JP6405908B2 - Multicolor molded product and molding method thereof - Google Patents

Description

  The present invention relates to a multicolor molded product and a molding method thereof, and more particularly to a multicolor molded product suitable for use as a transparent panel member for a roof or a window of a vehicle such as an automobile and a molding method thereof. As this multicolor molded product, a panel-shaped molded body that requires high designability on the design surface side is mentioned, and in particular as a transparent panel-shaped member such as a panoramic roof window, sunroof window, quarter window, rear window of an automobile, etc. A panel-shaped molded product made of resin suitable for use can be mentioned. The present invention also relates to a vehicle provided with a panel made of this multicolor molded product.

  As a resin window plate for automobiles, a two-color molded product in which a transparent resin panel is formed with an opaque resin at the periphery is disclosed in Patent Document 1 (JP 2008-94087) and Patent Document 2 (JP 2011-2011). 121305) and Patent Document 3 (Japanese Patent Laid-Open No. 2006-110992).

  In Patent Documents 1 to 3, as a method of forming a panel made of a two-color molded product having a frame-like portion provided on the peripheral edge of the panel body, a plate-like panel body (primary molded product) is injection molded, and then the panel A method is described in which a frame-like portion (secondary molded product) is injection-molded on the peripheral portion of one surface (rear surface) of the main body. That is, after the primary material is injected into the mold to form the primary molded product (panel body), the mold is opened so that the primary molded product remains attached to the core side, and then the secondary molded product is molded. A molding method is described in which a mold is closed, a secondary material is injected to form a secondary molded product (frame-shaped portion), and then a panel-shaped molded body is taken out from the mold.

  In paragraph 0023 of FIG. 5 and FIG. 5, when a frame-shaped portion is formed by injecting an opaque peripheral portion (2) to the peripheral portion of the rear surface of the panel body made of the transparent plastic material (1) in the mold. It is described that the injector is arranged along the periphery of the panel body.

JP2008-94087 JP2011-121305A JP 2006-110992 A

  When molding the panel-shaped molded article described in Patent Documents 1 to 3, as described in Patent Document 3, the gate for molding the frame-shaped part is opposed to the panel body along the peripheral edge of the panel body. When the second molding material constituting the frame-shaped portion is directly injected and filled on the surface of the panel main body, the gate of the panel main body is near the gate for injection-molding the frame-shaped portion (secondary molded product). It has been found that there is a problem that a dimple-like minute recess having a depth of about 1 to 20 μm is generated on the side opposite to the surface facing the portion (design surface side of the panel body). Furthermore, as a result of further research by the present inventors, the occurrence of the dimple-like micro-recesses is caused by the surrounding of the secondary material in the vicinity of the gate (second synthetic resin material constituting the secondary molded product) being cooled and solidified. This is because a large shrinkage force is generated as compared with the part, and in particular, when a crystalline component having a large shrinkage amount is present in the secondary material, it is recognized that minute recesses are easily revealed. Further, it was found that even if the minute recesses are not visually recognized immediately after molding, the minute recesses may appear when the shrinkage accompanying solidification further proceeds, such as one day later.

  In addition, when a hot runner is used for the gate for molding a secondary molded product, the temperature of the cavity surface around the secondary molded product gate becomes higher due to the temperature control of the hot runner, so cooling and solidification are delayed. It has also been found that minute recesses tend to become apparent because the panel body is affected by the secondary material shrinkage for a long time.

  In addition, when molding a multi-color molded product, when a secondary molded product is injection-molded on the rear surface of the primary molded product, the secondary material injected from the gate into the secondary molded product molding cavity is the rear surface of the primary molded product. At the opposite side of the gate, the primary molded product near the gate may be eroded and its thickness may be reduced. It has also been found that when the shrinkage force of the secondary molded product acts on the portion where the thickness of the primary molded product is small, the front side of the primary molded product is recessed to easily form a dimple-like minute recess.

  The present invention forms a secondary molded body by injecting a second synthetic resin material from a gate onto at least a part of a primary molded body made of a first synthetic resin material in a mold, and is integrated with the primary molded body. In the multicolor molded article and the molding method thereof, it is possible to prevent (including suppression; including the suppression, the same applies to the primary molded body in the vicinity of the gate due to molding shrinkage of the second molded body. ) For the purpose of.

  The multicolor molded article of the present invention includes a first molded body having a first plate surface and a second plate surface opposite to the first plate surface, and a synthetic resin material on at least a part of the second plate surface. In a multicolor molded product having a second molded body formed integrally with the first molded body by injection molding, on the plate surface opposite to the first molded body of the second molded body, A groove is formed around the gate mark of the second molded body, and the groove is formed by a convex portion of a cavity surface of a mold for molding the second molded body. The synthetic resin material which is a constituent material of the molded article 2 is a resin composition containing at least one selected from reinforcing materials and elastomers, or a resin composition containing two or more incompatible resins It is a thing.

In the present invention, it is preferable that the difference t ₂ −h between the depth h of the groove and the thickness t ₂ of the second molded body is 1 mm or more. Further, it is preferable that the ratio h / _{t 2} of the thickness _{t 2} of the depth h and the second molded body groove is 0.3 to 0.9. Further, it is preferable that the groove extends in a direction around the gate mark, and the groove exists in a range of 50% or more of the circumferential direction of the gate mark.

  In one aspect of the present invention, the bending elastic modulus of the constituent material of the second molded body is preferably equal to or higher than the bending elastic modulus of the constituent material of the first molded body.

  In one aspect of the present invention, the constituent material of the first molded body is preferably a non-reinforced resin composition, and the constituent material of the second molded body is preferably a reinforced resin composition containing a reinforcing material. . The reinforcing resin composition preferably contains a fibrous material, a plate-like material, or a needle-like material as a reinforcing material.

  In one embodiment of the present invention, the constituent material of the second molded body includes a crystalline resin.

  In one aspect of the present invention, the constituent material of the first molded body is translucent, and the constituent material of the second molded body is opaque.

  In one aspect of the present invention, the constituent material of the first molded body includes a polycarbonate resin, and the constituent material of the second molded body includes a polycarbonate resin and a polyester resin.

  In one aspect of the present invention, the second molded body is provided at the peripheral edge of the first molded body.

  The vehicle of the present invention includes a panel made of the multicolor molded product of the present invention.

  The molding method of the multicolor molded product of the present invention is a method of molding the multicolor molded product of the present invention, in which the movable mold holding the first molded body is molded into the second molded body. The mold is clamped to a stationary mold having a cavity, and a synthetic resin material is injected into the cavity from the gate of the stationary mold through a hot runner to form a second molded body. A protrusion protruding into the cavity is provided around the gate of the fixed mold for forming the second molded body, and the groove is formed by the protrusion.

  In the multicolor molded article and the molding method of the present invention, when the second molded body is injection-molded, a reinforcing material such as a fibrous material in the synthetic resin material injected from the gate, an elastomer, and an incompatible It becomes easy for the orientation component of the domain component formed by the resin component to be oriented in the thickness direction of the second molded body. The orientation component such as a reinforcing material or the like oriented in the thickness direction (hereinafter, the domain component formed by the reinforcing material, the elastomer, and the incompatible resin component may be collectively referred to as “orientation component”) is the second. Since the shrinkage in the thickness direction in the vicinity of the gate is constrained when the molded body is cooled and solidified, the shrinkage in the thickness direction in the vicinity of the gate is suppressed, so that the surface of the first molded body (first plate surface) is dimple-shaped. A concave portion is prevented from being generated. The effect of suppressing the dimple micro-recesses is particularly remarkable when the synthetic resin material constituting the second molded body is a reinforced resin composition containing a reinforcing material.

It is a block diagram of the multicolor molded product which concerns on embodiment. It is sectional drawing which shows the shaping | molding apparatus of the multicolor molded product which concerns on embodiment. It is a perspective view of the nozzle tip of a forming device. It is typical sectional drawing which shows the orientation of a fibrous reinforcement. It is a perspective view which shows another shape of a nozzle tip. It is explanatory drawing of an Example.

  The present invention provides a first molded body having a first plate surface and a second plate surface opposite to the first plate surface, and at least a part of the second plate surface by injection molding of a synthetic resin material. In a multicolor molded product having a first molded body and a second molded body formed integrally with the first molded body, the second molded body has a plate surface on the opposite side to the first molded body. A groove is formed around the gate trace of the body. The synthetic resin material which is a constituent material of the second molded body is a resin composition containing at least one selected from a reinforcing material and an elastomer, or contains two or more incompatible resins. It is a resin composition.

  In the present invention, “around the gate mark of the second molded body” refers to a region having a radius of 25 mm from the center of the gate mark of the second molded body.

  In the present invention, orientation components such as a reinforcing material, an elastomer, and a domain component are easily oriented in the thickness direction of the second molded body, and this orientation component causes the vicinity of the gate when the second molded body is cooled and solidified. By suppressing the shrinkage in the thickness direction, it is possible to prevent the dimple-like minute recesses from being formed on the surface (first plate surface) of the first molded body.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to specific embodiments.

  FIG. 1A is an overall sectional view of a panel as a multicolor molded product according to the embodiment, FIG. 1B is an enlarged view of a part thereof, and FIG. 1C is a plan view of this panel. 1A is a cross-sectional view taken along line AA in FIG.

  This panel 4 is a resin window glass of a vehicle. The panel 4 is two-color molded by a two-color molding apparatus shown in FIG. 2 to be described later, and includes a transparent plate-like panel body 1 as a first molded body (primary molded body), and the panel body 1. And a frame-like portion 2 as a second molded body (secondary molded body) provided so as to go around the entire peripheral edge of the rear surface. The frame-like portion 2 is opaque, and the inner side of the frame-like portion 2, that is, the panel plate central portion where the frame-like portion 2 does not overlap is a transparent region 3. On the rear surface of the panel main body 1, there is a recess 1a in which the synthetic resin material of the frame-like portion 2 enters at a position facing the vicinity of the gate mark G (FIG. 1B). The diameter of the gate mark G matches the aperture of the gate 14 (FIG. 2) for injection molding the frame-shaped part (secondary molded product) 2.

  On the surface of the frame-like part 2 opposite to the panel body 1, there is an annular groove 2 a surrounding the gate mark G. This groove 2a is a demolding mark of the convex part 31 (FIG. 3) of the nozzle chip 30 provided on the inner surface of the mold for injection molding the frame-like part 2 as described later. When the frame-shaped portion 2 is formed by molding using a mold having the convex portions 31, the orientation component such as a reinforcing material in the synthetic resin material has a thickness of the frame-shaped portion 2 as shown in FIG. It becomes easy to orientate in the direction, and shrinkage in the thickness direction of the frame-like portion 2 is suppressed.

  The depth h of the groove 2a is preferably 0.5 to 5 mm, particularly 1 to 4.5 mm, more preferably 1.1 to 4.3 mm, and particularly preferably 1.5 to 4 mm.

  If the depth h of the groove 2a is smaller than 0.5 mm, the orientation of the reinforcing material or the like tends to be less in the thickness direction of the frame-like portion 2, the shrinkage suppressing effect is less, and there is a risk of dimple-like microrecesses being generated. is there.

When the depth h of the groove 2a is larger than 5 mm, the orientation of the reinforcing material or the like becomes more in the thickness direction of the frame-like part 2, but the remaining thickness of the frame-like part 2 between the groove 2a and the panel body 1 is increased. Since (t ₂ -h) becomes too thin, the filling pressure may increase and unfilling may occur, or the filling density around the gate may decrease, and a donut-shaped minute recess may occur around the gate.

The ratio h / _{t 2} of the thickness _{t 2} of the depth h and the frame-like portion 2 of the groove 2a is 0.1 to 0.9, further 0.2 to 0.8, in particular 0.3 to 0.75 In particular, it is preferably 0.3 to 0.7, and at a percentage ratio h / t ₂ × 100%, it should be 10 to 90%, further 20 to 80%, particularly 30 to 75%, especially 30 to 70%. Is preferred. If this ratio is less than 10%, the orientation of the reinforcing material or the like becomes less in the thickness direction of the frame-like portion 2, so that the effect of suppressing shrinkage is small, and there is a possibility of generating dimple-like microrecesses. On the other hand, if it is larger than 90%, the orientation of the reinforcing material or the like becomes more in the thickness direction of the frame-like portion 2, but the remaining thickness of the frame-like portion 2 between the groove 2 a and the panel body 1 (t ₂ − Since h) becomes too thin, the filling pressure may increase and unfilling may occur, or the filling density around the gate may decrease, and a doughnut-shaped concave portion may be generated around the gate.

The difference between the depth h of the frame portion 2 the thickness _{t 2} and the groove 2a, namely the frame-shaped portion 2 of the remaining thickness _(t 2 -h) is, 0.5 to 3 mm, especially 0.75~2.5mm In particular, it is preferably 1 to 2 mm. When (t ₂ -h) is smaller than 0.5 mm, the filling pressure becomes high and unfilling may occur, or the filling density around the gate may be lowered, and a donut-shaped minute recess may be formed around the gate. When (t ₂ -h) is larger than 3 mm, the orientation component such as the reinforcing material is difficult to be oriented in the thickness direction of the frame-like portion 2, so that the effect of suppressing shrinkage is small and there is a possibility of generating dimple-like minute recesses.

The groove depth h, h / t ₂ ratio, and (t ₂ −h) values are preferably all within the above-mentioned preferable range, h, h / t ₂ , (t ₂ −h) It is desirable to design a product with the highest priority given to the item that reaches the limit value in the above range first among the three items.

The groove width W _{1 at} the back of the groove 2a may be the same as or smaller than W _2, and may be W ₁ = 0 mm. When the outer peripheral side of the peripheral wall surface of the groove 2a is smaller than the W ₁ W ₂ so that the tapered projections 31 of the nozzle tip 30 can be easily demolded. The taper angle is preferably 0.2 to 60 °, particularly preferably 0.5 to 45 °, and particularly preferably 1 to 30 °.

  If this taper angle is smaller than 0.2 °, mold release failure occurs, the shape directly under the gate is deformed or broken, and the groove 2a is pulled in the mold release direction at the time of mold release. There is a risk that a dent will be formed. On the other hand, when the taper angle is larger than 60 °, the shape rigidity and strength around the gate are lowered, which may be the starting point and the inflection point of the deformation of the entire panel molded body, and may lead to deformation or breakage due to external force. is there.

The width _{W 2} of the inlet side of the groove 2a is 0.5 to 10 mm, particularly 0.75～5Mm, especially 1~3mm is preferred.

If the width W ₂ of the groove 2a is greater than 10 mm, since the frame portion 2 of the length of the thin portion between the groove 2a and the panel main body 1 is long, unfilled or caused raise the filling pressure in the thickness direction Therefore, a portion oriented in the direction perpendicular thereto and a portion oriented in the direction perpendicular thereto are easily separated, and a doughnut-shaped concave portion may be generated at the target position around the gate mark G. On the other hand, if the width W ₂ of the groove 2a is smaller than 0.5 mm, but less effect on the orientation of such reinforcing material in the vicinity of the gate portion, or cracked by releasing failure to become a release of the thin protrusion In addition, there is a possibility that a depression is generated on the design surface side of the panel body 1 by pulling the gate portion.

The groove width _{W 1} of the inner portion of the groove 2a is 0.4～10Mm, particularly 0.7～5Mm, especially 0.9~3mm is preferred.

The groove width W ₁ of the inner portion of the groove 2a is greater than 10 mm, since the frame-shaped portion length of the second thin portion between the groove 2a and the panel main body 1 is long, unfilled occurs raises the filling pressure In addition, a portion oriented in the thickness direction and a portion oriented in the direction perpendicular thereto are easily separated clearly, and there is a possibility that a doughnut-shaped concave portion is generated at the target position around the gate mark G. On the other hand, if the groove width W ₁ of the inner portion of the groove 2a is smaller than 0.4 mm, but less effect on the orientation of such reinforcing material in the vicinity of the gate portion, by mold sticking to become the release of the thin protrusion There exists a possibility that a crack may arise or a dent may arise in the design surface side of the panel main body 1 by pulling a gate part.

  The diameter D of the gate mark G is preferably 1 to 20 mm, particularly 2 to 16 mm, particularly 3 to 12 mm.

  The distance from the outer periphery of the gate mark G to the inner periphery of the groove 2a is preferably −D / 10 to + D / 2 mm, more preferably −D / 100 to + D / 5 mm, and particularly preferably 0 to + D / 10 mm. If this distance is larger than the above range, the resin material injected from the gate has a flow that spreads in the circumferential direction of the gate. May lead to outbreak. On the other hand, if this distance is smaller than the above range, the valve gate wraps, so that the gate opening ratio decreases, the resin pressure increases and unfilling occurs, and in particular, a fibrous reinforcing material is included. In such a case, the reinforcing fiber is broken and shortened, so that the effect of suppressing shrinkage due to orientation is reduced, which may lead to the formation of dimple-like minute recesses. In addition, (-), such as -D / 10mm, means that the groove | channel 2a has entered into the gate trace center part side inside the outer periphery of the gate trace G, and exists.

The panel body 1 has a thickness t ₁ of 1 to 10 mm, particularly 1.5 to 8 mm, particularly 2 to 6 mm. If the thickness t 1 of the panel main body 1 is smaller than ₁ mm, the rigidity of the panel main body 1 at the time of forming the frame-like portion 2 is insufficient, and the frame-like portion 2 is significantly affected by the shrinkage of the frame-like portion 2. Since there is no resistance to the pulling force due to the shrinkage of 2, there is a possibility that a minute recess is formed on the front surface of the panel body (primary molded product) 1. When the thickness t ₁ of the panel body 1 is more than 10 mm, cooling and solidification of the thickness center portion of the panel body 1 is slow. May occur.

When the thickness t ₂ other than the portion of the frame-like portion 2 entering the recess 1a is somewhat large, the effect of the filling pressure and temperature during the secondary material injection molding is lessened, so the synthetic resin material of the frame-like portion is the panel body. This is advantageous for preventing the occurrence of dimple-like minute recesses.

The thickness _{t 2} of the frame portion 2 is preferably 1.5 to 10 mm, more preferably 1.8～8Mm, particularly preferably 2 to 5 mm. If the thickness of the frame-like part 2 is larger than 10 mm, the influence of the filling pressure and temperature when the secondary material is injection-molded becomes loose, but the influence of shrinkage becomes large because the thickness is too large, and dimple-like micro-recesses are generated. There is a risk. On the other hand, if the thickness of the frame-like part 2 is smaller than 1.5 mm, the influence of the filling pressure and temperature when the secondary material is injection-molded becomes significant, the depth d of the recess 1a becomes large, and the frame-like part Since the shrinkage of the intrusion region with respect to the surroundings appears as a large difference even though 2 is thin, there is a possibility of generating dimple-like minute recesses.

The ratio _t 1 / _{t 2} of the thickness _{t 2} of the panel body 1 the thickness _{t 1} and the frame-like section 2 is from 0.75 to 5, particularly 0.8 to 4, especially 1.0 to 3 is preferred.

  The shape of the recess 1a when the panel 4 is viewed from the front may be circular or may be substantially elliptical. In the panel 4 of FIG. 1, the secondary material injected from the gate flows in the side direction of the panel 4, so that the recess 1 a is not substantially circular but is generally elliptical.

  It is preferable that the recess 1a is deepest in the vicinity of the center facing the gate mark G, and the depth gradually decreases toward the periphery. Since the depth of the recesses gradually decreases toward the periphery, the continuity of contraction of the frame-like portion 2 is obtained, so that the generation of the dimple-like minute recesses is easily suppressed. If the depth does not gradually decrease toward the periphery, the frame-like portion 2 is locally contracted greatly, and dimple-like minute concave portions are likely to be generated.

  The depth (depth of the deepest portion) d of the recess 1a is preferably 4 mm or less, more preferably 3 mm or less, and particularly preferably 2.5 mm or less. If d is larger than 4 mm, the amount of shrinkage of the frame-like portion 2 increases, and the dimple-like microrecesses are likely to appear, so that the molding conditions such as adding a large amount of pressurization after the filled resin stops are satisfied. Adjustment is required. In order to reduce the dimple-like minute recess, d is preferably as small as possible. However, the depth d of the recess 1a is at least 0.O because the adhesion of the two-color molding is to melt and weld the surface of the first molded body by injection of the constituent material (secondary material) of the frame-like portion 2. It is preferable to melt the surface of the first molded body by injection of the secondary material so as to be 01 mm.

  Hereinafter, a recess region having a depth of 1% or more of the depth d of the deepest portion of the recess 1a may be referred to as a “substantial recess”. The maximum width of the substantial recess (when the substantial recess is elliptical, the major axis of the ellipse) is preferably 0.5 to 20 times, more preferably 0.5 to 15 times, particularly preferably the gate diameter (diameter). Is 0.5 to 10 times. If the width of the substantial recess is 20 times or more the gate diameter, there is a possibility that a wide range of gentle dimple-like recesses may occur.

  When the width of the substantial recess is less than 0.5 times the gate diameter, it becomes difficult to suppress the recess depth d to 4 mm or less, and there is a possibility that a dimple-like minute recess is generated. This is because the amount of heat of the secondary material is concentrated at a narrow point.

The ratio d / t ₁ between the depth d of the recess 1a and the thickness t ₁ of the panel body 1 is preferably 0.001 or more and 0.8 or less, more preferably 0.01 or more and 0.6 or less, and particularly preferably 0. .05 or more and 0.45 or less. When d / t ₁ is larger than 0.8, even if the recess depth d is suppressed, the erosion ratio with respect to the panel body increases and the thickness of the remaining panel body 1 becomes thin. The possibility of is increased. In particular, this effect is noticeable when the panel body 1 is thin. If d / t ₁ is smaller than 0.001, the welding area between the panel main body 1 and the frame-like portion 2 becomes small, so that the adhesion force becomes small, and the adhesion durability between the two tends to be low.

The maximum cross-sectional area of the substantial recess (when the substantial recess is elliptical, the area of the cross section corresponding to the major axis of the ellipse) is preferably 0.01 mm ^{2 to} 30 mm ² , more preferably 0.01 mm ^{2 to} 27 mm ^2. Hereinafter, it is particularly preferably 0.01 mm ² or more and 23 mm ² or less.

If the area of the substantial recess is larger than 30 mm ² , even if the recess depth d is suppressed, the region of the recess 1a becomes too wide, and there is a possibility that a gentle dimple-like concave portion having a wide range may be generated. In some cases, it is necessary to adjust the molding conditions such as adding a large amount of pressure after the filled resin stops.

If the area of the substantial recess is smaller than 0.01 mm ² , the region of the recess 1a is too narrow and the recess 1a is concentrated in one place, so that the shrinkage difference from the surroundings becomes large and dimple-like micro-recesses are generated. There is a risk.

  The depth d of the recess 1a, the maximum width and the maximum area of the substantial recess are determined by cutting a cross section of the molded body including the deepest portion of the dimple-like microrecess and observing the cross section with a microscope or the like. It can obtain | require by measuring using etc. In addition, the maximum width and the maximum area of the substantial recess mean measured values obtained for a cross section in which the width and the area of the recess 1a are maximum in the obtained cross section.

The panel 4 is curved so that the front surface (surface opposite to the frame-like portion 2) side of the panel body 1 is convex. The panel 4 has a substantially rectangular shape, but may have other shapes such as a square shape. There is no restriction | limiting in particular in the dimension of the panel 4, What is necessary is just to select and determine suitably according to the use. Usually, as window materials for automobiles, the area of the panel body 1 is usually 0.1 to 3.5 m ² , the area of the transparent region 3 is 400 cm ^{2 to} 3 m ² , and the width of the frame-like part 2 is 20 to 200 mm. It is. Among them, 0.2~2.5m ^2, an area of 600 cm ² to 2 m ^2, preferably the width of the frame-shaped portion 2 is 25～180Mm, the panel body 1 as the area of the transparent region 3 as the area of the panel body 1 as 0.2~2m ^2, 800cm ² ~1m ² as the area of the transparent region 3, the width of the frame-shaped portion 2 is more preferably 30 to 150 mm.

  This panel 4 is formed by two-color molding. Below, with reference to FIG. 2 (a), (b) and FIG. 3, the shaping | molding apparatus of the panel 4 and the shaping | molding method using the same are demonstrated. FIG. 2B is an enlarged view of a part of FIG. FIG. 3 is a perspective view of the nozzle tip.

  A cavity 11 a for molding the panel body 1 is provided in the movable mold 11. The movable mold 11 is clamped to a first fixed mold (not shown), and a first synthetic resin material (primary material) is injected to mold the panel body 1. After opening the movable mold 11 from the first fixed mold, the movable mold 11 is clamped to the second fixed mold 12, and the glass fiber is fed from the gate 14 of the hot runner 13 to the cavity 12a for forming the frame-shaped portion. A second synthetic resin material (secondary material) containing an orientation component such as a reinforcing material is injected to mold the frame-shaped portion 2.

  In this embodiment, the gate 14 portion of the fixed mold 12 is constituted by the nozzle tip 30. As shown in FIG. 3, the nozzle tip 30 includes a cylindrical convex portion 31 and a flange portion 32 provided on the rear end side of the convex portion 31. The flange portion 32 is provided with an insertion hole 33 for a bolt (not shown) for fixing the nozzle tip 30 to a fixed mold. The rear end side of the inner peripheral surface of the through hole 31a penetrating the cylindrical convex portion 31 in the axial direction is a valve seat made of a tapered surface as shown in FIG. The taper surface of the outer periphery of the abuts. The cylindrical convex portion 31 may be formed on the cavity surface of the fixed mold 12 by using another component such as the nozzle tip 30 as described above, or may be directly convex on the cavity surface of the second fixed mold 12. A shape may be formed.

  The valve pin 16 for opening and closing the gate 14 is moved back and forth in the axial direction by a drive device 20 such as a cylinder device. As described above, the gate 14 opens or closes when the tapered surface of the outer peripheral edge of the valve pin 16 is separated from or abuts against the valve seat formed of the tapered surface provided on the inner peripheral surface of the nozzle chip 30. .

  The diameter of the gate 14 (opening diameter in the inner surface of the cavity 12a) is preferably 1 mm or more, for example, 1 to 20 mm, particularly 2 to 16 mm, especially 3 to 12 mm. When the diameter of the gate 14 is less than 1 mm, there is a risk that the gate sealing time is shortened, the filling density is lowered, and the dimple-like minute recesses are easily developed. Further, the filling pressure of the resin at the time of injection molding of the secondary material (second synthetic resin material for molding the frame-like portion 2) becomes too high, and 2 on the rear surface of the panel body 1 which is the first molded body. The next material hits strongly and the recess 1a becomes deep. There is also a risk of insufficient filling (filling failure).

  The diameter of the valve pin 16 is preferably 2 to 24 mm, particularly 3 to 16 mm, and particularly 4 to 12 mm. If the diameter of the valve pin 16 is smaller than 2 mm, the shaft diameter is small and the gate becomes small, so that the gate sealing time is shortened, the filling density is lowered, and there is a risk that the dimple-like microrecesses are easily developed. Further, the filling pressure of the resin at the time of injection molding of the secondary material becomes too high, the secondary material strongly hits the rear surface of the panel body 1 which is the first molded body, and the recess 1a becomes deep. Moreover, insufficient filling (filling failure) may occur. If the diameter of the valve pin 16 is larger than 24 mm, it is greatly affected by the temperature of the hot runner tip, the cooling rate of the secondary material (frame-like part 2) in the vicinity of the gate part becomes small, the shrinkage force becomes large, and the dimple-like micro There is a possibility of forming a recess.

  The hot runner 13 incorporates a heater (not shown) for heating the manifold 17, the nozzle 19 and the like. The nozzle of the injection molding machine is connected to the nozzle touch part 18, and the second synthetic resin material (secondary material) from the injection molding machine (not shown) passes through the nozzle touch part 18, the manifold 17, the nozzle 19 and the gate 14. Then, it is injected into the cavity 12a and then held in pressure.

  Since the nozzle chip 30 is provided on the gate 14 and the convex portion 31 protrudes into the cavity 12a, the synthetic resin material injected from the gate 14 goes straight from the gate 14 and flows in the cavity 12a in the thickness direction. After that, it strikes the panel body 1 to change the flow direction and flows in the cavity 12a to be filled in the cavity 12a.

  Since the synthetic resin material from the gate 14 flows in the thickness direction in the cavity 12a, alignment components such as reinforcing materials such as glass fibers in the synthetic resin material are easily aligned in the flow direction as shown in FIG. Thus, the orientation component such as the reinforcing material oriented in the thickness direction of the cavity 12a in the vicinity of the gate 14 constrains the shrinkage of the synthetic resin material (frame portion 2) filled in the cavity 12a. Thereby, contraction of the frame-like portion 2 in the vicinity of the gate 14 is suppressed, and a dimple-like minute concave portion is prevented from being generated in the panel body 1.

  In the above description, the convex portion 31 has a cylindrical shape and the groove 2a has an annular shape. However, the convex portion is divided into two or three parts as shown in FIGS. 5 (a) and 5 (b). The convex portions 31A and 31B having a shape divided into the above may be used. When such a nozzle chip having slit-shaped convex portions 31A and 31B is used, instead of the annular groove 2a, two semicircular grooves or three half-circular arc shapes or more Perhaps arcuate grooves are formed.

  When forming a plurality of maybe arcuate grooves, it is preferable to arrange each groove at equal intervals in the circumferential direction. Further, it is preferable that the groove exists in a range of 50% or more, particularly 60% or more, particularly 70% or more of the outer peripheral length of the gate mark G. When this ratio is less than 50%, it becomes difficult for the orientation component such as the reinforcing material to be oriented in the thickness direction of the frame-shaped portion. When this ratio is small, it is preferable to increase the depth of the groove 2a so that the reinforcing material and the like can be easily oriented.

  5A and 5B, the slot is provided so as to cut the convex portions 31A and 31B vertically in the axial direction, but the slit is from the tip of the convex portion to the middle in the axial direction. It may be provided.

  After the second synthetic resin material injected into the cavity 12a is cooled and solidified, the mold is opened and the panel 4 is removed. In the frame-like portion 2 of the panel 4, the traces of the gate 14 remain as burrs or circular minute protrusions or dents, and the gate trace G is generated. In this embodiment, four gates 14 are provided, but the present invention is not limited to this. Moreover, the demolding trace of the convex part 31 becomes the groove 2a.

  The panel 4 removed from the mold as described above can be subjected to an annealing treatment preferably at 100 to 130 ° C., particularly 120 to 130 ° C. for 1 to 5 hours, particularly 1 to 2 hours, to remove the strain.

  Further, after applying the hard coat stock solution to the entire front surface of the panel body 1 of the panel 4 and the transparent region 3 in the rear surface of the panel body 1, it is cured by UV irradiation or heating to form a hard coating (hard coat layer). ) May be formed. However, depending on the composition of the synthetic resin material constituting the panel body 1, it is not necessary to form a hard coating.

  When this hard coating is formed, the annealing treatment may be combined with the temperature rise of the panel main body during the formation of the hard coating, for example, by the thermosetting treatment of the thermosetting hard coating.

  In a panel formed by a conventional method, dimple-like micro-recesses appear on the front surface of the panel body 1 due to secondary contraction of the frame-like part 2 caused by heat treatment in a later process, or the depth thereof increases. Sometimes. On the other hand, by making the recess 1a generated on the rear surface of the panel body 1 shallow, the shrinkage force when the frame-like portion 2 near the gate mark G is cooled and solidified is reduced, and dimples are formed on the front surface of the panel body 1. It is possible to prevent the formation of the minute concave portion.

  In the present invention, when the second synthetic resin material (secondary material) is injected into the cavity 12a as shown in FIG. 2, the second synthetic resin material injected from the gate 14 is the gate 14 of the rear surface of the panel body. It is preferable that the recess 1a is generated by eroding the vicinity of the gate facing portion facing the gate, and the thickness of the panel body 1 near the gate facing portion is reduced. In order to adjust the erosion (entrance) in the vicinity of the gate facing portion, it is preferable to adjust the thermal history given to the panel body 1 by the secondary material. Methods for adjusting the thermal history include using a resin composition with a low glass transition temperature and a low melting point as the secondary material, or increasing the number of gate points to reduce the required flow length, etc. It is effective to adjust the molding conditions such as the injection speed, filling time, injection rate, and surface progression coefficient defined below. Among the adjustments according to the molding conditions, it is more effective to adjust the surface progression coefficient.

Surface progression coefficient: Per unit time injected into the mold cavity from the discharge nozzle of the injection molding machine
Thermoplastic resin capacity (injection rate), mold cavity where thermoplastic resin is injected
Value divided by the thickness of

[Surface progression coefficient of secondary material]
Even with the same injection rate (filling speed in the cavity), the resin progression in the molded product varies depending on the thickness of the second molded product. It is preferable to define the value divided by the thickness of the molded product.

In the present invention, the surface progression coefficient is preferably 15 to 400 cm ³ / sec · cm, more preferably 20 to 300 cm ³ / sec · cm, still more preferably 25 to 250 cm ³ / sec · cm, and particularly preferably 30 to 200 cm. ³ / sec · cm.

When the surface progression coefficient is smaller than 15 cm ³ / sec · cm, the substantial injection rate is reduced, so that the filling time is increased, and the heat history given to the second plate surface of the first molded body is increased, and the concave is increased. The depth increases, which leads to the generation of dimple-like micro-recesses. On the other hand, when the surface progression coefficient is larger than 400 cm ³ / sec · cm, the substantial injection rate increases and the filling time decreases. However, the depth of the recess increases due to the effect of shear heat generation due to high-speed filling, and the dimple-like microrecesses Leads to outbreak.

[Secondary resin temperature]
When the resin temperature at the time of molding the secondary material is high, the second plate surface of the first molded body (panel main body) is easily melted, so that the depth of the recess is increased. Moreover, when the resin temperature of the secondary material is low, the second plate surface of the first molded body is hardly melted, so that the recess becomes small. Therefore, when the glass transition temperature of the constituent material (primary material) of the first molded body is Tg, the resin temperature when molding the secondary material is preferably Tg + 90 to 150 ° C., more preferably Tg + 100 to 130 ° C. Especially preferably, it is Tg + 100-120 degreeC.

  If the resin temperature at the time of molding the secondary material is lower than Tg + 90 ° C., there is an effect in reducing the recess depth d, but the heat of the secondary material can melt the second plate surface of the first molded body. Since it becomes impossible, the adhesiveness of the 1st molded object and 2nd molded object interface of a multicolor molded product comes to be inferior. On the other hand, if the temperature is higher than Tg + 150 ° C., the amount of heat of the secondary material is too large, and the recess 1a tends to be large and deep, leading to the generation of dimple-like minute recesses.

[Secondary material injection speed]
When the injection speed at the time of forming the secondary material is low, the heat history given to the first molded body by the secondary material becomes long, and therefore the recess depth d tends to increase. On the contrary, when the injection speed is high, the heat history given to the first molded body by the secondary material becomes short, and therefore the recess depth d tends to be small. Therefore, the range of the injection speed is preferably 15 to 200 mm / s, more preferably 20 to 150 mm / s, and particularly preferably 25 to 130 mm / s.

  When the injection speed is less than 15 mm / s, the filling time becomes longer, the heat history to the first molded body becomes longer, the depth of the recess becomes larger, and further, the orientation component such as the reinforcing material is added to the frame member. Since it becomes difficult to orient in the thickness direction, it may lead to the generation of dimple-like minute recesses. Moreover, there is a possibility that the injection speed is too slow and the possibility of being unfilled increases.

  When the injection speed is faster than 200 mm / s, the filling time is shortened, and orientation components such as reinforcing materials are easily oriented in the thickness direction. However, shear heat generation near the gate increases the resin temperature. In addition, the depth of the recess becomes too large, and there is a possibility that a dimple-like minute recess is generated.

[Secondary material filling time]
If the filling time at the time of forming the secondary material is long, the heat history given to the first molded body by the secondary material becomes long. Therefore, the recess depth d becomes large, and if the filling time is short, the secondary material becomes the first material. Since the heat history given to the molded body 1 becomes short, the recess depth d tends to be small. Accordingly, the range of the filling time is preferably 1 to 20 seconds, more preferably 1.3 to 18 seconds, and particularly preferably 1.6 to 15 seconds. The filling time depends on the size of the molded product.

  When the filling time exceeds 20 seconds, the filling time becomes long, the heat history to the first molded body becomes short, the depth of the recess becomes large, and further, the orientation component such as the reinforcing material has a thickness of the frame member. Since it becomes difficult to orient in the direction, it may lead to the generation of dimple-like minute recesses. In addition, there is a greater possibility that the injection speed will be too slow and unfilled.

  On the other hand, if the filling time is less than 1 second, orientation components such as reinforcing materials are easily oriented in the thickness direction, but shear heat generation occurs in the vicinity of the gate, resulting in a high resin temperature and a large recess depth. There is a risk that dimple-like minute recesses may occur.

[Secondary material injection rate]
In general, the injection speed is often specified, but the injection speed in the actual molded product is difficult to measure accurately because it is affected by the shape and thickness except for a regular shape such as a flat plate or strip. For this reason, it is often defined by the moving speed of the cylinder (injection speed of the molding machine), but the filling capacity varies depending on the cylinder diameter of the molding machine, and the resin traveling speed in the molded product also varies. In order to eliminate these effects, the resin filling speed is often expressed as an injection rate. The injection rate is the capacity of the thermoplastic resin per unit time injected from the discharge nozzle of the injection molding machine into the mold cavity.

In the present invention, the injection rate is preferably 5 to 250 cm ³ / s, more preferably 8 to 200 cm ³ / s, and particularly preferably 10 to 100 cm ³ / s.

If the injection rate is less than 5 cm ³ / s, the filling time becomes long, the heat history to the first molded body becomes long, the depth of the recess becomes too large, and the orientation component such as a reinforcing material is further in the frame. Since it becomes difficult to orient in the thickness direction of a member, there exists a possibility of leading to a dimple-like minute recessed part generation | occurrence | production. In addition, there is a high possibility that the resin progress rate in the molded product is too slow to become unfilled. On the other hand, when the injection rate is greater than 250 cm ³ / s, the filling time is shortened, and the orientation components such as the reinforcing material are easily oriented in the thickness direction, but the shear temperature is generated near the gate, so that the resin temperature is increased. As a result, the depth becomes high, the depth of the recess becomes large, and there is a possibility that a dimple-like minute recess is generated.

  Since holding pressure is a molding condition used for the purpose of supplementing the final stage of filling and shrinkage after stopping the flow, for the formation of a recess in which the secondary material moves and scrapes the surface of the primary molded body. There is no noticeable effect.

  Moreover, it is effective for preventing a micro recessed part to set the cooling time of a primary molded object (panel main body 1) long and to fully solidify. The cooling time of the primary molded body in the two-color molding varies depending on the resin temperature and the mold temperature, but is usually 5 to 90 seconds, preferably 10 to 85 seconds, more preferably 20 to 85 seconds, and further preferably 30 to 80. Seconds. In addition, an insert molding method is also effective for entering. In addition, when performing two-color molding by the insert molding method, preheating the primary molded body to the mold temperature for injection molding the secondary material suppresses the distortion of the design surface caused by the difference in shrinkage balance. It tends to be easy and preferable.

  Further, the vicinity of the gate opposite side of the primary molded body may be formed in a concave shape in advance. By making the shape of this portion concave in advance, the influence of the filling pressure and temperature when injection molding the secondary material is relaxed, so that the depth of the recess tends to be as small as 4 mm or less. It becomes easy to suppress the occurrence. When the concave shape is set in advance, the concave shape depth is usually 0.1 to 1 mm, preferably 0.2 to 0.8 mm, and more preferably 0.3 to 0.5 mm. If the depth of the concave shape prepared in advance is smaller than 0.1 mm, it becomes difficult to loosen the influence of the secondary material, which easily leads to the generation of a dimple-like minute concave portion. Further, when the depth of the concave shape to be made in advance exceeds 1 mm, the depth of the concave shape becomes deeper due to the influence of the secondary material, and it tends to lead to the generation of dimple-like micro concave portions.

  As a method of making the concave shape in the primary molded body in advance, the mold shape when forming the primary material is made concave, and the secondary shape is processed after the concave shape is processed in a separate process on the molded primary molded body. The secondary material is molded by attaching it to the mold for molding the material. The secondary material gate is pressed immediately before the secondary material is injected and filled as a mold structure in which the gate portion of the secondary material can be advanced and retracted. A method of keeping the mold shape concave when forming the primary material is preferable.

  In addition, there are a method of moving the secondary side gate so that it is movable and advancing and retreating, and a method of making the surface shape of the primary side into an uneven shape in advance.

  In the present invention, in order to compensate for the erosion (decrease in the thickness of the panel body 1) of the primary molded body (panel main body) in the vicinity of the gate facing portion of the primary molded body (panel body) injected by the injected secondary material, It may be thick.

  In the panel molded by the method of the present invention, when the frame-shaped part 2 is molded, in order to reduce the influence of the shrinkage force particularly in the vicinity of the inner periphery of the frame-shaped part 2, the panel center side of the frame-shaped part 2 (transparent region 3). The thickness of the edge of the side) may be reduced continuously or stepwise toward the panel center side.

  The present invention is not limited to two-color molding, but can be applied to two-color or more multi-color molding. Further, the present invention is not limited to a molding method for multicolor molding, and can be applied to a case where a multicolor molding machine such as a counter reversal type or a platen rotation type is used, or an insert type multicolor molding. In particular, in the case of multicolor molding using a multicolor molding machine, it is difficult to lengthen the cooling time of the primary molded body more than necessary, so the secondary molded material is molded with the temperature of the primary molded body being relatively high. In many cases, the effects of the present invention can be exhibited more effectively.

<Constituent materials for panels>
Next, materials suitable for molding automobile window glass and the like by the method of the present invention will be described.

  The constituent material of the panel body 1 is preferably translucent, and can be appropriately selected from conventionally known arbitrary materials as long as they are translucent resins. Here, the translucency is usually 10% or more, preferably 15% or more, more preferably as the total light transmittance in a plate-shaped molded product having a smooth thickness of 3 mm measured according to JIS K7105. It means 20% or more, and the haze value is usually 10% or less, preferably 5% or less, more preferably 3% or less. In a translucent resin containing a dye or pigment, the proportion of the dye or pigment used is usually 0.001 to 2 parts by weight, preferably 0.005 to 1 part by weight, based on 100 parts by weight of the resin. More preferably, it is 0.005-0.5 weight part.

  Examples of the constituent material of the panel body 1 include polystyrene resin, high impact polystyrene resin, hydrogenated polystyrene resin, polyacryl styrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, poly Methyl methacrylate resin, polyphenyl ether resin, polycarbonate resin, amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, poly Heat of ether sulfone, styrene thermoplastic elastomer, olefin thermoplastic elastomer, polyamide thermoplastic elastomer, polyester thermoplastic elastomer, polyurethane thermoplastic elastomer, etc. Plastic elastomers Kyora. Among these, light-transmitting resins such as polycarbonate resin and polymethylmethacrylate resin are preferable. From the viewpoint of impact resistance and heat resistance, polycarbonate resin (PC), especially aromatic polycarbonate resin is used as the main constituent resin. Those are preferred. The main constituent resin means that the ratio of the aromatic polycarbonate resin in all resin components is usually 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more.

  Examples of resins used in combination with PC as the main constituent resin include polystyrene resin, ABS resin, AS resin, AES resin, ASA resin, polyphenylene ether resin, polymethacryl methacrylate resin, and polyester resin. An alloy or a copolymer may be used as long as the properties are maintained.

  The PC used in the present invention is, for example, a linear or branched thermoplastic polymer obtained by reacting an aromatic dihydroxy compound and a carbonate precursor, or a small amount of a polyhydroxy compound in combination therewith. Or a copolymer. PC can be produced by a known method, and examples of the production method include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. .

  Examples of aromatic dihydroxy compounds used as raw materials include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane ( Also known as: tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4 -Hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, , 2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) Propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2 , 2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3- Bis (hydroxyaryl) alkanes such as hexafluoropropane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydride) Bis (hydroxyaryl) cycloalkanes such as xylphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 9,9-bis (4-hydroxyphenyl) fluorene; Cardiostructure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; dihydroxy diphenyls such as 4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether Aryl ethers; dihydroxydiaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4 '-Dihydroxy-3,3'- Dihydroxydiaryl sulfoxides such as dimethyldiphenyl sulfoxide; dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like.

  Among the above, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) is particularly preferable from the viewpoint of impact resistance. Two or more kinds of these aromatic dihydroxy compounds may be used in combination.

  As the carbonate precursor to be reacted with the aromatic dihydroxy compound, carbonyl halide, carbonate ester, haloformate and the like are used. Specifically, phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dimethyl carbonate And dialkyl carbonates such as diethyl carbonate; and dihaloformates of dihydric phenols. Two or more of these carbonate precursors may be used in combination.

  In the present invention, the PC may be a branched aromatic polycarbonate resin obtained by copolymerization of a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6- Tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, 1, In addition to polyhydroxy compounds such as 1,1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxyindole (also known as isatin bisphenol), 5-chloroisatin, Examples include 5,7-dichloroisatin and 5-bromoisatin. Among these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferable. The polyfunctional aromatic compound is used by substituting a part of the aromatic dihydroxy compound, and the amount used is usually 0.01 to 10 mol%, preferably 0.1%, based on the aromatic dihydroxy compound. ~ 2 mol%.

  Although the molecular weight of PC used for this invention is arbitrary, it is 10,000-35,000 normally as viscosity average molecular weight [Mv] converted from solution viscosity. By setting the viscosity average molecular weight to 10,000 or more, the mechanical strength is improved and it is suitable for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is 35,000 or less, the fluidity is lowered and the molding process becomes easy. In addition, when forming hard coatings, such as a hard coat, in a post process, Preferably a viscosity average molecular weight is 18,000-35,000, More preferably, it is 20,000-30,000. By setting the viscosity average molecular weight to 18,000 or more, it is possible to suppress a decrease in impact strength when a cured coating is formed on the surface. Two or more types of PCs having different viscosity average molecular weights may be mixed.

Here, the viscosity average molecular weight [Mv] means that the intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. is obtained with an Ubbelohde viscometer using methylene chloride as a solvent, and the Schnell viscosity formula (η = 1.23 × 10 ⁻⁴ M ^0.83 ).

  The terminal hydroxyl group concentration of the PC used in the present invention is usually 2,000 ppm or less, preferably 1,500 ppm or less, more preferably 1,000 ppm or less. In addition, the lower limit is usually 10 ppm, preferably 30 ppm, more preferably 40 ppm, especially for PC produced by the transesterification method.

  By setting the terminal hydroxyl group concentration to 10 ppm or more, a decrease in molecular weight can be suppressed, and the mechanical properties of the resin composition tend to be further improved. Moreover, it exists in the tendency which the residence heat stability and color tone of a resin composition improve more by making terminal group hydroxyl group density | concentration into 2,000 ppm or less. In the case of forming a hard coating such as a hard coat, by applying a terminal hydroxyl group concentration of 100 to 2,000 ppm, preferably 200 to 1,000 ppm, more preferably 300 to 1,000 ppm, a high terminal hydroxyl group concentration, Its adhesion and durability are improved. The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm with respect to the PC weight, and the measurement method is a colorimetric determination (Macromol. Chem. 88 215 (1965) by the titanium tetrachloride / acetic acid method. Method).

  Further, in order to improve the appearance of the molded product and the fluidity, the PC used in the present invention may contain an aromatic polycarbonate oligomer. The aromatic polycarbonate oligomer has a viscosity average molecular weight [Mv] of usually 1,500 to 9,500, preferably 2,000 to 9,000. The usage-amount of an aromatic polycarbonate oligomer is 30 weight% or less normally with respect to PC.

  Furthermore, the PC used in the present invention may contain not only virgin PC but also PC regenerated from used products, so-called material recycled PC. Used products include optical recording media such as optical discs, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields, and other vehicle transparent members, water bottle containers, glasses lenses, sound barriers, glass windows, waves, etc. Examples include building members such as plates. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The use ratio of the regenerated PC is usually 80% by weight or less, preferably 50% by weight or less based on virgin PC.

  In addition to the above-mentioned dyes or pigments, any conventionally known auxiliary agent can be added to the constituent material of the panel body. Examples thereof include mold release agents, heat stabilizers, antioxidants, and weather resistance improvements. Agents, heat ray absorbents, heat ray reflectors, alkali soaps, metal soaps, plasticizers, fluidity improvers, nucleating agents, flame retardants, anti-dripping agents and the like. The usage-amount of these adjuvants is suitably selected from a well-known range.

  As a constituent material of the frame-shaped part 2, a resin composition containing at least one selected from a reinforcing material and an elastomer, or a resin composition containing two or more incompatible resins is used. The Among them, it is preferable to use a reinforced resin composition containing a reinforcing material from the viewpoint that the effect of suppressing dimple-like microrecesses by orientation is large and the effect of improving rigidity, dimensional stability, and heat resistance is large. Hereinafter, the reinforced resin composition will be described.

  The shape of the reinforcing material may be any shape such as a spherical shape, a cubic shape, a granular shape, a needle shape, a plate shape, and a fiber shape, but it is easy to be oriented, and the dimple-like micro concave portion suppressing effect of the present invention is large. In view of high rigidity, a fibrous reinforcing material is preferable. Further, from the viewpoint of improving the dimensional stability of the finally obtained molded article, high rigidity, and good appearance, a plate shape or a needle shape is preferable, and a plate having a laser diffraction particle size (D50) of 10 μm or less. Or needle-like fillers are preferred. Among these, glass fiber is preferable.

  Examples of such reinforcing materials include titanium oxide, zinc oxide, barium sulfate, silica, calcium carbonate, iron oxide, alumina, calcium titanate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium sulfate, Sodium sulfate, calcium sulfite, magnesium silicate (talc), aluminum silicate (mica), calcium silicate (wollastonite), clay, glass beads, glass powder, glass flake, glass fiber, carbon fiber, silica alumina fiber, zirconia fiber, Boron fiber, boron nitride fiber, silicon nitride potassium titanate fiber, inorganic fiber such as metal fiber, organic fiber such as aramid fiber, biodegradable fiber, fluororesin fiber, polyester fiber, silica sand, silica, quartz powder, shirasu, Diatomaceous earth, why Carbon, iron powder, aluminum powder.

  Among these, fibrous materials represented by glass fibers, carbon fibers, aramid fibers, biodegradable fibers, etc., magnesium silicate (talc), aluminum silicate (mica), plate products represented by glass flakes, silicic acid Needle-like materials represented by calcium (wollastonite) and the like are preferable. Two or more kinds of reinforcing materials can be used in combination.

  When a fibrous material such as glass fiber is used as the reinforcing material, the weight average fiber length of the reinforcing fiber is usually 1.5 to 10 mm, preferably 1.8 to 5 mm, from the viewpoint of strength and dispersibility. Moreover, in order to improve mechanical strength, dimensional accuracy, and heat resistance, the weight average fiber length of the fibers in the frame-shaped portion is usually 0.1 to 5 mm, preferably 0.2 to 4 mm, more preferably 0.3 to. 3 mm. In order to keep the weight average fiber length of the fibers in the frame part high, the configuration of the injection cylinder of the injection molding machine is essential, especially the screw compression ratio is loosely compressed, the clearance is wide, and the check ring clearance is wide. It is effective to take. Moreover, as conditions at the time of injection molding, it is effective to mold the resin temperature at a high setting, the back pressure at the time of measurement is low, and the injection speed is low.

  The content of the reinforcing material is usually 2 to 50 parts by weight, preferably 3 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the total constituent material of the frame-like part. When the content of the reinforcing material is less than 2 parts by weight, the effect of improving rigidity, dimensional stability and heat resistance is small, and when it exceeds 50 parts by weight, the impact resistance may be lowered.

  The reinforcing material may be left untreated, but for the purpose of increasing the affinity with the resin component or the interfacial bond strength, surface treatment agents, higher fatty acids or their derivatives, derivatives such as salts, coupling agents It is preferable to treat with. When the surface treatment is performed in combination with various surfactants such as nonionic, cationic, and anionic types and dispersants such as various resins, the mechanical strength and kneadability are preferably improved. .

  The base resin of the reinforced resin composition preferably used as the constituent material of the frame-shaped part is not particularly limited, and various known arbitrary thermoplastic resins can be used. Specifically, for example, polycarbonate resin; thermoplastic polyester resin such as polyethylene terephthalate resin, polytrimethylene terephthalate, polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin) ), Styrene-based resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin); Polyolefin resins such as polyethylene resins and polypropylene resins; Polyamide resins; Polyimide resins; Polyether resins; Polyurethane resins; Polyphenylene ether resins; Id resins; polysulfone resins; and polymethacrylate resins and the like, which may be used in combination of two or more. Among these, PC and thermoplastic polyester resin are preferable from the viewpoint of thermal stability, rigidity, and adhesion to the panel body. In particular, when the constituent material of the frame-shaped part includes a crystalline resin, the minute concave part due to the contraction of the frame-shaped part is easily formed, and therefore the effect of improving the fine concave part of the present invention is remarkable and preferable. In addition, when heat treatment is performed in a subsequent process after molding, a dimple-like minute concave portion may appear on the front surface of the panel body 4 or its depth may increase due to secondary contraction of the frame-shaped portion. Even in such a case, the effect of the present invention is more remarkably exhibited. Among these, those using PC as the main material, in particular, combined use of PC and a thermoplastic polyester resin are preferable.

  As a constituent material of the frame-shaped part 2 of the present invention, a resin composition containing an elastomer can also be used. Similar to the reinforcing material described above, the elastomer component is oriented in the thickness direction of the frame-shaped portion, so that shrinkage in the thickness direction in the vicinity of the gate is suppressed when the frame-shaped portion is cooled and solidified, leading to suppression of the dimple-like minute recesses.

  There are no particular restrictions on the elastomer, and known ones can be used. For example, methyl methacrylate-butadiene-styrene copolymer (MBS resin), styrene-butadiene-styrene copolymer (SBS), and SBS are hydrogenated. Hydrogenated copolymer (SEBS), styrene-isoprene copolymer (SIS), copolymer hydrogenated by hydrogenating SIS (SIPS), TPR such as EPR, EPDM, etc. Olefin-based elastomers, polyester-based elastomers, silicone-based elastomers, acrylate-based elastomers, composite rubber-based graft copolymers in which vinyl monomers are graft-polymerized to composite rubbers composed of silicone-based rubber and acrylate-based rubber components, etc. Can be mentioned.

  Of these, a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith is preferable. The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

  The rubber component usually has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. And ethylene-α-olefin rubber, ethylene-acrylic rubber, fluororubber, and the like. These may be used alone or in admixture of two or more. Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable. .

  Specific examples of the monomer component that can be graft copolymerized with the rubber component include aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as acrylonitrile, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and glycidyl. Epoxy group-containing (meth) acrylic acid ester compounds such as (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acids such as maleic acid, phthalic acid and itaconic acid Examples thereof include acid compounds and anhydrides thereof (eg maleic anhydride). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, a layer containing at least one rubber component selected from the above-mentioned polybutadiene-containing rubber, polyalkyl acrylate-containing rubber, and polyorganosiloxane / polyalkyl acrylate-containing rubber is used as a core layer, and its surroundings. A core / shell type graft copolymer comprising a shell layer formed by (co) polymerizing (meth) acrylic acid ester or acrylonitrile / styrene is particularly preferable. The core / shell type graft copolymer preferably contains 40% by weight or more of rubber component, more preferably 60% by weight or more. Moreover, what contains 10 weight% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such a graft copolymer may be used individually by 1 type, or may use 2 or more types together.

  When the elastomer is stretched in the thickness direction of the frame-like portion and oriented in a layered manner, the effect of the present application appears particularly remarkably. From this point, the glass transition temperature of the elastomer is preferably −30 ° C. or lower, more preferably −35 ° C. or lower, further preferably −40 ° C. or lower, and −50 ° C. or lower. Is particularly preferred. By containing an elastomer having such a glass transition temperature, the flatness of the elastomer oriented in the thickness direction of the frame-shaped portion (ratio of the major axis to the minor axis of the elastomer described later) can be easily improved, and the dimple-like microrecesses are formed. It tends to be suppressed from occurring, which is preferable.

  The glass transition temperature of the elastomer can be measured by determining the peak temperature of loss tangent (tan δ) obtained by dynamic viscoelasticity measurement. Specifically, using a hot press machine heated at 200 ° C., the elastomer raw material was press-molded for 3 minutes in a 0.7 mm thick × 10 cm × 10 cm mold, and after water cooling, 0.7 mm thick × 5.5 mm Cut out a test piece of × 25 mm, perform dynamic viscoelasticity measurement at a temperature rise rate of 3 ° C./min and a frequency of 110 Hz in a temperature range of 50 to −100 ° C., and obtain a peak temperature of tan δ obtained. The glass transition temperature is assumed.

  The content of the elastomer is usually 2 to 40 parts by weight, preferably 3 to 30 parts by weight, and more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the total constituent material of the frame-like part. If the elastomer content is less than 2 parts by weight, the impact resistance improvement effect by the elastomer will be insufficient, and if it exceeds 40 parts by weight, the hardness of the resulting molded product will decrease, and the appearance and heat resistance will decrease. Prone to occur.

  As a constituent material of the frame-shaped part 2 of the present invention, a resin composition containing two or more incompatible resins can also be used. Similar to the reinforcing material and elastomer described above, the domain formed by the incompatible resin component is oriented in the thickness direction of the frame-shaped portion, thereby suppressing shrinkage in the thickness direction in the vicinity of the gate when the frame-shaped portion is cooled and solidified. This leads to suppression of the dimple-like minute recesses. In addition, the resin composition containing two or more incompatible resins has a sea-island structure in the central part of the thickness direction of the molded body observed with an electron microscope or the like, and one resin forms a matrix, and the other A combination of resins in which the resin takes a domain shape.

  Among the resins that can be used, among those exemplified as the base resin of the reinforced resin composition, two or more incompatible resins can be selected and used. In particular, it is more preferable to use a combination of a resin selected from a polycarbonate resin as a main component and a thermoplastic polyester resin such as a polyethylene terephthalate resin, a styrene resin such as an ABS resin, and a polyolefin resin such as a polyethylene resin as the remaining component. The polycarbonate resin is preferably used in such a ratio that it forms a matrix. In this case, domains of polyester resin, styrene resin, and polyolefin resin are formed in the matrix of the polycarbonate resin. In addition, these other resin components mixed with the polycarbonate resin may be oligomer components having a weight average molecular weight of 500 to 9,000.

  When the polycarbonate resin is contained, the content of the polycarbonate resin is usually 60 to 98 parts by weight, preferably 65 to 95 parts by weight, more preferably 70 to 93 parts by weight, with respect to 100 parts by weight of the total constituent material of the frame-like part. More preferably, it is 75-90 weight part. When the content of the polycarbonate resin is less than 60 parts by weight, the adhesion between the panel body and the frame-like part tends to be inferior, and the heat resistance and impact resistance of the frame-like part tend to be low. The chemical resistance of the shaped part may deteriorate, which is not preferable.

  In the present invention, it is preferable that the constituent resin material of the panel main body 1 is translucent and the constituent material of the frame-like portion 2 is non-translucent because the effect of improving the minute recesses is remarkable. In addition, it is desirable that the main components blended in 10% by weight or more of the constituent resin materials of the panel main body 1 and the frame-like portion 2 are the same in order to enhance the bonding property between them.

  In the present invention, it is preferable to use a polymer alloy composed of PC and a thermoplastic polyester resin as a constituent material of the frame-shaped part 2, and the ratio of PC to the total amount of both components is usually 50 to 95% by weight, preferably Is 60 to 90% by weight.

  The thermoplastic polyester resin is a polymer or copolymer obtained by condensation reaction of a dicarboxylic acid component composed of a dicarboxylic acid or a reactive derivative thereof and a diol component composed of a diol or an ester derivative thereof.

  In general, the thermoplastic polyester resin is produced by reacting a dicarboxylic acid component with a diol component in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc. This is done by discharging out of the system. The condensation reaction may be either a batch type or a continuous type, and the degree of polymerization may be increased by solid phase polymerization.

  The dicarboxylic acids may be either aromatic dicarboxylic acids or aliphatic dicarboxylic acids, but aromatic dicarboxylic acids are preferred from the viewpoints of heat resistance and dimensional stability. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylether dicarboxylic acid 4,4′-biphenylmethanedicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-ter-phenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid and the like can be mentioned. In addition, alkyl group-substituted products such as 5-methylisophthalic acid; reactive derivatives such as alkyl ester derivatives such as dimethyl terephthalate and diethyl terephthalate can also be used.

  Among the above, terephthalic acid, 2,6-naphthalenedicarboxylic acid and their alkyl ester derivatives are preferable, and terephthalic acid and its alkyl ester derivatives are more preferable. Two or more of these aromatic dicarboxylic acids may be used in combination, and together with the aromatic dicarboxylic acid, an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, or a fatty acid such as cyclohexanedicarboxylic acid. It is also possible to use a cyclic dicarboxylic acid in combination.

  The diols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, deca Aliphatic diols such as methylene glycol and 2,2-dimethyl-1,3-propanediol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanediol, trans- or cis-2,2, Alicyclic diols such as 4,4-tetramethyl-1,3-cyclobutanediol; aromas such as p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether) Group diols. These substitution products can also be used.

  Among the above, ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferable from the viewpoint of thermal stability, impact resistance, rigidity, and the like. 1,3-propanediol and 1,4-butanediol are more preferable, and ethylene glycol is particularly preferable. Two or more of these may be used in combination. Further, as the diol component, a long chain diol having a molecular weight of 400 to 6,000, that is, one or more of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like are used in combination with the above diols. It may be copolymerized.

  Further, the thermoplastic polyester resin used in the present invention can be branched by introducing a small amount of a branching agent. Examples of the branching agent include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, pentaerythritol and the like.

  Preferable specific examples of the thermoplastic polyester resin used in the frame portion include polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), polybutylene terephthalate resin (PBT), polyhexylene terephthalate resin, and polyethylene-naphthalate resin. (PEN), polybutylene naphthalate resin (PBN), poly (1,4-cyclohexanedimethylene terephthalate) resin (PCT), polycyclohexylcyclohexylate (PCC), and the like. Among these, polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), and polybutylene terephthalate resin (PBT) are preferable in terms of fluidity and impact resistance.

  The polyethylene terephthalate resin is a saturated polyester polymer or copolymer obtained by a condensation reaction of terephthalic acid as a main component as a dicarboxylic acid component and ethylene glycol as a diol component as a main component. The proportion of the ethylene terephthalate unit as the repeating unit is usually 70 mol% or more, preferably 80 mol% or more. In addition, in the polyethylene terephthalate resin, diethylene glycol, which is a side reaction product during polymerization, may be included as a copolymerization component. The amount of diethylene glycol is usually based on the total amount of the diol component used in the polymerization reaction. 0.5 to 6 mol%, preferably 0.5 to 5 mol%.

  Specific examples of other thermoplastic polyester resins include, for example, polypivalolactone resins obtained by ring-opening polymerization of lactones, poly (ε-caprolactone) resins, and liquid crystal polymers that form liquid crystals in a molten state (Thermotropic Liquid Crystal Polymer; TLCP) and the like. Specifically, commercially available liquid crystal polyester resins include “X7G” manufactured by Eastman Kodak Company, “Xyday” manufactured by Dartco Company, “Econol” manufactured by Sumitomo Chemical Co., Ltd., “ Vector "and the like.

  The intrinsic viscosity of the thermoplastic polyester resin used in the present invention is usually 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g. Here, the intrinsic viscosity means a value measured at 30 ° C. in a solvent of phenol / tetrachloroethane = 50/50 (weight ratio). When the intrinsic viscosity is less than 0.4, the impact resistance tends to decrease, and when it exceeds 1.5, the fluidity tends to decrease. The amount of terminal carboxyl groups of the thermoplastic polyester resin is usually 5 to 50 μeq / g, preferably 10 to 30 μeq / g. When the terminal carboxyl group amount is less than 5 μeq / g, the impact resistance tends to decrease, and when it exceeds 50 μeq / g, the moist heat resistance and the thermal stability tend to be insufficient.

Furthermore, as the thermoplastic polyester resin used in the present invention, not only virgin raw materials but also thermoplastic polyester resins regenerated from used products, so-called material recycled thermoplastic polyester resins can be used. . As used products, containers, films, sheets, fibers, and the like are mainly exemplified, and containers such as PET bottles are preferable. In addition, as the recycled thermoplastic polyester resin, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.

  Conductive carbon black and / or hollow nanocarbon fibers can be blended with the constituent material of the frame-like portion for the purpose of imparting antistatic properties and conductivity capable of electrostatic coating. Examples of the conductive carbon black include acetylene black obtained by thermally decomposing acetylene gas, and Ketjen black produced by crude incomplete combustion using crude oil as a raw material. Hollow nanocarbon fibers have an outer region consisting of an essentially continuous multi-layer of regularly arranged carbon atoms and an inner hollow region, with each layer and the hollow region being arranged substantially concentrically. There are essentially cylindrical fibrils. Furthermore, the regularly arranged carbon atoms in the outer region are graphite-like. The diameter of the hollow region is usually 2 to 20 nm. Such hollow nanocarbon fibers are sold by Hyperion Catharsis under the trade name “graphite fibrils” and are readily available.

  Further, in the present invention, the bending elastic modulus of the constituent material of the frame-shaped portion is equal to or higher than the bending strength elastic modulus of the constituent material of the panel body, so that the rigidity and strength of the panel are secured, and the mounting to the structural part is performed. To preferred. Furthermore, when the bending elastic modulus of the constituent material of the frame-shaped part is equal to or higher than the bending elastic modulus of the constituent material of the panel body, the minute concave part is easily formed due to the shrinkage of the frame-like part. Becomes prominent.

  Further, in the present invention, the panel body may be composed of a non-reinforced resin composition, whereas the frame-shaped portion is a reinforced resin from the viewpoint of securing the rigidity and strength of the panel and attaching to a structural component. It is preferable to be comprised with a composition. That is, it is preferable to blend a reinforcing material made of a fibrous material, a plate-like material, or a needle-like material into the resin material of the frame-like portion. Furthermore, in order to give the frame-shaped portion a thermal conductivity function, a filler having thermal conductivity can be included. Examples of the thermally conductive filler include carbon fiber, graphite, boron nitride, and magnesium silicate salt.

  When the primary material side such as a panel main body is composed of a non-reinforced resin composition and the secondary material side such as a frame is composed of a reinforced resin composition, the primary material and the secondary material on the mold side surface Due to the difference in rigidity, the secondary material contracts easily to pull the front surface of the primary material. Therefore, the effect of applying the present invention becomes remarkable in the case of such a combination of resin materials. Furthermore, since the secondary molded body also serves as a joint portion with the structural component, it is preferable that the joint portion is opaque so that the joint portion cannot be visually recognized from the design surface side. When the primary molded body is transparent and the secondary molded body is colored, the depth of color appears when viewed from the primary molded body side, making it easy to visually recognize the minute recesses on the front surface of the primary molded body such as the panel body. . Even in such a combination, the effect of the present invention is remarkable.

  As described above, in the present invention, in order to mainly prevent the panel body 1 from being damaged or deteriorated, a hard coat (hard film) as a protective film may be provided. Such a hard film may be provided only on the front surface opposite to the frame-like portion 2. The thickness of the hard coating is preferably 1/100 or less of the thickness of the panel body 1, and usually 1 to 50 μm, particularly preferably 5 to 20 μm.

  The hard coating may be a single layer, but may have a multilayer structure of two or more layers in order to improve the protection function and weather resistance. In the multilayer structure, it is preferable to set the hardness of the outermost layer to the maximum. As the hard coating having a multilayer structure, for example, it has at least one function among a functional layer of each of heat ray shielding, ultraviolet absorption, thermochromic, photochromic, electrochromic, primer layer, colored decoration layer, etc. It is preferable.

  A transparent resin is suitable for the constituent material of the hard coating. As such a transparent resin, a known material known as a hard coat agent can be used as appropriate. For example, various hard coat agents such as silicone, acrylic, silazane, and urethane can be used. I can do it. In these, in order to improve adhesiveness and a weather resistance, the 2-coat type hard coat which provides a primer layer before apply | coating a hard-coat agent is preferable. Examples of the coating method include spray coating, dip coating, flow coating, spin coating, and bar coating. Moreover, the method by a film insert, the method of apply | coating and transferring the chemical | medical agent suitable for a transfer film, etc. can be employ | adopted.

  A thin film having various functions (heat ray shielding, ultraviolet absorption, thermochromic, photochromic, and electrochromic functions) may be formed on the inner layer side with the hard coating as the outermost layer. Further, a functional layer having anti-fogging property, a layer having thermal conductivity, a heat ray for defogging, or the like may be disposed on the surface constituting the vehicle interior. At this time, the functional layer having antifogging properties is preferably a re-outer layer.

  A transparent resin layer may be provided between the surface of the panel body 1 and the hard coating.

  In the present invention, an uneven portion may be formed at the boundary between the rear surface of the panel main body 1 and the frame-shaped portion 2 to increase the bonding strength between the panel main body 1 and the frame-shaped portion 2. In the present invention, an attachment piece for attaching other components may be provided on the frame-like portion.

  The present invention is widely useful for industrial applications, and is suitable for multilayer molded products that require design properties on the design surface side. In particular, the present invention can be widely applied to automobile applications, and in particular, automotive glazing members such as back door windows, sunroofs, and rear quarter windows, and exterior panels such as back door panels, side door panels, roofs, fenders, and bonnets, It is suitable for exterior panel parts for automobiles. In addition to automotive exterior panel parts, the present invention has a wide range of construction machines such as canopies, lighting lenses, mirrors, motorcycle windshields, nameplates, solar cell covers or solar cell substrates, and display device covers. It can be used for applications.

[Examples 1 to 4]
A two-color molded product shown in FIGS. 6A and 6B simulating a panoramic roof of an automobile was molded using the injection molding apparatus shown in FIG. 2, and the depth of the dimple-like minute recesses was evaluated. 6A is a rear view of the panel, and FIG. 6B is a sectional view taken along the line VIb-VIb in FIG. 6A.

  In FIG. 6, reference numeral 51 denotes a test sample panel, which includes a panel main body 52 and a frame member 53 provided on the peripheral edge thereof. The outer dimensions of the panel main body 52 are 750 mm × 465 mm, and the thickness is 5 mm. The width of the short side of the frame member 53 is 97 mm, one width on the long side is 75 mm, and the other is 90 mm. The frame member 53 is provided at a position 3 mm inside from the outer edge of the panel body 52 (that is, L = 3 mm in FIG. 6B).

An annular groove 53a surrounding the gate trace is present on the surface of the frame-like portion 53 opposite to the panel main body 52. A width _W 2 = 2.0 mm on the inlet side of the groove 53a, as the groove width _{W 1} of the inner portion of the groove 53a is smaller than _{W 2,} the outer peripheral side of the peripheral wall surface taper angle 1 ° taper of the groove 53a The nozzle tip provided with was used. The depth h of the groove 53a was as follows. The distance from the outer periphery of the gate mark G to the inner periphery of the groove 53a was 0.5 mm.

Example 1: 1.0 mm
Example 2: 1.5 mm
Example 3: 2.0 mm
Example 4: 2.5 mm

The panel body 52 is curved such that the surface (front surface) opposite to the surface on which the frame member 53 is formed is convex toward the front surface, and the longitudinal direction (long side) is 10,000 R, short. The hand direction (short side) is a curved surface of 5,000R. In FIG. 6A, G _{1 to} G ₆ indicate gate portions, and broken lines W _{1 to} W ₆ indicate weld lines.

The thickness of the long side portion of the frame member 53 (between the corner portion _C 2 -C ₃ and between the corner portion _C 5 -C _6), as in FIG. 6 (a), is 3.5 mm. The thickness of the short side portion of the frame member 53 is 4.5 mm in the intermediate portions C ₁ and C ₄ in the side direction, and the intermediate portions C ₁ and C ₄ to the corner portions C ₂ , C ₆ , C ₃ , and C _5. The corners C ₂ , C ₆ , C ₃ , and C ₅ have a thickness of 3.5 mm.

  As a molding material for the panel body 52, Novalex 7022U-G (viscosity average molecular weight: 21,000) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used. The molding material of the frame member 53 is obtained by blending and mixing the following components with the following composition, and melt-kneading at a barrel temperature of 320 ° C. with a twin screw extruder (“TEM75BS” manufactured by Toshiba Machine Co., Ltd.). (MEP represents Mitsubishi Engineering Plastics Co., Ltd., and MCC represents Mitsubishi Chemical Co., Ltd.).

PC (MEP Iupilon S-3000FN) 32 parts by weight PC (MEP Iupilon E-2000FN) 47 parts by weight PET (MCC Novapex GG500) 21 parts by weight Glass fiber (Nippon Electric Glass T531DE, weight average fiber length 3 mm)
5.3 parts by weight Elastomer (Staffyroid MG1011 manufactured by Aika Industries Co., Ltd.) 3.2 parts by weight Stabilizer (ADEKA STAB 2112 manufactured by ADEKA) 0.03 parts by weight Carbon black (Royal Black 904G manufactured by Koshigaya Kasei Co., Ltd .: 40% by weight) %, Polystyrene: 60% by weight masterbatch) 1.0 part by weight

  A panel of a test sample was molded by the following method using the above materials.

  First, a panel body material pre-dried at 120 ° C. for 5 hours is injection-molded (injection temperature) into a cavity formed between a fixed mold and a first movable mold that are temperature-controlled at a mold temperature of 90 ° C. 300 ° C.) to form a panel body. The injection speed was a single speed of 50 mm / sec, and the injection holding pressure switching position was 2 mm. Molding was performed with a valve gate type hot runner. Injection compression molding was performed, the mold was opened by 2 mm before injection, and 700 t was re-clamped at the injection holding pressure switching position. The holding time for re-clamping at this time was 15 seconds.

  Next, after the panel body is cooled for 60 seconds, the first movable mold is opened, and the second movable mold that is controlled to a mold temperature of 90 ° C. is held with the panel body held in the first movable mold. The molds were matched, and a cavity formed between the second movable mold and the panel main body was filled with a molding material for a frame member preliminarily dried at 120 ° C. for 5 hours (injection resin temperature 270 ° C.). The initial speed was increased proportionally so that the injection speed became the speed shown in Table 1 when 10% of the measured value was filled. The measurement value was 210 mm, and the injection holding pressure switching position was 28 mm.

The filling time was 7.42 sec, and the injection peak pressure was as shown in Table 1. After filling, a holding pressure of 25 MPa was applied for 10 seconds to form a frame member. Molding was performed with a valve gate type hot runner. The gate number of the valve gate is 6 points G _{1 to} G ₆ shown in FIG. 6A, the gate diameter is 5 mm, and the valve pin diameter is 8 mm. All gates were opened at the same time, and resin filling was started at the same time. After the cooling time of 60 seconds, the second movable mold was opened, and the panel in which the molded panel body and the frame member were integrated was removed.

Injection speed, fill time, peak pressure, holding pressure, dwell time, injection rate of the gate shown in _{G 2} in FIG. 6 (a), the surface progression factor, a groove 53a depth h, the remaining thickness _(t 2 -h), The ratio h / t ₂ of the depth h of the groove 2a and the thickness t ₂ of the frame-like portion 53, the depth of the dimple-like microrecesses of the panel body, and the position facing the gate trace near the frame-like portion side of the panel body Table 1 shows the recess depth d, the substantial recess area, and the visual evaluation results. The visual evaluation was performed by visually observing the distortion (linearity) of the image by reflecting an electric lamp on the molded product. The evaluation criteria are as follows.

    ○: No distortion at all.

    Δ: Small distortion is observed.

    X: Large distortion is observed.

As described above, since the six valve gates are simultaneously opened and filled with resin, the injection rate differs slightly depending on the cavities carried by the respective gates. Therefore, the gate G ₂ shown in FIG. 6 (a), the emissivity and surface progression factor shown in Table 1.

  The depth of the dimple-like minute recesses, the recess depth d, and the substantial recess area were measured by the following methods.

[Dimple-like micro-recess depth]
A flat panel having a size of 100 mm × 100 mm including the dimple-like microrecesses of the panel obtained by the above method was cut out, and the surface roughness meter “Surfcom 3000A” manufactured by Toyo Seimitsu Co., Ltd. was used to increase the size of the dimple-like microrecesses. The surface of a 30 mm × 30 mm area was measured at a 1 mm pitch under the conditions of an operation speed of 6 mm / sec and a measurement length of 30 mm. From the obtained surface measurement results, two-dimensional data of the dimple-like microrecesses were extracted, and the maximum depth of the microrecesses was determined as the dimple-like microrecess depth.

[Recess depth d, substantial recess area]
A cross section including the deepest part of the dimple-like minute concave portion was cut out, and the cross section was observed with “Digital Microscope VHX-1000” manufactured by Keyence Corporation. About the obtained cross-sectional photograph, the recess depth d and the substantial recess area were measured using image analysis software “Image-Pro Plus (ver6.2J)” manufactured by Media Cybernetics. In addition, the substantial recess area is a measured value obtained for a cross section having the largest area among the obtained cross sections.

[Comparative Example 1]
A panel having no groove 53a was molded by using a nozzle chip 30 having no projection 31 as the nozzle chip 30 of the injection molding machine. Other conditions were the same as in Examples 1 to 4, and molding and various evaluations were performed. The results are shown in Table 1.

  As shown in Table 1, according to Examples 2 and 3 of the example of the present invention, no dimple-like microrecesses are generated on the front surface of the panel body, and in Examples 1 and 4, the dimple-like microrecesses are very small. The distortion of the visually recognized image was extremely small. On the other hand, in Comparative Example 1 in which no groove was provided around the gate trace, a large dimple-like minute concave portion was generated, and the visible distortion was large.

1 Panel body (first molded body)
1a Recess 2 Frame-shaped part (second molded body)
2a Groove 3 Transparent area 4 Panel 11 Movable type 11a, 12a Cavity 12 Second fixed type 13 Hot runner 14 Gate 16 Valve pin 17 Manifold 18 Nozzle touch part 19 Nozzle 20 Drive unit 30 Nozzle chip 31, 31A, 31B Protruding part 31a Through Hole 32 Flange 33 Insertion hole

Claims (12)

A first molded body having a first plate surface and a second plate surface opposite to the first plate surface;
In a multicolor molded article having a second molded body formed integrally with the first molded body by injection molding of a synthetic resin material on at least a part of the second plate surface,
A groove is formed in at least a part of a region within a radius of 25 mm from the center of the gate mark of the second molded body on the plate surface opposite to the first molded body of the second molded body. ,
The groove extends in a direction around the gate mark, and is present in a range of 50% or more of the circumferential direction of the gate mark.
The groove is formed by a convex portion of a cavity surface of a mold for molding the second molded body,
The synthetic resin material that is a constituent material of the second molded body includes a base resin, and an orientation component that is less shrinkable when the base resin is cooled and solidified than the base resin,
The alignment component is either at least one selected from the reinforcement and elastomer, or a domain component consisting of incompatible resin with respect to the base resin,
The multicolor molded product, wherein the orientation component is oriented in the thickness direction of the second molded body . 2. The multicolor molded product according to claim 1, wherein a difference t ₂ −h between a depth h of the groove and a thickness t ₂ of the second molded body is 1 mm or more. 3. The multicolor molding according to claim 1, wherein a ratio h / t ₂ between a depth h of the groove and a thickness t ₂ of the second molded body is 0.3 to 0.9. Goods. The multicolor according to any one of claims 1 to 3 , wherein a bending elastic modulus of a constituent material of the second molded body is equal to or higher than a bending elastic modulus of a constituent material of the first molded body. Molding. The constituent material of the first molded body is a non-reinforced resin composition, claims 1, wherein the constituent material of the second molded body is reinforced resin composition containing reinforcing material 4 The multicolor molded article according to any one of the above. The multicolor molded article according to claim 5 , wherein the reinforcing material contains a fibrous material, a plate-shaped material, or a needle-shaped material. The multicolor molded article according to any one of claims 1 to 6 , wherein the constituent material of the second molded body contains a crystalline resin. The constituent material of said 1st molded object is translucent, and the constituent material of the 2nd molded object is translucent, The multiple in any one of Claim 1 thru | or 7 characterized by the above-mentioned. Color molded product The constituent material of the first molded body are those that include a polycarbonate resin, any one of the constituent material of the second molded body claims 1, characterized in that those comprising a polycarbonate resin and polyester resin 8 1 The multicolor molded product according to item. The second molded body multicolor molding article according to any one of claims 1 to 9, characterized in that provided on the periphery of the first molded body. A vehicle comprising a panel made of the multicolor molded product according to any one of claims 1 to 10 . A method for molding the multicolor molded article according to any one of claims 1 to 10 ,
The movable mold holding the first molded body is clamped to a fixed mold having a cavity for molding the second molded body,
A step of injecting a synthetic resin material into the cavity from the fixed-type gate through a hot runner to form a second molded body,
Protrusions protruding into the cavity are provided around the gate of the fixed mold for molding the second molded body,
A method for forming a multicolor molded product, wherein the groove is formed by the convex portion.

Images