WO2015080019A1

WO2015080019A1 - Carbon fiber composite laminate

Info

Publication number: WO2015080019A1
Application number: PCT/JP2014/080746
Authority: WO
Inventors: 保西澤; 昌次伊藤; 田中　一也
Original assignee: 三菱レイヨン株式会社
Priority date: 2013-11-28
Filing date: 2014-11-20
Publication date: 2015-06-04
Also published as: JP6327127B2; JP2015127141A; JP6330632B2; JP2015127140A

Abstract

　The present invention provides a carbon fiber composite laminate having excellent balance among low linear expansion, surface attractiveness, and press formability. A carbon fiber composite laminate having at least a five-layer structure, wherein the laminate has a thermoplastic resin layer (A) containing 30-200 mass parts of inorganic filler to 100 mass parts of the thermoplastic resin, a carbon fiber layer (B), and a thermoplastic resin layer (C) having a thermoplastic resin as a main component and not containing the inorganic filler. The layers are layered in the order A/B/C/B/A, the maximum diameter of the carbon fiber bundles in layer (B) is 10-1000 µm, and the average length of the carbon fibers is 0.1 mm or more, and less than 5 mm.

Description

Carbon fiber composite laminate

The present invention relates to a laminate in which a thermoplastic resin and carbon fiber are combined.

In recent years, there is a growing need for molded products that are lightweight, high-strength, and excellent in heat resistance, such as housings for large electrical appliances, automobile and railway interior materials, and exterior materials. In particular, such a molded article is required to have a low responsiveness to dimensional change with respect to heat, that is, a low linear expansion material. Based on such a background, a low linear expansion material in which a thermoplastic resin and inorganic fibers are combined has been proposed.

For example, Patent Document 1 (Japanese Patent Laid-Open No. 2010-254276) discloses a laminate for an automobile exterior having a carbon fiber reinforced layer containing carbon fibers and a thermoplastic resin layer and having a specific linear expansion coefficient. And discloses that the thermoplastic resin layer is a polyolefin-based resin, and various inorganic fillers that are fillers may be included as additives.

Patent Document 2 (Japanese Patent Application Laid-Open No. 2008-45040) discloses that a main layer is composed of a thermoplastic resin (A) and a filler (B) composed of glass fiber and at least one filler other than glass fiber. Thus, there is disclosed a single-layer or multi-layer low-linear expansion extruded sheet in which the main layer contains the filler (B) in a specific ratio and has a specific linear expansion coefficient and Charpy impact strength.

Patent Document 3 (Japanese Patent Application Laid-Open No. 2007-169561) discloses (A) polypropylene resin, (B) elastomer, (C) talc, and (D) fine carbon fibers having a fiber diameter of 100 nm or less. A molded body is disclosed, which is characterized in that the average fiber length of the component (D) in the molded body is 2.5 μm or more.

JP 2010-254276 A JP 2008-45040 A JP 2007-169561 A

In the laminate disclosed in Patent Document 1, an attempt is made to express low linear expansion with a single carbon fiber reinforced layer, and a known filler or reinforcing fiber is further contained to improve the overall warpage. It is said that a thermoplastic resin layer may be provided. However, in this configuration, the formability (press formability) when the laminate is subjected to secondary processing by thermoforming or vacuum forming is not sufficient, and it is not sufficient from the viewpoint of reducing the weight of the laminate itself. Further, no consideration is given to the appearance failure due to the unevenness of the surface of the laminate depending on the carbon fiber used, and there is room for improvement in the appearance of the laminate.

Since the sheet disclosed in Patent Document 2 contains a considerable amount of glass fiber and filler in the main layer, it has low linear expansion, but press formability during secondary processing, particularly drawing die The following ability is not sufficient, and both formability and low linear expansion are not achieved.

The molded body disclosed in Patent Document 3 is excellent in press formability at the time of secondary processing, but low linear expansion is not sufficient because carbon fiber is too fine, and formability and low linear expansion Are not compatible.

That is, in the prior art, it has not been possible to obtain a laminate having a balance between low linear expansion, good surface appearance and followability to a drawing die during press molding.

An object of the present invention is to solve the above-mentioned conventional problems and to provide a carbon fiber composite laminate excellent in the balance between low linear expansion, good surface appearance and press formability.

As a result of intensive studies in view of the above problems, the present inventors have found that a specific carbon fiber composite laminate is excellent in balance between low linear expansion, good surface appearance and press formability, and completed the present invention. It came to do.

The carbon fiber composite laminate of the first aspect of the present invention (hereinafter sometimes referred to as “laminate of the first aspect”) is as follows.
[1] A carbon fiber composite laminate having at least a five-layer structure, wherein the thermoplastic resin layer (A layer) contains 30 to 200 parts by mass of an inorganic filler with respect to 100 parts by mass of the thermoplastic resin; A carbon fiber layer (B layer) and a thermoplastic resin layer (C layer) containing a thermoplastic resin as a main component and not containing the inorganic filler are provided in the order of A layer / B layer / C layer / B layer / A layer. And
A carbon fiber composite laminate in which the maximum diameter of the carbon fiber bundle in the B layer is 10 μm or more and 1000 μm or less, and the average fiber length of the carbon fibers is 0.1 mm or more and less than 5 mm.
[2] The thermoplastic resin used for the A layer and the C layer is at least one resin selected from the group consisting of a polyolefin resin, a polycarbonate resin, a polyamide resin, and a polyester resin. The carbon fiber composite laminate described.
[3] The carbon fiber composite laminate according to [1] or [2], wherein the inorganic filler used in the A layer is a plate-like particle having an aspect ratio of 20 or more and 500 or less.
[4] The carbon fiber composite laminate according to any one of [1] to [3], wherein the B layer is a layer formed using carbon fiber mat or carbon fiber paper as a carbon fiber material.
[5] The melt mass flow rate R _A (g / 10 min) of the thermoplastic resin of the A layer and the melt mass flow rate R _C (g / 10 min) of the thermoplastic resin of the C layer at the same temperature and the same load, The carbon fiber composite laminate according to any one of [1] to [4], which has a relationship of R _A ≧ _RC .
[6] The carbon fiber composite laminate according to any one of [1] to [5], wherein the maximum cross-sectional height (Rt) of the surface of the A layer is 3 μm or less.

The carbon fiber composite laminate of the second aspect of the present invention (hereinafter sometimes referred to as “laminate of the second aspect”) is as follows.
[1] A carbon fiber composite laminate having at least a five-layer structure, wherein the thermoplastic resin layer (A layer) contains 30 to 200 parts by mass of an inorganic filler with respect to 100 parts by mass of the thermoplastic resin; A layer / B layer / D layer of carbon fiber layer (B layer) and thermoplastic resin layer (D layer) containing 100 parts by mass or less of inorganic filler with respect to 100 parts by mass of thermoplastic resin / B layer / A layer in this order,
A carbon fiber composite laminate in which the maximum diameter of the carbon fiber bundle in the B layer is 10 μm or more and 1000 μm or less, and the average fiber length of the carbon fibers is 0.1 mm or more and less than 5 mm.
[2] The thermoplastic resin used for the A layer and the D layer is at least one resin selected from the group consisting of a polyolefin resin, a polycarbonate resin, a polyamide resin, and a polyester resin. The carbon fiber composite laminate described.
[3] The carbon fiber composite laminate according to [1] or [2], wherein the inorganic filler used in the A layer and the D layer is a plate-like particle having an aspect ratio of 20 or more and 500 or less.
[4] The carbon fiber composite laminate according to any one of [1] to [3], wherein the B layer is a layer formed using carbon fiber mat or carbon fiber paper as a carbon fiber material.
[5] The carbon fiber composite laminate according to any one of [1] to [4], wherein a content ratio of the inorganic filler in the D layer is equal to or less than a content ratio of the inorganic filler in the A layer.
[6] The carbon fiber composite laminate according to any one of [1] to [5], wherein the maximum cross-sectional height (Rt) of the surface of the A layer is 3 μm or less.

The carbon fiber composite laminate of the third aspect of the present invention (hereinafter sometimes referred to as “laminate of the third aspect”) is as follows.
[1] A carbon fiber composite laminate having at least a three-layer structure, wherein 30 to 200 parts by mass of plate-like inorganic particles having an aspect ratio of 20 to 500 with respect to 100 parts by mass of the thermoplastic resin. It has a thermoplastic resin layer (E layer) and a carbon fiber layer (B layer), and the E layer is a front and back layer, and the maximum diameter of the carbon fiber bundle in the B layer is 10 μm or more and 1000 μm or less. And an average fiber length of the carbon fibers is 0.1 mm or more and less than 5 mm.
[2] The carbon according to [1], wherein the thermoplastic resin used for the E layer is at least one resin selected from the group consisting of a polyolefin resin, a polycarbonate resin, a polyamide resin, and a polyester resin. Fiber composite laminate.
[3] The carbon fiber composite laminate according to [1] or [2], wherein the B layer is a layer formed using carbon fiber mat or carbon fiber paper as a carbon fiber material.
[4] The carbon fiber composite laminate according to any one of [1] to [3], wherein a maximum cross-sectional height (Rt) of the surface of the E layer is 3 μm or less.

In the following, the laminate of the first aspect, the laminate of the second aspect, and the laminate of the third aspect are collectively referred to as “the laminate of the present invention”.

According to the present invention, a carbon fiber composite having an excellent balance of low linear expansion, good surface appearance and press formability, and suitable for a casing of a large electrical appliance, an interior material of an automobile or a railway, an exterior material, etc. A laminate can be provided.

[I] Laminate of the first embodiment [thermoplastic resin layer (A layer)]
The thermoplastic resin layer (A layer) constituting the laminate of the first aspect is a layer containing 30 to 200 parts by mass of an inorganic filler with respect to 100 parts by mass of the thermoplastic resin, and the first aspect. It exists as a substantial front and back layer of the laminate.

[Thermoplastic resin]
The thermoplastic resin that can be used for the A layer is preferably at least one resin selected from the group consisting of polyolefin resins, polycarbonate resins, polyamide resins, and polyester resins. These resins may be used alone or in combination of two or more.
For example, by using a polyolefin-based resin, the laminate of the first aspect is excellent in moldability and particularly in impact resistance. Further, by using a polycarbonate resin, a polyamide resin, or a polyester resin, the laminate of the first aspect is excellent in moldability and particularly excellent in heat resistance.

<Polyolefin resin>
The polyolefin resin that can be used for the A layer is not particularly limited, and is a homopolymer obtained by polymerizing an α-olefin such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene. Or a copolymer is mentioned. Also, two or more of these homopolymers or copolymers can be mixed. Among these, it is preferable to use a polypropylene resin or a polyethylene resin, and it is particularly preferable to use a polypropylene resin from the viewpoint of lightness.

(Polypropylene resin)
The polypropylene-based resin used for the A layer is a resin in which propylene exceeds 50 mol%, preferably 70 mol% or more, more preferably 90 mol% or more, among the constituent monomers. Propylene homopolymer), or one of propylene and an α-olefin such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, or the like Examples thereof include random copolymers and block copolymers with two or more kinds. Among these, homopolypropylene is more preferably used from the viewpoint of rigidity and heat resistance.

In addition, the polypropylene resin may be one in which a part of its molecular structure is modified with acid or alkali. Specific examples include maleic acid-modified polypropylene resins and amine-modified polypropylene resins.

The polypropylene resin preferably has an isotactic pentad fraction (mmmm fraction) exhibiting stereoregularity of 80 to 99%. The isotactic pentad fraction of the polypropylene resin is more preferably 83 to 98%, still more preferably 85 to 97%. If the isotactic pentad fraction is within such a range, there is little possibility that the strength of the laminate of the first aspect is lowered. The upper limit of the isotactic pentad fraction is defined by the upper limit that can be obtained industrially at the present time, but this is not the case when a more regular resin is developed in the industrial level in the future. is not.
The isotactic pentad fraction (mmmm fraction) is the same direction for all five methyl groups that are side chains with respect to the main chain of carbon-carbon bonds composed of any five consecutive propylene units. Means the three-dimensional structure located at or its proportion. Signal assignment of the methyl group region is as follows. It conforms to Zambelli et al (Macromolecules 8,687, (1975)).

The melt mass flow rate R _A of the polypropylene resin used for the A layer is measured in accordance with JIS K7210 (1999) under conditions of a temperature of 230 ° C. and a load of 2.16 kgf, and is 0.1 g / 10 min or more and 60 g / 10 min or less. It is preferably 0.1 g / 10 min or more and 30 g / 10 min or less, more preferably 0.1 g / 10 min or more and 20 g / 10 min or less. When R _A is 0.1 g / 10 min or more, followability to the mold during press molding of the laminate of the first aspect becomes easy. On the other hand, when it is 60 g / 10 min or less, there is no risk of flowing out of the mold due to pressurization during press molding of the laminate of the first aspect, and resin impregnation between carbon fibers and fillers is facilitated.

Mw / Mn, which is a parameter indicating the molecular weight distribution of the polypropylene resin used for the A layer, is measured by a GPC (gel permeation chromatography) method according to JIS K7252-1 (2008), and is 1.5 or more and 10 Or less, more preferably 1.5 or more and 8 or less, and particularly preferably 1.5 or more and 6 or less. The smaller the Mw / Mn, the narrower the molecular weight distribution. When the Mw / Mn is 1.5 or more, the followability to the mold during press molding of the laminate of the first aspect becomes easy. On the other hand, when Mw / Mn is 10 or less, various mechanical properties of the laminate of the first aspect can be satisfied.

The production method of the polypropylene resin used for the A layer is not particularly limited, and a known polymerization method using a known olefin polymerization catalyst, for example, a multisite catalyst represented by a Ziegler-Natta type catalyst or a metallocene system. Examples thereof include a slurry polymerization method, a melt polymerization method, a bulk polymerization method, a gas phase polymerization method using a single site catalyst represented by a catalyst, and a bulk polymerization method using a radical initiator.

(Polyethylene resin)
The polyethylene-based resin used for the layer A is a resin in which ethylene is more than 50 mol%, preferably 70 mol% or more, more preferably 90 mol% or more among the constituent monomers. , Linear low density polyethylene, linear ultra low density polyethylene, medium density polyethylene, high density polyethylene, and copolymers based on ethylene, ie, ethylene and propylene, butene-1, pentene-1, hexene 1, α-olefins such as heptene-1 and octene-1; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; conjugates One or two selected from unsaturated compounds such as dienes and non-conjugated dienes It includes copolymers or multicomponent copolymer or a mixture composition with more comonomers.

Among these polyethylene resins, at least one polyethylene resin selected from low density polyethylene, linear low density polyethylene, and high density polyethylene is preferable, and the strength and heat resistance of the laminate of the first aspect are improved. High-density polyethylene is more preferable from the viewpoint.

The melt mass flow rate _RA of the polyethylene resin used for the A layer is measured in accordance with JIS K7210 (1999) under conditions of a temperature of 190 ° C. and a load of 2.16 kgf, and is 0.05 g / 10 min or more and 30 g / 10 min or less. It is preferably 0.1 g / 10 min or more and 20 g / 10 min or less, more preferably 1 g / 10 min or more and 20 g / 10 min or less. When _RA is 0.05 g / 10 min or more, the followability to the mold during press molding of the laminate of the first aspect becomes easy. On the other hand, when it is 30 g / 10 min or less, there is no fear of flowing out of the mold due to pressurization during press molding of the laminate of the first aspect, and resin impregnation between carbon fibers and fillers becomes easy.

The density of the polyethylene resin used for the A layer can be measured using a density gradient tube method according to JIS K7112 (1999), and is preferably 0.910 to 0.970 g / cm ^3. It is more preferably 930 to 0.970 g / cm ³ , further preferably 0.940 to 0.970 g / cm ³ . When the density is 0.910 g / cm ³ or more, the laminate of the first aspect satisfies various mechanical properties. On the other hand, if it is 0.970 g / cm < ³ > or less, the laminated body of a 1st aspect can maintain lightness.

The production method of the polyethylene resin used for the A layer is not particularly limited, and a known polymerization method using a known olefin polymerization catalyst, for example, a multisite catalyst or a metallocene catalyst represented by a Ziegler-Natta type catalyst. And a polymerization method using a single site catalyst represented by. As a polymerization method of the polyethylene resin, there are a one-stage polymerization, a two-stage polymerization, or a multistage polymerization more than that.

<Polycarbonate resin>
The polycarbonate resin used for the A layer may be either a homopolymer or a copolymer. Further, the polycarbonate-based resin may have a branched structure, a linear structure, or a mixture of a branched structure and a linear structure. A plurality of polycarbonate resins may be mixed and used.
The so-called polyester carbonate resin (resin having both ester bond and carbonate bond in the molecular chain) is also included in the polycarbonate resin.

Representative examples of the dihydric alcohol (diol) constituting the polycarbonate resin used in the A layer include bisphenols. In particular, 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is preferably used.
In addition, a diol other than bisphenol A may be used alone, or a polycarbonate resin using a plurality of diols may be used, and any of an aromatic diol, an aliphatic diol, and an alicyclic diol may be used.

The melt mass flow rate _RA of the polycarbonate resin used for the A layer is measured under the conditions of a temperature of 300 ° C. and a load of 1.2 kgf in accordance with JIS K7210 (1999), and is 1 g / 10 min or more and 40 g / 10 min or less. It is preferably 2 g / 10 min or more and 35 g / 10 min or less, more preferably 3 g / 10 min or more and 30 g / 10 min or less. When _RA is 1 g / 10 min or more, the followability to the mold during press molding of the laminate of the first aspect becomes easy. On the other hand, when it is 40 g / 10 min or less, there is no fear of flowing out of the mold due to pressurization during press molding of the laminate of the first aspect, and resin impregnation between carbon fibers and fillers is facilitated.

The method for producing the polycarbonate resin used for the A layer is not particularly limited, and a known polymerization method such as a phosgene method, a transesterification method, a pyridine method and the like can be mentioned.

<Polyamide resin>
The polyamide-based resin used for the A layer is preferably an aliphatic polyamide, obtained by ring-opening homopolymerization of ω-amino acids, obtained by ring-opening copolymerization of different ω-amino acids, or by copolymerization of diamine and dicarboxylic acid. Any of those obtained may be used. An aromatic polyamide or an aromatic-aliphatic polyamide can also be used.

In the case of aliphatic polyamide, the melt mass flow rate _RA of the polyamide-based resin used for the A layer is measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kgf in accordance with JIS K7210 (1999), 0.1 g / 10 min or more, It is preferably 60 g / 10 min or less, more preferably 0.5 g / 10 min or more and 30 g / 10 min or less, and particularly preferably 1 g / 10 min or more and 20 g / 10 min or less. When R _A is 0.1 g / 10 min or more, followability to the mold during press molding of the laminate of the first aspect becomes easy. On the other hand, when it is 60 g / 10 min or less, there is no risk of flowing out of the mold due to pressurization during press molding of the laminate of the first aspect, and resin impregnation between carbon fibers and fillers is facilitated.

The production method of the polyamide-based resin used for the A layer is not particularly limited, and a known polymerization method can be employed.

<Polyester resin>
The polyester-based resin that can be used for the A layer is preferably an aromatic polyester-based resin from the viewpoint of heat resistance and moldability, and specifically, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, and the like. Can be mentioned.

The melt mass flow rate _RA of the polyester-based resin used for the A layer is measured under conditions of a temperature of 230 ° C. and a load of 2.16 kgf in accordance with JIS K7210 (1999), and is 0.1 g / 10 min or more and 60 g / 10 min or less. It is preferably 0.5 g / 10 min or more and 30 g / 10 min or less, more preferably 1 g / 10 min or more and 20 g / 10 min or less. When R _A is 0.1 g / 10 min or more, followability to the mold during press molding of the laminate of the first aspect becomes easy. On the other hand, when it is 60 g / 10 min or less, there is no risk of flowing out of the mold due to pressurization during press molding of the laminate of the first aspect, and resin impregnation between carbon fibers and fillers is facilitated.

The manufacturing method of the polyester resin used for the A layer is not particularly limited, and a known polymerization method can be employed.

[Inorganic filler]
The A layer of the laminate of the first aspect contains 30 to 200 parts by mass of an inorganic filler with respect to 100 parts by mass of the thermoplastic resin.
The content of the inorganic filler is preferably 30 parts by mass or more and 160 parts by mass or less, and particularly preferably 30 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
By containing 30 parts by mass or more of the inorganic filler with respect to 100 parts by mass of the thermoplastic resin, the laminated body of the first aspect contributes to the improvement of low linear expansion. Moreover, it contributes to the improvement of the moldability of the laminated body of a 1st aspect by containing an inorganic filler 200 mass parts or less with respect to 100 mass parts of thermoplastic resins.

Specific examples of the inorganic filler used in the A layer include metal carbonates such as calcium carbonate, magnesium carbonate, and barium carbonate, metal sulfates such as calcium sulfate, barium sulfate, and magnesium sulfate, calcium oxide, magnesium oxide, Examples thereof include metal oxides such as zinc oxide, alumina, silica and titanium oxide, metal chlorides such as sodium chloride, magnesium chloride, silver chloride and calcium chloride, and clay minerals such as talc, clay, mica and montmorillonite.
Among these, talc or mica is preferably used from the viewpoint of low linear expansion and cost, and mica is particularly preferable.

The average particle size of the inorganic filler used in the A layer is preferably 1 μm or more and 500 μm or less, more preferably 5 μm or more and 300 μm or less, and particularly preferably 5 μm or more and 100 μm or less.
When the average particle size of the inorganic filler is 1 μm or more, the laminated body of the first aspect contributes to improvement of low linear expansion. Moreover, if an average particle diameter is 500 micrometers or less, it will contribute to the improvement of the surface external appearance of the laminated body of a 1st aspect.
In the present invention, the “average particle diameter of the inorganic filler” is, for example, a value obtained by averaging the minor axis and the major axis of a two-dimensional projection image when the filler is projected from a certain direction using an image analyzer. Can be calculated as a value obtained by further averaging the maximum value and the minimum value after calculating the projection images from 10 different directions.

The inorganic filler used in the A layer is preferably so-called plate-like particles having a relatively large aspect ratio (major axis / minor axis value). Specifically, the aspect ratio is preferably 20 or more and 500 or less, more preferably 20 or more and 300 or less, and particularly preferably 20 or more and 100 or less.
If the aspect ratio of the inorganic filler is 20 or more, the laminate of the first aspect is excellent in low linear expansion. On the other hand, if the aspect ratio of the inorganic filler is 500 or less, the laminate of the first aspect is excellent in surface appearance.
As for the aspect ratio of the inorganic filler, for example, the ratio of the minor axis to the major axis (major axis / minor axis) of the two-dimensional projection image when the filler is projected from a certain direction using an image analysis device is different from ten directions. Can be calculated as an average value.

The inorganic filler used for the A layer may be surface-treated. The surface treatment method is not particularly limited, and examples thereof include a method using a surface treatment agent such as a general silane coupling agent. By surface-treating the inorganic filler, effects such as improvement of the dispersibility of the inorganic filler in the thermoplastic resin and prevention of the inorganic filler from falling off from the A layer can be obtained.

These inorganic fillers may be used alone or in combination of two or more different materials, particle sizes, aspect ratios, presence / absence of surface treatment, type of surface treatment agent, and the like.

[Other ingredients]
When the laminate of the first aspect requires flame retardancy, the A layer can further contain a flame retardant. The flame retardant used in the A layer is not particularly limited, such as phosphorus flame retardants such as various condensed phosphate esters, nitrogen flame retardants such as melamine, phosphorus / nitrogen flame retardants such as phosphazene, brominated aromatic compounds, etc. One or more known flame retardants such as bromine flame retardants and antimony flame retardants such as antimony trioxide can be appropriately selected and used.

When the flame retardant is contained in the A layer, the content is preferably 20 parts by mass or more and 60 parts by mass or less, and 25 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. Is more preferably 30 parts by mass or more and 60 parts by mass or less.
By containing 20 parts by mass or more of the flame retardant with respect to 100 parts by mass of the thermoplastic resin, the laminate of the first aspect can exhibit excellent flame retardancy. On the other hand, by containing 60 parts by mass or less of the flame retardant with respect to 100 parts by mass of the thermoplastic resin, the laminate of the first aspect satisfies various mechanical properties.

In addition to the components described above, the A layer may appropriately contain other thermoplastic resins and additives generally added to the resin composition as long as the characteristics and effects of the present invention are not impaired. Specific examples of additives include pigments such as carbon black, weather resistance stabilizers, heat resistance stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, antiaging agents, and antioxidants. , Light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents or coloring agents.

[Method for producing layer A]
As will be described later, the laminate of the first embodiment is prepared by laminating the thermoplastic resin sheet constituting the A layer, the carbon fiber material constituting the B layer, and the thermoplastic resin sheet constituting the C layer, respectively. Can be obtained.
It does not specifically limit as a preparation method of the thermoplastic resin sheet which comprises A layer, A well-known melt film-forming method, such as a T die-cast method, a calendar method, a press method, is employable.

More specifically, the thermoplastic resin, the inorganic filler, and, if necessary, other components including a flame retardant are directly mixed to form a melt film, the thermoplastic resin, and the inorganic The filler and other components including a flame retardant as necessary can be melt-kneaded in advance to prepare pellets of the mixture, and a method of melt-forming a thermoplastic resin sheet using this can be mentioned.

[Thickness of layer A]
The thickness of the thermoplastic resin sheet constituting the A layer before producing the laminate of the first aspect is not particularly limited, but is preferably 0.5 mm or more and 2 mm or less, 0.5 mm or more, 1.5 mm More preferably, it is more preferably 0.5 mm or more and 1 mm or less. When the thickness of the thermoplastic resin sheet constituting the A layer is 0.5 mm or more, deterioration of the surface appearance such as the exposure of the carbon fiber layer of the B layer on the product surface after press molding can be suppressed. Moreover, if the thickness of the thermoplastic resin sheet which comprises A layer is 2 mm or less, lightness can be maintained.

The thickness of the A layer in the laminate of the first aspect is not particularly limited, but is preferably 0.5 mm or more and 2 mm or less, more preferably 0.5 mm or more and 1.5 mm or less, and It is particularly preferably 5 mm or more and 1 mm or less.
If the thickness of the A layer is 0.5 mm or more, deterioration of the surface appearance such as the exposure of the carbon fiber layer of the B layer on the product surface after press molding can be suppressed. Moreover, if the thickness of the A layer is 2 mm or less, the lightness can be maintained.

[Carbon fiber layer (B layer)]
The carbon fiber layer (B layer) constituting the laminate of the first aspect is a layer mainly composed of a carbon fiber material. By having a carbon fiber layer, it is possible to achieve excellent low linear expansion for the laminate of the first aspect.

The type of carbon fiber used for the B layer may be either pitch-based carbon fiber or PAN-based carbon fiber, and may be used in combination, but pitch-based carbon fiber is preferable from the viewpoint of low linear expansion. The pitch-based carbon fiber may be either a mesophase pitch-based carbon fiber or an isotropic pitch-based carbon fiber. From the viewpoint of improving the strength and low linear expansion of the laminate of the first aspect, the mesophase pitch is used. More preferred are carbon fibers.

The carbon fiber material used for the B layer is preferably a carbon fiber mat or carbon fiber paper. Both “carbon fiber mat” and “carbon fiber paper” are materials in which carbon fiber bundles are opened and dispersed, and formed and paper-formed by a wet method or a dry method to form a flat film.

Any carbon fiber material described above preferably contains a binder resin so that the carbon fibers do not easily dissociate, and may be a so-called prepreg in which carbon fiber is impregnated with a binder resin. In general, “carbon fiber mat” is distinguished from “carbon fiber paper” in terms of the content and thickness of the binder resin. Usually, the carbon fiber mat has a larger binder resin content and a larger thickness than the carbon fiber paper.

The binder resin is not particularly limited, and examples thereof include crystalline thermoplastic resins such as polyolefin resins, polyester resins, polyacetal resins, polyphenylene sulfide resins, and crystalline polyamide resins; aromatic vinyl compound resins (polystyrene elastomers). ), Polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyolefin elastomers, amorphous polyamide resins, and other amorphous thermoplastic resins; unsaturated polyester resins, vinyl ester resins, and other polyester resins; epoxy resins, phenols (resol type) Examples thereof include thermosetting resins such as resins, urea resins, melamine resins, polyimide resins, bismaleimide resins, and cyanate ester resins. Moreover, these copolymers, modified bodies, etc. may be sufficient and these may be used in combination of 2 or more types.

The content when the binder resin is contained in the carbon fiber material is preferably 1 part by mass or more and 90 parts by mass or less, and preferably 5 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the carbon fiber. More preferably, it is more preferably 10 parts by mass or more and 70 parts by mass or less.
By containing a binder resin in such a range, the carbon fiber can be stably formed into a carbon fiber material such as a carbon fiber mat or carbon fiber paper.

Among them, as the carbon fiber material used for the laminate of the first aspect, fiber opening can be promoted when making paper from the viewpoint of resin impregnation property, low linear expansion property, and cost, and the amount of carbon fiber can be kept high. Carbon fiber paper is particularly preferred.
The carbon fiber paper is usually produced by either a dry papermaking method or a wet papermaking method, but it is preferable to use one produced by a wet papermaking method from the viewpoint of better fiber opening.
Carbon fiber paper having a high basis weight (carbon fiber amount) is preferable from the viewpoint of low linear expansion, but preferably 20 to 100 g / m in view of the balance between productivity and cost of the paper itself. ² , more preferably 30 to 100 g / m ² , particularly preferably 40 to 100 g / m ² basis weight can be used.

In the laminated body of the first aspect, the maximum diameter of the carbon fiber bundle in the B layer is 10 μm or more and 1000 μm or less. The maximum diameter of the carbon fiber bundle in the B layer is more preferably 10 μm or more and 950 μm or less, and particularly preferably 10 μm or more and 900 μm or less.
Normally, the average fiber diameter of one carbon fiber is 7 to 10 μm, but these are aggregated into a carbon fiber bundle by electrostatic adhesion or a sizing agent. For such a carbon fiber bundle, by controlling the maximum diameter to 10 μm or more and 1000 μm or less in the laminate of the first aspect, the low linear expansion property and good surface appearance and press formability of the laminate of the first aspect are achieved. Balance can be maintained.
The maximum diameter of the carbon fiber bundle can be measured and evaluated by the method described in the examples described later.

Moreover, in the laminated body of a 1st aspect, the average fiber length of the carbon fiber in B layer is 0.1 mm or more and less than 5 mm. The average fiber length of the carbon fibers in the B layer is more preferably 0.1 mm or more and 4.5 mm or less, and particularly preferably 0.1 mm or more and 4.0 mm or less.
By controlling the average fiber length of the carbon fibers to be 0.1 mm or more and less than 5 mm, it is possible to maintain the balance between the low linear expansion property, good surface appearance and press formability of the laminate of the first aspect.
In addition, the average fiber length of carbon fiber can be measured and evaluated by the method as described in the Example mentioned later.

As a preferable method for setting the maximum diameter of the carbon fiber bundle in the B layer and the average fiber length of the carbon fibers in the above-mentioned range in the laminate of the first aspect, for example, when the carbon fiber material is produced, the fiber is sufficiently opened. The method of performing is mentioned. Specifically, when carbon fiber paper is produced by a wet papermaking method, a method of controlling the number of revolutions of a disaggregator used for fiber opening is exemplified. In the case of producing by a dry papermaking method, or for carbon fiber materials other than carbon fiber paper, the fiber opening may be performed by controlling the fiber opening conditions.

The maximum diameter of the carbon fiber bundle and the average fiber length of the carbon fiber are contradictory characteristics.If the fiber is excessively opened, the maximum diameter of the carbon fiber bundle becomes small, but the average fiber length becomes too short, resulting in low linear expansion. Not fully expressed. On the other hand, if the fiber opening is insufficient, the maximum diameter of the carbon fiber bundle becomes large, and the laminate may have a poor appearance or the press formability may be insufficient. The laminate of the first aspect can maintain the balance between low linear expansion, good surface appearance and press formability by controlling the maximum diameter of the carbon fiber bundle and the average fiber length of the carbon fibers within the above ranges. .

The preferable range of the maximum diameter of the carbon fiber bundle and the average fiber length of the carbon fiber in the carbon fiber material used for the B layer is the same as the range of the maximum diameter of the carbon fiber bundle and the average fiber length of the carbon fiber in the B layer. It is.

The thickness of the B layer in the laminate of the first aspect is not particularly limited, but is preferably 0.1 mm or more and 0.3 mm or less, more preferably 0.1 mm or more and 0.25 mm or less, and It is particularly preferably 1 mm or more and 0.2 mm or less.
If the thickness of the B layer is 0.1 mm or more, the laminate of the first aspect can exhibit excellent low linear expansion. Moreover, if the thickness of B layer is 0.3 mm or less, there are few surface unevenness | corrugations of the laminated body of a 1st aspect, and it is excellent in surface appearance.
The carbon fiber material used for the B layer has various thicknesses because the porosity varies depending on the type. Therefore, the carbon fiber material has a thickness such that the preferred thickness when it is provided in the laminate of the first aspect is in the above range. preferable.

[Thermoplastic resin layer (C layer)]
The thermoplastic resin layer (C layer) constituting the laminate of the first aspect is a layer containing a thermoplastic resin as a main component and not containing the inorganic filler, and is substantially a central layer of the laminate of the first aspect. Become.
Here, the “main component” means that the thermoplastic resin accounts for more than 50 mass%, preferably 70 mass% or more, more preferably 90 mass% or more (including 100 mass%) in the C layer.
In addition, “does not contain inorganic filler” means that the inorganic filler is not actively added and added, but it is allowed to contain a very small amount that does not affect the characteristics and effects of the laminate of the first aspect. This is the purpose.
C layer is composed mainly of thermoplastic resin and does not contain the inorganic filler, thus achieving light weight and low cost while maintaining good low linear expansion and press formability for the laminate of the first aspect. it can.

[Thermoplastic resin]
A preferable kind of the thermoplastic resin used for the C layer is the same as that used for the A layer. Among them, the same type of material as the A layer (for example, if the A layer is a polypropylene resin, the C layer is also a polypropylene resin) is preferable from the viewpoint of improving the interlayer adhesion of the laminate of the first aspect.

In the laminate of the first aspect, the melt mass flow rate R _A (g / 10 min) of the thermoplastic resin of the A layer and the melt mass flow rate R _C (g of the thermoplastic resin of the C layer at the same temperature and the same load. / 10 min) preferably has a relationship of R _A ≧ _RC .
When the laminate of the first aspect is produced, it is preferable that the fluidity characteristics of the A layer and the C layer are close to each other. However, since the A layer contains an inorganic filler, the fluidity characteristics are compared with the case of using only a thermoplastic resin. As a result, the melt mass flow rate tends to decrease. Therefore, it is preferable that R _A of the thermoplastic resin itself of the A layer is R _C or more.
However, if R _A is excessively large with respect to R _C, even thermoplastic resin layer A contain an inorganic filler, the balance of flow characteristics of the A layer and the C layer is deteriorated, 10 × R _C It is preferable that ≧ R _A ≧ _RC .

A preferable range for the melt mass flow rate R _C (g / 10 min) when the thermoplastic resin used for the C layer is a polypropylene resin, or a polyethylene resin or other thermoplastic resin is also used for the A layer. It is preferably the same as the preferable range of the melt mass flow rate R _A (g / 10 min) of the thermoplastic resin, and preferably has the relationship of R _A ≧ _{RC at} the same temperature and the same load.

[Other ingredients]
The layer C may appropriately contain other thermoplastic resins and additives generally blended into the resin composition within a range not impairing the characteristics and effects of the present invention. However, it does not contain what corresponds to the said inorganic filler.
Specific examples of additives include flame retardants, pigments such as carbon black, weather resistance stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents, Antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, colorants and the like can be mentioned.

[Method for producing layer C]
The method for producing the thermoplastic resin sheet constituting the C layer is not particularly limited, as is the case with the thermoplastic resin sheet constituting the A layer, and known melt film forming methods such as a T-die casting method, a calendar method, and a pressing method. Can be adopted.

[C layer thickness]
The thickness of the thermoplastic resin sheet constituting the C layer before producing the laminate of the first aspect is not particularly limited, but is preferably 0.5 mm or more and 2 mm or less, and is 1 mm or more and 2 mm or less. Is more preferable, and 1 mm or more and 1.5 mm or less are particularly preferable. If the thickness of the thermoplastic resin sheet which comprises C layer is 0.5 mm or more, the laminated body of a 1st aspect is excellent in press moldability. Moreover, if the thickness of the thermoplastic resin sheet which comprises C layer is 2 mm or less, the laminated body of a 1st aspect is excellent in low linear expansion property.

The thickness of the C layer in the laminate of the first aspect is not particularly limited, but is preferably 0.5 mm or more and 2 mm or less, more preferably 1 mm or more and 2 mm or less, and 1 mm or more and 1.5 mm. It is particularly preferred that
If the thickness of the C layer is 0.5 mm or more, the laminate of the first aspect is excellent in press moldability. Moreover, if the thickness of C layer is 2 mm or less, the laminated body of a 1st aspect is excellent in low linear expansion property.

[Other layers]
In the laminated body of the first aspect, other layers may be provided in addition to the A to C layers as long as the features and effects of the present invention are not impaired.
Specifically, the laminated body of the first aspect may have a configuration of A layer / B layer / C layer / B layer / A layer, but has a design property such as a printed layer on the outer side of the A layer, for example. A surface protective layer such as a layer or an antifouling layer can also be provided. Further, an adhesive layer or the like can be provided between the A layer and the B layer or between the B layer and the C layer as necessary.

[Method for Producing Laminate of First Aspect]
As described above, the laminate of the first aspect is prepared by laminating the thermoplastic resin sheet constituting the A layer, the carbon fiber material constituting the B layer, and the thermoplastic resin sheet constituting the C layer, respectively. It is obtained by doing.

More specifically, for example, a step of producing a thermoplastic resin sheet used for the A layer and the C layer, a step of producing a carbon fiber material used for the B layer by opening a carbon fiber bundle, and the heat The plastic resin sheet and the carbon fiber material are laminated so as to have a structure of A layer / B layer / C layer / B layer / A layer, and an appropriate one is selected according to the thermoplastic resin used for the A layer and the C layer. The laminate of the first aspect can be obtained by a manufacturing method including a step of press molding under temperature and pressure conditions.
The above manufacturing method may be a so-called batch method. While producing the thermoplastic resin sheets used for the A layer and the C layer, the carbon fiber material used for the B layer is supplied and these are continuously laminated. However, a continuous pressing method in which press molding is performed may be used.

For example, when the thermoplastic resin used for the A layer and the C layer is a polyolefin resin, the press molding temperature is preferably 180 to 230 ° C., more preferably 180 to 220 ° C., and 190 to 210 ° C. Is particularly preferred. The pressing pressure is preferably from 0.5 to 4.0 MPa, more preferably from 0.5 to 3.0 MPa, and particularly preferably from 1 to 3 MPa.
When the thermoplastic resin used for the A layer and the C layer is a polycarbonate resin, the press molding temperature is preferably 230 to 280 ° C., more preferably 240 to 280 ° C., and 250 to 280 ° C. Is particularly preferred. The pressing pressure is preferably from 0.5 to 4.0 MPa, more preferably from 0.5 to 3.0 MPa, and particularly preferably from 1 to 3 MPa.
By press-molding in such a range, a laminate excellent in the balance between low linear expansion and good surface appearance can be produced.

[II] Laminate of Second Aspect The laminate of the second aspect has the same configuration as the laminate of the first aspect except that the C layer of the laminate of the first aspect described above is replaced with a D layer described later. The A layer and the B layer are the same as the A layer and the B layer of the laminate of the first aspect as follows.

[Thermoplastic resin layer (A layer)]
The thermoplastic resin layer (A layer) constituting the laminate of the second aspect is a layer containing 30 to 200 parts by mass of an inorganic filler with respect to 100 parts by mass of the thermoplastic resin, and the second aspect. It exists as a substantial front and back layer of the laminate.
The A layer constituting the laminate of the second aspect is the same as the A layer constituting the laminate of the first aspect, and the preferred aspects and production methods thereof are also the same.

[Carbon fiber layer (B layer)]
The carbon fiber layer (B layer) constituting the laminate of the second aspect is a layer mainly composed of a carbon fiber material. By having the carbon fiber layer, excellent low linear expansion can be realized for the laminate of the second embodiment.
The B layer constituting the laminate of the second aspect is the same as the B layer constituting the laminate of the first aspect described above, and the preferred aspects and production methods thereof are also the same.

[Thermoplastic resin layer (D layer)]
The thermoplastic resin layer (D layer) constituting the laminate of the second embodiment is a layer containing an inorganic filler in an amount exceeding 0 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It becomes the center layer of the laminate of the second aspect.

[Thermoplastic resin]
A preferable kind of the thermoplastic resin used for the D layer is the same as that used for the A layer. Among them, the same type of material as the A layer (for example, if the A layer is a polypropylene resin, the D layer is also a polypropylene resin) is preferable from the viewpoint of improving the interlayer adhesion of the laminate of the second aspect.

In the laminate of the second embodiment, the melt mass flow rate R _A (g / 10 min) of the thermoplastic resin of the A layer and the melt mass flow rate R _D (g / g) of the thermoplastic resin of the D layer at the same temperature and the same load. 10 min), the preferred relationship differs depending on the content of the inorganic filler in the A layer and the content of the inorganic filler in the D layer. For example, the content of the inorganic filler in the D layer is equal to or less than the content of the inorganic filler in the A layer. In this case, it is preferable to have a relationship of R _A ≧ R _D.
When the laminate of the second embodiment is produced, it is preferable that the flow characteristics of the A layer and the D layer are close to each other. However, when the A layer contains more inorganic filler than the D layer, the flow characteristics of the molding material of the A layer are The melt mass flow rate tends to be smaller than the flow characteristics of the D layer molding material. Therefore, it is preferable that R _A of the thermoplastic resin itself of the A layer is R _D or more.
However, if _RA is excessively large with respect to _{RD, even} if the thermoplastic resin of the A layer contains more inorganic filler than the D layer, the balance between the flow characteristics of the A layer and the D layer becomes poor. It is preferable that 10 × R _D ≧ R _A ≧ R _D.
For example, when the content ratio of the inorganic filler in the A layer is less than the content ratio of the inorganic filler in the D layer, the melt mass flow rate R _A (g / g) of the thermoplastic resin of the A layer at the same temperature and the same load is used. 10 min) and the melt mass flow rate R _D (g / 10 min) of the thermoplastic resin of the D layer preferably have a relationship of R _D ≧ R _A , particularly 10 × R _A ≧ R _D ≧ R _A. It is preferable.

A preferable range for the melt mass flow rate R _D (g / 10 min) when the thermoplastic resin used for the D layer is a polypropylene resin, or a polyethylene resin or other thermoplastic resin is also used for the A layer. It is the same as the preferable range of the melt mass flow rate R _A (g / 10 min) of the thermoplastic resin, and preferably has the above relationship at the same temperature and the same load.

[Inorganic filler]
The D layer of the laminate of the second aspect contains an inorganic filler in an amount of more than 0 parts by mass and 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
The content of the inorganic filler is more preferably 5 parts by mass or more and 100 parts by mass or less, and particularly preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
By containing an inorganic filler more than 0 mass part with respect to 100 mass parts of thermoplastic resins, it contributes to the improvement of the low linear expansion property of the laminated body of a 2nd aspect. Moreover, it contributes to the improvement of the moldability of the laminated body of a 2nd aspect by containing an inorganic filler 100 mass parts or less with respect to 100 mass parts of thermoplastic resins.

Moreover, it is preferable that the content rate of the inorganic filler in D layer of the laminated body of a 2nd aspect is below the content rate of the inorganic filler in A layer.
By having the relationship which the content rate of the inorganic filler of A layer and D layer concerns, when manufacturing the laminated body of a 2nd aspect, a possibility that A layer will flow first becomes small, and production of the laminated body of a 2nd aspect is produced. In addition to improving the properties, it contributes to the weight reduction and press moldability of the laminate of the second embodiment.

Examples of the inorganic filler used in the D layer include those described above as the inorganic filler used in the A layer, and preferred examples thereof are also the same. Further, the preferred average particle diameter and aspect ratio of the inorganic filler used in the D layer are the same as the average particle diameter and aspect ratio of the inorganic filler used in the A layer for the same reason as in the A layer, This inorganic filler may also be surface-treated.

The inorganic filler used for the A layer and the inorganic filler used for the D layer may be the same or different. It is preferable that they are the same from the standpoint of material procurement.

[Other ingredients]
The D layer may appropriately contain other thermoplastic resins and additives that are generally blended into the resin composition within a range not impairing the characteristics and effects of the present invention.
Specific examples of additives include flame retardants, pigments such as carbon black, weather resistance stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents, Antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, colorants and the like can be mentioned.
In addition, when D layer contains a flame retardant, the suitable content rate is the same as that in A layer.

[Method for producing layer D]
The method for producing the thermoplastic resin sheet constituting the D layer is not particularly limited, as is the case with the thermoplastic resin sheet constituting the A layer, and known melt film forming methods such as a T-die casting method, a calendering method, and a pressing method. Can be adopted.

[D layer thickness]
The thickness of the thermoplastic resin sheet constituting the D layer before producing the laminate of the second aspect is not particularly limited, but is preferably 0.5 mm or more and 2 mm or less, and is 1 mm or more and 2 mm or less. Is more preferable, and 1 mm or more and 1.5 mm or less are particularly preferable. If the thickness of the thermoplastic resin sheet which comprises D layer is 0.5 mm or more, the laminated body of a 2nd aspect is excellent in press moldability and low linear expansion property. Moreover, if the thickness of the thermoplastic resin sheet which comprises D layer is 2 mm or less, the laminated body of a 2nd aspect is excellent in press moldability.

The thickness of the D layer in the laminate of the second aspect is not particularly limited, but is preferably 0.5 mm or more and 2 mm or less, more preferably 1 mm or more and 2 mm or less, and 1 mm or more and 1.5 mm. It is particularly preferred that
When the thickness of the D layer is 0.5 mm or more, the laminate of the second aspect is excellent in press moldability and low linear expansion. Moreover, if the thickness of D layer is 2 mm or less, the laminated body of a 2nd aspect is excellent in press moldability.

[Other layers]
The laminated body of the second aspect may be provided with other layers in addition to the A layer, B layer, and D layer as long as the features and effects of the present invention are not impaired.
Specifically, the layered product of the second embodiment may have a configuration of A layer / B layer / D layer / B layer / A layer, but has a design property such as a printed layer on the outer side of the A layer, for example. A surface protective layer such as a layer or an antifouling layer can also be provided. Further, an adhesive layer or the like can be provided between the A layer and the B layer or between the B layer and the D layer as necessary.

[Method for Producing Laminate of Second Aspect]
As described above, the laminate of the second aspect is prepared by respectively producing the thermoplastic resin sheet constituting the A layer, the carbon fiber material constituting the B layer, and the thermoplastic resin sheet constituting the D layer. It is obtained by doing. About the manufacturing method, it is the same as that of the manufacturing method of the laminated body of the above-mentioned 1st aspect except arrange | positioning D layer instead of C layer.

[III] Laminate of Third Embodiment [Thermoplastic Resin Layer (E Layer)]
The thermoplastic resin layer (E layer) constituting the laminate of the third aspect is 30 parts by mass or more and 200 parts by mass of plate-like inorganic particles having an aspect ratio of 20 or more and 500 or less with respect to 100 parts by mass of the thermoplastic resin. It is a layer to be contained below, and exists as the front and back layers of the laminate of the third embodiment.

[Thermoplastic resin]
Examples of the thermoplastic resin that can be used for the E layer include those similar to the thermoplastic resin that constitutes the A layer according to the laminate of the first aspect, and the preferred aspects thereof are also the same.

[Plate-like inorganic particles]
The E layer of the laminate of the third aspect contains 30 to 200 parts by mass of plate-like inorganic particles having an aspect ratio of 20 to 500 with respect to 100 parts by mass of the thermoplastic resin.
The content ratio of the plate-like inorganic particles is preferably 30 parts by mass or more and 160 parts by mass or less, and particularly preferably 30 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the polyolefin resin.
By containing 30 parts by mass or more of the plate-like inorganic particles with respect to 100 parts by mass of the polyolefin-based resin, the laminated body of the third aspect contributes to the improvement of low linear expansion. Moreover, it contributes to the improvement of the moldability of the laminated body of the 3rd aspect by containing 200 mass parts or less of plate-like inorganic particles with respect to 100 mass parts of polyolefin resin.

Specific examples of the plate-like inorganic particles used for the E layer include metal carbonates such as calcium carbonate, magnesium carbonate, and barium carbonate, metal sulfates such as calcium sulfate, barium sulfate, and magnesium sulfate, calcium oxide, and oxidation. Examples thereof include metal oxides such as magnesium, zinc oxide, alumina, silica, and titanium oxide, metal chlorides such as sodium chloride, magnesium chloride, silver chloride, and calcium chloride, and clay minerals such as talc, clay, mica, and montmorillonite.
Among these, talc or mica is preferably used from the viewpoint of low linear expansion and cost, and mica is particularly preferable.

The average particle size of the plate-like inorganic particles used for the E layer is preferably 1 μm or more and 500 μm or less, more preferably 5 μm or more and 300 μm or less, and particularly preferably 5 μm or more and 100 μm or less.
If the average particle diameter of the plate-like inorganic particles is 1 μm or more, the laminated body of the third aspect contributes to improvement of low linear expansion. Moreover, if an average particle diameter is 500 micrometers or less, it will contribute to the improvement of the surface external appearance of the laminated body of a 3rd aspect.
The average particle diameter of the plate-like inorganic particles can be calculated in the same manner as the average particle diameter of the inorganic filler in the A layer of the laminate of the first aspect described above.

The aspect ratio (major axis / minor axis value) of the plate-like inorganic particles used for the E layer is 20 or more and 500 or less, preferably 20 or more and 300 or less, and particularly preferably 20 or more and 100 or less. .
If the aspect ratio of the plate-like inorganic particles is 20 or more, the laminate of the third aspect is excellent in low linear expansion. On the other hand, if the aspect ratio of the plate-like inorganic particles is 500 or less, the laminate of the third aspect is excellent in surface appearance.
The aspect ratio of the plate-like inorganic particles can be calculated in the same manner as the aspect ratio of the inorganic filler in the A layer of the laminate of the first aspect described above.

The plate-like inorganic particles used for the E layer may be surface-treated. The surface treatment method is not particularly limited, and examples thereof include a method using a surface treatment agent such as a general silane coupling agent. By surface-treating the plate-like inorganic particles, the effects of improving the dispersibility of the plate-like inorganic particles in the thermoplastic resin and preventing the plate-like inorganic particles from falling off from the E layer can be obtained.

These plate-like inorganic particles may be used alone, or may be used in combination of two or more kinds having different materials, particle sizes, aspect ratios, presence / absence of surface treatment, types of surface treatment agents, and the like.

[Other ingredients]
When the laminate of the third aspect is required to have flame retardancy, the E layer can further contain a flame retardant. The flame retardant used for the E layer is not particularly limited, such as phosphorus flame retardants such as various condensed phosphate esters, nitrogen flame retardants such as melamine, phosphorus / nitrogen flame retardants such as phosphazenes, brominated aromatic compounds, etc. One or more known flame retardants such as bromine flame retardants and antimony flame retardants such as antimony trioxide can be appropriately selected and used.

When the flame retardant is contained in the E layer, the content ratio is preferably 20 parts by mass or more and 60 parts by mass or less, and 25 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. Is more preferably 30 parts by mass or more and 60 parts by mass or less.
By containing 20 parts by mass or more of the flame retardant with respect to 100 parts by mass of the thermoplastic resin, the laminate of the third aspect can exhibit excellent flame retardancy. On the other hand, by containing 60 parts by mass or less of the flame retardant with respect to 100 parts by mass of the thermoplastic resin, the laminate of the third aspect satisfies various mechanical properties.

In addition to the components described above, the E layer may appropriately contain other thermoplastic resins and additives generally added to the resin composition as long as the characteristics and effects of the present invention are not impaired. Specific examples of additives include pigments such as carbon black, weather resistance stabilizers, heat resistance stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, antiaging agents, and antioxidants. , Light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents or coloring agents.

[Method for producing layer E]
As will be described later, the laminate of the third aspect is obtained by producing a thermoplastic resin sheet constituting the E layer and a carbon fiber material constituting the B layer and laminating them.
It does not specifically limit as a preparation method of the thermoplastic resin sheet which comprises E layer, Well-known melt film-forming methods, such as a T die-cast method, a calendar method, a press method, are employable.

More specifically, the thermoplastic resin, the plate-like inorganic particles, and other components including a flame retardant as required, a method of directly mixing and melt-forming, the thermoplastic resin, Examples include a method of melt-kneading the plate-like inorganic particles and other components including a flame retardant as necessary to prepare a pellet of a mixture and melt-forming a thermoplastic resin sheet using the mixture. Can do.

[E layer thickness]
The thickness of the thermoplastic resin sheet constituting the E layer before producing the laminate of the third aspect is not particularly limited, but is preferably 0.5 mm or more and 2.5 mm or less, preferably 0.5 mm or more and 2 mm. Or less, more preferably 0.5 mm or more and 1.5 mm or less, and particularly preferably 0.5 mm or more and 1 mm or less. If the thickness of the thermoplastic resin sheet constituting the E layer is 0.5 mm or more, deterioration of the surface appearance such as the exposure of the carbon fiber layer of the B layer on the product surface after press molding can be suppressed. Moreover, if the thickness of the thermoplastic resin sheet which comprises E layer is 2.5 mm or less, lightness can be maintained.

Further, the thickness of the E layer in the laminate of the third aspect is not particularly limited, but is preferably 0.5 mm or more and 2.5 mm or less, more preferably 0.5 mm or more and 2 mm or less. More preferably, it is 5 mm or more and 1.5 mm or less, and particularly preferably 0.5 mm or more and 1 mm or less.

[Carbon fiber layer (B layer)]
The carbon fiber layer (B layer) constituting the laminate of the third aspect is a layer mainly composed of a carbon fiber material. By having the carbon fiber layer, excellent low linear expansion can be realized for the laminate of the third embodiment.
The B layer constituting the laminate of the third aspect is the same as the B layer constituting the laminate of the first aspect described above, and the preferred aspects and production methods thereof are also the same.

[Other layers]
In the laminated body of the third aspect, in addition to the E layer and the B layer, other layers may be provided as long as the features and effects of the present invention are not impaired.
Specifically, in the laminate of the third aspect, the E layer is the front and back layers, and for example, the structure of E layer / B layer / E layer may be used, but between the E layer and B layer, if necessary, An adhesive layer or the like can be provided. Furthermore, it can also be set as the laminated body which provided two B layers and provided the other layer between the layers like E layer / B layer / other layer / B layer / E layer.
Moreover, although the laminated body of a 3rd aspect uses E layer as front and back layers, it does not prevent providing a surface protection layer, such as a layer which has designability, such as a printing layer, and an antifouling layer in the further outside of E layer. .

[Method for Producing Laminate of Third Aspect]
As described above, the laminate of the third aspect can be obtained by preparing and laminating the thermoplastic resin sheet constituting the E layer and the carbon fiber material constituting the B layer.

More specifically, for example, a step of producing a thermoplastic resin sheet used for the E layer, a step of producing a carbon fiber material used for the B layer by opening a carbon fiber bundle, the thermoplastic resin sheet and A production method comprising a step of laminating the carbon fiber material so as to have a configuration of E layer / B layer / E layer, and press molding at an appropriate temperature and pressure condition according to the thermoplastic resin used for the E layer Thus, the laminate of the third aspect can be obtained.
The manufacturing method described above may be a so-called batch method. While producing the thermoplastic resin sheet used for the E layer, the carbon fiber material used for the B layer is supplied and press-molded while continuously laminating them. The continuous press method may be used.
The press molding conditions are the same as the press molding conditions in the method for manufacturing the laminate of the first aspect described above.

[IV] Physical Properties of the Laminate of the Present Invention The laminates of the present invention, that is, the laminates of the first, second, and third embodiments preferably have the following physical properties.

The maximum cross-sectional height (Rt) of the surface of the layer A of the laminate of the first embodiment and the second embodiment and the surface of the E layer of the laminate of the third embodiment is measured according to JIS B0601 (2013) and is 3 μm. Or less, more preferably 2.5 μm or less, and particularly preferably 2 μm or less.
When the maximum cross-sectional height (Rt) of the surface of the A layer and the E layer is 3 μm or less, the laminate of the present invention has a particularly good surface appearance. The maximum cross-sectional height (Rt) of the surface of the A layer and the E layer is preferably as small as possible, and the lower limit is not particularly defined.
Examples of the method for setting the maximum cross-sectional height (Rt) of the surfaces of the A layer and the E layer include the content ratio of the inorganic filler in the A layer or the plate-like inorganic particles in the E layer, and the B The method of adjusting the maximum diameter of the carbon fiber bundle in a layer in the range specified in this invention is mentioned.

The thickness of the laminate of the present invention is not particularly limited, but is preferably 1.7 mm or more and 5 mm or less, more preferably 1.7 mm or more and 4 mm or less, and 1.7 mm or more and 3 mm or less. It is particularly preferred.
When the thickness of the laminate of the present invention is 1.7 mm or more, the laminate of the present invention and a product obtained by press molding the laminate of the present invention are excellent in surface appearance. Moreover, if the thickness of the laminated body of this invention is 5 mm or less, the laminated body of this invention is excellent in low linear expansion property.

Further, the laminate of the present invention is excellent in low linear expansion, and the linear expansion coefficient measured according to JIS K7197 (2012) is preferably 5 × 10 ⁻⁵ / ° C. or less, preferably 1 × More preferably, it is 10 ⁻⁵ / ° C. or less.

Note that the two A layers included in the laminates of the first and second embodiments, that is, the A layer on one surface side and the A layer on the other surface side are not necessarily the same thermoplastic resin and inorganic filler. Need not be of the same thickness used in the same composition, the type of the thermoplastic resin and the inorganic filler, the content ratio of the inorganic filler, the content ratio of other components, etc. may differ, and the thickness May be different. Similarly, regarding the two B layers included in the laminate of the second aspect, the type of the carbon fiber material, the maximum diameter of the carbon fiber bundle, the average fiber length of the carbon fiber, the basis weight, the thickness, and the like may be different. . However, in the uniformity of the physical properties in the thickness direction of the laminate of the first embodiment and the second embodiment, the problem of warpage, ease of production, etc., two A layers in the laminate of the first embodiment and the second embodiment, It is preferable that the two B layers have the same physical properties or thicknesses made of the same material.

Similarly, the two E layers included in the laminate of the third embodiment are not necessarily required to have the same thickness using the same thermoplastic resin and plate-like inorganic particles in the same composition, and the thermoplastic resin and the plate. The shape of the particle-like inorganic particles, the content ratio of the plate-like inorganic particles, the content ratio of the other components, and the like may be different, and the thicknesses may be different. However, in the uniformity of physical properties in the thickness direction of the laminate of the third aspect, the problem of warpage, ease of production, etc., the two E layers in the laminate of the third aspect were each made of the same material. It is preferable that they have the same physical properties or thickness.

Hereinafter, examples for more specifically explaining the present invention will be shown, but the present invention is not limited to the specific modes shown in the examples.

[Measurement / Evaluation]
Measurement and evaluation in Examples and Comparative Examples were performed by the following methods and standards.

(1) Melt mass flow rate According to JIS K7210 (1999), the melt mass flow rate of the thermoplastic resin was measured.

(2) Mw / Mn
Mw / Mn of the thermoplastic resin was measured by a GPC (gel permeation chromatography) method according to JIS K7252-1 (2008).

(3) Maximum diameter of carbon fiber bundle in layer B A cross section in the thickness direction of the produced laminate was observed using an optical microscope. For the B layer, 50 visual fields having a height of 500 μm and a width of 2 mm were arbitrarily observed, and the maximum diameter of the carbon fiber bundle existing in the entire visual field was defined as the maximum diameter of the carbon fiber bundle in the B layer.

(4) Average fiber length of carbon fibers in layer B A cross section in the thickness direction of the produced laminate was observed using an optical microscope. Observe 50 fields of view of height 500 μm x width 2 mm for layer B, measure the length of each carbon fiber in the entire field of view one by one, and the average of this sum is the average fiber of carbon fibers in layer B It was long.

(5) Low linear expansion Using a TMA measuring device 7100 manufactured by Hitachi High-Tech Science Co., Ltd., the linear expansion coefficient from 20 ° C. to 150 ° C. was measured for the produced laminate in accordance with JIS K7197 (2012). Coefficients were calculated and evaluated according to the following criteria.
A: The linear expansion coefficient is 1 × 10 ⁻⁵ / ° C. or less. ○: The linear expansion coefficient is larger than 1 × 10 ⁻⁵ / ° C. and not more than 5 × 10 ⁻⁵ / ° C. ×: The linear expansion coefficient is 5 × 10 ⁻⁵ / ° C. Greater than

(6) Surface appearance (A or E layer maximum cross-sectional height (Rt))
Using a three-dimensional roughness meter manufactured by Kosaka Laboratory, the maximum cross-sectional height (Rt) of the surface of the layer A or layer E of the prepared laminate was measured according to JIS B0601 (2013). Evaluated by criteria.
○: The maximum cross-sectional height is 3 μm or less. X: The maximum cross-sectional height is larger than 3 μm.

(7) Press moldability Thermoplastic resin used for layer A and layer C, layer A and layer D, or layer E using a stepped shaping mold with a concavo-convex shape height of 10 mm for the produced laminate. When PP is a PP resin, the thermoplastic resin used for the A layer and the C layer, the A layer and the D layer, or the E layer is a PC resin under the conditions of temperature = 200 ° C., pressure = 2 MPa, and molding time = 15 minutes. In this case, press molding was performed under the conditions of temperature = 260 ° C., pressure = 2 MPa, molding time = 15 minutes, and the surface of the A layer or E layer was visually observed and evaluated according to the following criteria.
○: Carbon fiber is not exposed on the surface of the A layer or E layer and cracks are not generated. ×: The carbon fiber is exposed on the surface of the A layer or E layer, or a shaping type drawing. A state in which the laminate cannot follow and is cracked.

[Materials used]
The materials used in Examples and Comparative Examples are as follows.

<Thermoplastic resin>
Polypropylene (PP) resin: Novatec PP EA9 (Nippon Polypro Co., Ltd. homopolypropylene, melt mass flow rate (temperature = 230 ° C., load = 2.16 kgf) = 0.5 g / 10 min, Mw / Mn = 5)
Polycarbonate (PC) resin: Caliber 301-30 (Bisphenol-A homopolycarbonate manufactured by Sumika Stylon Co., Ltd., melt mass flow rate (temperature = 300 ° C., load = 1.2 kgf) = 30 g / 10 min)
<Inorganic filler>
Mica 1: muscovite W400 (made by Kirara Co., Ltd., plate-like inorganic particles having an average particle size = 18 μm and an aspect ratio = 35)
Mica 2: muscovite 200W (made by Kirara Co., Ltd., plate-like inorganic particles having an average particle size = 100 μm and an aspect ratio = 60)
Mica 3: muscovite 30-C (made by Kirara Co., Ltd., plate-like inorganic particles having an average particle size = 680 μm and an aspect ratio = 90)
<Other ingredients>
Flame retardant: Fire Cut P-1590 (Suzuhiro Chemical Co., Ltd. antimony flame retardant + bromine flame retardant)
Lubricant: MS-6 (12-hydroxystearic acid manufactured by Nitto Kasei Kogyo Co., Ltd.)
Antioxidant: IRGANOX B225 (Phosphorus heat stabilizer + hindered phenol antioxidant manufactured by BASF Corporation)
Carbon fiber: DIALEAD K6371T (Mesophase pitch carbon fiber manufactured by Mitsubishi Plastics, Inc.)

[Example and Comparative Example of Laminate of First Aspect]
[Example I-1]
(Preparation of sheet used for layer A)
Mica 1, flame retardant, lubricant, and antioxidant are mixed in proportions shown in Table 1 with respect to 100 parts by mass of PP resin, and supplied to a plastograph mixer manufactured by Toyo Seiki Co., Ltd., temperature = 190 ° C., Melting and kneading were carried out under the conditions of rotational speed = 50 rpm and kneading time = 5 minutes to obtain a resin composition. The obtained resin composition was sandwiched between two metal plates and press molded under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and an inorganic filler-containing polypropylene resin sheet having a thickness of 0.5 mm was obtained. Produced.

(Preparation of sheet used for layer C)
A PP resin was sandwiched between two metal plates and press molded under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and a polypropylene resin sheet having a thickness of 1 mm was produced.

(Production of carbon fiber material used for layer B)
The carbon fibers were opened and dispersed by a wet papermaking method using a disaggregator according to JIS P8220-1 (2012), and papermaking was performed to prepare carbon fiber paper having a weight of 100 g / m ² . At this time, the disaggregator was operated under the conditions of propeller rotation speed = 3000 rpm and rotation time = 10 seconds. The obtained carbon fiber paper is referred to as “highly spread paper”.

(Production of laminate)
The sheet used for the A layer and C layer and the carbon fiber material used for the B layer are stacked so as to have a configuration of A layer / B layer / C layer / B layer / A layer and sandwiched between two metal plates. Then, press molding was performed under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and a laminate having a thickness of 2 mm was produced. At this time, the thickness of the A layer = 500 μm, the thickness of the B layer = 150 μm, and the thickness of the C layer = 700 μm.
The obtained laminate was evaluated and the results are shown in Table 1.

[Example I-2]
A laminate was prepared in the same manner as in Example I-1, except that the content of mica 1 in the sheet used for layer A was changed as described in Table 1. At this time, the thickness of the A layer = 500 μm, the thickness of the B layer = 150 μm, and the thickness of the C layer = 700 μm.
The obtained laminate was evaluated and the results are shown in Table 1.

[Example I-3]
(Preparation of sheet used for layer A)
Mica 1 is mixed at a ratio shown in Table 1 with respect to 100 parts by mass of PC resin and supplied to a plastograph mixer manufactured by Toyo Seiki Co., Ltd., temperature = 260 ° C., rotation speed = 50 rpm, kneading time = 5. The resin composition was obtained by melt-kneading under the conditions of minutes. The obtained resin composition was sandwiched between two metal plates and press molded under the conditions of temperature = 260 ° C., pressure = 2 MPa, molding time = 15 minutes, and an inorganic filler-containing polycarbonate resin sheet having a thickness of 0.5 mm was obtained. Produced.

(Preparation of sheet used for layer C)
A PC resin was sandwiched between two metal plates and press molded under the conditions of temperature = 260 ° C., pressure = 2 MPa, molding time = 15 minutes, and a polycarbonate resin sheet having a thickness of 1.0 mm was produced.

(Production of laminate)
The sheet used for the produced A layer and C layer and the high-spread paper used for the B layer produced in Example I-1 are configured as A layer / B layer / C layer / B layer / A layer. The laminate was sandwiched between two metal plates and press-molded under the conditions of temperature = 260 ° C., pressure = 2 MPa, molding time = 15 minutes, and a laminate having a thickness of 2.0 mm was produced. At this time, the thickness of the A layer = 500 μm, the thickness of the B layer = 150 μm, and the thickness of the C layer = 700 μm.
The obtained laminate was evaluated and the results are shown in Table 1.

[Comparative Example 1]
A PP resin was sandwiched between two metal plates and press-molded under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and a single-layer polypropylene resin sheet having a thickness of 2 mm was produced.
The obtained sheet was evaluated and the results are shown in Table 1.

[Comparative Example 2]
As a sheet used for the A layer, a PP resin is sandwiched between two metal plates, press-molded under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and a polypropylene resin sheet having a thickness of 0.5 mm is obtained. Produced.
As in Example I-1, a high-spread paper used for the B layer and a sheet used for the C layer were prepared and stacked so as to have a configuration of A layer / B layer / C layer / B layer / A layer. The laminate was sandwiched between two metal plates, and press molded under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and a laminate having a thickness of 2 mm was produced. At this time, the thickness of the A layer = 425 μm, the thickness of the B layer = 150 μm, and the thickness of the C layer = 850 μm.
The obtained laminate was evaluated and the results are shown in Table 1.

[Comparative Example 3]
Mica 1, a flame retardant, a lubricant, and an antioxidant were mixed at a ratio shown in Table 1 with respect to 100 parts by mass of the PP resin to prepare a sheet used for the A layer in the same manner as in Example I-1.
Next, in the production of the carbon fiber material used for the B layer, the carbon fiber paper was prepared in the same manner as in Example I-1, except that the disintegrator was operated under the conditions of the rotation speed of the propeller = 500 rpm and the rotation time = 10 seconds. Produced. This carbon fiber paper is referred to as “low spread paper”.
A sheet used for the C layer was prepared in the same manner as in Example I-1, and was sandwiched between two metal plates so as to have a configuration of A layer / B layer / C layer / B layer / A layer. The laminate was press-molded under the conditions of 200 ° C., pressure = 2 MPa, and molding time = 15 minutes to produce a laminate having a thickness of 2 mm. At this time, the thickness of the A layer = 500 μm, the thickness of the B layer = 150 μm, and the thickness of the C layer = 700 μm.
The obtained laminate was evaluated and the results are shown in Table 1.

[Comparative Example 4]
Mica 1, a flame retardant, a lubricant, and an antioxidant were mixed at a ratio shown in Table 1 with respect to 100 parts by mass of the PP resin to prepare a sheet used for the A layer in the same manner as in Example I-1.
Next, in the production of the carbon fiber material used for the B layer, a carbon fiber paper was prepared in the same manner as in Example I-1, except that the disintegrator was operated under the conditions of the propeller rotation speed = 1000 rpm and the rotation time = 10 seconds. Produced. This carbon fiber paper is referred to as “standard spread paper”.
A sheet used for the C layer was prepared in the same manner as in Example I-1, and was sandwiched between two metal plates so as to have a configuration of A layer / B layer / C layer / B layer / A layer. The laminate was press-molded under the conditions of 200 ° C., pressure = 2 MPa, and molding time = 15 minutes to produce a laminate having a thickness of 2 mm. At this time, the thickness of the A layer = 500 μm, the thickness of the B layer = 150 μm, and the thickness of the C layer = 700 μm.
The obtained laminate was evaluated and the results are shown in Table 1.

[Comparative Example 5]
Mica 1, a flame retardant, a lubricant, and an antioxidant were mixed at a ratio shown in Table 1 with respect to 100 parts by mass of the PP resin to prepare a sheet used for the A layer in the same manner as in Example I-1.
A sheet used for the C layer was prepared in the same manner as in Example I-1, and was stacked between two metal plates so as to have a configuration of A layer / C layer / A layer. Temperature = 200 ° C., pressure = 2 MPa Then, press molding was carried out under the condition of molding time = 15 minutes to produce a laminate having a thickness of 2 mm. At this time, the thickness of the A layer = 500 μm and the thickness of the C layer = 1000 μm.
The obtained laminate was evaluated and the results are shown in Table 1.

[Comparative Example 6]
Although 100 parts by mass of PP resin was mixed with mica 1, flame retardant, lubricant, and antioxidant in the proportions shown in Table 1, an attempt was made to produce a sheet used for layer A as in Example I-1. The content of mica was too high to obtain a sheet.

[Example and Comparative Example of Laminate of Second Aspect]
[Example II-1]
(Preparation of sheet used for layer A)
Mica 1, flame retardant, lubricant, and antioxidant are mixed in proportions shown in Table 2 with respect to 100 parts by mass of PP resin, and supplied to a plastograph mixer manufactured by Toyo Seiki Co., Ltd., temperature = 190 ° C., Melting and kneading were carried out under the conditions of rotational speed = 50 rpm and kneading time = 5 minutes to obtain a resin composition. The obtained resin composition was sandwiched between two metal plates and press molded under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and an inorganic filler-containing polypropylene resin sheet having a thickness of 0.5 mm was obtained. Produced.

(Preparation of sheet used for layer D)
Mica 1, flame retardant, lubricant, and antioxidant are mixed in proportions shown in Table 2 with respect to 100 parts by mass of PP resin, and supplied to a plastograph mixer manufactured by Toyo Seiki Co., Ltd., temperature = 190 ° C., Melting and kneading were carried out under the conditions of rotational speed = 50 rpm and kneading time = 5 minutes to obtain a resin composition. The obtained resin composition was sandwiched between two metal plates and press-molded under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and an inorganic filler-containing polypropylene resin sheet having a thickness of 1 mm was produced. .

(Production of laminate)
The sheets used for the A layer and D layer and the carbon fiber material used for the B layer are stacked so as to have a configuration of A layer / B layer / D layer / B layer / A layer and sandwiched between two metal plates. Then, press molding was performed under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and a laminate having a thickness of 2 mm was produced. At this time, the thickness of the A layer = 500 μm, the thickness of the B layer = 150 μm, and the thickness of the D layer = 700 μm.
The obtained laminate was evaluated, and the results are shown in Table 2.

[Example II-2]
(Preparation of sheet used for layer A)
Mica 1, flame retardant, lubricant, and antioxidant are mixed in proportions shown in Table 2 with respect to 100 parts by mass of PC resin, and supplied to a plastograph mixer manufactured by Toyo Seiki Co., Ltd., temperature = 260 ° C., Melting and kneading were carried out under the conditions of rotational speed = 50 rpm and kneading time = 5 minutes to obtain a resin composition. The obtained resin composition was sandwiched between two metal plates and press molded under the conditions of temperature = 260 ° C., pressure = 2 MPa, molding time = 15 minutes, and an inorganic filler-containing polycarbonate resin sheet having a thickness of 0.5 mm was obtained. Produced.

(Preparation of sheet used for layer D)
Mica 1, flame retardant, lubricant, and antioxidant are mixed in proportions shown in Table 2 with respect to 100 parts by mass of PC resin, and supplied to a plastograph mixer manufactured by Toyo Seiki Co., Ltd., temperature = 260 ° C., Melting and kneading were carried out under the conditions of rotation speed = 50 rpm and kneading time = 15 minutes to obtain a resin composition. The obtained resin composition was sandwiched between two metal plates and press-molded under the conditions of temperature = 260 ° C., pressure = 2 MPa, molding time = 15 minutes, and an inorganic filler-containing polycarbonate resin sheet having a thickness of 1 mm was produced. .

(Production of laminate)
The sheet used for the prepared A layer and B layer and the high-spread paper used for the B layer prepared in Example II-1 are configured as A layer / B layer / D layer / B layer / A layer. The laminate was sandwiched between two metal plates and press-molded under the conditions of temperature = 260 ° C., pressure = 2 MPa, molding time = 15 minutes, and a 2 mm-thick laminate was produced. At this time, the thickness of the A layer = 500 μm, the thickness of the B layer = 150 μm, and the thickness of the D layer = 700 μm.
The obtained laminate was evaluated, and the results are shown in Table 2.

[Example II-3]
A laminate was prepared in the same manner as in Example II-1, except that the content of mica 1 in the sheet used for the D layer was changed as shown in Table 2. At this time, the thickness of the A layer = 500 μm, the thickness of the B layer = 150 μm, and the thickness of the D layer = 700 μm.
The obtained laminate was evaluated, and the results are shown in Table 2.

[Example II-4]
A laminate was prepared in the same manner as in Example II-1, except that the content of mica 1 in the sheet used for the D layer was changed as shown in Table 2. At this time, the thickness of the A layer = 500 μm, the thickness of the B layer = 150 μm, and the thickness of the D layer = 700 μm.
The obtained laminate was evaluated, and the results are shown in Table 2.

[Comparative Example 7]
A laminate was prepared in the same manner as in Example II-1, except that the content of mica 1 in the sheet used for the D layer was changed as shown in Table 2. At this time, the thickness of the A layer = 500 μm, the thickness of the B layer = 150 μm, and the thickness of the D layer = 700 μm.
The obtained laminate was evaluated, and the results are shown in Table 2.

[Example of Laminate of Third Aspect]
[Example III-1]
(Preparation of sheet used for E layer)
Mica 1, flame retardant, lubricant, and antioxidant are mixed in proportions shown in Table 3 with respect to 100 parts by mass of PP resin, and supplied to a plastograph mixer manufactured by Toyo Seiki Co., Ltd., temperature = 190 ° C., Melting and kneading were carried out under the conditions of rotational speed = 50 rpm and kneading time = 5 minutes to obtain a resin composition. The obtained resin composition is sandwiched between two metal plates, press molded under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and a plate-like inorganic particle-containing polypropylene resin having a thickness of 0.925 mm A sheet was produced.

(Production of laminate)
The sheet used for the E layer and the carbon fiber material used for the B layer are stacked so as to have a configuration of E layer / B layer / E layer and sandwiched between two metal plates, temperature = 200 ° C., pressure = 2 MPa Then, press molding was carried out under the condition of molding time = 15 minutes to produce a laminate having a thickness of 2 mm. At this time, the thickness of the E layer = 925 μm and the thickness of the B layer = 150 μm.
The obtained laminate was evaluated, and the results are shown in Table 3.

[Example III-2]
A laminate was prepared in the same manner as in Example III-1, except that the content ratio of mica 1 in the sheet used for the E layer was changed as shown in Table 3. At this time, the thickness of the E layer = 925 μm and the thickness of the B layer = 150 μm.
The obtained laminate was evaluated, and the results are shown in Table 3.

[Example III-3]
A laminate was prepared in the same manner as in Example III-1, except that the content ratio of mica 1 in the sheet used for the E layer was changed as shown in Table 3. At this time, the thickness of the E layer = 925 μm and the thickness of the B layer = 150 μm.
The obtained laminate was evaluated, and the results are shown in Table 3.

[Example III-4]
A laminate was produced in the same manner as in Example III-1, except that mica 1 in the sheet used for the E layer was changed to mica 2. At this time, the thickness of the E layer = 925 μm and the thickness of the B layer = 150 μm.
The obtained laminate was evaluated, and the results are shown in Table 3.

[Example III-5]
A laminate was prepared in the same manner as in Example III-1, except that mica 1 in the sheet used for the E layer was changed to mica 3. At this time, the thickness of the E layer = 925 μm and the thickness of the B layer = 150 μm.
The obtained laminate was evaluated, and the results are shown in Table 3.

[Example III-6]
(Preparation of sheets used for other layers)
A PP resin was sandwiched between two metal plates and press molded under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and a polypropylene resin sheet having a thickness of 1 mm was produced.

(Production of laminate)
The sheet used for the other layers produced, the sheet used for the E layer produced in Example III-2, and the high-spread paper used for the B layer produced in Example III-1 were E layer / B layer / others. The layers are stacked so as to have the structure of layer B / layer E and sandwiched between two metal plates, press-molded under conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and a thickness of 2 mm. A laminate was produced. At this time, the thickness of the E layer = 500 μm, the thickness of the B layer = 150 μm, and the thicknesses of the other layers = 700 μm.
The obtained laminate was evaluated, and the results are shown in Table 3.

[Example III-7]
(Preparation of sheet used for E layer)
Mica 1 is mixed at a ratio shown in Table 3 with respect to 100 parts by mass of PC resin and supplied to a plastograph mixer manufactured by Toyo Seiki Co., Ltd., temperature = 260 ° C., rotation speed = 50 rpm, kneading time = 5. The resin composition was obtained by melt-kneading under the conditions of minutes. The obtained resin composition is sandwiched between two metal plates, press molded under the conditions of temperature = 260 ° C., pressure = 2 MPa, molding time = 15 minutes, and a plate-like inorganic particle-containing polycarbonate resin having a thickness of 0.5 mm. A sheet was produced.

(Preparation of sheets used for other layers)
A PC resin was sandwiched between two metal plates and press molded under the conditions of temperature = 260 ° C., pressure = 2 MPa, molding time = 15 minutes, and a polycarbonate resin sheet having a thickness of 1 mm was produced.

(Production of laminate)
The sheet used for the produced E layer and other layers and the high spread paper used for the B layer produced in Example III-1 have a configuration of E layer / B layer / other layers / B layer / E layer. Thus, the laminate was sandwiched between two metal plates and press-molded under the conditions of temperature = 260 ° C., pressure = 2 MPa, molding time = 15 minutes, and a laminate having a thickness of 2 mm was produced. At this time, the thickness of the E layer = 500 μm, the thickness of the B layer = 150 μm, and the thicknesses of the other layers = 700 μm.
The obtained laminate was evaluated, and the results are shown in Table 3.

[Example III-8]
(Preparation of sheets used for other layers)
Mica 1, flame retardant, lubricant, and antioxidant are mixed in proportions shown in Table 3 with respect to 100 parts by mass of PP resin, and supplied to a plastograph mixer manufactured by Toyo Seiki Co., Ltd., temperature = 190 ° C., Melting and kneading were carried out under the conditions of rotational speed = 50 rpm and kneading time = 5 minutes to obtain a resin composition. The obtained resin composition was sandwiched between two metal plates and press molded under the conditions of temperature = 200 ° C., pressure = 2 MPa, molding time = 15 minutes, and a 1 mm thick plate-like inorganic particle-containing polypropylene resin sheet was obtained. Produced.

As shown in Tables 1 to 3, the carbon fiber composite laminates of the present invention produced in the examples have excellent balance between low linear expansion, good surface appearance and press formability.
On the other hand, those produced in the comparative examples do not satisfy the ranges specified in the present invention, the maximum diameter of the carbon fiber bundle, the average fiber length of the carbon fiber, low linear expansion, surface appearance, and press formability. At least one of them was insufficient.

The laminate of the present invention is a carbon fiber composite laminate that has an excellent balance of low linear expansion, good surface appearance and press formability, and can meet the demands for light weight and low cost. It can be suitably used for various molded products such as housings of electrical appliances, interior materials and exterior materials of automobiles and railways.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2013-245788 filed on November 28, 2013, which is incorporated by reference in its entirety.

Claims

A carbon fiber composite laminate having at least a five-layer structure, a thermoplastic resin layer (A layer) containing 30 to 200 parts by mass of an inorganic filler with respect to 100 parts by mass of a thermoplastic resin, and a carbon fiber layer (B layer) and a thermoplastic resin layer (C layer) containing thermoplastic resin as a main component and not containing the inorganic filler, in the order of A layer / B layer / C layer / B layer / A layer,
A carbon fiber composite laminate in which the maximum diameter of the carbon fiber bundle in the B layer is 10 μm or more and 1000 μm or less, and the average fiber length of the carbon fibers is 0.1 mm or more and less than 5 mm.
2. The carbon according to claim 1, wherein the thermoplastic resin used in the A layer and the C layer is at least one resin selected from the group consisting of a polyolefin resin, a polycarbonate resin, a polyamide resin, and a polyester resin. Fiber composite laminate.
The carbon fiber composite laminate according to claim 1 or 2, wherein the inorganic filler used in the A layer is a plate-like particle having an aspect ratio of 20 or more and 500 or less.
The carbon fiber composite laminate according to any one of claims 1 to 3, wherein the B layer is a layer made of carbon fiber mat or carbon fiber paper as a carbon fiber material.
The melt mass flow rate R A (g / 10 min) of the thermoplastic resin of the A layer and the melt mass flow rate R C (g / 10 min) of the thermoplastic resin of the C layer at the same temperature and the same load are R A ≧ The carbon fiber composite laminate according to any one of claims 1 to 4, which has an RC relationship.
The carbon fiber composite laminate according to any one of claims 1 to 5, wherein a maximum cross-sectional height (Rt) of the surface of the A layer is 3 µm or less.
A carbon fiber composite laminate having at least a five-layer structure, a thermoplastic resin layer (A layer) containing 30 to 200 parts by mass of an inorganic filler with respect to 100 parts by mass of a thermoplastic resin, and a carbon fiber layer (B layer) and thermoplastic resin layer (D layer) containing more than 0 part by mass and 100 parts by mass or less of inorganic filler with respect to 100 parts by mass of thermoplastic resin, A layer / B layer / D layer / B layer / A layer in order,
A carbon fiber composite laminate in which the maximum diameter of the carbon fiber bundle in the B layer is 10 μm or more and 1000 μm or less, and the average fiber length of the carbon fibers is 0.1 mm or more and less than 5 mm.
The carbon according to claim 7, wherein the thermoplastic resin used for the A layer and the D layer is at least one resin selected from the group consisting of polyolefin resins, polycarbonate resins, polyamide resins, and polyester resins. Fiber composite laminate.
The carbon fiber composite laminate according to claim 7 or 8, wherein the inorganic filler used in the A layer and the D layer is a plate-like particle having an aspect ratio of 20 or more and 500 or less.
The carbon fiber composite laminate according to any one of claims 7 to 9, wherein the B layer is a layer made of carbon fiber mat or carbon fiber paper as a carbon fiber material.
The carbon fiber composite laminate according to any one of claims 7 to 10, wherein a content ratio of the inorganic filler in the D layer is equal to or less than a content ratio of the inorganic filler in the A layer.
The carbon fiber composite laminate according to any one of claims 7 to 11, wherein a maximum cross-sectional height (Rt) of the surface of the A layer is 3 µm or less.
A carbon fiber composite laminate having at least a three-layer structure, comprising 30 to 200 parts by mass of plate-like inorganic particles having an aspect ratio of 20 to 500 with respect to 100 parts by mass of the thermoplastic resin. It has a plastic resin layer (E layer) and a carbon fiber layer (B layer), the E layer is a front and back layer, the maximum diameter of the carbon fiber bundle in the B layer is 10 μm or more, 1000 μm or less, And the carbon fiber composite laminated body whose average fiber length of this carbon fiber is 0.1 mm or more and less than 5 mm.
The carbon fiber composite laminate according to claim 13, wherein the thermoplastic resin used in the E layer is at least one resin selected from the group consisting of polyolefin resins, polycarbonate resins, polyamide resins, and polyester resins. body.
The carbon fiber composite laminate according to claim 13 or 14, wherein the B layer is a layer made of carbon fiber mat or carbon fiber paper as a carbon fiber material.
The carbon fiber composite laminate according to any one of claims 13 to 15, wherein a maximum cross-sectional height (Rt) of the surface of the E layer is 3 µm or less.