JP2008230238A - Fiber-reinforced composite material plate and molded article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber-reinforced composite material plate exhibiting the excellent strength of adhesion to another member on an end surface, and a molded article using the fiber-reinforced composite material plate. <P>SOLUTION: The fiber-reinforced composite material plate (I) comprises a continuous reinforced fiber group (A), a thermosetting resin (B), and a thermoplastic resin (C). At least one thermoplastic resin layer comprising a part of the continuous reinforced fiber group (A) and the thermoplastic resin (C) is formed in such a position that the shortest embedment distance T<SB>min</SB>of the thermoplastic resin layer of the fiber-reinforced composite material plate is 0.05-0.4 mm. At least either of the maximum resin impregnation thicknesses d<SB>mNmax</SB>and d<SB>mFmax</SB>as the maximum values of the resin impregnation thicknesses d<SB>mnN</SB>and d<SB>mnF</SB>of the thermoplastic resin is not less than 10 μm. Furthermore, the maximum sum total D<SB>max</SB>of the resin impregnation thicknesses of all the thermoplastic resin layers contained in the fiber-reinforced composite material plate is in the range of 10-90% of the thickness of the fiber-reinforced composite material plate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fiber-reinforced composite material plate excellent in adhesiveness. Specifically, the fiber-reinforced composite material plate of the present invention has a thermoplastic resin layer containing continuous reinforcing fibers on the end surface, and has particularly excellent properties of adhesion on the end surface.

  Furthermore, this invention relates to the molded article formed by joining the said fiber reinforced composite material board and another member. This molded body is preferably used for electrical / electronic equipment, office automation equipment, home appliances, medical equipment or automobile parts, aircraft parts, building materials, and the like.

  A molded body (FRP) composed of a thermosetting resin reinforced with a group of continuous reinforcing fibers is widely used as a member for forming various parts and structures. In recent years, FRPs made of these thermosetting resins have been used for various applications because of their light weight and mechanical properties, and there are parts and structures that join FRP and other members according to each application. Many have come to be used.

  Patent Document 1 describes a fiber reinforced composite material laminate having a thermoplastic resin layer on its surface, and the thermoplastic resin layer of the laminate enters the reinforcing fibers with an uneven shape, and the thermoplastic It is possible to develop excellent bonding with different materials by heat welding through the resin layer. Thus, although the laminated body of patent document 1 expresses the outstanding joining through the surface, it is strongly strengthening the joining in the end surface of a laminated board supposing the application to various further various uses. It was desired.

Patent Document 2 proposes a laminated composite in which a thermoplastic resin is disposed between layers of a fiber reinforced thermosetting resin prepreg. The laminated composite is intended to improve the impact resistance of the composite by allowing a thermoplastic resin to exist between the composite layers. The laminated composite is not intended to improve end face bonding, but has a structure in which a thermoplastic resin is present on the end face, and the effect of improving the bondability at the end face is assumed, but the effect is sufficient. It was not something.
International Publication No. 04/060658 Pamphlet International Publication No. 94/016003 Pamphlet

  An object of the present invention is to provide a fiber-reinforced composite material plate that exhibits excellent adhesive strength at the end face with other members and a molded article using the same, in order to improve the problems of the conventional technology. A molded article using the fiber-reinforced composite material plate is suitably used as a structural material for casings such as electric / electronic devices and portable information terminals, and transportation wing devices such as automobiles and airplanes.

The present invention for solving such problems has the following configuration. That is,
(1) A fiber-reinforced composite material plate (I) comprising a continuous reinforcing fiber group (A), a thermosetting resin (B), and a thermoplastic resin (C), and thermoplasticity in the fiber-reinforced composite material plate At least one layer of thermoplastic resin comprising a part of the continuous reinforcing fiber group (A) and the thermoplastic resin (C) at a position where the minimum embedding distance T _min of the resin layer is 0.05 to 0.4 mm. layers are formed, the thermoplastic which is the maximum value of the resin impregnation depth _{d MNN} in the resin impregnated maximum thickness _{d MNmax,} the resin-impregnated maximum thickness is the maximum value of the resin impregnation depth _{d MnF} in thermoplastic resin _{d MFMAX} when _{a, d MNmax} and / or _{d MFMAX} is not less 10μm or more, and the maximum sum _{D ma} resin impregnation depth of all of the thermoplastic resin layer included in the fiber-reinforced composite material plate But the fiber-reinforced composite material plate 10 to 90% of the thickness of the fiber-reinforced composite material plate. (2) The fiber reinforced composite material plate according to (1), wherein the maximum sum D _max of the resin impregnation thickness of the thermoplastic resin layer is 15 to 70% of the thickness of the fiber reinforced composite material plate.

(3) The fiber-reinforced composite material plate according to (1) or (2), wherein the degree of unevenness R at the interface of the thermoplastic resin layer is 10 μm or more.
(4) Some filaments of the continuous reinforcing fiber group (A) are in contact with at least the thermosetting resin (B), and the remaining filaments of the reinforcing fiber group (A) are in contact with at least the thermoplastic resin (C). The fiber-reinforced composite material plate according to any one of (1) to (3).

  (5) The fiber-reinforced composite material plate according to any one of (1) to (4), wherein the fiber-reinforced composite material plate has a thickness of 0.3 to 2 mm.

  (6) The fiber-reinforced composite material plate according to any one of (1) to (5), wherein the thermoplastic resin layer is continuous in the fiber-reinforced composite material plate.

  (7) The fiber-reinforced composite material plate according to any one of (1) to (6), wherein two or more thermoplastic resin layers are present in the fiber-reinforced composite material plate.

  (8) A thermoplastic resin layer made of a thermoplastic resin (C) including a part of the continuous reinforcing fiber group (A) is formed on at least a part of the surface of the fiber-reinforced composite material plate. The fiber reinforced composite material board as described in 1)-(7).

  (9) The fiber-reinforced composite material plate according to any one of (1) to (8), wherein the thermoplastic resin layer is disposed at a symmetrical position with respect to the thickness central axis of the fiber-reinforced composite material plate.

  (10) The end surface of the fiber-reinforced composite material plate has at least one uneven shape portion in a direction parallel to the surface of the composite material plate, and the surface in a direction parallel to the thickness direction of the uneven shape portion. The fiber reinforced composite according to any one of (1) to (9), wherein a thermoplastic resin layer made of the thermoplastic resin (C) including a part of the continuous reinforcing fiber bundle (A) is present at least in part. Material board.

  (11) The ratio L1 / L2 between the length L1 of the root portion of the concave portion of the concave and convex portion and the length L2 of the tip portion of the concave portion of the concave and convex portion is 0.1 or more and less than 1. (10) The fiber-reinforced composite material board described in 1.

(12) The fiber-reinforced composite material plate according to any one of (10) and (11), wherein a maximum depth L _max of the concave portion of the concave and convex portion is 1 to 50 mm.

  (13) The fiber-reinforced composite material plate according to any one of (1) to (12), wherein the continuous reinforcing fiber group (A) is a carbon fiber.

  (14) The fiber-reinforced composite material plate according to any one of (1) to (13), wherein the thermoplastic resin (C) is at least one resin selected from a polyamide resin, a polyester resin, and a polyolefin resin. .

  (15) The fiber-reinforced composite material plate according to any one of (1) to (14) and another member (II) are joined via the thermoplastic resin (C) present on the end face of the fiber-reinforced composite material plate. Integrated product.

  (16) The molded article according to (15), wherein the other member (II) is a thermoplastic resin composition.

(17) Absolute value (| SP ₁ −SP) of the difference between the SP value (SP ₁ ) of the thermoplastic resin (C) and the SP value (SP ₂ ) of the thermoplastic resin constituting the other member (II) The molded article according to (16), wherein ₂ |) is 1 or less.

(18) The molded article according to any one of (15) to (17), which is used for any one of electrical / electronic equipment, office automation equipment, home appliances, medical equipment, automobile parts, aircraft parts, and building materials.
It is.

  By using the fiber reinforced composite material plate of the present invention, it is possible to obtain a molded product having excellent adhesiveness at the end face with other members.

  An example of a schematic cross-sectional view of the end face of the fiber-reinforced composite material plate of the present invention is shown in FIG. In addition, measurement / evaluation of each parameter prescribed | regulated by this invention is the interface vicinity of the thermosetting resin (B) of a fiber reinforced composite material board (I), and a thermoplastic resin (C), and is evaluated and measured. Within the region, a fiber reinforced composite material plate in which the cross-sectional area of the reinforcing fibers forming the continuous reinforcing fiber group (A) is 150% or less of the minimum cross-sectional area of the reinforcing fibers is visible. This is based on the evaluation and measurement of the cross-sectional image of I). That is, when the cross-sectional area of the reinforcing fiber as shown in FIG. 1 does not become 150% or less of the minimum cross-sectional area of the reinforcing fiber on the end face (end face in the molded state) of the produced fiber-reinforced composite material plate (I). The portion of the reinforcing fiber that is evaluated and observed in the vicinity of the interface between the thermosetting resin (B) and the thermoplastic resin (C) by cutting or the like is the minimum cut of the reinforcing fiber on the measurement / evaluation surface as shown in FIG. A unified measurement / evaluation is performed by using a cross-section in which a reinforcing fiber having a cross-section of 150% or less of the area is visible as an end face.

FIG. 1 shows an example in which one thermoplastic resin layer 3 is formed inside a fiber reinforced composite material plate 1. The fiber reinforced composite material plate 1 according to the present invention has a minimum buried distance T of the thermoplastic resin layer 3 made of a part of the continuous reinforcing fiber group (A) and the thermoplastic resin (C) in the fiber reinforced composite material plate 1. It is important to set _min to 0.05 to 0.4 mm.

This is because, by adopting such a configuration, the adhesive strength with the other member (II) can be increased at the end face of the fiber-reinforced composite material plate 1. That is, by setting _Tmin within this range, the thermoplastic resin layer 3 can surely exist near the surface 5 of the fiber reinforced composite material plate 1 at the end face of the fiber reinforced composite material plate 1, It becomes possible to firmly adhere to other members (II) in the vicinity of the surface of the fiber reinforced composite material plate 1 and to stably exhibit excellent end face adhesive strength through the thermoplastic resin layer 3. Because it becomes. From such a viewpoint, T _min is preferably 0.075 to 0.2 mm, and more preferably 0.1 to 0.15 mm.

  Here, the “end face” defined in the present invention will be described using the fiber reinforced composite material plate (I) illustrated in FIG. 7. Other than the one surface 5 a and the other surface 5 b of the fiber reinforced composite material plate. It means surface 7.

In the present invention, the shortest burying distance T _min of the thermoplastic resin layer is defined as follows.

That is, when there is no thermoplastic resin on both surfaces of the fiber reinforced composite material plate (I) (FIG. 2-a), it is formed by the thermoplastic resin layer 3 and the thermosetting resin 2 closest to the one surface 5a. S _Np (1) is the position closest to the one surface 5a at the portion of the interface 6a, and the interface 6b formed by the thermoplastic resin layer 3 and the thermosetting resin 2 closest from the other surface 5b. When the position closest to the other surface 5b at the part is S _Np (2), the distance T (1) between S _Np (1) and the one surface 5a, S _Np (2) and the other surface Among the distances T (2) from the surface 5b, the shorter distance is defined as _Tmin .

When the thermoplastic resin 3f exists on the surface on one side (FIG. 2-b), the interface formed by the thermoplastic resin layer 3 and the thermosetting resin 2 closest to the surface 5a on the side where the thermoplastic resin does not exist. in 6a, the distance to the heat S _Np and the surface 5a of the heat side of the thermoplastic resin is not present in the position closest to the surface 5a of the side where the thermoplastic resin is absent and T _min.

When the thermoplastic resin 3f is present on the surfaces on both sides (FIG. 2-c), the thermoplastic resin layer 3 and the thermosetting layer closest to the one surface 5a except for the thermoplastic resin present on the one surface 5a. In the interface 6a on the side close to the surface 5a among the interfaces formed with the resin 2, the position closest to the one surface 5a is S _Np (1), except for the thermoplastic resin present on the other surface 5b. Of the interface formed by the thermoplastic resin layer 3 and the thermosetting resin 2 closest to the other surface 5b, the position closest to the other surface 5b is defined as S _Np ( 2), the position S _Fp (1) farthest from the one surface 5a at the interface 6f between S _Np (1) and the thermoplastic resin layer 3f present on the one surface 5a and the thermosetting resin 2 ) and the distance T (3) up to, S _{p (2)} and the other farthest from the other surface 5b at the interface 6f between the thermoplastic resin layer 3f and the thermosetting resin 2 on the surface 5b S _{Fp (2)} Distance T (4) to The shorter distance is T _min .

As shown in FIG. 3, the fiber reinforced composite material plate 1 according to the present invention may include two or more thermoplastic resin layers 3. In this case, at least one layer a thermoplastic resin layer is, buried shortest distance _{T min} is 0.05~0.4mm in fiber-reinforced composite material plate, preferably 0.075～0.2Mm, more preferably 0.1 It suffices to be present at a position of 0.15 mm.

The fiber-reinforced composite material plate according to the present invention has the following formula (1) Resin impregnation depth in the thermoplastic resin layer 3 which is calculated by d _MNN, the d _MnF, 10 part of the edge surface of at least a fiber-reinforced composite material plate It is important to _{set dmNmax} and / or _dmFmax to 10 μm or more when the thickest of those measured above is the resin impregnated maximum thickness _dmNmax and _dmFmax in the thermoplastic resin layer 3, respectively. . By _{setting the} resin impregnated maximum thickness _dmNmax and / or _dmFmax within this range, the thermoplastic resin layer 3 is firmly bonded to the end face of the fiber reinforced composite material plate 1, which is excellent from the viewpoint of adhesive strength. May exhibit the characteristics. The maximum values of the resin-impregnated maximum thicknesses _dmNmax and _dmFmax are not particularly limited from the viewpoint of increasing the adhesive strength, but if it is about 300 μm, it is sufficient to _exhibit the excellent adhesion intended by the present invention.

In the present invention, the resin impregnation thicknesses d _mnN and d _mnF are defined as follows. That is, the m-th thermoplastic resin layer shown in FIG. 3 (that is, the thermoplastic resin layer used for specifying _Tmin is used as the first thermoplastic resin layer, from the surface on the side used for specifying _Tmin ). For the m-th thermoplastic resin layer toward the opposite surface), the surface of the interface between the thermosetting resin (B) 2 and the thermoplastic resin (C) 3 used for specifying the T _min the side of the interface close to the 5 _{S MNN,} the far side of the interface from the surface 5 of the side used for certain of the _{T min} and _{S MnF.} An intermediate reference line S _mnM of the thermoplastic resin layer 3 is _obtained from each interface S _mnN and S _mnF , and this S _mnM is used as a reference. In the reinforcing fiber group (A) existing inside the thermoplastic resin layer 3 between the intermediate reference line S _mnM and the interface S _mnN , the reinforcing fiber in the position where the shortest distance to the intermediate reference line S _mnM is the longest. _Let F _{mnNF be} a distance from the intermediate reference line S _mnM to the reinforcing fiber F _{mnNF be} d _mnNF . Further, the reinforcing fiber in the position where the shortest distance to the intermediate reference line S _{mnM is} the shortest is F _mnNN, and the distance from the intermediate reference line S _mnM to the reinforcing fiber F _mnNN is d _mnNN . Similarly, in the reinforcing fiber group (A) existing inside the thermoplastic resin layer 3 between the intermediate reference line S _mnM and the interface S _mnF , the shortest distance to the intermediate reference line S _mnM is the longest position. A certain reinforcing fiber is F _mnFF, and a distance from the intermediate reference line S _mnM to the reinforcing fiber F _mnFF is d _mnFF . Further, the reinforcing fibers in the nearest position is shortest distance to the intermediate reference line _{S MNM} and _{F MnFN,} the distance from the intermediate reference line _{S MNM} until reinforcing fibers _{F MnFN} and _{d mnFN.} Then, d _mnN and d _mnF calculated from the equation (1) are defined as the resin impregnation thickness.

  The reinforcing fiber group (A) present in the thermoplastic resin layer or in the thermosetting resin layer represented by the present invention means that the entire interface of the reinforcing fiber group (A) in the observation cross section is thermoplastic. It is defined as being coated with a resin or thermosetting resin.

In the present invention, the center reference line S _{mnM serving} as a reference for obtaining the resin impregnated thicknesses d _mnN and d _mnF can be specified as follows. That is, at the end face of the fiber reinforced composite material plate (I) shown in FIG. 4, the surface of the fiber reinforced composite material plate (I) is placed within a range of 5 to 15 μm from one surface 5a to the paired surface 5b. 50 or more perpendicular lines are drawn in the thickness direction so as to be equally spaced, and this line is taken as a measurement line g _mnr . The intersection of this measurement line g _mnr and the interface S _mnN is P _mnrN , and the intersection of the interface S _mnF is P _mnrF . On the measurement line g _mnr , the distance between the intersection point P _mnrN and the intersection point P _mnrF is measured, and an intermediate position of the distance between the two points is _defined as P _mnrM . An intermediate position P _mnrM is obtained for each measurement line g _mnr , and a continuous line obtained by connecting adjacent intermediate positions P _mnrM with a straight line is defined as an intermediate reference line S _{mnM of the mth} thermoplastic resin layer 3.

Here, the subscript m individually identifies the thermoplastic resin layer formed inside the fiber-reinforced composite material plate, and as described above, the surface 5 on the side used for specifying _Tmin. The thermoplastic resin layers corresponding to m = 1, 2, 3,... In order from the surface closer to the surface 5 on the side used for specifying the T _min excluding the thermoplastic resin present in FIG. For example, in FIG. 1, since the thermoplastic resin layer 3 is one layer, only m = 1, and if there are ten thermoplastic resin layers, m = 1, 2,... 10 The subscript n is a number corresponding to the observed end face. When the number of observed end faces is 10, n = 1, 2,... . In addition, the subscript r is a number corresponding to the measurement line, and becomes r = 1, 2, 3... Sequentially from one side of the fiber reinforced composite material plate (I). = 1, 2, 3, ... 51.

  The schematic diagrams shown in FIGS. 1 and 3 to 6 can be confirmed by observing the end face of the fiber-reinforced composite material plate using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or an optical microscope. In order to adjust the contrast of observation, a staining process may be performed as necessary.

Further, the total sum of the maximum resin impregnation thicknesses _dmNmax in each thermoplastic resin layer (m = 1, 2,...) And the maximum resin impregnation thickness d _{mFmax in} each thermoplastic resin layer (m = 1, 2,...). the sum of the sum _(i.e., Σd mNmax + Σd mFmax) and was defined as the maximum sum _{D max} for all of the thermoplastic resin layer resin impregnation depth contained in the fiber reinforced composite material plate, said maximum sum _{D max} is a fiber-reinforced composite It is important that the thickness is 10 to 90% of the thickness h of the material plate.

Here, the thickness h of the fiber-reinforced composite material plate is a distance from the surface 5 on one side to the surface 5 on the opposite side in the end face. When the maximum total sum _Dmax is within the above range, a thermoplastic resin layer firmly integrated with the fiber-reinforced composite material plate (I) can be secured at the end face of the fiber-reinforced composite material plate enough for adhesion. . Considering the molding processability of fiber reinforced composite material plates, resins containing thermosetting resins are often more fluid in the molding process than thermoplastic resins, making it easier to impregnate the resin between reinforcing fiber groups. . Thus _{D max} preferably is small in consideration of the load of the process surface, it is preferable that _{D max} is 15 to 70 percent by consideration of the balance between molding processability and adhesive property, and more preferably from 20% to 50% . In the present invention, the unevenness degree R is defined as follows. In m-th thermoplastic resin layer 3 shown in FIG. 5, the longest distance among distances _{L MNN} between the _{P MnrM} and the _{P MnrN} and _{L MnF,} the shortest distance _{L mNN.} Let R be the absolute value of the difference between L _mNF and L _mNN as a value representing the degree of unevenness of the interface. It is preferable that the thermoplastic resin layer has a concavo-convex shape in order to improve adhesion between the thermosetting resin and the thermoplastic resin, and R is preferably 10 μm or more. More preferably, it is 20 micrometers or more, More preferably, it is 40 micrometers or more. Although there is no restriction | limiting in particular about the upper limit of R, About 200 micrometers is enough in order to express the outstanding adhesiveness.

  Further, some filaments of the continuous reinforcing fiber group (A) are in contact with at least the thermosetting resin (B), and the remaining filaments of the reinforcing fiber group (A) are in contact with at least the thermoplastic resin (C). It is preferable. This is because filaments having a group of reinforcing fibers are in contact with a thermosetting resin in part in the longitudinal direction and in other parts are in contact with a thermoplastic resin. Including skewered state. FIG. 12 shows a schematic diagram of a fiber-reinforced composite material plate in which reinforcing fiber groups are arranged in the longitudinal direction of the drawing in order to explain the above-described embodiment. Note that FIG. 12 also shows a model in which the portion surrounded by a broken-line square is three-dimensionally modeled. In the three-dimensional diagram, only the reinforcing fiber 4a and the thermoplastic resin 3 are visualized for convenience of expression. It is shown. The thermosetting resin is not visualized, and the portion of the reinforcing fiber 4a protruding from the thermoplastic resin 3 indicates a portion buried in the thermosetting resin. One of the reinforcing fiber groups 4a shown in FIG. 12 has a portion that penetrates both the thermoplastic resin and the thermosetting resin. In such a state, the thermosetting resin and the thermosetting resin This is preferable because the interface of the plastic resin is firmly integrated with the reinforcing fiber.

In order to determine the _{minimum embedding} distance T _min of the thermoplastic resin layer, the resin impregnation thickness d _mnN and d _mnF defined in the present invention, and the degree R of the uneven shape of the interface, the method of measuring the distance and width is not particularly limited. For example, there are a method of measuring using a cross-sectional image and image analysis software of a computer, and a method of measuring from a printed image using a measuring instrument such as a ruler or a caliper.

  The thickness of the fiber reinforced composite material plate is preferably thin from the viewpoint of increasing the degree of freedom of design of the molded product to be applied, specifically 0.3 to 2 mm, preferably 0.5 to 1.mm. 5 mm is more preferable, and 0.8 to 1.2 mm is more preferable.

  Moreover, no matter how the fiber reinforced composite material plate is processed, the end face always has a thermoplastic resin layer (C), and the end face can exhibit excellent adhesiveness, so the thermoplastic resin layer must be continuous. Is preferred. Here, “continuously” means a state in which the thermoplastic resin layer is continuously connected to the entire area (width or length direction) of the plate at the end face.

  However, in the same (one) thermoplastic resin layer on the end face to be observed / evaluated, the length of the discontinuous portion of the thermoplastic resin layer is 100 μm or less, and the fiber reinforced composite plate of the end face image ( In I), if the sum of the lengths of the discontinuous portions of the thermoplastic resin layer is 30% or less compared to the width of the evaluation region of the fiber reinforced composite material plate (I), it is “continuous”. You can judge. The “discontinuous portion length” as used herein refers to the shortest distance between the closest positions of one thermoplastic resin layer and the other thermoplastic resin layer in the portion where the thermoplastic resin layer is interrupted. To do.

  Furthermore, it is preferable that two or more thermoplastic resin layers are present in order to develop stable adhesiveness at the end face of the fiber-reinforced composite material plate. When two or more layers are present, the bonded portion is uniformly present on the end face of the fiber-reinforced composite material plate, and the entire end face can be easily and stably joined.

  In order to develop excellent adhesiveness at the end face of the fiber reinforced composite material plate, it is joined through the surface of the fiber reinforced composite material plate together with joining through the end surface of the fiber reinforced composite material plate. Is preferable from the viewpoint of strengthening adhesion, and a thermoplastic resin layer made of a thermoplastic resin (C) including a part of the continuous reinforcing fiber group (A) is formed on at least a part of the surface. Preferably it is.

The thermoplastic resin present on the surface preferably satisfies the conditions of the resin maximum thicknesses _dmNmax and _dmFmax of the thermoplastic resin layer formed inside the fiber-reinforced composite material plate from the viewpoint of adhesion.

  The fiber reinforced composite material plate of the present invention is a material in which the thermoplastic resin (C) is based on the thickness central axis of the fiber reinforced composite material plate in order to produce a fiber reinforced composite material plate with good dimensional accuracy while suppressing warping. It is preferable that they are arranged at symmetrical positions. Furthermore, by arranging the thermoplastic resin (C) in a symmetrical position, the bonded portion on the end surface is arranged in a symmetrical position in the thickness direction of the fiber-reinforced composite material plate, so that the adhesion is more stable. It is preferable because it is easily expressed. In addition, the "symmetrical position" said here means what was comprised so that it might become symmetrical in the process of manufacturing a fiber reinforced composite material board (I).

FIG. 6 is a schematic cross-sectional view for specifically explaining the “symmetrical position”. The thermoplastic resin layer 3 (s = 1) and the thermosetting resin 2 that are closest to the thickness center axis A at the portion (1) that faces the one surface side from the thickness center axis A of the fiber reinforced composite material plate (I). _L1N1 is the distance to the position closest to the thickness center axis A at the portion of the interface 6-2 formed by and the closest to the portion (2) from the thickness center axis A toward the other surface side When the distance to the position closest to the thickness center axis A at the portion of the interface 6-3 formed by the thermoplastic resin layer 3 (s = 1) and the thermosetting resin 2 is _L1N2 , L _1N1 value _{U 1a} obtained by dividing the smaller number in the larger numbers of _{L 1N2} is 0.7 to 1.0, similarly, site directed from the thickness center axis a on one surface side (1 ), The closest thermoplastic resin layer 3 (s = 1) and the thermosetting resin 2 In at the site of the interface 6-1 to be formed, the distance to the farthest to the thickness center axis A and L _1F1, at the site (2) towards than the thickness center axis A to the other surface side, Nearest heat When the distance to the position farthest from the thickness center axis A at the portion of the interface 6-4 formed by the plastic resin layer 3 (s = 1) and the thermosetting resin 2 is _L1F2 , this L if the value U _1b obtained by dividing the smaller number in the larger numbers of _1F1 and L _1F2 are 0.7 to 1.0, they are assumed to each other may be considered to be present in the "symmetrical positions" .

In the same manner, the thermoplastic resin layer 3 (s = n) that is nth closest to the thickness center axis A at the portion (1) that faces the one surface side from the thickness center axis A of the fiber reinforced composite material plate (I). _LnN1 is the distance to the position closest to the thickness center axis A at the interface portion formed between the thermosetting resin 2 and the thermosetting resin 2, and the portion (2) from the thickness center axis A toward the other surface side L _nN2 is the distance to the position closest to the thickness center axis A at the interface portion formed by the thermoplastic resin layer 3 (s) and the thermosetting resin 2 that is _nth closest to the thickness center axis A. In this case, the value U _na obtained by dividing the smaller value of L _nN1 and L _nN2 by the larger value is 0.7 to 1.0, and similarly, the nth thermoplastic resin layer 3 ( s = n) at the interface between the thermosetting resin 2 and the thickness center axis A Site toward the distance to the farthest on the one surface side (1) and _{L nF1} and other sites (2) toward the surface side and _{L nF2,} numerically smaller numerical Of the _{L nF1} and _{L nF2} if the value U _nb obtained by dividing the larger of 0.7 to 1.0, they are assumed to each other may be considered to be present in the "symmetrical position".

Here, the subscript s of L _sN1 , L _sN2 , L _sF1 and L _sF2 individually identifies the thermoplastic resin layer formed inside the fiber-reinforced composite material plate, and as described above, In the thermoplastic resin layer existing on each surface side from the thickness center axis A of the fiber reinforced composite material plate (I), s− = 1, 2, 3,... The thermoplastic resin to be used is shown. Further, when the number of the thermoplastic resin layers existing in the portions (1) and (2) from the thickness center axis A toward the two surface sides is greatly different from this definition, the thermoplastic resin is symmetrical from the thickness center axis A. In order to maintain a symmetrical position, the number of the thermoplastic resin layers is preferably the same. In the present invention, the thickness central axis is the distance h between the one surface and the other surface of the fiber reinforced composite material plate (I), as shown by A in FIG. 6, and the thickness h of the fiber reinforced composite material plate (I). In the middle position.

  Although there is no restriction | limiting in particular about the manufacturing method of the fiber reinforced composite material board of this invention, The film which consists of a thermoplastic resin in the fiber reinforced thermosetting resin prepreg which consists of a reinforced fiber group (A) and a thermosetting resin (B). A production method in which a layered substrate such as a nonwoven fabric or a non-woven fabric is laminated between necessary portions or prepregs, and is heated and press-molded at a temperature equal to or higher than the temperature at which the thermoplastic resin melts is preferable.

  In the fiber reinforced composite material plate of the present invention, a more preferable end surface shape for exhibiting excellent adhesion at the end surface is such that the end surface of the fiber reinforced composite material plate is parallel to the surfaces 5a and 5b as shown in FIG. A reinforcing fiber group having at least one concavo-convex shape portion in a flat plane (XY plane) direction and continuous with at least a part of the surface 7 in a direction parallel to the thickness direction (Z-axis direction) of the concavo-convex shape portion ( This is a shape in which the thermoplastic resin layer 3 made of the thermoplastic resin (C) including a part of A) exists. By adopting such a shape, the member to be joined can take a fitting structure with the concavo-convex shape portion of the composite material plate and can be joined via the thermoplastic resin layer 3 on the step surface. The bonding area can be made larger than that of the fiber reinforced composite material plate without any of the above, and more excellent adhesion can be expressed.

  The shape of the step is preferably an uneven shape in which the fitting structure is difficult to come off mechanically. For example, if the width L1 of the root portion of the concave / convex concave portion is narrower than the width L2 of the tip portion of the concave / convex concave portion, such as a comb-shaped concave / convex shape, the fitting structure is difficult to come out and the end face adhesion is secured. This is more preferable. Specifically, L1 / L2 is preferably 0.1 or more and less than 1. More preferably, it is 0.2-0.9, More preferably, it is 0.3-0.8. FIG. 11 shows examples of the concavo-convex shape portions L1 and L2.

  There is no particular limitation on the method of manufacturing the uneven portion in the surface direction on the end face of the fiber reinforced composite material plate.For example, in the portion where the uneven portion is formed, the layered base material of the prepreg or thermoplastic resin that is laminated in advance is used. The size is cut out by the size of the concave and convex portions, and the gaps created are sandwiched between spacers and heated and press-molded. There is a method of processing and forming the shape portion.

Here, the deepest depth L of the concave portion of the concave / convex shape portion of the end surface, which is the difference between the peak portion P ₁ and the valley portion P ₂ of the concave / convex shape portion shown in FIG. 7, is the maximum depth of the concave portion of the end surface. is the L _max, preferably from the viewpoint of easy processing aspects and concave and convex portion improves the bonding strength of the end face, the maximum depth L _max of the concave portion of the end surface is 1 to 50 mm, more preferably 1.2 -30 mm, more preferably 1.5-10 mm.

  The form of the continuous reinforcing fiber group (A) constituting the fiber-reinforced composite material plate of the present invention is not particularly limited. For example, a cloth composed of a large number of reinforcing fibers, a large number of reinforcing fibers arranged in one direction Examples thereof include a reinforced fiber group (unidirectional fiber group), a unidirectional cloth composed of the unidirectional fiber group, a combination thereof, and a multi-layer arrangement. Among these, from the viewpoint of productivity of the fiber-reinforced composite material as the base material, a cloth and a unidirectional fiber group are preferably used. The reinforcing fiber group may be composed of a plurality of fiber groups having the same form, or may be composed of a plurality of fiber groups having different forms. The number of reinforcing fibers constituting one reinforcing fiber group is usually 300 to 48,000, but considering the production of the base material, it is preferably 300 to 24,000, and more preferably 1,000. ~ 12,000.

  Here, the reinforcing fiber group (A) is composed of a large number of reinforcing fibers continuous in at least one direction, for example, over a length of 10 mm or more. The reinforcing fiber group (A) does not need to be continuous over the entire length in the length direction of the fiber reinforced composite material or over the entire width in the width direction of the fiber reinforced composite material, and may be divided in the middle. .

  Examples of the fiber material of the reinforcing fiber group used include, for example, metal fibers such as aluminum fibers, brass fibers and stainless fibers, glass fibers, polyacrylonitrile-based, rayon-based, lignin-based, pitch-based carbon fibers and graphite fibers. , Aromatic polyamide fibers, polyaramid fibers, PBO fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, nylon fibers, polyethylene fibers, and other organic fibers, and silicon carbide fibers, silicon nitride fibers, alumina fibers, silicon carbide fibers And boron fiber. Among these, carbon fibers having a small specific gravity, high strength, and high elastic modulus are preferably used. These are used alone or in combination of two or more. These fiber materials may be subjected to surface treatment. Examples of the surface treatment include a metal deposition treatment, a treatment with a coupling agent, a treatment with a sizing agent, and an adhesion treatment of an additive.

  Examples of the thermosetting resin (B) constituting the fiber-reinforced composite material plate of the present invention include unsaturated polyester, vinyl ester, epoxy, phenol (resol type), urea melamine, polyimide, bismaleimide and cyanate. Examples thereof include esters and the like, and copolymers, modified products, and resins obtained by blending at least two of them can also be used. An elastomer or a rubber component may be added to the thermosetting resin (B) in order to improve impact properties.

  In the present invention, an epoxy resin is preferably used as the thermosetting resin (B), particularly from the viewpoint of the mechanical properties of the molded product. Furthermore, the epoxy resin is preferably contained as a main component of the thermosetting resin (B) in order to express its excellent mechanical properties, and specifically, 60% by weight or more is preferably contained.

  Examples of the thermoplastic resin (C) constituting the fiber-reinforced composite material plate of the present invention include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PENp), In addition to polyester resins such as liquid crystal polyester, polyolefins such as polyethylene (PE), polypropylene (PP), and polybutylene, styrene resins, urethane resins, polyoxymethylene (POM), polyamide (PA), polycarbonate (PC ), Polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified PPE, polyimide (PI), polyamideimide (PAI), polyether Imide (PEI), Polysulfone (PSU), Modified PSU, Polyethersulfone (PES), Polyketone (PK), Polyetherketone (PEK), Polyetheretherketone (PEEK), Polyetherketoneketone (PEKK), Polyarylate (PAR), polyether nitrile (PEN), phenolic resin and phenoxy resin. The thermoplastic resin (C) may be a copolymer or modified body of the above resin and / or a resin blended with two or more types. Among these, for the specific purpose, it is preferable that one or more of the following thermoplastic resins (C) are contained in the thermoplastic resin in an amount of 60% by weight or more. From the viewpoint of the strength and impact resistance of the molded product, polyamide (PA) and polyester are preferably used. Further, from the viewpoint of heat resistance and chemical resistance, polyphenylene sulfide (PPS) and polyetherimide (PEI) are preferably used. From the viewpoint of the appearance of the molded product and dimensional stability, polycarbonate (PC) and styrene resin are particularly preferably used. From the viewpoint of hot water resistance, polyphenylene ether (PPE) is preferably used. From the viewpoints of moldability and lightness, a polyolefin-based resin is preferable, for example, a polypropylene resin. Among these, a polyamide resin is particularly preferably used from the viewpoint of the strength of the molded product.

  Further, other elastomers or rubber components may be added to the thermoplastic resin (C) in order to improve impact resistance. Depending on the application, etc. These fillers and additives may be contained. As fillers and additives, for example, inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, Examples include heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, and coupling agents.

  For example, the fiber-reinforced composite material plate 1 of the present invention can be combined with another member (II) 9 shown in FIG. 8 to form an integrated molded product 10 and ensure good adhesiveness. It is preferable to join via the thermoplastic resin (C) which exists in the end surface of the fiber reinforced composite material board 1. Here, the type of the other member (II) is not particularly limited, and known members such as thermosetting resin, thermoplastic resin, cement, concrete, fiber reinforced products thereof, wood, metal material, and paper material are available. Preferably used. In order to further improve the adhesion, the other member (II) is preferably subjected to a surface treatment, a primer treatment, a coating treatment with a thermoplastic resin, or the like according to circumstances.

  As the other member (II), a thermoplastic resin composition containing reinforcing fibers is particularly preferably used from the viewpoint of mechanical properties, and a thermoplastic resin is preferably used from the viewpoint of moldability. There is no restriction | limiting in particular as a thermoplastic resin to be used in either case, It can select according to the thought similar to said thermoplastic resin (C). Moreover, as a fiber which comprises the reinforced fiber mix | blended and used for said thermoplastic resin composition, it can select according to the idea similar to the fiber in the above-mentioned continuous reinforced fiber group. However, when the thermoplastic resin composition is formed by injection molding, it is preferable that the reinforcing fibers are short fibers and are uniformly dispersed in the thermoplastic resin composition. In this case, when the reinforcing fiber is carbon fiber or glass fiber, the blending ratio of the reinforcing fiber is 5 to 75% by weight with respect to the thermoplastic resin composition from the viewpoint of balance between moldability, strength and lightness. Preferably, it is 15 to 65% by weight.

When the other member (II) is a thermoplastic resin composition, the solubility parameter (SP value) (SP ₁ ) of the thermoplastic resin (C) is used from the viewpoint of increasing the adhesive strength with the fiber-reinforced composite material plate. The absolute value (| SP ₁ −SP ₂ |) of the difference from the SP value (SP ₂ ) of the thermoplastic resin constituting the thermoplastic resin composition as the other member (II) is preferably 1 or less. . More preferably, it is 0.8 or less, More preferably, it is 0.6 or less. Here, the SP value refers to a value calculated based on the repeating unit of the polymer at 25 ° C. determined by the method of Fedors. In the structural formula of the compound to be obtained, the evaporation energy of atoms and atomic groups Molar volume data, determined from equation (2).

  In the formula, Δei and Δvi represent the evaporation energy and molar volume of an atom or atomic group, respectively. The structural formula of the compound to be determined is determined using a general structural analysis technique such as IR, NMR, and mass spectrum.

In obtaining the SP value, the methods described in Documents 1 and 2 can be applied in detail.
[Reference 1] RFFedors, Polym. Eng. Sci., 14 (2), 147 (1974)
[Reference 2] Shinji Mukai and Noriyuki Kaneshiro “Practical Polymer for Engineers” (Kodansha, published on October 1, 1981), pp. 66-87 (2).

  The manufacturing method of the molded article using the fiber-reinforced composite material plate of the present invention is not particularly limited. For example, the manufacturing method uses a method in which another member (II) is bonded, pasted and then cooled at a temperature equal to or higher than the melting point or softening point of the thermoplastic resin layer constituting the fiber-reinforced composite material plate. It is done. The procedure for joining the fiber-reinforced composite material plate and the other member (II) is not particularly limited. For example, a fiber-reinforced composite material plate is preliminarily molded, and simultaneously with the molding of the other member (II), both are joined and integrated, (II) the fiber-reinforced composite material plate and the other member (II) Are separately formed in advance, and both are joined and integrated.

  A method of mechanically fitting and integrating the fiber reinforced composite material plate and the other member (II), a method of integrating both using mechanical coupling means such as bolts and screws, and an adhesive for both A method of integrating by using chemical bonding means such as may be used in combination as necessary.

  As a specific example of the integration method, a fiber-reinforced composite material plate is press-molded, processed or post-processed to a predetermined size as necessary, and then inserted into an injection mold, and then another member (II) There is a technique of injection molding a material for forming a mold into a mold.

  As a specific example of the integration method (II), a fiber reinforced composite material plate prepared by press molding a fiber reinforced composite material plate, processed or post-processed to a predetermined size as needed, and separately for injection molding is used. There is a method in which the other members (II) are molded in advance and integrated with each other by thermal bonding or ultrasonic welding.

  From the viewpoint of mass production of molded products, insert injection molding and outsert injection molding in the integrated method are preferably used. From the viewpoint of shape stability and precision of the bonded portion, the above-mentioned integration method (II) is preferably used, and thermal welding, vibration welding, ultrasonic welding, and laser welding can be preferably used.

  The fiber reinforced composite material plate of the present invention and a molded product using the same are used for electrical or electronic devices such as personal computers, displays, mobile phones, personal digital assistants, office automation devices, home appliances, and medical devices. It is preferably used in applications.

In addition, because other members such as complex shapes can be firmly joined to large molded products with excellent mechanical properties, it is also suitable for automobiles, motorcycles, bicycles, aircraft, building materials parts, members and panel skins. It is done.
Examples of these application groups are as follows.

<Electrical and electronic equipment>
The fiber reinforced composite material plate of the present invention and a molded body using the same are, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, and light. Pickup, oscillator, terminal board, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, display, FDD carriage, chassis, HDD, MO, motor It is preferably used for electric / electronic equipment products such as brush holders, parabolic antennas, notebook computers, mobile phones, digital still cameras, PDAs, portable MDs, liquid crystal displays, plasma displays, or parts, members, and housings thereof.

<Office automation equipment>
Further, the fiber-reinforced composite material plate of the present invention and a molded body using the same are preferably used for office products such as telephones, facsimiles, copiers, typewriters, word processors, or members and cases thereof. .

<Household appliances>
In addition, the fiber-reinforced composite material plate of the present invention and the molded body using the same are a casing, a VTR, a copy machine, a television, an iron, a hair dryer, a rice cooker, a microwave oven, an acoustic device, a vacuum cleaner, and a toiletry. It is preferably used for appliances, laser discs, compact discs, home appliances such as lighting, refrigerators and air conditioners, or members and casings thereof.

<Medical equipment>
In addition, the fiber-reinforced composite material plate of the present invention and a molded body using the same are preferably used for medical device products such as X-ray cassettes or parts and members thereof.

<Auto parts>
The fiber reinforced composite material plate of the present invention and a molded body using the same are various types of valves such as motor parts, alternator terminals, alternator connectors, IC regulators, light potentiometer bases, suspension parts, and exhaust gas valves. , Fuel related, exhaust system or various pipes for intake system, air intake nozzle snorkel, air cleaner box, resonator, intake manifold, stabilizer, various arms, various frames, various hinges, various bearings, fuel pump, gasoline tank, CNG tank, engine Cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position Sensor, Crankshaft position sensor, Air flow meter, Brake butt wear sensor, Thermostat base for air conditioner, Heating hot air flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, Wiper motor related parts, Distributor , Starter switch, starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel-related electromagnetic valve, connector for fuse, battery tray, AT bracket, headlamp support, pedal housing, handle, door beam, protector , Chassis, bulkhead, frame, subframe, armrest, horn terminal, Tep motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, noise shield, radiator support, spare tire cover, seat shell, solenoid bobbin, engine oil filter, ignition device case, under cover, scuff plate, pillar trim, propeller shaft, Motorcycles such as drive shafts, wheels, wheel covers, fenders, door mirrors, room mirrors, fascias, bumpers, bumper beams, bonnets, trunk hoods, aero parts, platforms, cowl louvers, roofs, instrument panels, spoilers and various modules It is preferably used for automobile parts to be included, or automobile parts and skins.

<Aircraft parts>
In addition, the fiber-reinforced composite material plate of the present invention and a molded body using the same are aircraft parts such as landing gear pods, winglets, spoilers, edges, ladders, elevators, failings, ribs, or members and outer parts. It is preferably used for a plate.

<Building materials>
Moreover, the fiber reinforced composite material board of this invention and a molded object using the same are preferably used for members or parts for building materials such as panels such as soundproof panels and heat insulation panels.

<Others>
Furthermore, the fiber-reinforced composite material plate of the present invention and the molded body using the same are various rackets, golf club shafts, yachts, boards, ski equipment, fishing rods, bicycle-related sports-related parts, members, and satellite-related products. It is preferably used for parts, game or entertainment product parts such as pachinko machines, slot machines, game machines, members and cases, optical instruments such as microscopes, binoculars, cameras, watches, precision machine related parts, members and cases, etc.

  That is, the molded body in which the face plate made of the fiber-reinforced composite material plate according to the present invention and the frame portion are integrated is the above-mentioned electric / electronic device, office automation device, home appliance, medical device, automobile component, aircraft component, or It is preferable to be used for building materials. Among these, it is preferably used in applications such as electric / electronic devices such as personal computers, displays, mobile phones, and portable information terminals, office automation devices, home appliances, and medical devices that require light weight and high rigidity.

  Furthermore, among the above applications, when the fiber-reinforced composite material plate according to the present invention is used for an electronic device casing having many complicated shapes, it is preferable in that it can sufficiently exhibit excellent adhesion with a frame portion with a thin wall. . Therefore, in the molded body having the top surface made of the fiber-reinforced composite material plate and the frame portion made of the thermoplastic resin composition according to the present invention, the electronic device casing in which the top surface and the frame portion are integrated. Among them, the fiber reinforced composite material plate and the frame portion are preferably used by an electronic device casing integrated through a thermoplastic resin layer existing on an end face.

  The present invention will be described in more detail and specifically based on examples and comparative examples. The evaluation method for each item is described.

[How to make a sample for end face observation]
A 10 mm square sample was cut out from the manufactured fiber-reinforced composite material plate, and its cross section was wet-polished to obtain Sample 1 for end face observation.

<Evaluation Method 1: Buried thermoplastic resin layer shortest distance _{T min>}
The range of the thickness h × width of 500 μm of the end face of the polished sample 1 is enlarged using an ultra-deep color 3D shape measuring microscope VK-9500 (controller part) / VK-9510 (measuring part) (manufactured by Keyence Corporation). Images were taken at a magnification of 400 times. In the embodiment of the present invention, since the thermoplastic resin layer is disposed only on one side on the surface, the interface between the thermoplastic resin layer and the thermosetting resin closest to the surface on which the thermoplastic resin layer is not disposed. In the interface closer to the surface where the thermoplastic resin layer is not disposed, the portion closest to the surface where the thermoplastic resin layer is not disposed and the thermoplastic resin layer is not disposed. The distance to the surface was measured as the minimum embedding distance T _min of the thermoplastic resin layer.

<Evaluation Method 2: Intermediate Reference Line S _mnm >
In the image processing software, the measurement lines g _mnr are shown at intervals of 10 μm so that the width of 500 μm of the fiber reinforced composite material plate (I) is divided into 50 equal parts in the image processing software. _Points are _shown at the intersections P _mnrN and P _mnrF of the interfaces S _mnN and S _mnF between the measurement line g _mnr , the thermoplastic resin layer, and the thermosetting resin. The distance of the intersection point _{P MnrN} and _{P MNRF} at each measurement line _{g mnr} was measured and plotted intermediate position _{S MnrM} between the intersection _{P MnrN} and _{P MNRF.} The plotted adjacent intermediate positions S _mnrM are connected by a straight line, and the obtained line is _defined as an intermediate reference line S _mnM of the m-th thermoplastic resin layer.

<Evaluation Method 3: Resin-impregnated thicknesses d _mnN and d _mnF and their maximum resin-impregnated thicknesses d _mnNmax and d _mFmax >
Images of the same range as in the evaluation method 1 were taken at 10 different positions, and the reinforcing fibers F _mnNF existing in the thermoplastic resin layer from the intermediate reference line S _mnM derived in the evaluation method 2 for these 10 images, The distances d _mnNF , d _mnNN , d _mnFF and d _mnFN to F _mnNN , F _mnFF and F _mnFN were measured, and the resin impregnation thicknesses d _mnN and d _mnF were calculated.

In each thermoplastic resin layer (m = 1, 2,...), The maximum values were measured as the resin impregnated maximum thicknesses d _mNmax and d _mFmax among d _mnN and d _mnF in images taken at 10 locations.

<Evaluation Method 4: Maximum total sum _{D n} and the resin impregnation depth of the resin impregnation depth _{D max>}
In 10 images taken by evaluation method 3, the resin impregnation thicknesses d _mnN and d _mnF in each thermoplastic resin layer (m = 1, 2,...) In each image are measured, and the resin impregnation in each image is performed. The sum total D _n of the thicknesses d _mnN and d _mnF was calculated. The maximum sum D _max at this time was determined.

<Evaluation method 5: Ratio of maximum sum D _max of resin impregnation thickness>
Maximum sum of evaluation methods 4 even stop the resin impregnation depth D _max and thickness of the fiber-reinforced composite material plate h, the equation (3) to calculate the percentage of maximum sum D _max of the resin impregnation depth.
Ratio of maximum sum D _max of resin impregnation thickness = (D _max / h) × 100 (3).

<Evaluation Method 6: Integrated Adhesive Strength>
From the molded article 11 in which the fiber reinforced resin composite material plate 1 and the other member (II) 10 shown in FIG. 8 are integrated, the integrated end face of L _a = 45 mm shown in FIG. A sample with L _b = 7 mm and b = 15 mm is cut out, the dotted line portion of the other member (II) 9 shown in FIG. 9-a is cut off, and the sample having the shape as shown in FIG. Ron "(registered trademark) 5565 type universal material testing machine (manufactured by Instron Japan Co., Ltd.) is fixed with chucks attached at the top and bottom, and the evaluation is performed with the number of evaluation samples n being 5 at a tensile speed of 1.6 mm / min. It was. The adhesive strength of the molded product was calculated from the maximum breaking load P at this time, the thickness h and width b of the fiber reinforced composite material plate, and Equation (4).
Adhesive strength [MPa] = {maximum breaking load P [N] / (plate thickness h [mm] × width b [mm])} Equation (4).

  In the evaluation, the adhesive strength was 9 MPa or more as AAA, 7 MPa or more and less than 9 MPa as AA, 5 MPa or more and less than 7 MPa as A, 3 MPa or more as less than 5 MPa as B, and C as less than 3 MPa.

<Evaluation Method 7: Degree R of Interface Roughness>
An image in the same range as in Evaluation Method 1 was taken, and the central axis of the thickness was written in the image. The distances L _mNF and L _mNN from the central axis of the thickness to the interface between each thermoplastic resin layer and the thermosetting resin layer were measured, and the degree R of the interfacial uneven shape was determined from the absolute value of the difference.

<Evaluation Method 8: Symmetry of Disposition of Thermoplastic Resin Layer U _na , U _nb >
An image in the same range as in Evaluation Method 1 was taken, and the central axis of the thickness was written in the image. The distances L _sN1 , L _sN2 , L _sF1, and L _sF2 from the central axis of the thickness to the interface between each thermoplastic resin layer and the thermosetting resin layer are measured, and the arrangement of the thermoplastic resin layers is symmetrical from the ratio. Sex was evaluated.

(Example 1)
(Example 1-1: Fiber reinforced composite material plate A1)
The thermosetting resin is an epoxy resin, and consists of a group of reinforcing fibers composed of a large number of carbon fibers arranged in one direction. The prepreg (Toray Industries, Inc.) has a reinforcing fiber content of 67% by weight (W _f ). ) Made from TORAYCA prepreg P3052S-12), 8 rectangular prepreg sheets having a predetermined size, copolymer polyamide resin ("Amilan" (registered trademark) CM8000, manufactured by Toray Industries, Inc., polyamide 6/66/610) / 612 copolymer, melting point 128 ° C.) 3 films (thickness 50 μm) were cut out. In FIG. 10, these eight prepreg sheets 9 and three films 11 are shown in perspective view.

  The direction of the long side of the sheet cut into a rectangle is 0 °, and the fiber direction is 90 °, 0 °, film, 90 °, 0 °, 0 °, 90 ° film, 0 °, 90 °, film from the top. As shown, eight prepregs 9 and three films 11 were sequentially laminated from the bottom (indicated by an arrow A).

Next, the thermosetting resin was cured by heating the laminate 12 composed of the prepreg sheet 8 and the film 11 at 150 ° C. for 30 minutes while applying a surface pressure of 0.6 MPa with a press molding machine. After the curing, the mixture was cooled at room temperature to produce a fiber reinforced composite material plate A1 having an average thickness of 1.0 mm.
The fiber-reinforced composite material plates and molded articles produced in the examples were evaluated by the evaluation methods 1 to 5. The results are shown in Table 1.

(Example 1-2: Molded product A2)
A molded product A2 shown in FIG. 8 is manufactured. The fiber reinforced composite material plate A1 was inserted into an injection mold (not shown). A long fiber pellet (TLP1146S manufactured by Toray Industries, Inc.) having a matrix resin made of a polyamide resin and a carbon fiber content of 20% by weight (Wf) was prepared. Using this pellet, an injection-molded material having a shape as shown in FIG. 8 was formed by injection molding to produce a molded product A2. The injection molding was performed using a J350EIII injection molding machine manufactured by Nippon Steel Works, Ltd., and the cylinder temperature was 280 ° C. The molded product produced in the example was evaluated by Evaluation Method 6. The results are shown in Table 1.

(Example 2)
(Example 2-1: fiber reinforced composite material plate B1)
Same as Example 1-1 so that the fiber direction is 90 °, 0 °, film, 90 °, film, 0 °, 0 °, film, 90 ° film, 0 °, 90 °, film from the top. Eight prepreg sheets and five copolymer polyamides ("Amilan" (registered trademark) CM8000 manufactured by Toray Industries, Inc., polyamide 6/66/610/612 copolymer, melting point 128 ° C.) (thickness 50 μm) from the bottom Laminated sequentially. Molding was performed under the same conditions as in Example 1-1 to produce a fiber reinforced composite material B1 having an average thickness of 1.0 mm.

(Example 2-2: Molded product B2)
In the same manner as in Example 1-2, the fiber reinforced composite material plate B1 was inserted into an injection mold to produce a molded product B2.

(Example 3)
(Example 3-1: Fiber reinforced composite material plate (C1)
A fiber-reinforced composite material plate C1 was produced in the same manner as in Example 1-1 except that the molding temperature during press molding was adjusted to 110 ° C.

(Example 3-2: Molded product C2)
In the same manner as in Example 1-2, the fiber-reinforced composite material plate C1 was inserted into an injection mold to produce a molded product C2.

Example 4
(Example 4-1: Fiber reinforced composite material plate D1)
Example 1-1 so that the fiber direction is 45 °, −45 °, film, 45 °, −45 °, −45 °, 45 °, film, −45 °, 45 °, film from the top 8 sheets of the same prepreg sheet and 5 films of copolymerized polyamide ("Amilan" (registered trademark) CM8000 manufactured by Toray Industries, Inc., polyamide 6/66/610/612 copolymer, melting point 128 ° C.) (thickness 50 μm) The layers were laminated sequentially. Molding was performed under the same conditions as in Example 1-1 to produce a fiber-reinforced composite material D1 having an average thickness of 1.0 mm.

(Example 4-2: Molded product D2)
In the same manner as in Example 1-2, the fiber-reinforced composite material plate B1 was inserted into an injection mold to produce a molded product D2.

(Example 5)
Example 5-1 Fiber Reinforced Composite Material Plate (E1)
The fiber direction is 90 ° from the top, film, 0 °, film, 90 °, film, 0 °, film, film, 0 °, film, 90 °, film, 0 °, film, 90 °, film The same prepreg sheet as in Example 1-1 and copolymer polyamide (“Amilan” (registered trademark) CM8000 manufactured by Toray Industries, Inc., polyamide 6/66/610/612 copolymer, melting point 128 ° C.) Nine sheets (thickness 50 μm) were sequentially laminated from the bottom. Molding was performed under the same conditions as in Example 1-1 to produce a fiber reinforced composite material E1 having an average thickness of 1.2 mm.

(Example 5-2: Molded product E2)
In the same manner as in Example 1-2, the fiber reinforced composite material plate E1 was inserted into an injection mold to produce a molded product E2.

(Example 6)
(Example 6-1: fiber reinforced composite material plate F1)
After manufacturing a fiber-reinforced composite material plate in the same manner as in Example 5-1, the shape of the notch shown in FIG. 7 is a square shape with a side of 5 mm (L = 5 mm) in the fiber-reinforced composite material plate. The shape portion was applied to the outer peripheral end portion by cutting to produce a fiber-reinforced composite material plate F1 having 15 square uneven shape portions with a side of 5 mm per 100 mm length on the outer peripheral end portion.

(Example 6-2: Molded product F2)
In the same manner as in Example 1-2, the fiber-reinforced composite material plate F1 was inserted into an injection mold to produce a molded product F2.

(Example 7)
(Example 7-1: fiber reinforced composite material plate G1)
After manufacturing a fiber reinforced composite material plate in the same manner as in Example 5-1, the fiber reinforced composite material plate has an isosceles trapezoidal shape (L1 = 8 mm, L2 = 6 mm, L = 5 mm) shown in FIG. The concavo-convex shape portion was applied to the outer peripheral end portion by cutting to produce a fiber-reinforced composite material plate G1 having eight isosceles trapezoidal concavo-convex shape portions per 100 mm in length at the outer peripheral end portion.

(Example 7-2: Molded product G2)
In the same manner as in Example 1-2, the fiber reinforced composite material plate G1 was inserted into an injection mold to produce a molded product G2.

(Example 8)
(Example 8-1: Fiber reinforced composite material plate (H1)
Example 1- so that the fiber direction is 90 ° from the top, film, 0 °, film, 90 °, 0 °, film, 0 °, 90 °, film, 0 °, film, 90 °, film 8 prepreg sheets same as 1 and copolymerized polyamide ("Amilan" (registered trademark) CM8000 manufactured by Toray Industries, Inc., polyamide 6/66/610/612 copolymer, melting point 128 ° C), 6 films (thickness 50 µm) Were sequentially laminated from the bottom. Molding was performed under the same conditions as in Example 1-1 to produce a fiber reinforced composite material H1 having an average thickness of 1.2 mm.

(Example 8-2: Molded product H2)
In the same manner as in Example 1-2, the fiber reinforced composite material plate H1 was inserted into an injection mold to produce a molded product H2.

(Comparative Example 1)
(Comparative Example 1-1: Fiber-reinforced composite material plate I1)
Eight prepreg sheets and copolymerized polyamide as in Example 1-1 so that the fiber direction is 90 °, 0 °, 90 °, 0 °, 0 °, 90 ° 0 °, 90 ° from the top. (Toray Industries, Inc. "Amilan" (registered trademark) CM8000, polyamide 6/66/610/612 copolymer, melting point 128 ° C) 1 film (thickness 50 µm) was laminated in order from the bottom. Molding was performed under the same conditions as in Example 1-1 to produce a fiber-reinforced composite material I1 having an average thickness of 1.0 mm.

(Comparative Example 1-2: Molded product I2)
In the same manner as in Example 1-2, the fiber reinforced composite material plate I1 was inserted into an injection mold to produce a molded product I2.

(Comparative Example 2)
(Comparative Example 2-1: Fiber Reinforced Composite Material Plate J1)
In the same manner as in Example 1-1, a prepreg sheet and a copolymer polyamide (“Amilan” (registered trademark) CM8000 manufactured by Toray Industries, Inc., polyamide 6/66/610/612 copolymer, melting point 128 ° C.) (Thickness 50 μm) was laminated.

  Next, the thermosetting resin was cured by heating the laminate composed of the prepreg sheet and the film with a press molding machine at 100 ° C. for 30 minutes while applying a surface pressure of 0.6 MPa. After the curing, the mixture was cooled at room temperature to produce a fiber reinforced composite material plate J1 having an average thickness of 1.0 mm.

(Comparative Example 2-2: Molded product J2)
In the same manner as in Example 1-2, the fiber reinforced composite material plate J1 was inserted into an injection mold to produce a molded product J2.

(Comparative Example 3)
(Comparative Example 3-1: Fiber Reinforced Composite Material Plate K1)
Fiber direction is 90 ° from the top, 0 °, film, 90 °, 0 °, 90 °, 0 °, 90 °, 0 °, 0 °, 90 ° 0 °, 90 °, 0 °, 90 ° 0 °, 90 °, 16 prepreg sheets as in Example 1-1 and copolymerized polyamide (“Amilan” (registered trademark) CM8000 manufactured by Toray Industries, Inc., polyamide 6/66/610/612) Two films (thickness: 128 ° C.) made of coalesced (melting point: 128 ° C.) were laminated sequentially from the bottom. Molding was performed under the same conditions as in Example 1-1 to produce a fiber reinforced composite material K1 having an average thickness of 2.0 mm.

(Comparative Example 3-2: Molded product K2)
In the same manner as in Example 1-2, the fiber reinforced composite material plate K1 was inserted into an injection mold to produce a molded product K2.

  In Examples 1 to 5, the fiber-reinforced composite material plate and the other member were excellent in adhesion at the end surfaces. Further, in Examples 6 and 7 in which the concavo-convex shape portion was provided at the end portion, a cutting process was required for adjusting the laminated plate, but excellent end face adhesion was exhibited. In Example 7, since the arrangement of the thermoplastic resin is asymmetric, warping was observed in the fiber-reinforced composite material plate, but the end face adhesion was excellent. On the other hand, in Comparative Example 1, only a very small amount of thermoplastic resin was present on the end face, and it was not adhered to the injection material member. In Comparative Example 2, the thermoplastic resin was not impregnated between the reinforcing fiber groups, and although it adhered, sufficient adhesive strength could not be obtained. In Comparative Example 3, the adhesive strength was insufficient because the amount of the thermoplastic resin layer impregnated between the reinforcing fiber groups was small with respect to the thickness of the fiber-reinforced composite material plate.

It is a schematic cross section of an example of the end surface of the fiber reinforced composite material board of this invention. It is a schematic cross section of an example of the end surface of the fiber reinforced composite material board of this invention. It is a schematic cross section of an example of the end surface of the fiber reinforced composite material board of this invention. It is a schematic cross section of an example of the end surface of the fiber reinforced composite material board of this invention. It is a schematic cross section for demonstrating resin impregnation thickness. It is a schematic cross section for demonstrating a center reference line. It is a schematic cross section explaining the degree of unevenness of the thermoplastic resin interface. It is a schematic cross section for demonstrating the symmetrical position of a thermoplastic resin layer. It is a model perspective view of an example of the uneven | corrugated shaped part formed in an end surface. FIG. 4 is a schematic perspective view of a uniform state in which the fiber-reinforced composite material plate of the present invention and another member (II) are integrated. It is sectional drawing of the one aspect | mode of the sample for adhesion evaluation cut out from the molded article. It is sectional drawing of the one aspect | mode of the sample for adhesion evaluation cut out from the molded article. It is a model perspective view of an example of the structure of the fiber reinforced composite material board of this invention. It is a model perspective view of an example of the uneven | corrugated shaped part formed in an end surface. It is a schematic diagram of an example of the interface structure of the thermosetting resin and thermoplastic resin of the fiber reinforced composite material board of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Fiber reinforced composite material board 2 Thermosetting resin layer 3 Thermoplastic resin layer 4 Reinforcement fiber group 5 Surface (of fiber reinforced composite material board) 6 Interface (end of thermosetting resin and thermoplastic resin) 7 End face 8 Prepreg 9 Others Part (II)
10 Molded product 11 Film 12 Laminate

Claims (18)

A fiber-reinforced composite material plate (I) comprising a continuous reinforcing fiber group (A), a thermosetting resin (B), and a thermoplastic resin (C), wherein the thermoplastic resin layer of the fiber-reinforced composite material plate At least one thermoplastic resin layer composed of a part of the continuous reinforcing fiber group (A) and the thermoplastic resin (C) is formed at a position where the shortest burying distance T _min is 0.05 to 0.4 mm. is, if the thermoplastic is the maximum value of the resin impregnation depth _{d MNN} in the resin impregnated maximum thickness _{d MNmax,} the resin-impregnated maximum thickness is the maximum value of the resin impregnation depth _{d MnF} in thermoplastic resin was _{d MFMAX a, d MNmax} and / or _{d MFMAX} is not less 10μm or more, and the maximum sum _{D max} for all of the thermoplastic resin layer of the resin impregnation depth contained in the fiber-reinforced composite material plate, Fiber-reinforced composite material plate 10 to 90% of the thickness of the fiber-reinforced composite material plate. The fiber-reinforced composite material plate according to claim 1, wherein a maximum sum D _max of resin impregnation thicknesses of the thermoplastic resin layer is 15 to 70% of a thickness of the fiber-reinforced composite material plate. The fiber-reinforced composite material plate according to claim 1 or 2, wherein a degree R of the uneven shape at the interface of the thermoplastic resin layer is 10 µm or more. Some filaments of the continuous reinforcing fiber group (A) are in contact with at least the thermosetting resin (B), and the remaining filaments of the reinforcing fiber group (A) are in contact with at least the thermoplastic resin (C). The fiber-reinforced composite material plate according to any one of claims 1 to 3. The fiber-reinforced composite material plate according to any one of claims 1 to 4, wherein the fiber-reinforced composite material plate has a thickness of 0.3 to 2 mm. The fiber-reinforced composite material plate according to any one of claims 1 to 5, wherein a thermoplastic resin layer is continuously formed in the fiber-reinforced composite material plate. The fiber-reinforced composite material plate according to any one of claims 1 to 6, wherein two or more thermoplastic resin layers are present in the fiber-reinforced composite material plate. The thermoplastic resin layer which consists of a thermoplastic resin (C) which contains a part of continuous reinforcing fiber group (A) further is formed in at least one part of the surface of the said fiber reinforced composite material board, Claim 1 The fiber-reinforced composite material plate according to 7. The fiber-reinforced composite material plate according to claim 1, wherein the thermoplastic resin layer is disposed at a symmetric position with respect to the thickness center axis of the fiber-reinforced composite material plate. The end surface of the fiber reinforced composite material plate has at least one uneven shape portion in a direction parallel to the surface of the composite material plate, and at least a part of the end surface in the direction parallel to the thickness direction in the uneven shape portion. The fiber reinforced composite material board according to any one of claims 1 to 9, wherein a thermoplastic resin layer comprising a thermoplastic resin (C) including a part of the continuous reinforcing fiber group (A) is present. The ratio L1 / L2 between the length L1 of the root portion of the concave portion of the concave and convex portion and the length L2 of the tip portion of the concave portion of the concave and convex portion is 0.1 or more and less than one. Fiber reinforced composite material board. The uneven maximum depth _{L max} of the concave-shaped portions is 1 to 50 mm, fiber-reinforced composite material plate according to any one of claims 10 or 11. The fiber-reinforced composite material plate according to any one of claims 1 to 12, wherein the continuous reinforcing fiber group (A) is a carbon fiber. The fiber-reinforced composite material plate according to any one of claims 1 to 13, wherein the thermoplastic resin (C) is at least one resin selected from a polyamide resin, a polyester resin, and a polyolefin resin. The fiber-reinforced composite material plate according to any one of claims 1 to 14 and another member (II) are joined and integrated through a thermoplastic resin (C) present on an end surface of the fiber-reinforced composite material plate. Molding. The molded article according to claim 15, wherein the other member (II) is a thermoplastic resin composition. Absolute value (| SP ₁ −SP ₂ |) of the difference between the SP value (SP ₁ ) of the thermoplastic resin (C) and the SP value (SP ₂ ) of the thermoplastic resin constituting the other member (II) The molded article according to claim 16, wherein is 1 or less. The molded article according to any one of claims 15 to 17, which is used for any of electric / electronic equipment, office automation equipment, home appliances, medical equipment, automobile parts, aircraft parts, and building materials.