin sheet-like structure.

2. The continuous fiber-reinforced thermoplastic resin sheet-like structure according to claim 1, wherein the amount of the continuous fiber-reinforced material in the core material layer is in the range of 10 to 80% by weight.

3. The continuous fiber reinforced thermoplastic resin sheet-like structure according to claim 1 or 2, wherein the thermoplastic resin in the core layer at least partially shows an affinity for the continuous fiber reinforced material. object.

4. The continuous fiber-reinforced thermoplastic resin sheet-like structure according to any one of claims 1 to 3, wherein the thermoplastic resin used for the core material layer is polypropylene.

5. The continuous fiber reinforced thermoplastic resin sheet-like structure according to any one of claims 1 to 4, wherein the continuous fiber reinforced material is a long glass fiber.

6. The continuous fiber-reinforced thermoplastic resin sheet-like structure according to any one of claims 1 to 5, wherein the average thickness of the skin material layer is in the range of 0.2 to 1.0 mm.

7. The continuous fiber-reinforced thermoplastic resin sheet-like structure according to any one of claims 1 to 6, wherein the thermoplastic resin used for the skin material layer is polypropylene.