WO2019065565A1 - Multi-layer sheet - Google Patents

Abstract

The present invention relates to a multi-layer sheet obtained by laminating a vibration-damping layer and a polycarbonate layer, wherein (1) the vibration-damping layer is present on and/or close to the surface of the multi-layer sheet, and (2) the vibration-damping layer is a sheet-like compact of a polyester resin composition containing: a thermoplastic polyester resin (A) that is constituted from components including a dicarboxylic acid component and a diol component; a component (B) that is a plasticizer and/or an elastomer; and an inorganic filler (C). This multi-layer sheet exhibits sufficient rigidity and impact strength due to having a polycarbonate layer, and also exhibits an excellent vibration-damping effect due to a high loss coefficient. Therefore, this multi-layer sheet can be suitably used as a material for audio equipment, products such as appliances, vehicles, buildings, industrial equipment, or parts thereof, as well as a vibration-damping material for casings.

Description

Laminated sheet

The present invention relates to a laminated sheet for a damping material.

In recent years, vibration countermeasures for various devices have been required, and in particular, in the fields of automobiles, home appliances, precision instruments and the like. As one of the materials having high damping property, there is a material (patent document 1) in which a metal plate and a vibration absorbing material such as rubber, asphalt or the like are laminated (patent document 1), and a resin sheet to which damping property is given. However, the material using the metal plate has a problem that the product itself becomes heavy. Furthermore, there is a problem that the single sheet of the resin sheet to which the vibration damping property is imparted is low in rigidity and there are many in which there is no self-supporting property.

JP, 2016-186207, A

The present invention relates to the following [1].
[1] A laminated sheet in which a damping layer and a polycarbonate layer are laminated,
The damping layer is present on the surface and / or near the surface of the laminated sheet,
The damping layer contains a thermoplastic polyester resin (A) composed of a component containing a dicarboxylic acid component and a diol component, a component (B) which is a plasticizer and / or an elastomer, and an inorganic filler (C) The laminated sheet which is a sheet-like molded object of the polyester resin composition formed.

FIG. 1: is a schematic diagram which shows the cross-section of the one aspect | mode of the lamination sheet of this invention. FIG. 2: is the model (A) and (B) which shows the cross-section of the various aspect of the lamination sheet of this invention. FIG. 3: is the model (A) and (B) which shows the cross-section of the aspect of the lamination sheet as comparison object. FIG. 4 is a schematic view (A) showing a cross-sectional structure of one aspect of the laminated sheet of the present invention and a schematic view (B) showing a cross-sectional structure of one aspect of the laminated sheet as a comparative object. FIG. 5 is a schematic view showing a cross-sectional structure of various aspects of the laminated sheet of the present invention.

Detailed Description of the Invention

The present invention relates to a laminated sheet having sufficient rigidity and impact strength to an extent that metal material is unnecessary, and having excellent vibration damping properties.

The laminated sheet of the present invention has sufficient rigidity and impact strength to such an extent that a metal material is unnecessary, and can exhibit excellent vibration damping properties.

Hereinafter, the laminated sheet of the present invention will be described in detail.
1. Laminated Sheet The laminated sheet of the present invention is a laminated sheet in which a damping layer and a polycarbonate layer are laminated,
The damping layer is present on the surface and / or near the surface of the laminated sheet,
The damping layer contains a thermoplastic polyester resin (A) composed of a component containing a dicarboxylic acid component and a diol component, a component (B) which is a plasticizer and / or an elastomer, and an inorganic filler (C) It is one of the features of the invention that it is a sheet-like molded product of the polyester resin composition.

The present invention is characterized in the position where the damping layer is present. From the viewpoint of imparting rigidity and self-supporting property to the laminated sheet, vibration control is performed with a two-layer structure in which the damping material is simply attached to the sheet serving as a base (made of polycarbonate or the like) having self-supporting properties. It is conceivable to have a three-layer structure sandwiching the material. However, although a sheet having a two-layer structure in which a damping material is simply attached to a sheet serving as a base material can provide high damping properties, it is not sufficient in terms of strength and heat resistance. On the other hand, although a sheet having a three-layer structure in which a damping material is sandwiched between sheets serving as a base material can maintain strength, the damping property is not significantly improved. Then, the present inventors examined the position of the damping material (damping layer) in a lamination sheet, and completed the present invention.

By having such a feature at the position where the damping layer is present, sufficient rigidity, impact strength and damping property of the laminated sheet can be improved while securing the self-supporting property of the laminated sheet. The mechanism by which the laminated sheet of the present invention exerts an excellent damping effect is presumed as follows. By arranging the damping layer on the surface side of the laminated sheet or near the surface, ie, on the surface side of the center of the laminated sheet, when distortion such as bending is applied to the sheet, the strain energy is applied to the damping layer on the surface side As a result, energy loss occurs, and it is considered that damping property is developed. Further, by increasing the thickness of the damping layer on the surface side, it is expected that the strain energy of the damping layer on the surface side will further increase, thereby further improving the damping property. Further, by increasing the thickness of the damping layer on the surface side, it is expected that the strain energy of the damping layer on the surface side will further increase, thereby further improving the damping property. Furthermore, in the embodiment in which the damping layer is present in the vicinity of the surface of the laminated sheet, that is, when the polycarbonate layer is laminated on both the upper surface and the lower surface of the damping layer, It can also be expected to improve chemical resistance and suppress bleed and outgassing.

Since the laminated sheet of the present invention has rigidity, impact strength and excellent vibration damping properties, it can be used as a speaker, television, radio cassette player, headphone, audio component, microphone, etc. as a material for an audio equipment case; Parts and housing materials as electric drills, electric tools such as electric screwdrivers, computers, projectors, servers, electric products with cooling fans such as POS systems, washing machines, clothes dryers, air conditioner indoor machines, sewing machines, dish washing Machines, fan heaters, complex machines, printers, scanners, hard disk drives, video cameras, etc .; parts of electric products with vibration source and housings as electric toothbrushes, electric shavers, massage machines etc .; Parts and housing materials for generators, gas generators, etc .; Parts and housing materials for refrigerators, vending machines, outdoor units of air conditioners, dehumidifiers, household generators; materials for automobile parts such as dashboards, instrument panels, floors, doors, roofs, etc. interior materials Materials for engines, such as oil pans, front covers, lockers, etc .; interior materials for floors, walls, side plates, ceilings, doors, chairs, tables, etc., as housing materials for railway parts, casings and parts around motors, Various protective covers, etc .; Materials for airplane parts, such as interior materials such as floors, walls, side plates, ceilings, chairs, and tables, casings and parts around engines, etc. Cases for engine room as materials for marine parts Wall materials, enclosures and wall materials for measurement rooms; Walls, ceilings, floors, partition boards, soundproof walls, shutters, curtain rails, piping ducts, stairs, doors, etc. as building materials ; As industrial equipment parts for material, shooter, elevators, escalators, conveyor, tractors, bulldozers, the mower or the like; as an industrial transporting member, kerosene cans, drums, can be used in the composite container, tank trucks, shipping cases and the like.

<Layer composition>
The layer configuration of the laminated sheet of the present invention will be described.
The thickness (ie, total thickness) of the entire laminated sheet of the present invention is preferably 0.3 mm or more, more preferably 1.0 mm or more, still more preferably 1. 5 mm or more, more preferably 2.0 mm or more, still more preferably 2.5 mm or more, preferably 30 mm or less, more preferably 10 mm or less, still more preferably from the viewpoint of mass, strength and rigidity required for use It is 5.0 mm or less.

[Polycarbonate layer]
A polycarbonate layer is a sheet-like molded object shape | molded from the below-mentioned polycarbonate resin composition. The use of the polycarbonate layer can impart self-supporting property, chemical resistance, volatility resistance and impact resistance to the laminated sheet of the present invention.

In the present specification, the polycarbonate layer is not limited to a single layer, but may be a layer composed of a plurality of layers (for example, a layer formed by thermocompression pressing of a plurality of polycarbonate layers) or a single polycarbonate layer. Treat as. The same applies to the damping layer.

The thickness of the polycarbonate layer is preferably 0.05 mm or more, more preferably 0.10 mm or more, still more preferably 0.15 mm or more from the viewpoint of the characteristics of the molding method for producing the thin sheet to be used. From the viewpoint of the characteristics of the molding method for producing the object plate, it is preferably 10 mm or less, more preferably 5.0 mm or less, and still more preferably 3.5 mm or less. When there are a plurality of polycarbonate layers, for example, when two layers of polycarbonate layer 2 and polycarbonate layer 3 are present as in the laminated sheet shown in FIG. 2B, the thickness referred to here is the thickness of each polycarbonate layer.

When there are a plurality of polycarbonate layers, an aspect in which the damping layer is sandwiched by the polycarbonate layers, that is, an aspect in which the damping layer is present in the vicinity of the surface of the laminated sheet (for example, FIG. 2B, FIG. 4A, FIG. 5A or FIG. Shown laminated sheet). In this case, it is desirable that at least one of the polycarbonate layers be the same as or thinner than the damping layer from the viewpoint of achieving both high strength and high damping properties. Specifically, in the case of such an embodiment, the thickness of at least one of the polycarbonate layers is preferably 1.0 times or less, more preferably 0.5 times or less, still more preferably 0.25 times or less of the thickness of the damping layer The lower limit is preferably 0.01 times or more.

[Damping layer]
The damping layer is a sheet-like molded product of a polyester resin composition comprising the component (A), the component (B) and the component (C) described later. The number of damping layers in the laminated sheet may be one or more. When a plurality of damping layers are present in the laminated sheet, one damping layer is present on the surface of the laminated sheet and the remaining damping layers are present in the vicinity of the surface, or two damping layers are present. The aspect (for example, the lamination sheet shown in FIG. 5B) which exists in the surface, and the aspect (for example, the lamination sheet shown in FIG. 5A or FIG. 5C) in which all of a plurality of damping layers exist near the surface are assumed. These aspects are also included in the laminated sheet of the present invention.

The thickness of the damping layer is preferably 0.05 mm or more, more preferably 0.2 mm or more, still more preferably 0.4 mm or more, from the viewpoint of the characteristics of the molding method for producing the thin sheet to be used. From the viewpoint of the characteristics of the molding method for producing a thick plate, it is preferably 10 mm or less, more preferably 5.0 mm or less, and still more preferably 1.0 mm or less. When a lamination sheet has multiple damping layers, the thickness said here is each thickness of each damping layer.

A polycarbonate layer is laminated on one or both of the upper and lower surfaces of the damping layer.
When a polycarbonate layer is laminated on one side of the damping layer, the laminated sheet has a structure in which the damping layer is exposed on the surface of the laminated sheet, that is, an embodiment in which the damping layer is present on the surface of the laminated sheet. . The cross-sectional structure of this embodiment is schematically shown in FIG. 2A. In the laminated sheet shown in FIG. 2A, the polycarbonate layer 2 is laminated on the upper surface of the damping layer 1.

When a polycarbonate layer is laminated on both the upper surface and the lower surface of the damping layer, such a laminate sheet has a structure in which the polycarbonate layer is exposed on the surface of the laminate sheet, that is, "a damping layer exists near the surface of the laminate sheet" It is. The cross-sectional structure of this embodiment is schematically shown in FIG. 2B. In the laminated sheet shown in FIG. 2B, the polycarbonate layer 2 is laminated on the upper surface of the damping layer 1 and the polycarbonate layer 3 is laminated on the lower surface of the damping layer 1. In the case of such a structure, effects such as further improvement of rigidity and impact strength, improvement of chemical resistance, suppression of bleeding and outgassing can also be expected.

In the present specification, that the damping layer is present in the vicinity of the surface of the laminated sheet means that the damping layer is not present on the surface of the laminated sheet and the damping layer is shown in the sectional view of the laminated sheet (FIG. 1). It means that the whole of the vibration layer exists on the surface side (S or S ′ in FIG. 1) than the center line (dotted line in FIG. 1) of the cross section. From the viewpoint of improving the damping property, the damping layer is preferably within 40%, more preferably within 33%, still more preferably within 30%, still more preferably within 25% of the thickness direction from the surface of the laminated sheet. Is preferably within 20%, more preferably within 15%, and even more preferably within 10%. On the other hand, from the viewpoint of maintaining high chemical resistance, high elastic modulus or high strength of the laminated sheet, the damping layer is preferably 0.05% or more, more preferably 0.25% in the thickness direction from the surface of the laminated sheet. The content is more preferably 0.5% or more, still more preferably 1.0% or more, still more preferably 5.0% or more, and still more preferably 10% or more.

Here, the fact that the damping layer is present within 40% of the thickness direction from the surface of the laminated sheet will be specifically described with reference to FIG. FIG. 1 schematically shows a cross-sectional view of the laminated sheet of the present invention when the damping layer is one layer and the polycarbonate layer is two layers, and the surface of the laminated sheet on the side closer to the damping layer 1 That is, let S be the top surface and S 'be the other surface. The thickness direction from the surface is the direction from S to S 'indicated by the direction of the arrow on the right side of FIG. When the thickness of the entire laminated sheet is a percentage, that is, S is 0% and S 'is 100%, the relative position in the thickness direction of the damping layer 1 can be indicated by the percentage of the thickness of the laminated sheet . For example, in the laminated sheet shown in FIG. 1, when the thicknesses of the polycarbonate layer 2, the damping layer 1 and the polycarbonate layer 3 are respectively 2 mm, 2 mm and 16 mm, the position in the thickness direction of the damping layer 1 is 10 to 20%. Can be shown. Thus, “within 40% of the thickness direction from the surface of the laminated sheet” means that the whole damping layer is present within 40% of the thickness direction when the thickness of the entire laminated sheet is indicated by percentage. . At this time, it is also said that "the position ratio is within 40%" or "the relative position (%) of the damping layer from the upper surface of the laminated sheet is within 40%". One of the preferred embodiments of the present invention is a laminated sheet in which at least one layer of the damping layer is in a proportion of 10 to 40%.

The proportion of the damping layer in the laminated sheet is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more in terms of volume fraction, from the viewpoint of improving damping performance, and high elastic modulus or strength From the viewpoint of maintaining the volume fraction, it is preferably 70% or less, more preferably 50% or less, still more preferably 34% or less, and still more preferably 25% or less. When a plurality of damping layers exist in the laminated sheet, the volume fraction referred to here is the sum of the respective damping layers.

The laminated sheet of the present invention is compatible with the rigidity and impact strength of the laminated sheet and the damping property. The total thickness of the polycarbonate layer and the total thickness of the damping layer depend on the situation where the laminated sheet is applied, that is, the scene where importance is placed on rigidity and impact strength, or where the damping property of the laminated sheet is emphasized. The preferred relationship with can vary. Here, the total thickness of the polycarbonate layer is the sum of the thicknesses of all the polycarbonate layers present in the laminated sheet, and the total thickness of the damping layer is the total of the thicknesses of all the damping layers present in the laminated sheet It is. In an embodiment in which the rigidity and impact strength of the laminated sheet are emphasized, the total thickness of the polycarbonate layer is preferably equal to or greater than the total thickness of the damping layer. Specifically, the total thickness of the damping layer is 100% In the above case, the total thickness of the polycarbonate layer is preferably 100% or more, more preferably 200% or more, still more preferably 300% or more, and the upper limit is preferably 2000% or less, more preferably Is less than 1000%. On the other hand, in the embodiment in which the damping performance of the laminated sheet is emphasized, the total thickness of the polycarbonate layer is preferably equal to or less than the total thickness of the damping layer. Specifically, the total thickness of the damping layer is 100 When it is%, the total thickness of the polycarbonate layer is preferably 100% or less, more preferably 67% or less, and the lower limit is preferably 33% or more.

The damping layer constituting the laminated sheet of the present invention, that is, the surface presence amount of the elastomer in the sheet-like molded product of the polyester resin composition is the polycarbonate resin composition sheet (also referred to as "PC sheet" in this specification). From the viewpoint of adhesion, it is preferably 0.5% or more, more preferably 1% or more, still more preferably 5% or more, and from the viewpoint of maintaining the elastic modulus, preferably 50% or less, more preferably 40 % Or less, more preferably 30% or less. The surface existing amount of the elastomer is determined by immersing the sheet-like molded product of the polyester resin composition in a solvent to remove the elastomer, and observing the molded product after treatment with an SEM. Specifically, the surface abundance of the elastomer is indicated by the area% of the void portion per fixed area, where the void portion of the molded article after the treatment is a region where the elastomer was present.

The particle diameter of the elastomer in the damping layer constituting the laminated sheet of the present invention is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more from the viewpoint of adhesion to the PC sheet On the other hand, in view of maintaining the elastic modulus, it is preferably 100 μm or less, more preferably 70 μm or less, and still more preferably 50 μm or less. The particle size of the elastomer is determined by observing the molded body after removal of the elastomer, which is obtained by the same method as the method for determining the "surface amount of the elastomer" described above, by SEM. Specifically, the diameter of each void is measured, with the void portion of the molded body as the area where the elastomer was present. The diameter of a total of 100 holes is measured, and the average value is taken as the particle size of the elastomer.

The damping layer constituting the laminated sheet of the present invention preferably has a large surface area from the viewpoint of adhesion to polycarbonate. Here, the large surface area means that the "surface area / area of arbitrarily designated area" is large. From the viewpoint of adhesion to polycarbonate, the “surface area / area of arbitrarily designated area” is preferably 1 or more, more preferably 2 or more, still more preferably 5 or more, still more preferably 8 or more, while the sheet shape Preferably, it is 100 or less, more preferably 50 or less from the viewpoint of the stability of The “surface area / area of arbitrarily designated area” can be measured using a three-dimensional image obtained by a confocal laser microscope.

<Resin component>
Next, resin components constituting each layer will be specifically described.
[Polycarbonate]
In the present invention, the polycarbonate used for the polycarbonate layer has a structure containing a carbonic acid ester bond in the main chain of the molecule, ie,-(O-R-OCO)-(where R is an aliphatic group, an aromatic group) There is no particular limitation as long as one having both an aliphatic group and an aromatic group, and one having a linear structure or a branched structure as a unit structure. By using the sheet-like molding of the polycarbonate resin composition containing such a polycarbonate, the lamination sheet which has the self-supporting property in which the metal plate for holding a shape is unnecessary can be obtained.

From the viewpoint of adhesion to the damping layer, polycarbonate copolymerized with a specific monomer is more preferable.

The melt flow rate (MFR) of the polycarbonate used in the polycarbonate layer is preferably 0.1 g / 10 min or more, more preferably 0.1 g / 10 min or more, under the conditions of 300 ° C. and 1.2 kgf, from the viewpoint of extrusion molding and extruder characteristics. 0.5 g / 10 min or more, more preferably 1.0 g / 10 min or more, preferably 20 g / 10 min or less, more preferably 15 g / 10 min or less, from the viewpoint of heat press formability Is less than 8.0 g / 10 min. Specifically, the MFR value of polycarbonate is measured by the method described in the examples below.

The polycarbonate resin composition in the present invention may contain various additives such as a general ultraviolet light absorber, a heat stabilizer, a colorant, a release agent, a lubricant, an antistatic agent and the like.

When there are a plurality of polycarbonate layers, the compositions of the resin compositions constituting them may be the same or different. For example, the composition of the resin composition constituting the polycarbonate layer 2 and the composition of the resin composition constituting the polycarbonate layer 3 shown in FIG. 2B may be identical to or different from each other.

[Polyester resin composition]
The polyester resin composition used for the damping layer in the present invention comprises a thermoplastic polyester resin (A) composed of a dicarboxylic acid component and a diol component, a component (B) which is a plasticizer / or elastomer, and an inorganic filler (C) is contained. In the present invention, when there are a plurality of damping layers, the composition of the polyester resin composition that constitutes each damping layer may be the same or different.

Generally, when an inorganic filler is added to the resin, the elastic modulus of the entire resin composition is improved while the loss factor is decreased. The reduction of the loss factor is due to the reduction of the amount of energy loss in the resin portion because the proportion of the resin in the resin composition is reduced by the addition of the filler. Therefore, in the present invention, by adding a plasticizer and / or an elastomer to such a system, by imparting flexibility and facilitating energy loss, the loss coefficient is improved and the elastic modulus of the resin composition is increased. While reducing the loss factor. Furthermore, in the polyester resin composition used in the present invention, friction occurs at the interface between the resin or the plasticizer and / or the elastomer and the inorganic filler to cause energy loss, which further suppresses the loss factor reduction. It is estimated that

The upper limit of the mass average molecular weight of the thermoplastic polyester resin (A) in the present invention is preferably 300,000. The upper limit does not change depending on the type of thermoplastic polyester resin (A) used, but from the viewpoint of improving the loss coefficient, as the lower limit, for example, polybutylene terephthalate resin is used as the thermoplastic polyester resin (A) In the case, 70,000 or more is preferable, 80,000 or more is more preferable, and 100,000 or more is still more preferable. When using polytrimethylene terephthalate resin as a thermoplastic polyester resin (A), 60,000 or more is preferable and 70,000 or more is more preferable. When using a polyethylene terephthalate resin as a thermoplastic polyester resin (A), 30,000 or more is preferable, 40,000 or more is more preferable, 50,000 or more is still more preferable. In addition, since the polyester resin composition in this invention has the absolute crystallinity degree mentioned later, a minimum changes with values of absolute crystallinity degree (Xc), and if absolute crystallinity degree is 5% or more and 37% or less, Even if the mass average molecular weight of the thermoplastic polyester resin (A) used is less than 50,000, performance can be exhibited, and, for example, 20,000 or more can be mentioned. When the absolute crystallinity degree exceeds 37%, the mass average molecular weight of the thermoplastic polyester resin (A) to be used is preferably 50,000 or more. The mass average molecular weight of the thermoplastic polyester resin (A) can be measured according to the method described in the examples described later.

The lower limit of the absolute crystallinity degree (Xc) of the polyester resin composition in the present invention may be preferably 5%, but it is as follows according to the type of thermoplastic polyester resin (A) used from the viewpoint of improving the loss coefficient. Range is indicated. For example, when using a polybutylene terephthalate resin as the thermoplastic polyester resin (A), 10% or more is preferable, 15% or more is more preferable, 20% or more is more preferable, 25% or more is more preferable, 35% or less is preferable 30% or less is more preferable, and 28% or less is still more preferable. When using polytrimethylene terephthalate resin as a thermoplastic polyester resin (A), 10% or more is preferable, 15% or more is more preferable, 20% or more is still more preferable, and 35% or less is preferable. When using a polyethylene terephthalate resin as the thermoplastic polyester resin (A), 10% or more is preferable, 15% or more is more preferable, 20% or more is more preferable, 25% or more is more preferable, and 35% or less is preferable. In addition, since the thermoplastic polyester resin (A) in the present invention has the above-described mass average molecular weight, the value of the absolute crystallinity degree varies depending on the value of the mass average molecular weight of the resin (A). If the mass average molecular weight of the resin (A) is 50,000 or more and 150,000 or less, the performance can be exhibited even in the case of more than 37%, and for example, preferably 40% or less as the upper limit. When the mass average molecular weight is less than 50,000, it is preferably 37% or less. In addition, in this specification, the absolute crystallinity degree of a polyester resin composition means the ratio of the crystal part in matrix resin, and it can measure according to the method as described in the below-mentioned Example.

Further, the thermoplastic polyester resin (A) and the polyester resin composition in the present invention preferably have a mass average molecular weight and an absolute crystallinity within the ranges described above, and as the combination thereof, the thermoplastic polyester resin (A) When polybutylene terephthalate resin is used, the mass average molecular weight is preferably 70,000 to 150,000 and the absolute crystallinity is preferably 25% to 35%. The mass average molecular weight is 100,000 to 150,000 and the absolute crystallinity is 25 % Or more and 35% or less are more preferable. When the thermoplastic polyester resin (A) is a polyethylene terephthalate resin, the mass average molecular weight is 30,000 to 150,000 and the absolute crystallinity is preferably 10% to 35%, and the mass average molecular weight is 40,000 to 150,000. The absolute crystallinity is more preferably 20% or more and 35% or less.

[Thermoplastic polyester resin (A)]
The thermoplastic polyester resin (A) in the present invention is composed of a dicarboxylic acid component and a diol component, and can be obtained by a combination of polycondensation of the dicarboxylic acid component and the diol component. In the present specification, the dicarboxylic acid component includes dicarboxylic acid and its lower ester derivative, and these are collectively referred to as a dicarboxylic acid component.

As a dicarboxylic acid component which constitutes thermoplastic polyester resin (A), aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, and dicarboxylic acid having a furan ring can be used. Specifically, examples thereof include terephthalic acid and the like, which are listed in paragraph 0014 of JP-A-2016-89148. The dicarboxylic acid components can be used alone or in combination of two or more.

As a diol component which comprises a thermoplastic polyester resin (A), an aliphatic diol, an alicyclic diol, an aromatic diol, and the diol which has a furan ring can be used. Specifically, for example, 1,4-butanediol and the like, those listed in paragraph 0015 of JP-A-2016-89148 can be mentioned. The diol components can be used alone or in combination of two or more.

In addition, as a combination of a dicarboxylic acid component and a diol component, from the viewpoint of improving the Tg of the thermoplastic polyester resin (A) and improving the vibration damping property and the rigidity, an aromatic ring, an alicyclic ring, or a furan ring is a dicarboxylic acid or It is preferable to include it in one or both of the diols. Specific examples thereof include those listed in paragraph 0016 of JP-A-2016-89148.

The polycondensation of the dicarboxylic acid component and the diol component is not particularly limited, and can be carried out according to a known method.

The thermoplastic polyester resin (A) obtained has a glass transition temperature (Tg) of preferably 20 ° C. or more, more preferably 25 ° C. or more, still more preferably 30 ° C. or more, still more preferably, from the viewpoint of improving molding processability. 35 ° C or higher. Further, from the viewpoint of improving the vibration damping property, it is preferably 160 ° C. or less, more preferably 150 ° C. or less, still more preferably 140 ° C. or less, still more preferably 130 ° C. or less. In order for the glass transition temperature to be the above temperature, it is effective to control the skeleton structure of the polyester resin. For example, when a thermoplastic polyester resin is prepared by using a rigid component such as an aromatic dicarboxylic acid component or an alicyclic diol component as a raw material, it is possible to increase the glass transition temperature. In addition, in this specification, the glass transition temperature of resin can be measured in accordance with the method as described in the below-mentioned Example.

Moreover, it is preferable that the thermoplastic polyester resin (A) in this invention has crystallinity from a vibration suppression viewpoint. As a method of preparing a thermoplastic polyester resin having crystallinity, a method using a dicarboxylic acid component and a diol component having high purity, and a method using a dicarboxylic acid component with a small amount of side chains and a diol component can be mentioned. In the present specification, having crystallinity means heating the resin from 25 ° C. to 300 ° C. at a heating rate of 20 ° C./min according to JIS K 7122 (1999), and holding for 5 minutes in that state, Then, when cooled at −20 ° C./min so as to be 25 ° C. or lower, this is a resin in which an exothermic peak associated with crystallization is observed. More specifically, it refers to a resin in which the crystallization enthalpy ΔHmc obtained from the area of the exothermic peak is 1 J / g or more. The thermoplastic polyester resin (A) constituting the present invention preferably has a crystallization enthalpy ΔHmc of 5 J / g or more, more preferably 10 J / g or more, still more preferably 15 J / g or more, still more preferably 30 J / g or more It is preferable to use a resin. In addition, in this specification, the crystallization enthalpy of resin can be measured according to the method as described in the below-mentioned Example.

Specific examples of the thermoplastic polyester resin (A) include, for example, those listed in paragraph 0020 of JP-A-2016-89148, and from the viewpoint of damping property, terephthalic acid and 1,4-butanediol Preferred is polybutylene terephthalate (PBT resin, Tg: 50 ° C.). The thermoplastic polyester resins (A) can be used alone or in combination of two or more.

In the polyester resin composition, the content of the thermoplastic polyester resin (A) is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more from the viewpoint of improving the loss coefficient. Further, from the viewpoint of improving the rigidity, 90% by mass or less is preferable, 80% by mass or less is more preferable, 75% by mass or less is more preferable, and 70% by mass or less is more preferable.

In the present invention, the mass average molecular weight of the thermoplastic polyester resin (A) is preferably 30,000 or more, more preferably 50,000 or more, still more preferably 70,000 or more, from the viewpoint of improving the damping property. From the viewpoint of improving the properties, it is preferably at most 300,000, more preferably at most 200,000, further preferably at most 150,000. Specifically, the mass average molecular weight of the thermoplastic polyester resin (A) is measured by the method described in the following examples.

[Component (B) which is a plasticizer and / or an elastomer]
As a component (B) in this invention, 1 type (s) or 2 or more types selected from the group which consists of a plasticizer and an elastomer are used. In the present specification, the plasticizer and / or the elastomer may be collectively referred to as component (B).

(Plasticizer)
The plasticizer in the present invention contains one or more selected from the group consisting of polyester plasticizers, polyhydric alcohol ester plasticizers, polyhydric carboxylic acid ester plasticizers, and bisphenol plasticizers. Is preferred.

As a plasticizer, a low volatility plasticizer is preferable from the viewpoint of suppressing a change in sheet physical properties of the laminated sheet in the manufacturing process. Specifically, plasticizers having a 5% mass loss temperature of 200 ° C. or more are preferable, plasticizers of 220 ° C. or more are more preferable, plasticizers of 240 ° C. or more are more preferable, and plasticizers of 260 ° C. or more are more preferable. Here, the measurement of the 5% mass loss temperature of the plasticizer is carried out under the condition that the temperature is raised at 10 ° C./min in an air atmosphere. Furthermore, the weight retention of the plasticizer at 260 ° C. in an air atmosphere for 5 minutes isothermally maintained is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. From the viewpoint of improving, it is preferably 100% or less, more preferably 98% or less.

Specific examples of the polyester plasticizer include those listed in paragraph 0024 of JP-A-2016-89148. Preferred examples include, for example, mixed diesters of adipic acid and diethylene glycol monomethyl ether / benzyl alcohol.

Examples of the polyhydric alcohol ester plasticizer include those listed in paragraph 0025 of JP-A-2016-89148.

Examples of polyvalent carboxylic acid ester plasticizers include those listed in paragraph 0026 of JP-A-2016-89148.

Examples of the bisphenol-based plasticizer include those listed in paragraph 0027 of JP-A-2016-89148.

As a plasticizer, from the viewpoint of improving the loss coefficient, a polyester-based plasticizer, a polyhydric alcohol ester-based plasticizer, a polyvalent carboxylic acid, preferably having a (poly) oxyalkylene group or an alkylene group having 2 to 10 carbon atoms Polyester-based plasticizer, polyhydric alcohol ester-based plasticizer, containing one or more selected from the group consisting of ester-based plasticizers and bisphenol-based plasticizers, and more preferably having a (poly) oxyalkylene group And one or more selected from the group consisting of polyhydric carboxylic acid ester plasticizers and bisphenol plasticizers. Here, the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group. The oxyalkylene group is preferably one having an alkylene group having preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms, and an oxyethylene group, an oxypropylene group or an oxybutylene group Preferably, oxyethylene or oxypropylene is more preferred.

The plasticizer preferably contains one or more selected from the group consisting of the following compound groups (A) to (C) from the viewpoint of improving the loss coefficient, and the following compound group (A) It is more preferable to contain one or more selected from the group consisting of and (B). When two or more kinds are used in combination, the same compound group may be used, or different compound groups may be used.
Compound Group (A) An ester compound having two or more ester groups in the molecule, wherein at least one of the alcohol components constituting the ester compound has an average of 0 to 2 alkylene oxides per one hydroxyl group. .5-5 mol added alcohol which is an alcohol, ester compound group (B) Formula (I):
R ¹ O-CO-R ² -CO-[(OR ³ ) _m O-CO-R ² -CO-] _n OR ¹ (I)
(Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6) And n represents a number of 1 to 12, provided that all R ^{2 s} may be the same or different, and all R ^{3 s} may be the same or different)
Compound compound group (C) represented by: an ester compound having two or more ester groups in the molecule, wherein the alcohol component constituting the ester compound is a monoalcohol

Compound group (A)
The ester compound contained in the compound group (A) is a polyhydric alcohol ester or polyhydric carboxylic acid ether ester having two or more ester groups in the molecule, and at least one of alcohol components constituting the ester compound. An ester compound which is an alcohol having an average of 0.5 to 5 moles of an alkylene oxide of 2 to 3 carbon atoms added per hydroxyl group is preferable.

Specific compounds include esters of acetic acid and glycerin with an average of 3 to 6 moles of ethylene oxide adduct of glycerin (addition of 1 to 2 moles of ethylene oxide per hydroxyl group), and average addition mole number of acetic acid and ethylene oxide is 4 to 6, esters of polyethylene glycol with polyethylene glycol, esters of succinic acid and polyethylene glycol monomethyl ether having an average addition mole number of ethylene oxide of 2 to 3 (addition of 2 to 3 moles of ethylene oxide per hydroxyl group), adipic acid and diethylene glycol monomethyl Esters with ether, Esters of terephthalic acid with polyethylene glycol monomethyl ether (2 to 3 moles of ethylene oxide added per hydroxyl group) with an average addition mole number of ethylene oxide of 2-3, 1,3,6-hexanetricarboxylic acid Acid and di Esters of Chi glycol monomethyl ether.

Compound group (B)
R ¹ in the formula (I) represents an alkyl group having 1 to 4 carbon atoms, and two in one molecule are present at both ends of the molecule. R ¹ may be linear or branched as long as it has 1 to 4 carbon atoms. The carbon number of the alkyl group is preferably 1 to 4 and more preferably 1 to 2 from the viewpoint of exhibiting coloring resistance and a plasticizing effect. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, iso-butyl group can be mentioned, and among them, from the viewpoint of improving the loss factor, methyl A group and an ethyl group are preferable, and a methyl group is more preferable.

R ² in the formula (I) represents an alkylene group having 2 to 4 carbon atoms, and a linear alkylene group is mentioned as a preferable example. Specifically, ethylene, 1,3-propylene and 1,4-butylene are mentioned, and from the viewpoint of improving the loss factor, ethylene, 1,3-propylene and 1,4-butylene are preferable. Preferably, ethylene is more preferred. However, all R ^{2 s} may be the same or different.

R ³ in the formula (I) represents an alkylene group having 2 to 6 carbon atoms, and OR ³ is present as an oxyalkylene group in the repeating unit. R ³ may be linear or branched as long as it has 2 to 6 carbon atoms. The number of carbon atoms of the alkylene group is preferably 2 to 6, and more preferably 2 to 3 from the viewpoint of improving the loss coefficient. Specifically, ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2-methyl-1,3 -Propylene group, 1,2-pentylene group, 1,4-pentylene group, 1,5-pentylene group, 2,2-dimethyl-1,3-propylene group, 1,2-hexylene group, 1,5-hexylene And 1,6-hexylene, 2,5-hexylene, 3-methyl-1,5-pentylene, among which ethylene, 1,2-propylene, and 1,3-propylene are preferred. preferable. However, all R ^{3 s} may be the same or different.

M represents the average number of repetition of the oxyalkylene group, and from the viewpoint of heat resistance, the number is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.

N represents the average number of repeating units (average degree of polymerization) of the repeating units, and is a number of 1 to 12. The damping material is preferably a number of 1 to 12, more preferably a number of 1 to 6, and still more preferably a number of 1 to 5 from the viewpoint of improving the loss coefficient. The average degree of polymerization may be determined by analysis such as NMR, but can be calculated according to the method described in paragraph 0100 of JP-A 2016-89148.

As specific examples of the compound represented by the formula (I), R ¹ is all methyl group, R ² is ethylene group or 1,4-butylene group, R ³ is ethylene group or 1,3-propylene group And m is a number of 1 to 4 and n is a number of 1 to 6; R ¹ is all methyl, R ² is ethylene or 1,4-butylene, R ³ is ethylene or 1, Compounds having a 3-propylene group, m being a number of 1 to 3 and n being a number of 1 to 5 are more preferable.

The compound represented by the formula (I) is not particularly limited as long as it has the above-mentioned structure, but a compound obtained by reacting the following (1) to (3) is preferable. In addition, (1) and (2), or (2) and (3) may form an ester compound. (2) may be an acid anhydride or an acid halide.
(1) a monohydric alcohol having an alkyl group having 1 to 4 carbon atoms (2) a dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms (3) a dihydric alcohol having an alkylene group having 2 to 6 carbon atoms

(1) Monohydric alcohol having alkyl group having 1 to 4 carbon atoms A monohydric alcohol having an alkyl group having 1 to 4 carbon atoms is an alcohol containing the above R ¹ , specifically, methanol, Ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, tert-butanol can be mentioned. Among them, methanol, ethanol, 1-propanol and 1-butanol are preferable, methanol and ethanol are more preferable, and methanol is still more preferable from the viewpoint of improving the loss factor.

(2) Dicarboxylic Acid Having an Alkylene Group Having 2 to 4 Carbons The dicarboxylic acid having an alkylene group having 2 to 4 carbons is a dicarboxylic acid containing the above-mentioned R ^2. Specifically, succinic acid, Glutaric acid, adipic acid and their derivatives such as succinic anhydride, glutaric anhydride, dimethyl succinate, dibutyl succinate, dimethyl glutarate, dimethyl adipate and the like can be mentioned. Among them, from the viewpoint of improving the loss factor, succinic acid, adipic acid and derivatives thereof, for example, succinic anhydride, dimethyl succinate, dibutyl succinate, dimethyl adipate are preferable, and succinic acid and its derivatives, for example, Succinic anhydride, dimethyl succinate and dibutyl succinate are more preferred.

(3) Dihydric alcohol having an alkylene group having 2 to 6 carbon atoms The dihydric alcohol having an alkylene group having 2 to 6 carbon atoms is a dihydric alcohol containing the above R ³ , specifically, Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,5-hexanediol, Examples include 1,6-hexanediol and 3-methyl-1,5-pentanediol. Among them, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, tetraethylene glycol and 1,4-butanediol are preferable from the viewpoint of improving the loss coefficient, and diethylene glycol and triethylene glycol, 1,2-propanediol and 1,3-propanediol are more preferable, and diethylene glycol, triethylene glycol and 1,3-propanediol are more preferable.

Therefore, as the above (1) to (3),
(1) The monohydric alcohol is one or more selected from the group consisting of methanol, ethanol, 1-propanol, and 1-butanol, and (2) the dicarboxylic acid is succinic acid, adipic acid, glutaric acid, and And one or more selected from the group consisting of derivatives thereof, wherein (3) the dihydric alcohol is diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, tetraethylene glycol, and Preferably, it is one or more selected from the group consisting of 1,4-butanediol,
(1) One or two or more selected from the group consisting of methanol and ethanol, and (2) One or more selected from the group consisting of succinic acid, adipic acid, and derivatives thereof More than two, and (3) the dihydric alcohol is one or more selected from the group consisting of diethylene glycol, triethylene glycol, 1,2-propanediol, and 1,3-propanediol Preferably
(1) monohydric alcohol is methanol, (2) dicarboxylic acid is one or more selected from the group consisting of succinic acid and derivatives thereof, (3) dihydric alcohol is diethylene glycol, triethylene glycol, More preferably, it is one or more selected from the group consisting of and 1,3-propanediol.

The method for obtaining the ester compound represented by the formula (I) by reacting the above (1) to (3) is not particularly limited, but, for example, the methods of the following aspect 1 and aspect 2 can be mentioned.
Embodiment 1: A step of esterification reaction of (2) dicarboxylic acid and (1) monohydric alcohol to synthesize a dicarboxylic acid ester, and a step of esterifying reaction of the obtained dicarboxylic acid ester and (3) dihydric alcohol Method aspect 2 including: Method including batch reaction of (1) monohydric alcohol, (2) dicarboxylic acid, and (3) dihydric alcohol

Among these, the method of aspect 1 is preferable from the viewpoint of adjusting the average degree of polymerization. In addition, reaction of each process mentioned above can be performed according to a well-known method.

The compound represented by the formula (I) is preferably 1.50 mg KOH / g or less, more preferably 1.00 mg KOH / g or less, from the viewpoint of improving the loss coefficient, and the hydroxyl value is a loss coefficient From the viewpoint of improving the pH, it is preferably 10.0 mg KOH / g or less, more preferably 5.0 mg KOH / g or less, and still more preferably 3.0 mg KOH / g or less. In the present specification, the acid value and the hydroxyl value of the plasticizer can be measured according to the method described in paragraph 0099 of JP-A-2016-89148.

The number average molecular weight of the compound represented by the formula (I) is preferably 300 to 1,500, more preferably 300 to 1000, from the viewpoint of color resistance, from the viewpoint of improving the loss coefficient. In the present specification, the number average molecular weight of the plasticizer can be calculated according to the method described in paragraph 0100 of JP-A-2016-89148.

The saponification value of the compound represented by the formula (I) is preferably 500 to 800 mg KOH / g, and more preferably 550 to 750 mg KOH / g from the viewpoint of improving the loss coefficient. In the present specification, the saponification value of the plasticizer can be measured according to the method described in paragraph 0099 of JP-A-2016-89148.

From the viewpoint of improving the loss coefficient, the compound represented by the formula (I) preferably has an alkyl esterification ratio (terminal alkyl esterification ratio) to two molecular ends of 95% or more, more preferably 98% or more. It is. In the present specification, the terminal alkyl esterification rate of the plasticizer can be calculated according to the method described in paragraph 0100 of JP-A 2016-89148.

From the viewpoint of shortening the vibration time, the ether group value of the compound represented by the formula (I) is preferably 0 to 8 mmol / g, and more preferably 0 to 6 mmol / g. In the present specification, the ether group value of the plasticizer can be calculated according to the method described in paragraph 0100 of JP-A-2016-89148.

Compound group (C)
Specifically, the ester compound contained in the compound group (C) is preferably an ester of adipic acid and 2-ethylhexanol (DOA) and an ester of phthalic acid and 2-ethylhexanol (DOP).

Among the plasticizers, the content of one or more selected from the group consisting of polyester plasticizers, polyhydric alcohol ester plasticizers, polyhydric carboxylic acid ester plasticizers, and bisphenol plasticizers, preferably It is selected from the group consisting of polyester-based plasticizers, polyhydric alcohol ester-based plasticizers, polyvalent carboxylic acid ester-based plasticizers, and bisphenol-based plasticizers having a poly (oxyalkylene) group or an alkylene group having 2 to 10 carbon atoms. From polyester plasticizers, polyhydric alcohol ester plasticizers, polyhydric carboxylic acid ester plasticizers, and bisphenol plasticizers having one or more contents, more preferably (poly) oxyalkylene groups A group consisting of one or more selected from the group consisting of: and such compound groups (A) to (C) The content of one or more compounds selected is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, further preferably from the viewpoint of improving the loss coefficient. It is 95% by mass or more, more preferably substantially 100% by mass, and still more preferably 100% by mass. Here, substantially 100% by mass means a state in which a trace amount of impurities and the like are inevitably contained. In the present specification, the content of the plasticizer means the total content when a plurality of compounds are contained.

The content of the plasticizer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass from the viewpoint of improving the loss coefficient with respect to 100 parts by mass of the thermoplastic polyester resin (A). The amount is more preferably 10 parts by mass or more, and preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less, still more preferably 25 parts by mass or less from the viewpoint of suppressing rigidity reduction. is there.

In addition, the content of the plasticizer in the polyester resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, from the viewpoint of improving the loss coefficient From the viewpoint of suppression, it is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

(Elastomer)
In the present invention, one or two or more elastomers are used from the viewpoint of the improvement of the damping property in the high temperature range and the low temperature range. As an elastomer in the present invention, a thermoplastic elastomer is preferable.

The content of the elastomer is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, and 15 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A), from the viewpoint of improving the loss coefficient in the low temperature range. The above is more preferable. Moreover, from a viewpoint of rigidity fall suppression, 50 mass parts or less are preferable, 40 mass parts or less are more preferable, and 35 mass parts or less are still more preferable.

The content of the elastomer in the polyester resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 9.5% by mass or more, from the viewpoint of improving the loss coefficient Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.

In the present invention, as the component (B), a plasticizer and an elastomer may be used in combination, and it is possible to use a plasticizer alone or two or more types and an elastomer alone or a combination of two or more types. By using a plasticizer and an elastomer in combination, the loss coefficient in the room temperature region is further improved, and the loss coefficient is also improved in a wide temperature region such as a low temperature region or a high temperature region.

From the viewpoint of improving the loss coefficient, the total content of the plasticizer and the elastomer in combination is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more with respect to 100 parts by mass of the thermoplastic polyester resin (A). 25 parts by mass or more is more preferable. Moreover, from a viewpoint of rigidity fall suppression, 60 mass parts or less are preferable, 50 mass parts or less are more preferable, and 40 mass parts or less are still more preferable.

In addition, the mass ratio of the plasticizer and the elastomer (plasticizer / elastomer) in the combined use is preferably 10/90 to 90/10, and 30/70 to 70/30 from the viewpoint of improving the loss coefficient in a wide temperature range. More preferable.

(Thermoplastic elastomer)
Use of a thermoplastic elastomer as the elastomer is preferable because the effect of improving the damping properties in the high temperature range and the low temperature range is exhibited. Furthermore, by using together with the plasticizer, the vibration damping property can be further improved in a wide temperature range in the high temperature range and the low temperature range.

The thermoplastic elastomer preferably has a glass transition temperature Tg of −40 ° C. or higher, and preferably 20 ° C. or lower, from the viewpoint of improving the damping performance in the high temperature range and the low temperature range. The glass transition temperature of the thermoplastic elastomer can be measured according to the method described in the examples below.

The thermoplastic elastomer in the present invention includes styrene thermoplastic elastomer, olefin thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, urethane thermoplastic elastomer, nitrile thermoplastic elastomer, fluorine thermoplastic elastomer And at least one selected from polybutadiene-based thermoplastic elastomers and silicone-based thermoplastic elastomers, and as styrene-based thermoplastic elastomers, polystyrene-vinyl-polyisoprene-polystyrene block copolymer, copolymer of styrene and butadiene, and The hydrogen additive can be mentioned, for example, “Hybler” manufactured by Kuraray Plastics, “Tough Tech” “S.O.E” (registered trademark) manufactured by Asahi Kasei Co., Ltd., Formula company manufactured by Kuraray Co., Ltd. "Septon" (registered trademark), manufactured by Mitsubishi Chemical Co., Ltd. "Rabalon" there is a (registered trademark), and the like. Examples of the olefin-based thermoplastic elastomer include those in which an olefin-based rubber (EPR, EPDM) is finely dispersed in a matrix of an olefin-based resin (polyethylene, polypropylene, etc.). Trademarks, "Espolex" (registered trademark) manufactured by Sumitomo Chemical Co., Ltd., and the like. Examples of polyester-based thermoplastic elastomers include copolymers of polybutylene terephthalate and polyether and the like, and examples thereof include Hytrel (registered trademark) manufactured by Toray DuPont Co., Ltd. Examples of polyamide-based thermoplastic elastomers include those obtained by transesterification and condensation polymerization reactions using block copolymers of nylon and polyester or polyol, lactams, and dicarboxylic acid polyether diols as raw materials. As a urethane type thermoplastic elastomer, there is, for example, "TPU" manufactured by Nippon Polyurethane Industry Co., Ltd. As a nitrile thermoplastic elastomer, what emulsion-polymerized acrylonitrile and butadiene, etc. are mentioned. Examples of the fluorine-based thermoplastic elastomer include copolymers of vinylidene fluoride and hexafluoropropylene, copolymers of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene, etc. For example, manufactured by Showa Highpolymer Co., Ltd. There are "Eraftol" (registered trademark), DuPont "Viton" (registered trademark) series, and the like. Polybutadiene-based and silicone-based thermoplastic elastomers include organic silicon polymer bonds in which an organic group or the like is directly bonded to the silicon atom with a siloxane bond as a skeleton, and examples thereof include KBM series made by Shin-Etsu Silicone. As a thermoplastic elastomer, a styrene-based thermoplastic elastomer is preferable from the viewpoint of the improvement of the damping property in the high temperature range and the low temperature range.

(Styrenic thermoplastic elastomer)
In the styrenic thermoplastic elastomer (hereinafter sometimes referred to as styrenic elastomer) in the present invention, block A formed by polymerization of a styrenic compound constituting the hard segment, and conjugated diene constituting the soft segment are polymerized. The block B is composed of Examples of the styrene compound used for the polymer block A include styrene compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and 1,3-dimethylstyrene; vinyl naphthalene, Polycyclic aromatic compounds having a vinyl group such as vinyl anthracene and the like are mentioned, and among these, polymers of styrene compounds are preferable, and polymers of styrene are more preferable. The conjugated diene used for the polymer block B includes, for example, butadiene, isoprene, butylene, ethylene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like, preferably polyisoprene, polybutadiene, and The copolymer of isoprene and butadiene is mentioned, It is the block copolymer which superposed | polymerized 1 type (s) or 2 or more types selected from these conjugated diene monomers. Further, in the block B, a styrenic compound used for the polymer block A may be copolymerized. In the case of each copolymer, any form of a random copolymer, a block copolymer, and a tapered copolymer can be selected as the form thereof. Alternatively, a hydrogenated structure may be used.

Specific examples of such styrenic elastomers include polystyrene-isoprene block copolymer (SIS), polystyrene-polybutadiene copolymer (SEBS), polystyrene-hydrogenated polybutadiene copolymer (SEBS), polystyrene-hydrogenated Polyisoprene-polystyrene block copolymer (SEPS), polystyrene-vinyl-polyisoprene-polystyrene block copolymer (SHIVS), polystyrene-hydrogenated polybutadiene-hydrogenated polyisoprene-polystyrene block copolymer, polystyrene-hydrogenated polybutadiene -Polyisoprene-polystyrene block copolymer etc. are mentioned. These may be used alone or in combination of two or more. Among them, polystyrene-vinyl-polyisoprene-polystyrene block copolymer is preferably used in the present invention, and commercially available products of such block copolymers include “Hylar” series manufactured by Kuraray Plastics Co., Ltd. .

The styrene content in the styrenic elastomer is preferably 10% by mass or more, more preferably 15% by mass or more, preferably 30% by mass or less, from the viewpoint of improving the damping performance in the high temperature range and the low temperature range. Preferably it is 25 mass% or less. In the present specification, the high temperature range means 35 to 80 ° C., the low temperature range means -20 to 10 ° C., and the styrene content in the styrenic elastomer is described in the following examples. It can be measured according to the method of

As a styrene-type elastomer, a styrene isoprene block copolymer and / or a styrene butadiene block copolymer are preferable.

(Styrene isoprene block copolymer)
The styrene isoprene block copolymer in the present invention is a block copolymer having a polystyrene block at both ends, and having at least one block of a polyisoprene block or a vinyl-polyisoprene block therebetween. In addition, an isoprene block or a butadiene block may be copolymerized or may have a hydrogenated structure.

Specific examples of such styrene-isoprene block copolymer include polystyrene-isoprene block copolymer (SIS), polystyrene-hydrogenated polyisoprene-polystyrene block copolymer (SEPS), polystyrene-vinyl-polyisoprene Polystyrene block copolymer (SHIVS), polystyrene-hydrogenated polybutadiene-hydrogenated polyisoprene-polystyrene block copolymer, polystyrene-hydrogenated polybutadiene-polyisoprene-polystyrene block copolymer, and the like. These may be used alone or in combination of two or more. Among them, polystyrene-vinyl-polyisoprene-polystyrene block copolymer is preferably used in the present invention, and commercially available products of such block copolymers include “Hylar” series manufactured by Kuraray Plastics Co., Ltd. .

(Styrene butadiene block copolymer)
The styrene butadiene block copolymer in the present invention is a block copolymer having a polystyrene block at both ends and having a polybutadiene block or a hydrogenated substance thereof in between. In addition, an isoprene block or a butadiene block may be copolymerized or may have a hydrogenated structure.

Specific examples of such a styrene-butadiene block copolymer include polystyrene-polybutadiene copolymer (SEBS), polystyrene-hydrogenated polybutadiene copolymer (SEBS), polystyrene-polybutadiene copolymer (SBS), polystyrene And hydrogenated polybutadiene copolymers (SBS) and the like. These may be used alone or in combination of two or more. In the present invention, among these, polystyrene-hydrogenated polybutadiene copolymer (SEBS) is preferably used, and as a commercial product of such a block copolymer, "S.O.E" manufactured by Asahi Kasei Co., Ltd. may be mentioned. Be

From the viewpoint of adhesion to polycarbonate, elastomers with few or no unsaturated bonds are preferable. As a preferable elastomer from this viewpoint, the thing hydrogenated among various said elastomers is mentioned.
Furthermore, from the viewpoint of adhesion to polycarbonate, an elastomer that is resistant to oxidative degradation or does not undergo oxidative degradation is preferable. As a preferable elastomer from this viewpoint, the thing hydrogenated among various said elastomers is mentioned.
Furthermore, from the viewpoint of adhesion to polycarbonate, it is preferable to use polystyrene-hydrogenated polybutadiene copolymer (SEBS).

[Inorganic filler (C)]
The polyester resin composition in the present invention contains an inorganic filler (C) from the viewpoint of rigidity improvement. The inorganic filler (C) in the present invention is not particularly limited as long as it is a known inorganic filler, and is an inorganic filler generally used for reinforcing a thermoplastic resin, specifically, a plate-like filler, One or more selected from the group consisting of granular fillers, acicular fillers, and fibrous fillers can be used.

The plate-like filler has an aspect ratio (length of the longest side of the largest surface of the plate-like body / thickness of the surface) of 20 or more and 150 or less. From the viewpoint of obtaining good dispersibility in the polyester resin composition, improving the flexural modulus, and / or improving the loss factor, the length of the plate-like filler (length of the longest side in the largest surface) It is preferably 1.0 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, further preferably 20 μm or more, preferably 150 μm or less, more preferably 100 μm or less, further preferably 50 μm or less, still more preferably 40 μm or less More preferably, it is 30 μm or less. The thickness is not particularly limited, but from the same viewpoint, preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, still more preferably 0.2 μm or more, preferably 5 μm or less. More preferably, it is 3 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less, and still more preferably 0.5 μm or less. Further, the aspect ratio of the plate-like filler is preferably 30 or more, more preferably 40 or more, still more preferably 50 or more, and preferably 120 or less, more preferably 100 or less, from the same viewpoint. Preferably it is 90 or less, More preferably, it is 80 or less. Specific examples of the plate-like filler include, for example, those listed in paragraph 0064 of JP-A-2016-89148, such as mica. In addition, the side length and thickness of a plate-shaped filler can be calculated | required by observing 100 fillers selected at random with an optical microscope, and calculating the number average.

The particulate filler is not limited to those having a spherical shape, but also to those having a cross-sectional elliptical or substantially oval shape, and has an aspect ratio (longest diameter of granular body / shortest diameter of granular body) One or more and less than two, and one close to one is preferable. The average particle diameter of the particulate filler is preferably 1.0 μm or more, more preferably from the viewpoint of obtaining good dispersibility in the polyester resin composition, improving the flexural modulus, and / or improving the loss factor. The thickness is 5 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. Specific examples of the particulate filler include those listed in paragraph 0065 of JP-A-2016-89148. The diameter of the particulate filler can be determined by cutting 100 fillers randomly selected, observing the cross section with an optical microscope, and calculating the number average.

The needle-like filler has an aspect ratio (particle length / particle diameter) in the range of 2 or more and less than 20. The length (particle length) of the needle-like filler is preferably 1.0 μm from the viewpoint of obtaining good dispersibility in the polyester resin composition, improving the flexural modulus, and / or improving the loss factor. Or more, more preferably 5 μm or more, still more preferably 10 μm or more, still more preferably 20 μm or more, still more preferably 30 μm or more, preferably 150 μm or less, more preferably 100 μm or less, still more preferably 80 μm or less, more preferably 60 μm or less It is. The particle diameter is not particularly limited, but from the same viewpoint, preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.5 μm or more, preferably 20 μm or less, more preferably 15 μm or less, further Preferably it is 10 micrometers or less. Further, the aspect ratio of the needle-like filler is preferably 5 or more, and preferably 10 or less from the same viewpoint. Specific examples of the needle-like filler include those listed in paragraph 0066 of JP-A-2016-89148. The particle length and particle diameter of the needle-like filler can be determined by observing 100 fillers randomly selected with an optical microscope and calculating the number average. When the particle size has a minor axis and a major axis, the major axis is used to calculate.

The fibrous filler is one having an aspect ratio (average fiber length / average fiber diameter) of more than 150. The length (average fiber length) of the fibrous filler is preferably 0.15 mm or more, more preferably 0.2 mm or more, and still more preferably 0.5 mm or more, from the viewpoint of improving bending modulus and loss coefficient. More preferably, it is 1 mm or more, preferably 30 mm or less, more preferably 10 mm or less, and still more preferably 5 mm or less. The average fiber diameter is not particularly limited, but from the same viewpoint, it is preferably 1 μm or more, more preferably 3 μm or more, preferably 30 μm or less, more preferably 20 μm or less, further preferably 10 μm or less. The aspect ratio is preferably 200 or more, more preferably 250 or more, still more preferably 500 or more, and preferably 10000 or less, more preferably 5000 or less, still more preferably 1000 or less, from the same viewpoint. More preferably, it is 800 or less. Specific examples of fibrous fillers include those listed in paragraph 0067 of JP-A-2016-89148. In addition, the fiber length and fiber diameter of a fibrous filler can be calculated | required by observing 100 fillers selected at random with an optical microscope, and calculating the number average. When the fiber diameter has a short diameter and a long diameter, it is calculated using the long diameter. Further, the fiber diameter may be not only a circle having the same major axis and minor axis, but also an oval having different major axis and minor axis (for example, major axis / minor axis = 4) or cocoon type (for example, major axis / minor axis = 2) . On the other hand, when melt-kneading a resin and a fibrous filler in order to prepare a resin composition using a kneader such as a twin-screw extruder, the fibrous filler is cut by the shear force in the kneading section and the average is Although the fiber length is shortened, the average fiber length of the fibrous filler in the resin is preferably 100 to 800 μm, more preferably 200 to 700 μm, and still more preferably 300 to 600 μm from the viewpoint of improving the loss coefficient and rigidity.

The granular, plate-like or needle-like filler may be coated or converged with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as epoxy resin, aminosilane or epoxy It may be treated with a coupling agent such as silane.

These fillers can be used alone or in combination of two or more, and fillers of different shapes may be combined. Among them, at least one selected from the group consisting of a plate-like filler, a needle-like filler, and a fibrous filler, from the viewpoint of improving the flexural modulus and suppressing the decrease in loss coefficient. More preferably, it is 1 type, or 2 or more types selected from the group which consists of a plate-like filler and a needle-like filler, More preferably, it is 1 type or 2 or more types of a plate-like filler. Specifically, mica, talc and glass fiber are preferably used, mica and talc are more preferably used, and mica is more preferably used. The plate-like filler is oriented in the direction of flow in the injection-molded product, etc., so the tensile modulus in the direction of orientation and the flexural modulus in the direction perpendicular to the direction of orientation are significantly improved compared to other fillers. Also, it is presumed that the loss coefficient is further suppressed because there are many interfaces that affect the friction generated when the molded body vibrates. The content of the plate-like filler in the inorganic filler is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more from the viewpoint of suppressing the loss coefficient decrease.

From the viewpoint of rigidity improvement, the content of the inorganic filler (C) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and 20 parts by mass or more with respect to 100 parts by mass of the thermoplastic polyester resin (A). Is more preferable, and 30 parts by mass or more is further preferable. Further, from the viewpoint of suppressing a decrease in loss factor, 80 parts by mass or less is preferable, 70 parts by mass or less is more preferable, 60 parts by mass or less is more preferable, 50 parts by mass or less is more preferable, 45 parts by mass or less is more preferable . In addition, content of an inorganic filler is the total mass of the inorganic filler used, and when several compounds are contained, it means the thing of total content.

Further, in the polyester resin composition, the content of the inorganic filler is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, further preferably 20% by mass from the viewpoint of rigidity improvement. % Or more, more preferably 23% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less from the viewpoint of suppressing a decrease in loss factor.

In the present invention, the mass ratio of the component (B) to the inorganic filler (C) (component (B) / inorganic filler (C)) is 10/90 to 60 / from the viewpoint of improving the elastic modulus and the loss factor. 40 is preferable, 25/75 to 50/50 is more preferable, and 40/60 to 47/53 is further preferable.

[Organic crystal nucleating agent (D)]
The polyester resin composition in the present invention can contain an organic crystal nucleating agent from the viewpoint of improving the crystallization rate of the polyester resin, improving the crystallinity of the polyester resin, and improving the flexural modulus.

As the organic crystal nucleating agent, known organic crystal nucleating agents can be used, and organic carboxylic acid metal salts, organic sulfonic acid salts, carboxylic acid amides, phosphorus compound metal salts, metal salts of rosins, alkoxy metal salts, And organic nitrogen-containing compounds can be used. Specifically, for example, those listed in paragraph 0074 of JP-A-2016-89148 can be mentioned.

The content of the organic crystal nucleating agent (D) is preferably 0.01 parts by mass or more, more preferably 100 parts by mass of the thermoplastic polyester resin (A), from the viewpoint of improving the bending elastic modulus and the loss coefficient. Is 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoint of improving flexural modulus and loss factor Is 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1 part by mass or less. In the present specification, the content of the organic crystal nucleating agent means the total content of all the organic crystal nucleating agents contained in the polyester resin composition.

The polyester resin composition in the present invention is a lubricant other than the above components, which is a lubricant, an inorganic crystal nucleating agent, a hydrolysis inhibitor, a flame retardant, an antioxidant, a hydrocarbon wax and an anionic surfactant. An ultraviolet absorber, an antistatic agent, an antifogging agent, a light stabilizer, a pigment, an antifungal agent, an antibacterial agent, a foaming agent, etc. can be contained in the range which does not impair the effect of the present invention. Similarly, it is possible to contain other polymer materials and other resin compositions as long as the effects of the present invention are not impaired.

The polyester resin composition in the present invention may be prepared without particular limitation as long as it contains a thermoplastic polyester resin (A), a component (B) which is a plasticizer and / or an elastomer, and an inorganic filler (C). it can. For example, materials such as thermoplastic polyester resin, plasticizer and / or elastomer, and inorganic filler, and, if necessary, various additives, may be sealed kneader, single- or twin-screw extruder, open-roll type kneader, etc. The composition can be prepared by melt-kneading using a known kneader. After melt-kneading, the melt-kneaded product may be dried or cooled according to a known method. The raw materials can also be subjected to melt-kneading after being uniformly mixed in advance using a Henschel mixer, a super mixer, or the like. In addition, in order to promote the plasticity of a polyester resin at the time of melt-kneading, a supercritical gas may be made to melt-mix.

The melt-kneading temperature is not generally set depending on the type of thermoplastic polyester resin to be used, but from the viewpoint of improving the moldability and prevention of deterioration of the polyester resin composition, it is preferably 220 ° C. or more, more preferably 225 ° C. or more It is preferably 230 ° C. or more, preferably 300 ° C. or less, more preferably 290 ° C. or less, still more preferably 280 ° C. or less, still more preferably 260 ° C. or less, still more preferably 250 ° C. or less, more preferably 240 ° C. or less . The melt-kneading time can not be determined generally depending on the melt-kneading temperature and the type of the kneader, but it is preferably 15 to 900 seconds.

2. Method of Manufacturing Laminated Sheet Next, a method of manufacturing the laminated sheet of the present invention will be described.
The laminated sheet of the present invention can be produced by a conventionally known method. For example, a method in which each layer is separately formed in advance and then laminated or thermocompression-pressed, a method in which the upper or lower surface of the previously formed layer is coated to form another layer, and respective resin layers are laminated by coextrusion And the like. Hereinafter, as an example of the manufacturing method, a method will be described more specifically, in which each layer is separately formed in advance, each layer is stacked, and then thermocompression bonding is performed.

<Manufacture of polycarbonate layer>
A sheet-like molded article molded from a polycarbonate resin composition used as a polycarbonate layer is to obtain a desired thickness by a known method such as inflation molding, extrusion sheet molding, press molding, cast molding and the like. Can.

<Manufacturing of damping layer>
A damping layer of a desired thickness can be produced by feeding the melt-kneaded product of the polyester resin composition prepared as described above to, for example, a known extruder or drawing machine and drawing.

<Conditions of thermocompression bonding press>
The layers produced as described above are superimposed in a predetermined order. Set in a press, press-fit under the conditions of pressure 1 to 7MPa, temperature 160 to 190 ° C, press time 0.5 to 2.0 minutes, and then cool down to room temperature to obtain a predetermined laminated sheet Can. In the case of producing a laminated sheet by a thermocompression bonding press, changes in the thickness of the polycarbonate layer and the damping layer are almost negligible before and after the pressing.

With respect to the embodiment described above, the present invention further discloses the following laminated sheet.

<1> A laminated sheet in which a damping layer and a polycarbonate layer are laminated,
The damping layer is present on the surface and / or near the surface of the laminated sheet,
The damping layer contains a thermoplastic polyester resin (A) composed of a component containing a dicarboxylic acid component and a diol component, a component (B) which is a plasticizer and / or an elastomer, and an inorganic filler (C) The laminated sheet which is a sheet-like molded object of the polyester resin composition formed.

The relative position (%) of the damping layer from the upper surface of the <2> laminated sheet is preferably 40% or less, more preferably 33% or less, still more preferably 30% or less, still more preferably 25% or less Preferably it is 20% or less, more preferably 15% or less, more preferably 10% or less, and preferably 0.05% or more, more preferably 0.25% or more, still more preferably 0.5% or more The laminated sheet according to <1>, which is more preferably 1.0% or more, further preferably 5.0% or more, further preferably 10% or more.
The ratio of the damping layer in the <3> laminated sheet is preferably 1% or more, more preferably 5% or more, still more preferably 10% or more, and preferably 70% or less, in volume fraction. The laminated sheet according to <1> or <2>, which is preferably 50% or less, more preferably 34% or less, and further preferably 25% or less.
<4> The laminated sheet according to any one of <1> to <3>, wherein the thermoplastic polyester resin (A) contains polybutylene terephthalate.
<5> The laminated sheet according to any one of <1> to <4>, wherein the inorganic filler (C) comprises a plate-like filler.
<6> The laminated sheet according to any one of <1> to <5>, wherein the component (B) contains one or more plasticizers and one or more elastomers.
<7> The laminated sheet according to any one of <1> to <6>, wherein at least one layer of the vibration damping layer is in a position ratio of 10 to 40%.
<8> The thickness of each polycarbonate layer is preferably 0.05 mm or more, more preferably 0.10 mm or more, still more preferably 0.15 mm or more, and preferably 10 mm or less, more preferably 5.0 mm or less The laminated sheet according to any one of the above <1> to <7>, which is more preferably 3.5 mm or less.
<9> The thickness of each damping layer is preferably 0.05 mm or more, more preferably 0.2 mm or more, still more preferably 0.4 mm or more, and preferably 10 mm or less, more preferably 5.0 mm or less The laminated sheet according to any one of <1> to <8>, which is more preferably 1.0 mm or less.
The thickness of the entire <10> laminated sheet is preferably 0.3 mm or more, more preferably 1.0 mm or more, still more preferably 1.5 mm or more, still more preferably 2.0 mm or more, further preferably 2.5 mm or more And the laminated sheet according to any one of the above <1> to <9>, which is preferably 30 mm or less, more preferably 10 mm or less, still more preferably 5.0 mm or less.
When the total thickness of the <11> damping layer is 100%, the total thickness of the polycarbonate layer is preferably 100% or more, more preferably 200% or more, still more preferably 300% or more, and preferably 2000 % Or less, more preferably 1000% or less, according to any one of the items <1> to <10>.
<12> Thermoplastic polyester resin (A) is preferably polybutylene terephthalate; plasticizers are preferably polyester plasticizers, polyhydric alcohol ester plasticizers, polyhydric carboxylic acid ester plasticizers, bisphenol plasticizers And the elastomer is preferably polystyrene-isoprene block copolymer (SIS), polystyrene-polybutadiene copolymer (SEBS), polystyrene-hydrogenated polybutadiene copolymer (SEBS). Polystyrene-hydrogenated polyisoprene-polystyrene block copolymer (SEPS), polystyrene-vinyl-polyisoprene-polystyrene block copolymer (SHIVS), polystyrene-hydrogenated polybutadiene-hydrogenated polyisoprene-polystyrene One or more styrenic elastomers selected from the group consisting of styrene block copolymers and polystyrene-hydrogenated polybutadiene-polyisoprene-polystyrene block copolymers; and inorganic fillers (C) are preferably plate-like filled The laminated sheet according to any one of the above <1> to <11>, which is an agent, more preferably mica and / or talc.

The content of the thermoplastic polyester resin (A) in the <13> polyester resin composition is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, still more preferably 70% by mass or less; content of the plasticizer in the polyester resin composition is preferably 1% by mass or more More preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less; polyester resin composition The content of the elastomer contained therein is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 9.5% by mass or more. And preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less; the content of the inorganic filler in the polyester resin composition is preferably 5% by mass or more, more The content is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 23% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less The laminated sheet according to any one of the above <1> to <12>, which is more preferably 30% by mass or less.
The total content of the plasticizer and the elastomer when used in combination is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 25 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). The laminated sheet according to any one of the above <1> to <13>, which is not less than 60 parts by mass, preferably not more than 60 parts by mass, more preferably not more than 50 parts by mass, still more preferably not more than 40 parts by mass. .
<15> The mass ratio of the plasticizer and the elastomer (plasticizer / elastomer) in the combined use is preferably 10/90 to 90/10, more preferably 30/70 to 70/30. The laminated sheet of any one of 14>.
The mass ratio of the component (B) to the inorganic filler (C) (component (B) / inorganic filler (C)) is preferably 10/90 to 60/40, more preferably 25/75 to 50 The laminated sheet according to any one of the above <1> to <15>, which is / 50, more preferably 40/60 to 47/53.
<17> A preferred arrangement of each layer in the laminated sheet is a group consisting of polycarbonate layer (PC) / damping layer (PBT), PC / PBT / PC, PC / PBT / PC / PBT / PC, and PBT / PC / PBT The laminated sheet according to any one of <1> to <16>, which is one or more selected from the group consisting of
The <18> loss factor is preferably 0.04 or more, more preferably 0.05 or more, still more preferably 0.06 or more, still more preferably 0.07 or more. A laminated sheet according to item 1.
<19> Any of the above <1> to <18>, wherein the flexural modulus is preferably 2.7 or more, more preferably 2.8 or more, further preferably 2.9 or more, still more preferably 3.1 or more. Or laminated sheet according to item 1.

Hereinafter, the present invention will be specifically described by way of examples. Note that this example is merely an example of the present invention and does not mean any limitation. Parts in the examples are parts by weight unless otherwise stated. In addition, "atmospheric pressure" shows 101.3 kPa and "normal temperature" shows 25 degreeC.

<Mass Average Molecular Weight of Thermoplastic Polyester Resin (A)>
Gel Permeation Chromatography (TOSOH: EcoSEC HLC-) was prepared by completely dissolving 0.6 mg of pellet sample in 2 g of HFIP (1,1,1,3,3,3-Hexafluoro-2-propanol Wako Pure Chemical Industries, Ltd.). The molecular weight is measured using 8320 GPC). Regarding the measurement conditions, the eluent is HFIP / 0.5 mM Na trifluoroacetate, the flow rate is 0.2 mL / min, and the measurement temperature is 40 ° C. Polystyrene (made by Tosoh Corp.) is used as a standard polymer for preparation of a standard curve. In addition, when several peaks and shoulders are recognized, it is set as molecular weight distribution of polyester resin as a single peak.

<Absolute crystallinity (Xc) of polyester resin composition>
X-ray incident angles of flat plate specimens (127 mm × 12.7 mm × 1.6 mm) obtained by press-molding a polyester resin composition using XRD (manufactured by Rigaku: MiniFlex II DESKTOP X-ray DIFFRACTOMETER) The diffracted light at 2θ = 5 ° to 40 ° is measured, and the absolute crystallinity degree is calculated from the intensities of the peak and the halo.

<Glass transition temperature of thermoplastic polyester resin and elastomer>
A flat test piece (40 mm × 5 mm × 0.4 mm) of a sheet-like molded product or an elastomer of a polyester resin composition prepared in the same manner as described later is produced. Next, using a DMA device (manufactured by SII, EXSTAR 6000), with a measurement frequency of 1 Hz, the temperature is raised from -50 ° C. to 250 ° C. at a heating rate of 2 ° C./min. Calculated as a transition point.

<Enthalpy of crystallization of thermoplastic polyester resin>
About 7 mg of a thermoplastic polyester resin sample is weighed, and the resin is heated from 25 ° C. to 300 ° C. at a temperature rising rate of 20 ° C./min according to JIS K 7122 (1999) using a DSC (Perkin Elmer Co., DSC 8500) Then, after holding for 5 minutes in that state, when cooling at −20 ° C./min so as to be 25 ° C. or less, the enthalpy of crystallization is calculated from the exothermic peak accompanying crystallization.

<Styrene content of styrenic elastomer>
The elastomer is dissolved in deuterated chloroform, and the H-NMR spectrum of the sample solution is measured at an observation width of 15 ppm. In addition, a calibration curve is previously obtained from the peak area and concentration of styrene in the H-NMR spectrum of a polystyrene / deuterated chloroform solution of three different concentrations, and using this calibration curve, the peak area of styrene in the sample solution is used. Calculate the content.

<MFR of polycarbonate>
In accordance with ASTM D1238, the test temperature is 300 ° C. and the test load is 1.2 kgf.

Production Example 1 and Production Example 3 (Production of Sheet-Like Molding of Polyester Resin Composition)
The raw materials of the polyester resin composition shown in Table 1 are melt-kneaded at 240 ° C. using a co-directional meshing type twin screw extruder (TEX-28V manufactured by Japan Steel Works, Ltd.), and strand cut is performed to obtain a resin composition. Pellets were obtained. The pellets obtained were dried by dehumidification at 110 ° C. for 3 hours to make the water content 500 ppm or less.

Next, the obtained pellets were fed to a 50 mm single screw extruder and melt-kneaded at 240 ° C., and then the melt-kneaded product was formed into a sheet by a roll controlled to a roll temperature of 90 ° C. and a cooled roll Thereafter, a sheet having a width of 450 mm and a thickness of 0.5 mm was wound up to obtain a sheet-like formed product of the polyester resin composition (abbreviated as "PBT sheet").

 

In addition, the detail of the raw material in Table 1 is as follows.
[Thermoplastic polyester resin]
PBT (700FP): polybutylene terephthalate resin, Duranex 700FP (Polyplastics Co., Ltd., non-reinforced, glass transition temperature: 50 ° C., crystallization enthalpy ΔHmc: 44 J / g)
[Plasticizer]
DAIFATTY-101: mixed diester of adipic acid and diethylene glycol monomethyl ether / benzyl alcohol = 1/1 (made by Daihachi Chemical Industry Co., Ltd.); 5% mass loss temperature: 235 ° C.
[Elastomer]
Styrene isoprene block copolymer: HYBLER 5127 (manufactured by Kuraray Plastics, glass transition temperature: 8 ° C., styrene content: 20% by mass)
Polystyrene-hydrogenated polybutadiene copolymer: S.I. O. E. S1605 (manufactured by Asahi Kasei Corporation, glass transition temperature: 8 ° C., styrene content: 67% by mass)
[Inorganic filler]
Mica: A-21S (Yamaguchi Mica Co., length of longest side of largest face: 23 μm, thickness of largest face: 0.33 μm, aspect ratio: 70)

Production Example 2 (Production of Polycarbonate Resin Composition Sheet)
Single-shaft extrusion of 50 mm diameter with a 500 mm wide die and a film take-up device attached to the end of a pellet of polycarbonate resin (Sabik, trade name: LEXAN, MFR: 7 g / 10 min (300 ° C., 1.2 kgf)) The film was formed at a barrel temperature of 260 to 300 ° C. while being supplied to a machine to obtain a PC sheet having a thickness of 0.5 mm.

Production Example 4 (Production of Polycarbonate Resin Composition Sheet)
Single-shaft extrusion of 50 mm diameter with a 500 mm wide die and a film take-up device attached to the end of a pellet of polycarbonate resin (Sabik, trade name: LEXAN, MFR: 7 g / 10 min (300 ° C., 1.2 kgf)) While feeding to a machine, a film was formed at a barrel temperature of 260 to 300 ° C. to obtain a PC sheet having a thickness of 0.25 mm.

Example 1 (manufacture of laminated sheet)
One PBT sheet produced in Production Example 1 and two PC sheets produced in Production Example 2 were prepared. Two PC sheets were laminated on the upper surface of one PBT sheet. Next, the three laminates are integrated by heating and compressing for 1 minute under the conditions of a pressure of 0.2 to 3 MPa using a press set at a press heating temperature of 165 ° C., and then cooled to room temperature by a cooling press It cooled. Thus, a laminated sheet having a thickness of 1.5 mm was produced.

The manufactured laminated sheet has a structure in which a PC sheet as the polycarbonate layer 2 is laminated on the upper surface of the PBT sheet as the damping layer 1, and the cross section corresponds to the cross sectional view of FIG. 2A. .

Example 2 (manufacture of laminated sheet)
One PBT sheet produced in Production Example 1 and eight PC sheets produced in Production Example 2 were prepared. One PC sheet was laminated on the upper surface of one PBT sheet, and seven PC sheets were laminated on the lower surface of the PBT sheet. Next, the nine laminates are integrated by heating and compressing for 2 minutes under the conditions of a pressure of 0.2 to 3 MPa using a press set to a press heating temperature of 165 ° C., and then cooled to room temperature by a cooling press It cooled. Thus, a laminated sheet having a thickness of 4.5 mm was produced.

In the produced laminated sheet, a PC sheet as the polycarbonate layer 2 is laminated on the upper surface of the PBT sheet as the damping layer 1, and a PC sheet as the polycarbonate layer 3 is laminated on the lower surface of the damping layer 1. It is a structure, and its cross section corresponds to the cross section of FIG. 2B.

Example 3 (manufacture of laminated sheet)
One PBT sheet produced in Production Example 1 and 14 PC sheets of 0.25 mm thickness produced in Production Example 4 were prepared. One PC sheet was laminated on the upper surface of one PBT sheet, and 13 PC sheets were laminated on the lower surface of the PBT sheet. Next, the 15 laminates are integrated by heating and compressing for 2 minutes under conditions of a pressure of 0.2 to 3 MPa using a press set to a press heating temperature of 165 ° C., and then cooled to room temperature by a cooling press It cooled. Thus, a laminated sheet having a thickness of 4.0 mm was produced.

In the produced laminated sheet, a PC sheet as the polycarbonate layer 2 is laminated on the upper surface of the PBT sheet as the damping layer 1, and a PC sheet as the polycarbonate layer 3 is laminated on the lower surface of the damping layer 1. It is a structure, The cross section corresponded to the cross section of FIG. 4A.

Comparative Example 1 (Production of Laminated Sheet)
One PBT sheet produced in Production Example 1 and two PC sheets produced in Production Example 2 were prepared. One PC sheet was laminated on the upper surface of one PBT sheet, and one PC sheet was laminated on the lower surface of the PBT sheet. Next, the three laminates are integrated by heating and compressing for 1.5 minutes under the conditions of a pressure of 0.2 to 3 MPa using a press whose press heating temperature is set at 165 ° C., and then the cooling press It cooled to normal temperature. Thus, a laminated sheet having a thickness of 1.5 mm was produced.

In the produced laminated sheet, a PC sheet as the polycarbonate layer 2 is laminated on the upper surface of the PBT sheet as the damping layer 1, and a PC sheet as the polycarbonate layer 3 is laminated on the lower surface of the damping layer 1. It is a structure, and its cross section corresponds to the cross section of FIG. 3A.

Comparative Example 2 (Production of Laminated Sheet)
One PBT sheet produced in Production Example 1 and eight PC sheets produced in Production Example 2 were prepared. Four PC sheets were laminated on the upper surface of one PBT sheet, and four PC sheets were laminated on the lower surface of the PBT sheet. Next, the nine laminates are integrated by heating and compressing for 1.5 minutes under the conditions of a pressure of 0.2 to 3 MPa using a press whose press heating temperature is set to 165 ° C., and then by a cooling press It cooled to normal temperature. Thus, a laminated sheet having a thickness of 4.5 mm was produced.

In the produced laminated sheet, a PC sheet as the polycarbonate layer 2 is laminated on the upper surface of the PBT sheet as the damping layer 1, and a PC sheet as the polycarbonate layer 3 is laminated on the lower surface of the damping layer 1. It is a structure, and the cross section corresponds to the cross section of FIG. 3B.

Comparative Example 3 (Production of Laminated Sheet Formed Only from Damping Layer)
Four PBT sheets manufactured in Production Example 1 were prepared. Four PBT sheets were laminated, and then the four laminates were heated and compressed for 1.5 minutes under a pressure of 0.2 to 3 MPa using a press set to a heating temperature of 225 ° C. And then cooled to room temperature by a cooling press. Thus, a laminated sheet having a thickness of 2.0 mm was produced.
The produced laminated sheet was a laminated sheet formed only of the PBT sheet as the damping layer 1.

Comparative Example 4 (Production of Laminated Sheet)
One PBT sheet produced in Production Example 1 and seven PC sheets produced in Production Example 2 were prepared. Four PC sheets were laminated on the upper surface of one PBT sheet, and three PC sheets were laminated on the lower surface of the PBT sheet. Next, the eight laminates are integrated by heating and compressing for 1.5 minutes under the conditions of a pressure of 0.2 to 3 MPa using a press whose press heating temperature is set to 165 ° C., and then the cooling press It cooled to normal temperature. Thus, a laminated sheet having a thickness of 4.0 mm was produced.
In the produced laminated sheet, a PC sheet as the polycarbonate layer 2 is laminated on the upper surface of the PBT sheet as the damping layer 1, and a PC sheet as the polycarbonate layer 3 is laminated on the lower surface of the damping layer 1. It is a structure, and the cross section corresponds to the cross section of FIG. 4B.

The characteristics of each of the obtained laminated sheets were evaluated in accordance with the following test examples. The results are shown in Table 2. In addition, the description of the evaluation result about Example 2, Comparative Example 2 and Comparative Example 3 was omitted.

Test Example 1 [Loss Factor]
Each laminated sheet is cut into a size of 127 mm × 12.7 mm × thickness (2.0 to 4.5) mm (the thickness depends on the thickness of the laminated sheet obtained in each example and comparative example), and flat plate test pieces And
The loss factor of the flat plate test piece was calculated by the half width method from the peak of the secondary resonance of the frequency response function measured by the central excitation method based on JIS K 7391. The oscillator was Type 3160, the amplifier was Type 2718, the exciter was Type 4810, and the acceleration sensor was Type 8001 (all manufactured by B & K), and the loss coefficient measurement software MS18143 was used. The measurement environment was controlled by a thermostatic bath (manufactured by ESPEC, PU-3J), and was measured at 23 ° C. As the loss factor of the laminated sheet is higher, it can be judged that the vibration damping is faster, that is, the damping effect of the laminated sheet is higher.

Test Example 2 (Stiffness)
Each laminated sheet was cut into a size of 30 mm × 25 mm × thickness (2.0 to 4.5) mm (the thickness depends on the thickness of the laminated sheet obtained in each of the examples and comparative examples) to obtain flat test pieces. . A flat plate test piece was subjected to a bending test at a distance between supporting points of 24 mm and a test speed of 1 mm / min using a TENSILON universal material tester (RTC-1250A manufactured by Orientec Co., Ltd.) based on JIS K7171. The flexural modulus was determined. When the bending elastic modulus is 2.0 GPa or more, it can be judged that the bending elastic modulus is high and the rigidity is good.

 

It has been found that the laminated sheet (of the example) of the present invention has a high loss coefficient and a high elastic modulus, and is excellent in both the self-supporting property and the damping effect. In addition, sufficient stiffness and impact strength are expected to be high. On the other hand, laminated sheets (Comparative Examples 1, 2 and 4) in which the damping layer is not at a predetermined position have a low loss coefficient and are therefore poor in damping effect, and are formed of only damping layers Comparative Example 3) was found to be low in rigidity because the elastic modulus was low. Furthermore, even if it was a lamination sheet which combined a polycarbonate layer and a damping layer, when it did not have the layered structure of the present invention, it turned out that both rigidity and a damping effect can not be satisfied (comparative example 1) , 2 and 4).

Example 4 (manufacture of laminated sheet)
Two PBT sheets produced in Production Example 1 and six PC sheets produced in Production Example 2 were prepared. One PC sheet is laminated on the lower surface of one PBT sheet, four PC sheets are laminated on the upper surface of the PBT sheet, one PBT sheet is laminated on the upper surface of the PC sheet, and the upper surface of the PBT sheet One PC sheet was laminated. Next, the eight laminates are integrated by heating and compressing for 2 minutes under the conditions of a pressure of 0.2 to 3 MPa using a press set to a press heating temperature of 165 ° C., and then cooled to room temperature by a cooling press It cooled. Thus, a laminated sheet having a thickness of 4.0 mm was produced.

The produced laminated sheet has a structure in which the polycarbonate layer 2, the damping layer 4 and the polycarbonate layer 5 are laminated on the upper surface of the damping layer 1, and the polycarbonate layer 3 is laminated on the lower surface of the damping layer 1. The cross section corresponds to the cross sectional view of FIG. 5A.

Example 5 (manufacture of laminated sheet)
Two PBT sheets produced in Production Example 1 and six PC sheets produced in Production Example 2 were prepared. Six PC sheets were laminated on the upper surface of one PBT sheet, and one PBT sheet was laminated on the upper surface of the PC sheet. Next, the eight laminates are integrated by heating and compressing for 2 minutes under the conditions of a pressure of 0.2 to 3 MPa using a press set to a press heating temperature of 165 ° C., and then cooled to room temperature by a cooling press It cooled. Thus, a laminated sheet having a thickness of 4.0 mm was produced.
The manufactured laminated sheet has a structure in which the polycarbonate layer 2 and the damping layer 4 are laminated on the upper surface of the damping layer 1, and the cross section thereof corresponds to the cross sectional view of FIG. 5B.

Example 6 (manufacture of laminated sheet)
Two PBT sheets produced in Production Example 1 and 12 PC sheets of 0.25 mm thickness produced in Production Example 4 were prepared. One PC sheet is laminated on the lower surface of one PBT sheet, ten PC sheets are laminated on the upper surface of the PBT sheet, one PBT sheet is laminated on the upper surface of the PC sheet, and the upper surface of the PBT sheet One PC sheet was laminated. Next, the 14 laminates are integrated by heating and compressing for 2 minutes under conditions of a pressure of 0.2 to 3 MPa using a press set at a press heating temperature of 165 ° C., and then cooled to room temperature by a cooling press It cooled. Thus, a laminated sheet having a thickness of 4.0 mm was produced.

The produced laminated sheet has a structure in which the polycarbonate layer 2, the damping layer 4 and the polycarbonate layer 5 are laminated on the upper surface of the damping layer 1, and the polycarbonate layer 3 is laminated on the lower surface of the damping layer 1. The cross section corresponds to the cross sectional view of FIG. 5C.

Example 7 (Production of Laminated Sheet)
A laminated sheet having a thickness of 1.5 mm was produced under the same conditions as in Example 1 except that the PBT sheet produced in Production Example 3 was used instead of the PBT sheet produced in Production Example 1.
The manufactured laminated sheet has a structure in which a PC sheet as the polycarbonate layer 2 is laminated on the upper surface of the PBT sheet as the damping layer 1, and the cross section corresponds to the cross sectional view of FIG. 2A. .

 

From Examples 4 to 6, even if the laminated sheet has a plurality of damping layers, the loss coefficient is high and the elastic modulus is also high as long as the conditions of the present invention are satisfied, that is, self-supporting It turned out that it is excellent in both and the damping effect. Furthermore, it was found that sufficient damping performance can be secured even if the PC sheet is set relatively thick. Furthermore, a laminated sheet (Example 7) obtained using a polystyrene-hydrogenated polybutadiene copolymer as an elastomer is comparable to a laminated sheet (Example 1) obtained using a styrene isoprene block copolymer It was found to show the loss factor and modulus of elasticity of That is, it was found that a polystyrene-hydrogenated polybutadiene copolymer can also be preferably used as an elastomer.

The laminated sheet of the present invention has sufficient rigidity and impact strength to have a polycarbonate layer, and also has a high loss coefficient and is excellent in the damping effect, so for example, a speaker, a television, a radio cassette player, a headphone, an audio component Alternatively, it can be suitably used as a material for an acoustic device such as a microphone, an electric product, a product such as a vehicle, a building, an industrial device or a part thereof, or a damping material for a housing.

1 damping layer 2 polycarbonate layer 3 polycarbonate layer 4 damping layer 5 polycarbonate layer

Claims (9)

1. A laminated sheet in which a damping layer and a polycarbonate layer are laminated,
   The damping layer is present on the surface and / or near the surface of the laminated sheet,
   The damping layer contains a thermoplastic polyester resin (A) composed of a component containing a dicarboxylic acid component and a diol component, a component (B) which is a plasticizer and / or an elastomer, and an inorganic filler (C) The laminated sheet which is a sheet-like molded object of the polyester resin composition formed.
2. The laminated sheet according to claim 1, wherein the relative position (%) of the damping layer from the upper surface of the laminated sheet is within 30%.
3. The lamination sheet of Claim 1 or 2 whose ratio of the damping layer in a lamination sheet is 1% or more and 70% or less in a volume fraction.
4. The laminated sheet according to any one of claims 1 to 3, wherein the thermoplastic polyester resin (A) comprises polybutylene terephthalate.
5. The laminated sheet according to any one of claims 1 to 4, wherein the inorganic filler (C) comprises a plate-like filler.
6. The laminated sheet according to any one of claims 1 to 5, wherein the component (B) contains one or more plasticizers and one or more elastomers.
7. The laminated sheet according to any one of claims 1 to 6, wherein at least one layer of the damping layer is present at a position ratio of 10 to 40%.
8. The laminated sheet according to any one of claims 1 to 7, wherein the thickness of each polycarbonate layer is 0.05 mm or more and 10 mm or less.
9. The laminated sheet according to any one of claims 1 to 8, wherein the thickness of each damping layer is 0.05 mm or more and 10 mm or less.

Images