JP2021020331A - Long plate-like material - Google Patents

Abstract

To provide a long plate-like material which is flexible and from which a molded product with little fluff after being heat processed is produced.SOLUTION: A long plate-like material of this invention includes a continuous reinforcing fiber and a continuous thermoplastic resin fiber. Along a longitudinal direction, the long plate-like material includes edge areas (A) each of which is 0.25-30 mm thick from an end and which do not include the continuous reinforcing fiber but include the continuous thermoplastic fiber. Along the longitudinal direction of the long plate-like material, a ratio of the continuous reinforcing fiber in a central area (B), which lies on an inner side of each of the edge areas (A), is 25-75 vol.% relative to the central area (B). A ratio of the continuous reinforcing fiber is 20-60 vol% relative to the entire area of the long plate-like material, and an impregnation rate of the continuous thermoplastic resin fiber into the continuous reinforcing fiber is 30% or lower.SELECTED DRAWING: Figure 1

Description

The present invention relates to a long flat plate material. In particular, it relates to a long flat plate material used as a fiber reinforced resin material.

Thermoplastic resins are widely used as various molding materials. In recent years, it has been studied to use a fibrous thermoplastic resin (thermoplastic resin fiber) as various molding materials. In particular, in order to improve the strength of molded products, mixed yarns in which continuous reinforcing fibers are blended with continuous thermoplastic resin fibers and other fiber reinforced resin materials are also known (Patent Documents 1 to 3).

Japanese Unexamined Patent Publication No. 2014-173196 JP-A-2018-154126 JP-A-2017-128072

The material containing the continuous reinforcing fiber and the continuous thermoplastic resin fiber as described above has an advantage that it is more supple and can easily correspond to various shapes as compared with the so-called impregnated type prepreg. On the other hand, since the material containing the continuous reinforcing fiber and the continuous thermoplastic resin fiber promotes the impregnation of the continuous thermoplastic resin fiber into the continuous reinforcing fiber at the time of heating, it depends on the heating and pressurizing conditions and the desired shape of the molded product. It was found that it is difficult to sufficiently apply pressure to the end portion, and after heating and pressurization, a portion where the impregnation of the continuous thermoplastic resin fiber has not sufficiently progressed may be formed. If the impregnation does not proceed sufficiently, fluffing may be observed in the obtained molded product.
An object of the present invention is to solve such a problem, and an object of the present invention is to provide a long flat plate-shaped material which is supple and can obtain a molded product with less fluffing after heat processing.

As a result of the study by the present inventor based on the above problems, it is a long flat plate material containing continuous reinforcing fibers and continuous thermoplastic resin fibers, and the end portion in the longitudinal direction does not contain continuous reinforcing fibers. It has been found that the above problems can be solved by providing a terminal region containing continuous thermoplastic resin fibers. Specifically, the above problem was solved by the following means.
<1> A long flat plate-like material containing continuous reinforcing fibers and continuous thermoplastic resin fibers, and the longitudinal direction of the long flat plate-like material is a region of 0.25 to 30 mm from each end. Continuous reinforcing fibers in the central region (B) inside the terminal region (A) in the longitudinal direction of the long flat plate material, including the terminal region (A) containing continuous thermoplastic resin fibers without containing continuous reinforcing fibers. The ratio of the continuous reinforcing fibers in the entire region of the long flat plate-like material is 20 to 60% by volume, and the ratio of the continuous thermoplastic resin fibers is 25 to 75% by volume of the central region (B). A long flat plate material having an impregnation rate of 30% or less in the continuous reinforcing fibers.
<2> The long flat plate-like material according to <1>, wherein the continuous thermoplastic resin fiber contains a polyamide resin.
<3> The continuous thermoplastic resin fiber is composed of a constituent unit derived from a diamine and a constituent unit derived from a dicarboxylic acid, and 50 mol% or more of the constituent units derived from diamine is a polyamide resin derived from xylylenediamine. The long flat plate-like material according to <1>.
<4> The long flat plate-shaped material according to any one of <1> to <3>, wherein the moisture content of the continuous thermoplastic resin fiber measured according to JIS L 1096 is 4% or less.
<5> The long flat plate-like material according to any one of <1> to <4>, wherein the continuous thermoplastic resin fiber contains a thermoplastic resin having a melting point of 240 ° C. or lower.
<6> The long flat plate-like material according to any one of <1> to <5>, wherein the continuous reinforcing fiber contains at least one selected from carbon fiber and glass fiber.
<7> The long flat plate-like material according to any one of <1> to <6>, wherein the dispersity of the continuous reinforcing fibers in the central region (B) is 60% or more.
<8> The long flat plate-like material according to any one of <1> to <7>, wherein the impregnation rate of the continuous thermoplastic resin fiber in the central region (B) is 10% or less.
<9> The long flat plate-shaped material according to any one of <1> to <8>, wherein the width of the long flat plate-shaped material is 5 to 100 mm.
<10> The long flat plate-like material according to any one of <1> to <9>, wherein the thickness of the long flat plate-like material is 0.1 to 0.5 mm.

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a long flat plate-like material which is supple and can obtain a molded product with less fluffing after heat processing.

It is a schematic diagram which shows an example of the long flat plate-like material of this invention. This is an example of an image obtained by observing a cross-sectional view of a long flat material under a microscope.

The contents of the present invention will be described in detail below. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the present specification, various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.

The long flat plate-shaped material of the present invention is a long flat plate-shaped material containing continuous reinforcing fibers and continuous thermoplastic resin fibers, and the longitudinal direction of the long flat plate-shaped material is 0.25 to 0.25, respectively, from the end. A central region of 30 mm, which does not contain continuous reinforcing fibers but contains end regions (A) containing continuous thermoplastic resin fibers, and is inside the end region (A) in the longitudinal direction of the long flat plate material. The proportion of continuous reinforcing fibers in (B) is 25 to 75% by volume of the central region (B), and the proportion of continuous reinforcing fibers in the entire region of the long flat plate material is 20 to 60% by volume. It is characterized in that the impregnation rate of the continuous thermoplastic resin fiber into the continuous reinforcing fiber is 30% or less.
With such a configuration, it is possible to provide a long flat plate-like material that is supple and can obtain a molded product with less fluffing after heating and pressurization. More specifically, in the present invention, by having the terminal region (A), an excellent effect is exhibited. That is, the long flat plate-shaped material of the present invention usually advances the impregnation of continuous thermoplastic resin fibers during heat processing, but the long flat plate-shaped material of the present invention has an end portion when, for example, hot pressing is performed. Even if the pressure is not sufficiently applied, it is possible to make it difficult to form a region that is not impregnated even after pressing. Further, when the long flat plate-shaped material is heat-processed, the continuous reinforcing fibers can be prevented from sticking out. Therefore, it is possible to prevent fluffing of the obtained molded product from occurring.

<Long flat plate material>
The present invention relates to a long flat plate material. FIG. 1 is a schematic view showing an example of a long flat plate-shaped material, in which 1 shows a long flat plate-shaped material, 2 shows a central region (B), and 3 shows a terminal region (A).
The long flat plate-shaped material of the present invention is sufficiently long in the longitudinal direction with respect to the width direction, for example, the longitudinal direction is preferably 3 times or more, more preferably 5 times or more, the width direction. It may be 10 times or more. The form of the long flat plate-shaped material includes what is called a tape-shaped or ribbon-shaped material.

In the present invention, the fiber length direction of the continuous reinforcing fiber and the fiber length direction of the continuous thermoplastic resin fiber are the longitudinal directions of the long flat plate material, respectively. However, when the continuous reinforcing fiber and / or the continuous thermoplastic resin fiber is twisted, the direction of the central axis of the twist is the fiber length direction. The same applies to the case where the continuous reinforcing fiber and / or the continuous thermoplastic resin fiber has undulations. In the present invention, the continuous reinforcing fiber and the continuous thermoplastic resin fiber are preferably linear. The term "straight line" as used herein means not only a straight line in a geometrical sense but also a range normally recognized as a straight line by those skilled in the art in the technical field of the present invention.

The length of the long flat plate material in the longitudinal direction is usually 10 cm or more, preferably 1 m or more, more preferably 100 m or more, still more preferably 1,000 m or more. The length of the long flat plate material in the longitudinal direction is preferably 20,000 m or less, more preferably 10,000 m or less, and further preferably 7,000 m or less.

The width (direction perpendicular to the longitudinal direction) of the long flat plate material is preferably 5 mm or more, more preferably 7 mm or more, further preferably 10 mm or more, and further preferably 12 mm or more. preferable. By setting it to the above lower limit value or more, fluffing of the molded product can be suppressed more effectively. The width of the long flat plate material is preferably 100 mm or less, more preferably 65 mm or less, further preferably 35 mm or less, and further preferably 33 mm or less. By setting the value to the upper limit or less, the long flat plate material becomes more supple.

The thickness of the long flat plate material is preferably 0.1 mm or more, more preferably 0.15 mm or more, and further preferably 0.2 mm or more. By setting the value to the lower limit or more, the wound body tends to be stable when the long flat plate-shaped material is wound around the core material. The thickness of the long flat plate material is preferably 0.5 mm or less, more preferably 0.45 mm or less, further preferably 0.4 mm or less, and 0.3 mm or less, 0. It may be 25 mm or less. By setting the value to the upper limit or less, the flexibility becomes higher.

The width-to-thickness ratio (width / thickness) of the long flat material is preferably 30 or more, more preferably 40 or more, further preferably 50 or more, and further 60 or more. It may be 70 or more. By setting it to the above lower limit value or more, fluffing of the molded product can be suppressed more effectively. The width-to-thickness ratio (width / thickness) of the long flat plate material is preferably 600 or less, more preferably 300 or less, further preferably 250 or less, and 200 or less. More preferably, it may be 180 or less, 160 or less, 140 or less. By setting the value to the upper limit or less, the width of the terminal region tends to be more stable.

The long flat plate-shaped material of the present invention has a region of 0.25 to 30 mm from the end in the longitudinal direction, and does not contain continuous reinforcing fibers, but contains continuous thermoplastic resin fibers (A) (FIG. 1). 3) is included. The width of the terminal region (A) (one length of 3 in FIG. 1) is 0.25 mm or more, preferably 0.5 mm or more, more preferably 1 mm or more, and 2 mm or more. Is even more preferable. By setting it to the above lower limit value or more, fluffing of the obtained molded product can be suppressed more effectively. Further, the terminal region (A) is preferably 20 mm or less, more preferably 15 mm or less, further preferably 12 mm or less, further preferably 10 mm or less, and further preferably 7 mm or less. It is even more preferably 5 mm or less. By setting the value to the upper limit or less, the physical properties of the obtained molded product become more stable.
In the long flat plate-shaped material of the present invention, there are two terminal regions (A), but the widths of the two terminal regions may be the same or different, but they may be the same. preferable.

As described above, the terminal region (A) does not contain continuous reinforcing fibers. Since the terminal region (A) does not contain the continuous reinforcing fibers in this way, fluffing of the molded product can be suppressed more effectively. However, not including continuous reinforcing fibers means that the content is "zero" in the geometric sense, and even if a small amount of continuous reinforcing fibers that are unintentionally contained in the manufacturing process is contained. It's a good idea.
Further, in the terminal region (A) of the long flat plate-shaped material of the present invention, the continuous thermoplastic resin fiber preferably occupies 90% by mass or more, more preferably 95% by mass or more, and 98% by mass. It is more preferable to occupy% or more.

The long flat plate-shaped material of the present invention has a central region (B) (2 in FIG. 1) inside the terminal region (A) in the longitudinal direction. The central region (B) contains continuous reinforcing fibers and continuous thermoplastic resin fibers. The width of the central region (B) (2 in FIG. 1) is preferably 4 mm or more, more preferably 5 mm or more, further preferably 6 mm or more, and even more preferably 7 mm or more. Productivity tends to be improved by setting the value to the lower limit or higher. The width of the central region (B) is preferably 34 mm or less, more preferably 30 mm or less, further preferably 28 mm or less, and may be 25 mm or less. By setting the value to the upper limit or less, the suppleness can be maintained more effectively. In the present invention, the central region (B) is preferably a length equal to or greater than at least one width (preferably each of both widths) of the terminal region (A), and the central region (B) is the terminal region (b. It is more preferable that the width is 3 mm or more larger than at least one width (preferably both widths) of A). Further, the upper limit of the difference between at least one width (preferably both widths) of the central region (B) and the terminal region (A) is preferably 25 mm or less, and more preferably 15 mm or less.

Further, in the long flat plate material of the present invention, the ratio of the lengths of the terminal region (A) and the central region (B) in the width direction (one length of 3 in FIG. 1: length of 2). Is preferably 1: 1 to 10, more preferably 1: 1 to 7, further preferably 1: 1 to 5, and preferably 1: 1.5 to 3.5. More preferred. Within such a range, the fluffing of the molded product is suppressed and the physical characteristics of the obtained molded product tend to be excellent in a well-balanced manner. When the widths of the two end regions (A) are different from each other, it is preferable that either the longer one or the shorter one satisfies the above range, and it is more preferable that both satisfy the above range.

In the long flat plate-shaped material of the present invention, the ratio of the continuous reinforcing fibers in the central region (B) is 25% by volume or more, preferably 30% by volume or more, preferably 32% by volume of the central region (B). It is more preferably 32% by volume or more, and more preferably 32% by volume or more. By setting the value to the lower limit or higher, a molded product having better mechanical properties can be obtained. The proportion of the continuous reinforcing fibers in the central region (B) is 75% by volume or less, preferably 65% by volume or less, more preferably 55% by volume or less, and 52% by volume or less. May be good. By setting the value to the upper limit or less, fluffing of the molded product can be suppressed more effectively.

Further, the proportion of the continuous reinforcing fibers in the entire region of the long flat plate-shaped material of the present invention is 20% by volume or more, preferably 25% by volume or more, and more preferably 30% by volume or more. By setting the value to the lower limit or higher, a molded product having better mechanical properties can be obtained. The proportion of the continuous reinforcing fibers in the entire region is 60% by volume or less, preferably 55% by volume or less, more preferably less than or equal to 45% by volume, further preferably 40% by volume. It is more preferably% or less, and may be 35% by volume or less. By setting the value to the upper limit or less, fluffing of the molded product can be suppressed more effectively.

In the long flat plate-shaped material of the present invention, the continuous thermoplastic resin fiber and the continuous reinforcing fiber preferably occupy 90% by volume or more, more preferably 95% by volume or more, and 98% by volume or more. It is even more preferable to occupy. Further, in the long flat plate-shaped material of the present invention, the continuous thermoplastic resin fiber and the continuous reinforcing fiber preferably occupy 90% by mass or more, more preferably 95% by mass or more, and 98% by mass. It is more preferable to occupy the above.

In the long flat plate-shaped material of the present invention, the impregnation rate of the continuous thermoplastic resin fiber into the continuous reinforcing fiber in the central region (B) is preferably 30% or less, more preferably 20% or less. It is more preferably% or less, further preferably 5% or less, further preferably 3% or less, and may be 1% or less. The impregnation rate is measured according to the method described in Examples described later. With such an impregnation rate, suppleness is achieved.

In the long flat plate-shaped material of the present invention, the dispersity of the continuous reinforcing fibers in the central region (B) is preferably 60% or more, more preferably 70% or more, and more preferably 80% or more. It is even more preferably 85% or more, and even more preferably more than 90%. The degree of dispersion is measured according to the method described in Examples described later. With such a dispersity, impregnation tends to be quick and productivity tends to be superior.

In the long flat plate-shaped material of the present invention, the impregnation rate, the degree of dispersion, the ratio of the continuously reinforced resin fibers, and the like may be substantially uniform in all the regions of the central region (B), which deviates from the gist of the present invention. These values may be composed of a plurality of regions having different values, as long as they do not.
Further, the long flat plate-shaped material shown in FIG. 1 is composed of two terminal regions (A) and a central region (B) continuous with the terminal region (A), but the terminal region (A) A third region may be provided between and the central region (B), or within the central region (B).

<Continuous reinforcement fiber>
The long flat plate material of the present invention contains continuous reinforcing fibers.
The continuous fiber means a fiber having a thickness of more than 50 mm, and a fiber having a length of more than 1 m is practical. The cross section of the reinforcing fiber in the present invention may be circular or flat. Only one type of continuous reinforcing fiber may be used, or two or more types may be used. The average fiber length of the continuous reinforcing fibers used in the present invention is not particularly limited, but is preferably in the range of 1 to 100,000 m, more preferably 100 to 10,000 m, from the viewpoint of improving molding processability. , More preferably 1,000 to 5,000 m.

The continuous reinforcing fibers used in the present invention include inorganic fibers such as glass fibers, carbon fibers, alumina fibers, boron fibers, ceramic fibers, metal fibers (steel fibers, etc.), and plant fibers (Kenaf, bamboo fibers, etc.). Included), aramid fiber, polyoxymethylene fiber, aromatic polyamide fiber, polyparaphenylene benzobisoxazole fiber, organic fiber such as ultrahigh molecular weight polyethylene fiber and the like. Among them, it is preferable to contain at least one of carbon fiber, aramid fiber and glass fiber, more preferably to contain at least one selected from carbon fiber and glass fiber, and to contain at least one of carbon fiber. More preferred.

As the continuous reinforcing fiber used in the preferred embodiment of the present invention, it is preferable to use one treated with a treatment agent. Examples of such treatment agents include focusing agents and surface treatment agents, and those described in paragraphs 093 and 0094 of Japanese Patent No. 4894982 are preferably adopted, and the contents thereof are incorporated in the present specification.

Examples of the surface treatment agent include those composed of functional compounds such as epoxy compounds, acrylic compounds, isocyanate compounds, silane compounds, and titanate compounds. For example, silane coupling agents and titanate cups. It is a ring agent or the like, and a silane-based coupling agent is preferable.

The converging agent is preferably at least one of an epoxy resin, a urethane resin, a silane compound, an isocyanate compound, a titanate compound, and a polyamide resin, and is preferably an epoxy resin, a urethane resin, a silane coupling agent, and water. It is more preferably at least one of an insoluble polyamide resin and a water-soluble polyamide resin, further preferably at least one of an epoxy resin, a urethane resin, a water-insoluble polyamide resin and a water-soluble polyamide resin, and a water-soluble polyamide resin. It is more preferable to have.

The amount of the treatment agent is preferably 0.001 to 1.5% by mass, more preferably 0.1 to 1.2% by mass, and 0.3 to 1.1% by mass of the continuous reinforcing fiber. It is more preferably%.

As a method for treating the continuous reinforcing fiber with a treatment agent, a known method can be adopted. For example, the continuous reinforcing fiber may be immersed in a solution of the treatment agent to attach the treatment agent to the surface of the continuous reinforcing fiber. The treatment agent can also be air blown onto the surface of the continuous reinforcing fibers. Further, the continuous reinforcing fiber which has already been treated with the surface treatment agent or the treatment agent may be used, or after washing off the commercially available surface treatment agent or the treatment agent, the desired amount of the treatment agent is obtained again. In addition, the surface treatment may be performed again.

<Continuous thermoplastic resin fiber>
The thermoplastic resin fiber used in the present invention is a continuous fiber containing a thermoplastic resin, and is derived from a thermoplastic resin composition containing a thermoplastic resin (the thermoplastic resin composition may consist only of a thermoplastic resin). It is a continuous fiber composed. Here, the continuous fiber means a fiber having a thickness of more than 50 mm, and a fiber having a length of more than 1 m is practical. The average fiber length of the continuous thermoplastic resin fiber used in the present invention is not particularly limited, but is preferably in the range of 1 to 100,000 m, more preferably 100 to 10 from the viewpoint of improving molding processability. It is 3,000 m, more preferably 1,000 to 5,000 m.
The cross section of the continuous thermoplastic resin fiber in the present invention may be circular or flat.
Only one type of continuous thermoplastic resin fiber may be used, or two or more types may be used.

The continuous thermoplastic resin fiber used in the present invention is usually produced by using a continuous thermoplastic resin fiber bundle in which continuous thermoplastic resin fibers are bundled, but the total per one continuous thermoplastic resin fiber bundle. The fineness is preferably 40 to 600 dtex, more preferably 50 to 500 dtex, and even more preferably 100 to 400 dtex. With such a range, the dispersed state of the continuous thermoplastic resin fiber in the obtained central region (B) becomes better. The number of fibers constituting the continuous thermoplastic resin fiber bundle is preferably 1 to 200 f, more preferably 5 to 100 f, further preferably 10 to 80 f, and preferably 20 to 50 f. Especially preferable. In particular, as will be described in detail later, when the material of the present invention is formed using a long flat plate-like material, the dispersed state of the continuous thermoplastic resin fiber becomes better.
The continuous thermoplastic resin fiber used in the present invention can be formed from a thermoplastic resin composition. The thermoplastic resin composition may consist of only one or more of the thermoplastic resins, or may contain other components.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, polyamide resins, polyethylene terephthalates, polyester resins such as polybutylene terephthalate, polycarbonate resins, polyoxymethylene resins (polyacetylene resins), polyetherketones, and polyetheretherketones. , Polyetherketone ketones, polyetherketone resins such as polyetheretherketoneketone, polyethersulfone resin, polyethersulfide resin, polyphenylene sulfide resin, thermoplastic polyetherimide, thermoplastic polyamideimide, total aromatic polyimide, semi-polyetherketone Thermoplastic polyimide resins such as aromatic polyimide can be used, and it is preferably at least one of a polyamide resin, a polyetherketone resin, and a polyphenylene sulfide resin, and more preferably contains at least a polyamide resin.

Examples of the polyamide resin used in the present invention include polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyhexamethylene terephthalamide (polyamide 6T), and polyhexamethylene isophthalamide. (Polyamide 6I), polyamide 66 / 6T, polyxylylene adipamide, polyxylylene sebacamide, polyxylylene dedecamide, polyamide 9T, polyamide 9MT, polyamide 6I / 6T and the like.

Among the above-mentioned polyamide resins, from the viewpoint of moldability and heat resistance, they are composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 50 mol% or more of the diamine-derived structural unit is xylylenedi. A polyamide resin derived from amine (hereinafter, may be referred to as "XD-based polyamide") is preferable.

When the polyamide resin is a mixture, the ratio of the XD-based polyamide in the polyamide resin is preferably 50% by mass or more, more preferably 80% by mass or more, and further 90% by mass or more, particularly. May be 95% by mass or more.

The XD-based polyamide is derived from xylylenediamine in a constituent unit derived from diamine, preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more. , More preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more of the constituent units derived from dicarboxylic acid. It is preferably derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
The xylylenediamine preferably contains at least metaxylylenediamine, more preferably composed of 30 to 100 mol% of metaxylylenediamine and 70 to 0 mol% of paraxylylenediamine, and 50 to 100 mol. More preferably, it consists of% metaxylylenediamine and 50-0 mol% paraxylylenediamine.

Examples of diamines other than m-xylylenediamine and paraxylylenediamine that can be used as the raw material diamine component of XD-based polyamide include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, and octa. An aliphatic diamine such as methylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis (amino) Methyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane , Bis (aminomethyl) decarin, bis (aminomethyl) tricyclodecane and other alicyclic diamines, bis (4-aminophenyl) ether, paraphenylenediamine, bis (aminomethyl) naphthalene and other diamines having an aromatic ring, etc. Can be exemplified, and one kind or a mixture of two or more kinds can be used.
When a diamine other than xylylenediamine is used as the diamine component, it is less than 50 mol%, preferably 30 mol% or less, more preferably 1 to 25 mol%, and particularly preferably 1 to 25 mol% of the constituent unit derived from diamine. It is used at a ratio of 5 to 20 mol%.

Examples of α, ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms that are preferable to be used as the raw material dicarboxylic acid component of the polyamide resin include succinic acid, glutaric acid, pimeric acid, suberic acid, adipic acid, and adipic acid. , Sebacic acid, undecanedioic acid, dodecanedioic acid and other aliphatic dicarboxylic acids can be exemplified, and one kind or a mixture of two or more kinds can be used. Among these, the melting point of the polyamide resin is suitable for molding. Since it is in the range, adipic acid and / or sebacic acid is preferable, and sebacic acid is more preferable.

Examples of the dicarboxylic acid component other than the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1, 3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3- Examples of naphthalenedicarboxylic acids such as naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid can be exemplified, and one kind or a mixture of two or more kinds can be used.

When a dicarboxylic acid other than α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is used as the dicarboxylic acid component, terephthalic acid and isophthalic acid may be used from the viewpoint of molding processability. When these are used, the ratio of terephthalic acid and isophthalic acid is preferably 30 mol% or less of the constituent unit derived from dicarboxylic acid, more preferably 1 to 30 mol%, and particularly preferably 5 to 20 mol%. is there.

In the present specification, the constituent unit composed of a diamine-derived constituent unit and a dicarboxylic acid-derived constituent unit contains these components as main components, but does not completely exclude other constituent units, and ε -It may contain constituent units derived from lactams such as caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid. In the present invention, the total of the diamine-derived structural unit and the dicarboxylic acid-derived structural unit in the polyamide resin preferably occupies 90% by mass or more, and more preferably 95% by mass or more of all the structural units.

In the first embodiment of the polyamide resin used in the present invention, 80 mol% or more of the diamine-derived structural unit is derived from m-xylylenediamine, and 80 mol% or more of the dicarboxylic acid-derived structural unit is derived from adipic acid. It is an aspect.
In the second embodiment of the polyamide resin used in the present invention, 10 to 90 mol% of the diamine-derived structural unit is derived from m-xylylenediamine, 90 to 10 mol% is derived from paraxylylenediamine, and the dicarboxylic acid. In this embodiment, 80 mol% or more of the constituent units of origin are derived from sebacic acid.

The polyamide resin used in the present invention preferably has a number average molecular weight (Mn) of 6,000 to 30,000, more preferably 8,000 to 28,000, and even more preferably 9,000 to 26, It is 000, more preferably 10,000 to 24,000, and even more preferably 11,000 to 22,000. Within such a range, the heat resistance, elastic modulus, dimensional stability, and molding processability of the obtained molded product become better.

The number average molecular weight (Mn) referred to here is the following formula from the terminal amino group concentration [NH ₂ ] (μ equivalent / g) and the terminal carboxyl group concentration [COOH] (μ equivalent / g) of the polyamide resin. It is calculated.
Number average molecular weight (Mn) = 2,000,000 / ([COOH] + [NH ₂ ])

The method for producing the polyamide resin can be described in paragraphs 0052 to 0053 of JP2014-173196A, and these contents are incorporated in the present specification.

In the present invention, the continuous thermoplastic resin preferably contains a thermoplastic resin having a melting point of 240 ° C. or lower (preferably a polyamide resin), and more preferably contains a thermoplastic resin having a melting point of 219 ° C. or lower. It is more preferable to contain a thermoplastic resin at 215 ° C. or lower. By setting it to the above lower limit value or less, the influence of moisture during molding can be reduced. The lower limit of the melting point of the thermoplastic resin is, for example, 170 ° C. or higher, preferably 190 ° C. or higher. Within such a range, the heat resistance tends to be superior.
The glass transition point (preferably polyamide resin) of the thermoplastic resin contained in the continuous thermoplastic resin fiber is preferably 50 to 100 ° C., more preferably 55 to 100 ° C., and particularly preferably 60 to 100 ° C. .. Within this range, the heat resistance of the obtained molded product tends to be better.
The glass transition point is a glass transition point measured by heating and melting the sample once to eliminate the influence of the thermal history on the crystallinity, and then raising the temperature again.
A differential scanning calorimeter (DSC) is used to measure the melting point and glass transition point, the sample amount is about 1 mg, nitrogen is flowed at 30 mL / min as the atmospheric gas, and the temperature rise rate is 10 ° C / min. The melting point can be obtained from the temperature of the peak top of the heat absorption peak observed when the mixture is heated from room temperature to a temperature higher than the expected melting point and melted. Next, the molten thermoplastic resin is rapidly cooled with dry ice and heated again to a temperature equal to or higher than the melting point at a rate of 10 ° C./min to determine the glass transition point and melting point.
As the differential scanning calorimetry (DSC), for example, DSC-60 manufactured by SHIMADZU CORPORATION can be used.

Further, various contained components may be included in the continuous thermoplastic resin fiber used in the present invention or the thermoplastic resin composition as a raw material thereof, as long as the object and effect of the present invention are not impaired. For example, elastomers, fillers other than continuous reinforcing fibers, antioxidants, stabilizers such as heat stabilizers, hydrolysis resistance improvers, weather stabilizers, matting agents, UV absorbers, nucleating agents, plasticizers, dispersants. , Flame retardants, antistatic agents, color inhibitors, antigelling agents, colorants, mold release agents, lubricants and other additives can be added. These details can be taken into consideration in paragraphs 0130 to 0155 of Japanese Patent No. 4894982, and these contents are incorporated in the present specification.
Further, a melt-moldable fluororesin having a functional group (for example, at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group) possessed by a surface treatment agent for continuous reinforcing fibers. May include. The details of the fluororesin can be referred to in paragraphs 0023 to 0053 of JP-A-2019-099955, and these contents are incorporated in the present specification.

In the present invention, 80% by mass or more (preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more) of the continuous thermoplastic resin fiber is a thermoplastic resin (preferably polyamide resin). Is exemplified.

The continuous thermoplastic resin fiber in the present invention is preferably a continuous thermoplastic resin fiber having a treatment agent for the continuous thermoplastic resin fiber on its surface. These details can be taken into account in paragraphs 0064 to 0065 of WO 2016/159340, the contents of which are incorporated herein by reference.
Since the continuous thermoplastic resin fiber has a surface treatment agent, it is possible to suppress the breakage of the continuous thermoplastic resin fiber in the manufacturing process of the long flat plate material and the subsequent processing process.
The amount of the surface treatment agent for the continuous thermoplastic resin fiber is, for example, 0.1 to 2.0% by mass of the thermoplastic resin fiber. The lower limit value is preferably 0.5% by mass or more, and more preferably 0.8% by mass or more. The upper limit value is preferably 1.8% by mass or less, more preferably 1.5% by mass or less. Within such a range, the dispersion of the continuous thermoplastic resin fiber becomes good, and a more homogeneous central region (B) can be easily obtained. Further, when manufacturing a long flat plate material, the continuous thermoplastic resin fibers generate frictional force with a machine or frictional force between fibers, and at that time, the continuous thermoplastic resin fibers may be cut. It is possible to prevent fiber cutting more effectively by setting the range to. Further, although mechanical stress is applied to the continuous thermoplastic resin fiber in order to obtain a homogeneous long flat plate material, it is possible to more effectively prevent the continuous thermoplastic resin fiber from being cut by the stress at that time. ..
The type of the surface treatment agent is not particularly specified as long as it has a function of converging continuous thermoplastic resin fibers and continuous reinforcing fibers. Treatment agents include ester compounds, alkylene glycol compounds, polyolefin compounds, phenyl ether compounds, polyether compounds, silicone compounds, polyethylene glycol compounds, amide compounds, sulfonate compounds, phosphate compounds, and carboxy compounds. A rate compound and a combination of two or more thereof are preferable, and an ester compound is more preferable.

The continuous thermoplastic resin fiber also preferably has a moisture content of 5% or less, more preferably 4% or less, further preferably 3% or less, and 2% or less, as measured according to JIS L 1096. Is more preferable. The lower limit may be 0%, but 0.001% or more is practical.

The method for treating the continuous thermoplastic resin fiber with a surface treatment agent is not particularly defined as long as the intended purpose can be achieved. For example, a continuous thermoplastic resin fiber in which a surface treatment agent is dissolved in a solution is added, and the treatment agent is attached to the surface of the continuous thermoplastic resin fiber. Alternatively, the treatment agent can be air-blown on the surface of the continuous thermoplastic resin fiber.

<Manufacturing method of long flat plate material>
The long flat plate material can be produced by a known method.
For example, the thermoplastic resin composition is melt-extruded by an extruder, extruded into a strand shape, and stretched while being wound by a roll to obtain a continuous thermoplastic resin fiber bundle wound on a wound body.
Each fiber is pulled out from the winding body of the continuous thermoplastic resin fiber obtained above and the winding body of the continuously reinforcing fiber prepared in advance, and is opened by air blowing while passing through a plurality of guides. While opening the fibers, the continuous thermoplastic resin fibers and the continuous reinforcing fibers are bundled. At this time, it is preferable to apply air blow while passing through a plurality of guides and to proceed with homogenization and control of the width dimension while preparing the flat plate shape. At the time of this air blow, the continuous reinforcing fibers and the continuous thermoplastic resin fibers may be surface-treated with the above-mentioned treatment agent, or the fibers of the fiber bundle which has been surface-treated in advance may be unwound from the winding body and used.

The long flat plate-shaped material according to the preferred embodiment of the present invention is preferably produced by using a continuous thermoplastic resin fiber bundle and a continuous reinforcing fiber bundle. The total fineness of the fibers used in the production of one long flat plate material (the total fineness of the continuous thermoplastic resin fibers used in the production of one long flat plate material and the total fineness of the continuous reinforcing fibers are added. The combined value) is preferably 1000 to 100,000 dtex, more preferably 1,500 to 50,000 dtex, further preferably 2,000 to 50,000 dtex, and particularly preferably 3,000 to 30,000 dtex.

The total number of fibers used in the production of one long flat plate material (the total number of fibers of continuous thermoplastic resin fibers and the total number of fibers of continuous reinforcing fibers) is the total number of fibers. It is preferably 100 to 100,000 f, more preferably 1,000 to 100,000 f, further preferably 1,500 to 70,000 f, and even more preferably 2,000 to 20,000 f. Within such a range, the mixed fiber property of the continuous thermoplastic resin fiber and the continuous reinforcing fiber in the long flat plate-shaped material is improved, and a molded product having better physical properties and texture can be obtained. In addition, there are few regions where any of the fibers is biased, and the fibers are more likely to be dispersed more uniformly.

In the present invention, for example, it is preferable that the fiber material of the continuous thermoplastic resin fiber or the continuous reinforcing fiber is opened and formed into a tape shape or a ribbon shape in a state where the fibers are parallel to each other.

<Use of long flat plate material>
The long flat plate-shaped material according to the preferred embodiment of the present invention can be wound around a core material (roll) as it is to form a wound body.
The long flat plate material can be used as various molding materials, and can also be processed into woven fabrics, braids, knitted fabrics, and the like.
The long flat plate-shaped material of the present invention can be molded by hot pressing, pultrusion molding, ultrasonic molding, laser molding, molding with a 3D printer, mold molding, internal pressure molding, or the like. In particular, since the long flat plate-shaped material of the present invention is supple, it is suitable for producing a molded product having recesses and protrusions.
The long flat plate-shaped material of the present invention includes, for example, parts and housings of personal computers, OA equipment, AV equipment, electric / electronic equipment such as mobile phones, optical equipment, precision equipment, toys, home / office electrical products, and further. It can be suitably used for parts such as automobiles, aircraft, and ships.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Thermoplastic resin>
MPXD10: Xylylene sebacamide resin synthesized according to the following synthesis example, melting point 213 ° C., number average molecular weight 15400
MXD6: Metaxylylene adipamide resin (manufactured by Mitsubishi Gas Chemical Company, Inc., grade S6001), melting point 237 ° C, number average molecular weight 16800
PA6: Polyamide resin 6, manufactured by Ube Industries, Ltd., 1022B, melting point 220 ° C.

<< Synthesis example of MPXD10 >>
10 kg (49.4 mol) of sebacic acid (TA grade manufactured by Ito Oil Co., Ltd.) and acetic acid in a reaction vessel equipped with a stirrer, a splitter, a total crimp, a thermometer, a dropping funnel and a nitrogen introduction tube, and a strand die. 11.66 g of sodium / sodium hypophosphite monohydrate (molar ratio = 1 / 1.5) was charged, and after sufficient nitrogen substitution, 170 while stirring the inside of the system under a small amount of nitrogen stream. It was heated and melted to ° C.
M-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc.) and para-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc.) have a molar ratio of 70/30 mixed xylylenediamine 6.647 kg (metaxylylenediamine 34. 16 mol (16 mol, paraxylylenediamine 14.64 mol) was added dropwise to molten sebacic acid under stirring, and the internal temperature was continuously raised to 240 ° C. over 2.5 hours while discharging the generated condensed water to the outside of the system. It was warm.
After completion of the dropping, the internal temperature was raised, and when the temperature reached 250 ° C., the pressure inside the reaction vessel was reduced, and the internal temperature was further raised to continue the melt polycondensation reaction at 255 ° C. for 20 minutes. Then, the inside of the system was pressurized with nitrogen, and the obtained polymer was taken out from the strand die and pelletized to obtain a polyamide resin MPXD10.
The melting point of the obtained polyamide resin was 213 ° C., and the number average molecular weight was 15400.

<Continuous reinforcement fiber>
<< Continuous Carbon Fiber (CF) >>
Made by Mitsubishi Rayon, Pyrofil-TR-50S-12000-AD, 8000dtex, number of fibers 12000f. The surface is treated with epoxy resin.
<< Continuous Glass Fiber (GF) >>
It is surface-treated with Nitto Boseki Co., Ltd., ECG 75 1/0 0.7Z, fineness 687dtex, number of fibers 400f, and sizing agent.

Examples 1 to 7 and Comparative Examples 1 and 2
<Manufacturing of continuous thermoplastic resin fibers>
The thermoplastic resin shown in Table 1 is melt-extruded by a single-screw extruder having a screw having a diameter of 30 mm, extruded into a strand shape from a die with 60 holes, stretched while being wound by a roll, and a fiber bundle of the continuous thermoplastic resin. Was wound around the winding body for 800 m. The melting temperature was the melting point of the continuous thermoplastic resin + 15 ° C.

<Surface treatment of thermoplastic resin fibers>
By filling a deep vat with an oil agent (polyoxyethylene hardened castor oil (Kao, Emanon 1112)) and installing a roller with a rubberized surface so that the lower part of the roller is in contact with the oil agent, the roller is rotated. , The oil was always attached to the roller surface. The oil agent was applied to the surface of the continuous thermoplastic resin fiber by bringing the continuous thermoplastic resin fiber into contact with the roller.

<Measurement method of moisture content of continuous thermoplastic resin fiber>
The surface-treated continuous thermoplastic resin fiber was measured according to JIS L 1096, and the water content was measured.

<Manufacturing of long flat plate materials>
The long flat plate material was produced according to the following method.
Each fiber is pulled out from a continuous thermoplastic resin fiber winding body having a length of 1 m or more and a continuous reinforcing fiber winding body having a length of 1 m or more, and the fibers are opened by air blowing while passing through a plurality of guides. Was done. While opening the fibers, continuous thermoplastic resin fibers and continuous reinforcing fibers were bundled, and air blow was applied while passing through a plurality of guides to promote homogenization.
The obtained long flat plate-shaped material had a fineness of about 13000 dtex and a number of fibers of about 13500 f when using carbon fiber, and a fineness of about 15000 dtex and a number of fibers of about 10000 f when using glass fiber. The obtained long flat plate-shaped material was wound around a core material having a diameter of 5 cm.
In Example 4, the long flat plate-shaped material described in Example 1 was slightly impregnated as shown in Table 1 by heating both sides with a heating roll before winding it around the core material.
The materials obtained were all supple.

<Dimension measurement of long flat material>
The width of the end region (A) and the width of the center region (B) of the long flat plate-shaped material were measured using calipers in the state of the wound body wound around the core material. The measurement was performed at any 10 locations and calculated as a number average value. The width of the terminal region in the table is the sum of both ends. Moreover, the width of the terminal region (A) was almost the same.
The thickness of the long flat plate-shaped material was linearly unwound 1 m from the wound body without applying vibration or twist, measured at any 10 locations with a micrometer, and calculated as a number average value.

<Measurement method of impregnation rate>
The impregnation rate of the central region (B) of the long flat plate material was measured as follows.
The long flat plate material is cut to an appropriate length, the terminal region (A) is removed, the surface is embedded with epoxy resin, the surface corresponding to the cross section of the long flat plate material is polished, and the cross-sectional view is shown in ultra-depth. Photographed using a color 3D shape measuring microscope. With respect to the obtained cross-sectional photograph, a region impregnated with the thermoplastic resin of the continuous reinforcing fiber was selected using image analysis software ImageJ, and the area thereof was measured. The impregnation rate is shown as a region / cross section (unit%) impregnated with the thermoplastic resin of the continuous reinforcing fiber.
As the ultra-depth color 3D shape measurement microscope, VK-9500 (controller unit) / VK-9510 (measurement unit) (manufactured by KEYENCE) was used.

<Measurement method of dispersion>
The dispersity of the central region (B) of the long flat plate material was measured as follows.
After cutting the long flat plate material to an appropriate length and removing the terminal region (A), it is embedded with epoxy resin, and the cross section perpendicular to the longitudinal direction of the long flat plate material is polished to obtain a cross-sectional view. Photographed using an ultra-deep color 3D shape measuring microscope. As shown in FIG. 2, in the photographed image, six auxiliary lines are drawn radially at equal intervals, and the lengths of the continuous reinforcing fiber regions on each auxiliary line are a1, a2, a3 ... ai (i = n). I surveyed. In addition, the length of the region of the continuous thermoplastic resin fiber on each auxiliary line was measured as b1, b2, b3 ... bi (i = m). Based on the result, the degree of dispersion was calculated by the following formula.
As the ultra-depth color 3D shape measurement microscope, VK-9500 (controller unit) / VK-9510 (measurement unit) (manufactured by KEYENCE) was used.

<Moldability (fluffing)>
A long flat plate material was cut to 150 mm, and 20 layers were laminated in the same direction on a smooth aluminum plate. A 1 mm thick aluminum spacer was placed around it so as not to come into contact with the long flat plate-like material, a smooth aluminum plate was applied from above, and press molding was performed at a melting point of + 15 ° C. at 0.3 MPa for 1 minute. The moldability (fluffing) of the obtained molded product was visually evaluated as follows. The test was performed 10 times for each example, and the average value was calculated.
A: No fluffing B: There were 1-2 fluffing C: There were 3-5 fluffing D: There were 6 or more fluffing

<Moldability (foaming)>
From the above molded product, the moldability (foaming) was visually evaluated as follows.
A: There was no noticeable foaming.
B: There was a molded product with foam on both sides.
C: There was a molded product whose entire surface was foamed.

In Table 1 above, Vf indicates the volume ratio (volume%) of the continuous reinforcing fibers in each region.
As is clear from the above results, the long flat plate-like material of the present invention effectively suppressed fluffing.

1 Long flat plate material 2 Central area (B)
3 Terminal region (A)

Claims (10)

A long flat plate material containing continuous reinforcing fibers and continuous thermoplastic resin fibers.
The longitudinal direction of the long flat plate material is a region of 0.25 to 30 mm from the end, and includes a terminal region (A) containing continuous thermoplastic resin fibers without containing continuous reinforcing fibers.
The proportion of the continuous reinforcing fibers in the central region (B) inside the terminal region (A) in the longitudinal direction of the long flat plate material is 25 to 75% by volume of the central region (B).
The proportion of continuous reinforcing fibers in the entire region of the long flat plate material is 20 to 60% by volume.
A long flat plate-like material having an impregnation rate of the continuous thermoplastic resin fiber into the continuous reinforcing fiber of 30% or less. The long flat plate-like material according to claim 1, wherein the continuous thermoplastic resin fiber contains a polyamide resin. The continuous thermoplastic resin fiber is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 50 mol% or more of the diamine-derived structural unit contains a polyamide resin derived from xylylenediamine. Item 2. The long flat plate-like material according to Item 1. The long flat plate-shaped material according to any one of claims 1 to 3, wherein the moisture content of the continuous thermoplastic resin fiber measured according to JIS L 1096 is 4% or less. The long flat plate-like material according to any one of claims 1 to 4, wherein the continuous thermoplastic resin fiber contains a thermoplastic resin having a melting point of 240 ° C. or lower. The long flat plate-like material according to any one of claims 1 to 5, wherein the continuous reinforcing fiber contains at least one selected from carbon fiber and glass fiber. The long flat plate-like material according to any one of claims 1 to 6, wherein the dispersity of the continuous reinforcing fibers in the central region (B) is 60% or more. The long flat plate-like material according to any one of claims 1 to 7, wherein the impregnation rate of the continuous thermoplastic resin fiber in the central region (B) is 10% or less. The long flat plate material according to any one of claims 1 to 8, wherein the width of the long flat material is 5 to 100 mm. The long flat plate material according to any one of claims 1 to 9, wherein the thickness of the long flat material is 0.1 to 0.5 mm.