TW201919902A - 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 vibration damping material.

In recent years, countermeasures against vibrations of various devices have been required, and they are considered to be necessary especially in the fields of automobiles, home appliances, and precision equipment. As one of the materials having high vibration damping property, a material obtained by bonding a metal plate to a vibration absorbing material such as rubber or asphalt (Patent Document 1), or a resin sheet having vibration damping property can be cited. However, the use of a metal plate material has a problem that the product itself becomes heavy. Furthermore, there is a problem that most individual individuals of a resin sheet provided with a vibration damping property are those having low rigidity and no independence.
[Prior technical literature]
[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2016-186207

The present invention relates to the following [1].
[1] A laminated sheet, which is obtained by laminating a vibration damping layer and a polycarbonate, and the vibration damping layer exists on the surface and / or near the surface of the laminated sheet,
A sheet-shaped molded body of the vibration-controlling layer-based polyester resin composition containing a thermoplastic polyester resin (A) composed of a component including a dicarboxylic acid component and a diol component, and plasticized And / or an elastomer component (B) and an inorganic filler (C).

The present invention relates to a laminated sheet having rigidity and impact strength sufficient to the extent that a metal material is not required, and excellent vibration damping properties.

The laminated sheet of the present invention has sufficient rigidity and impact strength to the extent that a metal material is not required, and can exhibit excellent vibration damping properties.

Hereinafter, the laminated sheet of this invention is demonstrated in detail.
1. Laminated sheet One of the features of the laminated sheet of the present invention is that it is formed by laminating a vibration damping layer and a polycarbonate, and the vibration damping layer exists on the surface and / or near the surface of the laminated sheet,
A sheet-shaped molded body of the vibration-controlling layer-based polyester resin composition containing a thermoplastic polyester resin (A) composed of a component including a dicarboxylic acid component and a diol component, and plasticized And / or an elastomer component (B) and an inorganic filler (C).

In the present invention, the existence position of the vibration-damping layer is characteristic. From the viewpoint of imparting rigidity or independence to the laminated sheet, it is considered to have a two-layer structure of a vibrating material attached only to a sheet that becomes a substrate having independence (made of polycarbonate, etc.), or Become a three-layer structure of the base material sheet sandwiching vibration material. However, although a sheet having a two-layer structure in which only a vibration-controlling material is attached to a sheet that is a base material, high vibration-controlling properties can be obtained, but the strength or heat resistance are insufficient. On the other hand, although a three-layered structure in which a vibrating material is sandwiched between a sheet serving as a base material maintains strength, the vibration damping property does not improve much. Therefore, the present inventors have studied the position of the vibration-damping material (vibration-damping layer) in the laminated sheet, and completed the present invention.

By having such characteristics in the existence position of the vibration-damping layer, the independence of the laminated sheet can be ensured, and the rigidity, impact strength, and vibration-damping property of the laminated sheet can be sufficiently improved. The mechanism by which the laminated sheet of the present invention exhibits excellent vibration damping effects is presumed as follows. It is thought that since the vibration damping layer is arranged on or near the surface of the laminated sheet, that is, closer to the surface side than the center of the laminated sheet, when strain such as bending is applied to the sheet, the strain energy is biased toward the vibration damping layer on the surface side. As a result, energy loss is caused and vibration damping performance is exhibited. Furthermore, it is estimated that by increasing the thickness of the vibration damping layer on the surface side, the strain energy of the vibration damping layer on the surface side is further increased, and it is considered that the vibration damping property is further improved. Furthermore, it is estimated that by increasing the thickness of the vibration damping layer on the surface side, the strain energy of the vibration damping layer on the surface side is further increased, and it is considered that the vibration damping property is further improved. Furthermore, when the vibration damping layer is present near the surface of the laminated sheet, that is, when the polycarbonate layer is a two-layer layer on the upper and lower surfaces of the vibration damping layer, in addition to the excellent vibration damping effect, it can be expected. The effect of improving the chemical resistance of the sheet to be the base material, the suppression of bleeding and outgassing.

Since the laminated sheet of the present invention has rigidity, impact strength, and excellent vibration damping property, it can be used for speakers, televisions, recorders, earphones, audio components, microphones, etc. as materials for the frame of audio equipment; furthermore, it can be used as Parts of electrical products with electric motors and electric drills for frame materials, electric tools such as electric screwdrivers, computers, projectors, servers, POS (Point of Sale terminal) systems, etc. Electrical products, washing machines, clothes dryers, air-conditioning indoor units, sewing machines, dishwashers, heaters, multi-functional machines, printers, scanners, hard drives, camcorders, etc .; can be used as a vibration source Electric toothbrushes, electric razors, massagers, etc. for electrical parts and frame materials; generators, gas generators, etc. that can be used as parts for electrical products with prime movers and materials for the frame; can be used as Refrigerators, vending machines, air-conditioning outdoor units, dehumidifiers, household generators for electrical product parts and housing materials with compressors; Used as materials for automotive parts, such as dashboards, dashboards, floor panels, doors, windows, and other interior materials, oil pans, front shells, rocker chamber covers, and other engine surrounding materials; can be used as rail parts Materials such as flooring, walls, side panels, ceilings, doors, chairs, tables and other interior materials, frames or parts around the motor, various protective covers, etc .; can be used as floors, walls, side panels, and ceiling panels as materials for aircraft parts , Chairs, tables and other interior materials, frames or parts around the engine, etc .; can be used as the engine room as the material or parts of the engine room frame or wall material, the measurement room of the frame or the wall material; can be used for Walls, ceilings, floors, partitions, soundproof walls, shutters, curtain rails, piping, steps, doors, etc. used as construction materials; chute, elevator, escalator, and transportation used as materials for industrial machine parts Machines, tractors, bulldozers, lawn mowers, etc .; kerosene tanks, steel drums, composite containers, tank trucks, and transport boxes that can be used as industrial transport components.

<Layer Structure>
The layer structure of the laminated sheet of this invention is demonstrated.
As the overall thickness (ie, the total thickness) of the laminated sheet of the present invention, from the viewpoint of strength and rigidity required for use, it is preferably 0.3 mm or more, more preferably 1.0 mm or more, and even more preferably 1.5 mm. Above, more preferably 2.0 mm or more, and even more preferably 2.5 mm or more. From the viewpoint of the quality, strength, and rigidity required for use, it is preferably 30 mm or less, more preferably 10 mm or less, and more preferably It is preferably below 5.0 mm.

[Polycarbonate layer]
The polycarbonate layer is a sheet-like molded body formed from the following polycarbonate resin composition. By using a polycarbonate layer, independence, chemical resistance, volatility, and impact resistance can be imparted to the laminated sheet of the present invention.

In this specification, the polycarbonate layer is not only a single layer, but also a layer composed of a plurality of layers (for example, a layer formed by subjecting a plurality of polycarbonate layers to heat compression bonding and pressing), which can also be used as a layer of polymer. The carbonate layer is processed. The same applies to the vibration damping layer.

The thickness of the polycarbonate layer is preferably 0.05 mm or more, more preferably 0.10 mm or more, and still more preferably 0.15 mm or more from the viewpoint of the characteristics of the molding method used to manufacture the sheet material. From the viewpoint of the characteristics of the forming method of the thick plate used, it is preferably 10 mm or less, more preferably 5.0 mm or less, and even more preferably 3.5 mm or less. When the polycarbonate layer has a plurality of layers, for example, when there are two layers of the polycarbonate layer 2 and the polycarbonate layer 3 like the laminated sheet shown in FIG. 2B, the thicknesses described herein are each Various thicknesses of the polycarbonate layer.

When the polycarbonate layer has a plurality of layers, it is a state in which the vibration damping layer is sandwiched by the polycarbonate layer, that is, a state in which the vibration damping layer exists near the surface of the laminated sheet (for example, FIG. 2B, FIG. 4A). 5A or 5C). In this case, from the viewpoint of considering both high strength and high vibration damping property, it is preferable that at least one of the polycarbonate layer is the same as or thinner than the vibration damping layer. Specifically, in this case, at least one thickness of the polycarbonate layer is preferably 1.0 times or less, more preferably 0.5 times or less, and still more preferably 0.25 times or less as the thickness of the vibration-damping layer. The limit is preferably 0.01 times or more.

[Vibration layer]
The vibration-damping layer is a sheet-shaped molded body of a polyester resin composition containing the following component (A), component (B), and component (C). The number of vibration damping layers in the laminated sheet may be one or a plurality of layers. In the case where a plurality of vibration damping layers are present in the laminated sheet, it is assumed that one vibration damping layer exists on the surface of the laminated sheet and the remaining vibration damping layers exist near the surface, or two vibration damping layers exist. The state on the surface (such as the laminated sheet shown in FIG. 5B) and the state where a plurality of vibration damping layers are present near the surface (such as the laminated sheet shown in FIG. 5A or 5C). The laminated sheet included in the present invention.

As the thickness of the vibration-controlling layer, from the viewpoint of the characteristics of the forming method used to manufacture the sheet material, it is preferably 0.05 mm or more, more preferably 0.2 mm or more, and still more preferably 0.4 mm or more. From the viewpoint of the characteristics of the method for forming a thick plate, the thickness is preferably 10 mm or less, more preferably 5.0 mm or less, and still more preferably 1.0 mm or less. In the case where the laminated sheet has a plurality of vibration-damping layers, the thickness described herein refers to the thickness of each vibration-damping layer.

A polycarbonate layer is formed on one of the upper surface and the lower surface of the vibration damping layer, or a two-area layer.
In the case of a polycarbonate layer which is an area of the vibration damping layer, the laminated sheet has a structure in which the vibration damping layer is exposed on the surface of the laminated sheet, that is, a state in which the vibration damping layer exists on the surface of the laminated sheet. The cross-sectional structure of this aspect is schematically shown in FIG. 2A. The laminated sheet shown in FIG. 2A has a polycarbonate layer 2 on the surface area above the vibration damping layer 1.

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

In this specification, the so-called vibration damping layer exists near the surface of the laminated sheet, which means that the vibration damping layer does not exist on the surface of the laminated sheet, and when the situation is shown in the cross-sectional view of the laminated sheet (Figure 1), The vibration layer as a whole exists on the surface side (S or S 'in FIG. 1) than the center line of the cross section (single dotted line in FIG. 1). From the viewpoint of improving the vibration damping property, the vibration damping layer is preferably within 40%, more preferably within 33%, and more preferably within 30% of the thickness direction from the surface of the laminated sheet. It is preferably within 25%, more preferably within 20%, still more preferably within 15%, and still more preferably within 10%. On the other hand, from the viewpoint that the laminated sheet maintains higher chemical resistance, higher elastic modulus, or higher strength, the vibration-damping layer exists in the thickness direction from the surface of the laminated sheet. It is preferably at least 0.05%, more preferably at least 0.25%, still more preferably at least 0.5%, still more preferably at least 1.0%, even more preferably at least 5.0%, and even more preferably at least 10%.

Here, referring to FIG. 1, a concrete description will be given of a vibration damping layer within 40% of the thickness direction from the surface of the laminated sheet. FIG. 1 schematically shows a cross-sectional view of the laminated sheet of the present invention when the vibration damping layer is one layer and the polycarbonate layer is two layers. The surface of the laminated sheet near the vibration damping layer 1 side, that is, the upper surface Let it be S and let the other surface be S '. The thickness direction from the surface is a direction from S to S ′ shown in the arrow direction on the right side of FIG. 1. When the thickness of the entire laminated sheet is set as a percentage, that is, when S is set to 0% and S ′ is expressed as 100%, the relative position in the thickness direction of the vibration-damping layer 1 may be the thickness of the laminated sheet The percentage is expressed. For example, in the laminated sheet shown in FIG. 1, if the thicknesses of the polycarbonate layer 2, the vibration damping layer 1, and the polycarbonate layer 3 are set to 2 mm, 2 mm, and 16 mm, the vibration damping layer can be set. The position in the thickness direction of 1 is expressed as 10 to 20%. In this way, the so-called existence within 40% in the thickness direction from the surface of the laminated sheet means that when the entire thickness of the laminated sheet is expressed as a percentage, the entire damping layer exists within 40% of the thickness direction . At this time, it also means "the position ratio is within 40%" or "the relative position (%) of the vibration damping layer from the upper surface of the laminated sheet is within 40%". As a preferred aspect of the present invention, a laminated sheet having at least one layer of the vibration control layer at a position ratio of 10 to 40% can be cited.

From the viewpoint of improving the damping property, the ratio of the damping layer in the laminated sheet is preferably 1% or more in terms of volume fraction, more preferably 5% or more, and still more preferably 10% or more. From the viewpoint of higher elastic modulus or strength, the volume fraction is preferably 70% or less, more preferably 50% or less, still more preferably 34% or less, and still more preferably 25% or less. When there are a plurality of vibration-damping layers in the laminated sheet, the volume fraction described herein is the total of the vibration-damping layers.

The laminated sheet of the present invention can take into account the rigidity or impact strength and vibration damping properties of the laminated sheet. According to the situation in which the laminated sheet is applied, that is, the rigidity or impact strength is valued, or the vibration damping property of the laminated sheet is valued, there is a better relationship between the total thickness of the polycarbonate layer and the total thickness of the vibration damping layer. Subject to change. Here, the total thickness of the polycarbonate layer refers to the total thickness of all the polycarbonate layers present in the laminated sheet, and the total thickness of the vibration damping layer refers to the thickness of all the vibration damping layers present in the laminated sheet. Total. In the aspect that attaches importance to the rigidity or impact strength of the laminated sheet, the total thickness of the polycarbonate layer is preferably the same as or thicker than the total thickness of the vibration-damping layer, specifically, the total thickness of the vibration-damping layer When it is set to 100%, the total thickness of the polycarbonate layer is preferably 100% or more, more preferably 200% or more, even more preferably 300% or more, and the upper limit value is preferably 2000% or less, and more preferably Below 1000%. On the other hand, in the aspect that attaches importance to the vibration damping performance of the laminated sheet, it is preferable that the total thickness of the polycarbonate layer is the same as or thinner than the total thickness of the vibration damping layer. When the total thickness is 100%, the total thickness of the polycarbonate layer is preferably 100% or less, more preferably 67% or less, and the lower limit value is preferably 33% or more.

From the viewpoint of adhesiveness with a polycarbonate resin composition sheet (also referred to as "PC sheet" in this specification), the polyester resin composition constituting the vibration-making layer of the laminated sheet of the present invention, that is, the polyester resin composition The amount of the surface of the elastomer in the sheet-shaped formed body is preferably 0.5% or more, more preferably 1% or more, and further preferably 5% or more. On the other hand, from the viewpoint of maintaining the elastic modulus, It is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less. The amount of the surface of the elastomer is obtained by immersing the sheet-like molded body of the polyester resin composition in a solvent to remove the elastomer, and observing the processed molded body with a scanning electron microscope (SEM). . Specifically, the void portion of the formed body after the treatment is defined as a region where the elastomer is present, and the area of the void portion per a certain area represents the amount of surface presence of the elastomer.

From the viewpoint of adhesiveness with the PC sheet, the particle diameter of the elastomer in the vibration-controlling layer constituting the laminated sheet of the present invention is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1. From the viewpoint 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 diameter of the elastomer can be determined by observing the molded body obtained by removing the elastomer by the same method as the method for determining the "surface presence of the elastomer" by SEM. Specifically, the void portion of the formed body is a region where an elastomer is present, and the diameter of each void is measured. The diameter of a total of 100 pores was measured, and the average value was defined as the particle diameter of the elastomer.

From the viewpoint of adhesiveness with polycarbonate, the surface area of the vibration-controlling layer constituting the laminated sheet of the present invention is preferably large. Here, a larger surface area means a larger "surface area / area of an arbitrary designated area". From the viewpoint of adhesiveness with polycarbonate, the "surface area / area of an arbitrary designated area" is preferably 1 or more, more preferably 2 or more, still more preferably 5 or more, and still more preferably 8 or more. On the one hand, from the viewpoint of stability of the sheet shape, it is preferably 100 or less, and more preferably 50 or less. The "surface area / area of an arbitrary designated area" can be measured using a three-dimensional image obtained using a confocal laser microscope.

＜ Resin composition ＞
Next, the resin component which comprises each layer is demonstrated concretely.
[Polycarbonate]
In the present invention, as long as the polycarbonate used in the polycarbonate layer has a structure including a carbonate bond in the main chain of the molecule, it is-(OR-OCO)-(here, R is an aliphatic group, an aromatic group There is no particular limitation on those containing both an aliphatic group and an aromatic group and having a linear structure or a branched structure) as the unit structure. By using such a sheet-shaped molded article of a polycarbonate resin composition containing polycarbonate, a laminated sheet having independence without requiring a metal plate for maintaining the shape can be obtained.

From the standpoint of adhesiveness with the vibration-controlling layer, a polycarbonate copolymerized with a specific monomer is more preferred.

The melt flow rate (MFR) of the polycarbonate used as the polycarbonate layer is preferably 0.1 g / 300 under conditions of 300 ° C and 1.2 kgf from the viewpoints of extrusion molding and characteristics of an extruder. 10 minutes or more, more preferably 0.5 g / 10 minutes or more, more preferably 1.0 g / 10 minutes or more, and from the viewpoint of hot press formability, 20 g / 10 minutes or less is more preferable, and 15 g is more preferable. / 10 minutes or less, more preferably 8.0 g / 10 minutes or less. The MFR value of polycarbonate is specifically measured by the method described in the following examples.

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

When the polycarbonate layer has a plurality of layers, the composition of the resin composition constituting them may be the same or different. For example, the composition of the resin composition constituting the polycarbonate layer 2 shown in FIG. 2B and the composition of the resin composition constituting the polycarbonate layer 3 may be the same or different, respectively.

[Polyester resin composition]
The polyester resin composition used for the vibrating layer in the present invention contains a thermoplastic polyester resin (A) composed of a dicarboxylic acid component and a diol component, a component (B) as a plasticizer and / or an elastomer, and Inorganic filler (C). In the present invention, when the vibration-controlling layer has a plurality of layers, the composition of the polyester resin composition constituting each vibration-controlling layer may be the same or different.

When an inorganic filler is generally added to a resin, the elastic modulus of the entire resin composition is increased, and on the other hand, the loss coefficient is reduced. The reason for the decrease in the loss coefficient is that the resin ratio in the resin composition is reduced by adding a filler, and therefore the amount of energy loss in the resin portion is reduced. Therefore, in the present invention, by adding a plasticizer and / or an elastomer to the system, flexibility is imparted, and energy loss is easily caused, thereby increasing the loss coefficient and increasing the elastic modulus of the resin composition while suppressing it. Reduction of loss factor. Furthermore, it is estimated that in the polyester resin composition used in the present invention, friction occurs at the interface between the resin or plasticizer and / or elastomer and the inorganic filler, which causes energy loss and further suppresses a reduction in loss coefficient.

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 value does not change depending on the type of the thermoplastic polyester resin (A) used, but from the viewpoint of increasing the loss coefficient, as the lower limit value, for example, a polybutylene terephthalate resin is used as In the case of the thermoplastic polyester resin (A), it is preferably 70,000 or more, more preferably 80,000 or more, and even more preferably 100,000 or more. When using a polytrimethylene terephthalate resin as a thermoplastic polyester resin (A), it is preferable that it is 60,000 or more, and it is more preferable that it is 70,000 or more. When a polyethylene terephthalate resin is used as the thermoplastic polyester resin (A), it is preferably 30,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more. Furthermore, since the polyester resin composition in the present invention has the following absolute crystallinity, the lower limit varies depending on the value of the absolute crystallinity (Xc). If the absolute crystallinity 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 expressed, and examples thereof include 20,000 or more. When the absolute crystallinity exceeds 37%, the mass average molecular weight of the thermoplastic polyester resin (A) 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 following examples.

The lower limit of the absolute crystallinity (Xc) of the polyester resin composition in the present invention is preferably 5%. From the viewpoint of improving the loss coefficient, it is shown according to the type of the thermoplastic polyester resin (A) used. The following range. For example, when using a polybutylene terephthalate resin as the thermoplastic polyester resin (A), it is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, and even more preferably 25% or more, and preferably 35% or less, more preferably 30% or less, and still more preferably 28% or less. In the case where a polytrimethylene terephthalate resin is used as the thermoplastic polyester resin (A), it is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, and more preferably 35%. %the following. In the case where a polyethylene terephthalate resin is used as the thermoplastic polyester resin (A), it is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, and even more preferably 25. % Or more, and preferably 35% or less. Furthermore, since the thermoplastic polyester resin (A) in the present invention has the above-mentioned mass average molecular weight, the value of the absolute crystallinity varies depending on the value of the mass average molecular weight of the resin (A). Specifically, if the The mass average molecular weight of the resin (A) is 50,000 or more and 150,000 or less, and performance can be exhibited even when it exceeds 37%. For example, as an upper limit, 40% or less is preferred. 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 of a polyester resin composition means the ratio of the crystal part in a matrix resin, and can be measured according to the method described in the following Example.

The thermoplastic polyester resin (A) or the polyester resin composition in the present invention preferably has a mass average molecular weight or absolute crystallinity within the above range. As a combination thereof, the thermoplastic polyester resin (A) is a polymer pair. In the case of a butyl phthalate resin, the mass average molecular weight is preferably 70,000 to 150,000 and the absolute crystallinity is 25% to 35%, more preferably, the mass average molecular weight is 100,000 or more and 15 10,000 or less and absolute crystallinity of 25% or more and 35% or less. In the case where the thermoplastic polyester resin (A) is a polyethylene terephthalate resin, the mass average molecular weight is preferably 30,000 or more and 150,000 or less and the absolute crystallinity is 10% or more and 35% or less. The mass average molecular weight is preferably 40,000 or more and 150,000 or less and the absolute crystallinity is 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 a dicarboxylic acid component and a diol component. In addition, in this specification, a dicarboxylic acid component contains a dicarboxylic acid and its lower ester derivative, and these are collectively called a dicarboxylic acid component.

As the dicarboxylic acid component constituting the thermoplastic polyester resin (A), an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, an aromatic dicarboxylic acid, and a dicarboxylic acid having a furan ring can be used. Specifically, for example, those listed in paragraph 0014 of Japanese Patent Laid-Open No. 2016-89148, such as terephthalic acid, may be mentioned. A dicarboxylic acid component can be used individually or in combination of 2 or more types.

As a diol component constituting the thermoplastic polyester resin (A), an aliphatic diol, an alicyclic diol, an aromatic diol, and a diol having a furan ring can be used. Specific examples include those listed in paragraph 0015 of Japanese Patent Laid-Open No. 2016-89148, such as 1,4-butanediol. The diol component can be used alone or in combination of two or more.

Moreover, as a combination of a dicarboxylic acid component and a diol component, it is preferable that it is either a dicarboxylic acid or a diol from a viewpoint of improving the Tg of a thermoplastic polyester resin (A), and improving vibration control property and rigidity. One or both of them include an aromatic ring, an alicyclic ring, and a furan ring. Specifically, for example, those listed in paragraph 0016 of Japanese Patent Laid-Open No. 2016-89148 can be cited.

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

From the viewpoint of improving the formability, the glass transition temperature (Tg) of the obtained thermoplastic polyester resin (A) is preferably 20 ° C or higher, more preferably 25 ° C or higher, and further preferably 30 ° C or higher, and furthermore, It is preferably at least 35 ° C. From the viewpoint of improving the vibration damping property, the temperature is preferably 160 ° C or lower, more preferably 150 ° C or lower, still more preferably 140 ° C or lower, and even more preferably 130 ° C or lower. In order to set the glass transition temperature to the above temperature, it is effective to control the skeleton structure of the polyester resin. For example, if a thermoplastic polyester resin is prepared using a rigid component such as an aromatic dicarboxylic acid component or an alicyclic diol component as a raw material, the glass transition temperature can be increased. In addition, in this specification, the glass transition temperature of a resin can be measured according to the method described in the following Example.

From the viewpoint of vibration damping properties, the thermoplastic polyester resin (A) in the present invention preferably has crystallinity. Examples of the method for producing a thermoplastic polyester resin having crystallinity include a method using a dicarboxylic acid component and a diol component having a high purity, and a method using a dicarboxylic acid component and a diol component having a small number of side chains. In the present specification, the term "having crystallinity" refers to a resin that is heated from 25 ° C to 300 ° C at a temperature increase rate of 20 ° C / min in accordance with JIS K 7122 (1999), and is maintained in this state for 5 After 15 minutes, cooling was performed at -20 ° C / min so that the temperature became 25 ° C or lower. At this time, an exothermic peak accompanied by crystallization was 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 uses a crystallization enthalpy ΔHmc of preferably 5 J / g or more, more preferably 10 J / g or more, still more preferably 15 J / g or more, and still more preferably 30 J / g of resin. In addition, in this specification, the crystallization enthalpy of a resin can be measured according to the method described in the following Example.

Specific examples of the thermoplastic polyester resin (A) include, for example, those listed in paragraph 0020 of Japanese Patent Laid-Open No. 2016-89148. From the viewpoint of vibration damping properties, terephthalic acid and Polybutylene terephthalate (PBT resin, Tg: 50 ° C) composed of 1,4-butanediol. The thermoplastic polyester resin (A) can be used alone or in combination of two or more.

From the viewpoint of improving the loss coefficient, the content of the thermoplastic polyester resin (A) in the polyester resin composition 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 rigidity, it is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and still more preferably 70% by mass or less.

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, and even more preferably 70,000 or more, from the viewpoint of improving vibration damping properties. From the viewpoint of improving the formability, it is preferably 300,000 or less, more preferably 200,000 or less, and still more preferably 150,000 or less. The mass average molecular weight of the thermoplastic polyester resin (A) is specifically measured by the method described in the following examples.

[As a plasticizer and / or an elastomer component (B)]
As the component (B) in the present invention, one kind or two or more kinds selected from the group consisting of a plasticizer and an elastomer are used. In addition, in this specification, a plasticizer and / or an elastomer may be collectively described as a component (B).

(Plasticizer)
As the plasticizer in the present invention, it is preferable to include a group selected from the group consisting of a polyester plasticizer, a polyol ester plasticizer, a polycarboxylic acid ester plasticizer, and a bisphenol plasticizer. One or more of them.

From the viewpoint of suppressing changes in the physical properties of the laminated sheet during the manufacturing process, a low-volatile plasticizer is preferred as the plasticizer. Specifically, a 5% plasticizer having a mass reduction temperature of 200 ° C or higher is preferred, a plasticizer of 220 ° C or higher is more preferred, a plasticizer of 240 ° C or higher is further preferred, and 260 ° C is further preferred. The above plasticizers. Here, the measurement of the 5% mass reduction temperature of the plasticizer is performed under the condition that the temperature is increased at 10 ° C./min in an air atmosphere. Furthermore, the weight retention rate of the plasticizer when isothermal holding is performed at 260 ° C for 5 minutes in an air atmosphere is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. On the other hand, From the viewpoint of improving the loss coefficient, it is preferably 100% or less, and more preferably 98% or less.

Specific examples of the polyester-based plasticizer include those listed in paragraph 0024 of Japanese Patent Application Laid-Open No. 2016-89148. Preferred examples include mixed diesters of adipic acid and diethylene glycol monomethyl ether / benzyl alcohol.

Specific examples of the polyhydric alcohol ester plasticizer include those listed in paragraph 0025 of Japanese Patent Laid-Open No. 2016-89148.

Examples of the polycarboxylic acid ester-based plasticizer include those listed in paragraph 0026 of Japanese Patent Application Laid-Open No. 2016-89148.

Examples of the bisphenol-based plasticizer include those listed in paragraph 0027 of Japanese Patent Application Laid-Open No. 2016-89148.

As a plasticizer, from the viewpoint of improving the loss coefficient, it is preferable to include a polyester-based plasticizer or a polyol ester system selected from the group consisting of a (poly) oxyalkylene group or an alkylene group having 2 to 10 carbon atoms. One or two or more of a group consisting of a plasticizer, a polycarboxylic acid-based plasticizer, and a bisphenol-based plasticizer, more preferably a polyester selected from the group consisting of a polyester having a (poly) oxyalkylene group One or two or more of the group consisting of a plasticizer, a polyol ester plasticizer, a polycarboxylic acid ester plasticizer, and a bisphenol plasticizer. Furthermore, (poly) oxyalkylene means oxyalkylene or polyoxyalkylene. As the oxyalkylene group, those having a carbon number of 2 to 10, more preferably a carbon number of 2 to 6, and even more preferably 2 to 4 are further preferred, and oxyalkylene and oxypropylene are further preferred. Or oxybutyl, more preferably oxyethyl or oxypropyl.

As a plasticizer, from the viewpoint of improving the loss coefficient, it is preferable to include one or two or more selected from the group consisting of the following compound groups (A) to (C), and it is more preferable to include One or two or more selected from the group consisting of the following compound groups (A) and (B). When two or more types are used in combination, they may be the same compound group or different compound groups.
Compound group (A) is an ester compound having two or more ester groups in the molecule, and at least one of the alcohol components constituting the ester compound is an average carbon number of 0.5 to 5 moles for each hydroxyl group. 2 to Alcohol compound group (B) of alkylene oxide of 3 Compound represented by formula (I):
R ¹ O-CO-R ² -CO-[(OR ³ ) _m O-CO-R ² -CO-] _n OR ¹ (I)
(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² represents an alkylene group having 2 to 4 carbon atoms, R ³ represents an alkylene group having 2 to 6 carbon atoms, and m represents 1 to 6 Number, n is a number from 1 to 12, where all R ² may be the same or different, and all R ³ may be the same or different)
Compound group (C) is an ester compound having two or more ester groups in the molecule, and the alcohol component constituting the ester compound is a monoalcohol

Compound group (A)
As the ester compound contained in the compound group (A), an ester compound is preferred, which is a polyhydric alcohol ester or polycarboxylic acid ether ester having two or more ester groups in the molecule, and at least the alcohol component constituting the ester compound One is an alcohol having an alkylene oxide of 2 to 3 carbon atoms with an average of 0.5 to 5 moles added to each hydroxyl group.

As specific compounds, preferred are esters of acetic acid and glycerol ethylene oxide with an average of 3 to 6 moles (1 to 2 moles of ethylene oxide added to each hydroxyl group), acetic acid and epoxy Polyethylene glycol esters with an average addition mole number of 4 to 6 for ethane, and polyethylene glycol monomethyl ether with an average addition mole number of 2 to 3 for succinic acid and ethylene oxide (for each The average addition mole number of the esters of each hydroxyl group to ethylene oxide is 2 to 3 moles, the ester of adipic acid and diethylene glycol monomethyl ether, and the terephthalic acid and ethylene oxide are 2 to Polyethylene glycol monomethyl ether of 3 (addition of 2 to 3 moles of ethylene oxide per hydroxyl group), ester of 1,3,6-hexanetricarboxylic acid and diethylene glycol monomethyl ether .

Compound group (B)
R ¹ in the formula (I) represents an alkyl group having 1 to 4 carbon atoms, two of which are present in one molecule and are present at both ends of the molecule. As long as R ^{1 has a} carbon number of 1 to 4, it may be linear or branched. The carbon number of the alkyl group is preferably from 1 to 4 and more preferably from 1 to 2 from the viewpoints of color resistance and plasticizing effect. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, and isobutyl. Among them, it is preferable from the viewpoint of improving the loss coefficient. Methyl and ethyl, more preferably methyl.

R ² in formula (I) represents an alkylene group having 2 to 4 carbon atoms. As a preferred example, a linear alkylene group can be mentioned. Specific examples include ethylene, 1,3-propyl, and 1,4-butyl. From the viewpoint of improving the loss coefficient, ethylene, 1,3-propyl, 1,4-Butyl, more preferably ethyl. However, all of R ² 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 exists in the form of an oxygen alkylene group in a repeating unit. As long as R ^{3 has a} carbon number of 2 to 6, it may be linear or branched. From the viewpoint of increasing the loss coefficient, the number of carbons of the alkylene group is preferably from 2 to 6, and more preferably from 2 to 3. Specific examples include ethylene, 1,2-butylene, 1,3-butylene, 1,2-butylene, 1,3-butylene, and 1,4-butylene , 2-methyl-1,3-propanyl, 1,2-pentyl, 1,4-pentyl, 1,5-pentyl, 2,2-dimethyl-1,3- Hexyl, 1,2-hexyl, 1,5-hexyl, 1,6-hexyl, 2,5-hexyl, 3-methyl-1,5-hexyl, among these, preferred is Ethyl, 1,2-propyl, 1,3-propyl. However, all of R ³ may be the same or different.

m represents an average repeating number of oxyalkylene groups. From the viewpoint of heat resistance, a number of 1 to 6 is preferable, a number of 1 to 4 is more preferable, and a number of 1 to 3 is more preferable.

n represents the average repeating number (average degree of polymerization) of the repeating unit, and is a number from 1 to 12. From the viewpoint of increasing the loss coefficient as the vibration-damping material, the number is preferably from 1 to 12, more preferably from 1 to 6, and even more preferably from 1 to 5. The average degree of polymerization can also be obtained by analysis such as NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance), and can be calculated according to the method described in paragraph 0100 of Japanese Patent Laid-Open No. 2016-89148.

As specific examples of the compound represented by formula (I), it is preferred that all of R ¹ is methyl, R ² is ethyl or 1,4-butyl, and R ³ is ethyl or 1,3- Compounds in which propyl is the number of 1-4 and n is the number of 1-6, more preferably R ^{1 is} all methyl, R ² is ethyl or 1,4-butyl, and R ³ is Ethyl or 1,3-propylene, m is a number from 1 to 3, and n is a number from 1 to 5.

The compound represented by formula (I) is not particularly limited as long as it has the above-mentioned structure, and it is preferably obtained by reacting the following raw materials (1) to (3). Furthermore, (1) and (2) or (2) and (3) may form an ester compound. (2) It may also be an acid anhydride or a hafnium halide.
(1) Alkyl monohydric alcohol having 1 to 4 carbon atoms
(2) Dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms
(3) Glycols with 2-6 alkylene groups

(1) Monohydric alcohol having an alkyl group having 1 to 4 carbons As the monohydric alcohol having an alkyl group having 1 to 4 carbons, an alcohol containing R ¹ described above, specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, third butanol. Among these, from the viewpoint of improving the loss coefficient, methanol, ethanol, 1-propanol, and 1-butanol are preferable, methanol, ethanol, and methanol are more preferable.

(2) A dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms As a dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms, it is a dicarboxylic acid containing R ² described above, and specifically, may be Examples: Succinic acid, glutaric acid, adipic acid, and derivatives thereof, such as succinic anhydride, glutaric anhydride, dimethyl succinate, dibutyl succinate, dimethyl glutarate, adipic acid Dimethyl Etc. Among them, from the viewpoint of improving the loss coefficient, succinic acid, adipic acid, and derivatives thereof such as succinic anhydride, dimethyl succinate, dibutyl succinate, and dimethyl adipate are preferred, More preferred are succinic acid and its derivatives, such as succinic anhydride, dimethyl succinate, and dibutyl succinate.

(3) A diol having an alkylene group having 2 to 6 carbons As a diol having an alkylene group having 2 to 6 carbons, it is a diol containing R ³ described above, and specifically, may be Examples: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethylamine 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1, 5-pentanediol, 2,5-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol. Among these, from the viewpoint of improving the loss coefficient, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, tetraethylene glycol, 1,4-butanediol, and the like are more preferable. Diethylene glycol, triethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol are preferred, and diethylene glycol, triethylene glycol, and 1,3-propylene glycol are more preferred.

Therefore, as (1) to (3) above,
Preferably, (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 selected from the group consisting of succinic acid, One or more of a group consisting of adipic acid, glutaric acid, and derivatives thereof. (3) The diol is selected from the group consisting of diethylene glycol, triethylene glycol, 1,2- One or more of propylene glycol, 1,3-propylene glycol, tetraethylene glycol, and 1,4-butanediol;
More preferably, (1) the monohydric alcohol is one or more selected from the group consisting of methanol and ethanol, and (2) the dicarboxylic acid is selected from the group consisting of derivatives of succinic acid, adipic acid, and the like One or two or more of the group consisting of (3) a diol is one selected from the group consisting of diethylene glycol, triethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol One or more than two;
Further preferably, (1) the monohydric alcohol is methanol, (2) the dicarboxylic acid is one or two or more selected from the group consisting of succinic acid and its derivatives, and (3) the glycol is selected from the group consisting of One or two or more of the group consisting of ethylene glycol, triethylene glycol, and 1,3-propanediol.

The method for obtaining the ester compound represented by formula (I) by reacting the above (1) to (3) is not particularly limited, and examples thereof include the following methods 1 and 2.
Aspect 1: including a step of synthesizing dicarboxylic acid ester by (2) dicarboxylic acid and (1) monohydric alcohol, and esterifying the obtained dicarboxylic acid ester with (3) dihydric alcohol Method aspect 2 of the reaction method: A method including the step of reacting (1) a monohydric alcohol, (2) a dicarboxylic acid, and (3) a dihydric alcohol together

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

With regard to the compound represented by formula (I), the acid value is preferably 1.50 mgKOH / g or less, more preferably 1.00 mgKOH / g or less, from the viewpoint of increasing the loss coefficient, and the hydroxyl value from the viewpoint of increasing the loss coefficient. It is preferably 10.0 mgKOH / g or less, more preferably 5.0 mgKOH / g or less, and still more preferably 3.0 mgKOH / g or less. In addition, in this specification, the acid value and the hydroxyl value of a plasticizer can be measured according to the method described in the paragraph 0099 of Unexamined-Japanese-Patent No. 2016-89148.

From the viewpoint of improving the loss coefficient and the viewpoint of coloring resistance, the number average molecular weight of the compound represented by the formula (I) is preferably 300 to 1500, and more preferably 300 to 1,000. In this specification, the number average molecular weight of the plasticizer can be calculated according to the method described in paragraph 0100 of Japanese Patent Laid-Open No. 2016-89148.

From the viewpoint of improving the loss coefficient, the saponification value of the compound represented by formula (I) is preferably 500 to 800 mgKOH / g, and more preferably 550 to 750 mgKOH / g. In addition, in this specification, the saponification value of a plasticizer can be measured according to the method described in the paragraph 0099 of Japanese Patent Laid-Open No. 2016-89148.

With respect to the compound represented by formula (I), from the viewpoint of improving the loss coefficient, the alkyl esterification rate (terminal alkyl esterification rate) of the two molecular ends is preferably 95% or more, and more preferably 98%. the above. In this specification, the terminal alkyl esterification rate of the plasticizer can be calculated according to the method described in paragraph 0100 of Japanese Patent Laid-Open No. 2016-89148.

From the viewpoint of shortening the vibration time, the ether value of the compound represented by formula (I) is preferably 0 to 8 mmol / g, and more preferably 0 to 6 mmol / g. In this specification, the ether value of the plasticizer can be calculated according to the method described in paragraph 0100 of Japanese Patent Laid-Open No. 2016-89148.

Compound group (C)
As the ester compound included in the compound group (C), specifically, an ester of adipic acid and 2-ethylhexanol (DOA), and an ester of phthalic acid and 2-ethylhexanol (DOP) are preferable. ).

Among the plasticizers, one or two selected from the group consisting of a polyester plasticizer, a polyol ester plasticizer, a polycarboxylic acid ester plasticizer, and a bisphenol plasticizer. The above content is preferably selected from polyester-based plasticizers having (poly) oxyalkylene groups or alkylene groups having 2 to 10 carbon atoms, polyol ester-based plasticizers, and polycarboxylic acid ester-based plasticizers. The content of one or two or more of the group consisting of an agent and a bisphenol-based plasticizer is more preferably selected from a polyester-based plasticizer having a (poly) oxyalkylene group, and a polyol ester-based plastic. The content of one or two or more of a group consisting of a plasticizer, a polycarboxylic acid plasticizer, and a bisphenol plasticizer, and selected from the group consisting of the compound group (A) to (C) From the viewpoint of increasing the loss coefficient, the content of one or two or more compounds in the group is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. It is preferably 95% by mass or more, more preferably substantially 100% by mass, and still more preferably 100% by mass. Here, substantially 100% by mass refers to a state in which trace amounts of impurities and the like are inevitably contained. In addition, in this specification, content of the said plasticizer means the total content when it contains a several compound.

From the viewpoint of increasing the loss coefficient, the content of the plasticizer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass based on 100 parts by mass of the thermoplastic polyester resin (A). The above is more preferably 10 parts by mass or more, and from the viewpoint of suppressing the decrease in rigidity, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less, and even more preferably 25 parts by mass Mass parts or less.

From the viewpoint of increasing the loss coefficient, the content of the plasticizer in the polyester resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more to suppress rigidity. From the viewpoint of reduction, 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, from the viewpoint of improving vibration damping properties in a high temperature region and a low temperature region, one kind or two or more kinds of elastomers may be used. As the elastomer in the present invention, a thermoplastic elastomer is preferred.

From the viewpoint of increasing the loss coefficient in the low temperature region, the content of the elastomer is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, and more preferably 100 parts by mass of the thermoplastic polyester resin (A). 15 parts by mass or more. From the viewpoint of suppressing a decrease in rigidity, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 35 parts by mass or less.

From the viewpoint of improving the loss coefficient, 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 further preferably 9.5% by mass or more. From a viewpoint, it is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.

In the present invention, as the component (B), a plasticizer and an elastomer may be used in combination, and a single or two or more plasticizers may be used in combination with a single or two or more elastomers. By using a plasticizer and an elastomer together, the loss coefficient in the room temperature region is further increased, and the loss coefficient is also increased in a wide temperature region such as a low temperature region or a high temperature region, which is preferable.

From the viewpoint of increasing the loss coefficient, 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, based on 100 parts by mass of the thermoplastic polyester resin (A). It is more preferably 25 parts by mass or more. From the viewpoint of suppressing a decrease in rigidity, it is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 40 parts by mass or less.

From the viewpoint of improving the loss coefficient in a wide temperature range, the mass ratio of the plasticizer to the elastomer (plasticizer / elastomer) is preferably 10/90 to 90/10, more preferably It is 30/70 ~ 70/30.

(Thermoplastic elastomer)
By using a thermoplastic elastomer as the elastomer, the effect of improving the damping properties in a high temperature region and a low temperature region is exhibited, so it is preferable. Furthermore, by using it in combination with a plasticizer, it is possible to further improve the vibration damping performance in a wide temperature range in a high temperature region and a low temperature region.

Regarding the thermoplastic elastomer, the glass transition temperature Tg is preferably -40 ° C or higher, and more preferably 20 ° C or lower, from the viewpoint of improving vibration damping properties in a high temperature region and a low temperature region. The glass transition temperature of the thermoplastic elastomer can be measured according to the method described in the following examples.

The thermoplastic elastomer in the present invention is preferably selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, and a urethane-based thermoplastic elastomer. At least one of a thermoplastic elastomer, a nitrile-based thermoplastic elastomer, a fluoro-based thermoplastic elastomer, a polybutadiene-based thermoplastic elastomer, and a silicone-based thermoplastic elastomer. Examples of the styrene-based thermoplastic elastomer include polystyrene- Ethylene-polyisoprene-polystyrene block copolymers or copolymers of styrene and butadiene and their hydrides, such as "HYBRAR" manufactured by Kuraray Plastics, and "Tuftec" manufactured by Asahi Kasei Corporation "SOE" (registered trademark), "Septon" (registered trademark) manufactured by Kuraray Co., Ltd., and "Rabalon" (registered trademark) manufactured by Mitsubishi Chemical Corporation. Examples of the olefin-based thermoplastic elastomer include finely dispersing an olefin-based rubber (EPR (Ethylene Propylene Rubber, ethylene-propylene rubber), EPDM (Ethylene Propylene Diene Monomer, ethylene-propylene-diene (M-based) rubber)) in an olefin. Based on resins (polyethylene, polypropylene, etc.), such as "Thermorun" (registered trademark) manufactured by Mitsubishi Chemical Corporation, and "Espolex" (registered trademark) manufactured by Sumitomo Chemical Co., Ltd. Examples of the polyester-based thermoplastic elastomer include a copolymer of polybutylene terephthalate and polyether, and examples thereof include "Hytrel" (registered trademark) manufactured by Dupont-Toray Co., Ltd. and the like. Examples of the polyamide-based thermoplastic elastomer include those obtained by subjecting a block copolymer of nylon to a polyester or a polyol, or lactam, or a dicarboxylic acid polyether glycol ester to a transesterification and polycondensation reaction. Examples of the urethane-based thermoplastic elastomer include "TPU" manufactured by Nippon Polyurethane Industry Co., Ltd. Examples of the nitrile thermoplastic elastomer include those obtained by emulsion polymerization of acrylonitrile and butadiene. Examples of the fluorine-based thermoplastic elastomer include a copolymer of vinylidene fluoride and hexafluoropropylene, and a copolymer of vinylidene fluoride and hexafluoropropylene and tetrafluoroethylene. For example, "Erafutoru" manufactured by Showa Polymer Co., Ltd. "(Registered trademark)," Viton "(registered trademark) series made by Dupont, etc. Examples of the polybutadiene-based and polysiloxane-based thermoplastic elastomers include an organic silicon polymer bond having a siloxane bond as a skeleton and directly bonding an organic group to a silicon atom thereof. For example, Shin- KBM series made by Etsu Silicones, etc. As the thermoplastic elastomer, a styrene-based thermoplastic elastomer is preferred from the viewpoint of improving vibration damping properties in a high temperature region and a low temperature region.

(Styrenic thermoplastic elastomer)
The styrene-based thermoplastic elastomer (hereinafter sometimes referred to as a styrene-based elastomer) in the present invention includes a block A obtained by polymerizing a styrene compound constituting a hard segment, and a conjugated diene constituting a soft segment. Polymerized block B. Examples of the styrene-based compound used in the polymer block A include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and 1,3- Styrene compounds such as dimethylstyrene; polycyclic aromatic compounds with vinyl groups such as vinyl naphthalene and vinyl anthracene. Among these, polymers of styrene compounds are preferred, and styrene compounds are more preferred. polymer. Examples of the conjugated diene used in the polymer block B include butadiene, isoprene, butene, ethylene, 1,3-pentadiene, 2,3-dimethyl-1, 3-butadiene and the like are preferably polyisoprene, polybutadiene, and a copolymer of isoprene and butadiene, selected from 1 of the conjugated diene monomers. One or two or more block copolymers. The block B may be copolymerized with a styrene-based compound used in the polymer block A described above. In the case of each copolymer, as the form, any form of a random copolymer, a block copolymer, and a tapered copolymer can be selected. Moreover, it may be a hydrogenated structure.

Specific examples of such styrene-based elastomers include polystyrene-isoprene block copolymer (SIS), polystyrene-polybutadiene copolymer (SEBS), and polystyrene. -Hydrogenated polybutadiene copolymer (SEBS), polystyrene-hydrogenated polyisoprene-polystyrene block copolymer (SEPS), polystyrene-ethylene-polyisoprene-polystyrene Block copolymer (SHIVS), polystyrene-hydrogenated polybutadiene-hydrogenated polyisoprene-polystyrene block copolymer, polystyrene-hydrogenated polybutadiene-polyisoprene-polybenzene Ethylene block copolymers and the like. These can be used alone or in combination of two or more. In the present invention, a polystyrene-ethylene-polyisoprene-polystyrene block copolymer is preferably used. As a commercially available product of such a block copolymer, "Kuraray Plastics" HYBRAR "series.

From the viewpoint of improving the damping properties in the high temperature region and the low temperature region, the styrene content in the styrene-based elastomer is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 30% by mass Below, it is more preferably 25% by mass or less. In this specification, the high temperature region means 35 to 80 ° C, and the low temperature region means -20 to 10 ° C. The styrene content in the styrene-based elastomer can be measured according to the method described in the following examples.

The styrene-based elastomer is preferably a styrene-isoprene block copolymer and / or a styrene-butadiene block copolymer.

(Styrene / isoprene block copolymer)
The styrene-isoprene block copolymer in the present invention has at least one block having a polystyrene block at both ends and a polyisoprene block or an ethylene-polyisoprene block therebetween. Block copolymer. The isoprene block or the butadiene block may be copolymerized or may have a hydrogenated structure.

Specific examples of such a styrene-isoprene block copolymer include polystyrene-isoprene block copolymer (SIS), polystyrene-hydrogenated polyisoprene- Polystyrene block copolymer (SEPS), polystyrene-ethylene-polyisoprene-polystyrene block copolymer (SHIVS), polystyrene-hydrogenated polybutadiene-hydrogenated polyisoprene -A polystyrene block copolymer, a polystyrene-hydrogenated polybutadiene-polyisoprene-polystyrene block copolymer, and the like. These can be used alone or in combination of two or more. In the present invention, a polystyrene-ethylene-polyisoprene-polystyrene block copolymer is preferably used. As a commercially available product of such a block copolymer, "Kuraray Plastics" HYBRAR "series.

(Styrene / butadiene block copolymer)
The styrene-butadiene block copolymer in the present invention is a block copolymer having polystyrene blocks at both ends and a polybutadiene block or a hydrogenated product thereof between them. The isoprene block or the 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-hydrogenated polybutadiene copolymer (SBS), etc. These can be used alone or in combination of two or more. In the present invention, a polystyrene-hydrogenated polybutadiene copolymer (SEBS) is preferably used. As a commercially available product of such a block copolymer, "S.O.E" manufactured by Asahi Kasei Co., Ltd. is mentioned.

From the viewpoint of adhesion to polycarbonate, an elastomer having fewer unsaturated bonds or having no unsaturated bonds is preferred. From this viewpoint, as the preferable elastomer, among the above-mentioned various elastomers, hydrogenated ones can be mentioned.
Furthermore, from the viewpoint of adhesiveness with polycarbonate, an elastomer that is less susceptible to oxidative degradation or oxidative degradation is not preferred. From this viewpoint, as the preferable elastomer, among the above-mentioned various elastomers, hydrogenated ones can be mentioned.
Furthermore, from the viewpoint of adhesiveness with polycarbonate, it is preferable to use a polystyrene-hydrogenated polybutadiene copolymer (SEBS).

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

The plate-shaped filler means 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 of elasticity, and / or increasing the loss coefficient, the length of the plate-like filler (the length of the longest side in the largest surface) is preferably 1.0 μm Above, more preferably 5 μm or more, still more preferably 10 μm or more, still more preferably 20 μm or more, and more preferably 150 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, and more preferably It is preferably 40 μm or less, and further preferably 30 μm or less. The thickness is not particularly limited. From the same viewpoint, it is 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, and preferably 5 μm or less. , More preferably 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. In addition, 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 still more preferably 120 or less, and more preferably 100 or less. It is more preferably 90 or less, and still more preferably 80 or less. Specific examples of the plate-shaped filler include those listed in paragraph 0064 of Japanese Patent Application Laid-Open No. 2016-89148, such as mica. The side length and thickness of the plate-shaped filler can be determined by observing 100 randomly selected fillers with an optical microscope and calculating the average value of the numbers.

The granular fillers are not only those with a true spherical shape, but also those with a certain degree of ellipse or approximately ellipse in the cross section, and have an aspect ratio (longest diameter of the granular body / shortest diameter of the granular body) Those above and less than two are preferably close to one. From the viewpoint of obtaining good dispersibility in the polyester resin composition, improving the flexural modulus of elasticity, and / or increasing the loss coefficient, the average particle diameter of the granular filler is preferably 1.0 μm or more, and more preferably 5 μm Above, still more preferably 10 μm or more, still more preferably 20 μm or more, and more preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. Specific examples of the granular filler include those listed in paragraph 0065 of Japanese Patent Laid-Open No. 2016-89148. The diameter of the granular filler can be determined by cutting 100 randomly selected fillers, observing the cross section with an optical microscope, and calculating the average value of the numbers.

The acicular fillers are those having an aspect ratio (particle length / particle diameter) of 2 or more and less than 20. The length (particle length) of the acicular filler is preferably 1.0 μm or more from the viewpoints of obtaining good dispersibility in the polyester resin composition, improving the flexural modulus of elasticity, and / or increasing the loss coefficient. 5 μm or more, further preferably 10 μm or more, further preferably 20 μm or more, still more preferably 30 μm or more, and more preferably 150 μm or less, more preferably 100 μm or less, and still more preferably 80 μm or less , More preferably 60 μm or less. The particle diameter is not particularly limited. From the same viewpoint, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.5 μm or more, and preferably 20 μm or less, and more preferably 15 μm or less. And more preferably 10 μm or less. The aspect ratio of the acicular filler is preferably 5 or more from the same viewpoint, and more preferably 10 or less. Specific examples of the needle-shaped filler include those listed in paragraph 0066 of Japanese Patent Application Laid-Open No. 2016-89148. The particle length and particle diameter of the acicular filler can be determined by observing 100 randomly selected fillers with an optical microscope and calculating an average of the numbers. When the particle diameter has a short diameter and a long diameter, the long diameter is used for calculation.

The fibrous filler refers to an aspect ratio (average fiber length / average fiber diameter) exceeding 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 even more preferably 0.5 mm or more from the viewpoint of increasing the bending elastic modulus and increasing the loss coefficient. It is more preferably 1 mm or more, and 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. From the same viewpoint, it is preferably 1 μm or more, more preferably 3 μm or more, and preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm. the following. From the same viewpoint, the aspect ratio is preferably 200 or more, more preferably 250 or more, still more preferably 500 or more, still more preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 1,000 or less, and more preferably 800 or less. Specific examples of the fibrous filler include those listed in paragraph 0066 of Japanese Patent Application Laid-Open No. 2016-89148. The fiber length and fiber diameter of the fibrous filler can be determined by observing 100 randomly selected fillers with an optical microscope and calculating an average of the numbers. When the fiber diameter has a short diameter and a long diameter, the long diameter is used for calculation. In addition, the fiber diameter can be not only a circle with the same major and minor diameters, but also an oval (e.g. major / minor diameter = 4) or cocoon type (such as major / minor diameter) having a major and minor diameter different. = 2). On the other hand, when a resin composition is produced using a kneading machine such as a biaxial extruder, and the resin and the fibrous filler are melt-kneaded for this purpose, the fibrous filler is cut by the shear force in the kneading section. The average fiber length is shortened, but from the viewpoint of increasing the loss coefficient and improving the rigidity, the average fiber length of the fibrous filler in the resin is preferably 100 to 800 μm, more preferably 200 to 700 μm, and more It is preferably 300 ~ 600 μm.

The granular, plate-like, or needle-shaped filler may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or an amine silane or an epoxy silane. Coupling agents and the like are processed.

These fillers may be used singly or in combination of two or more kinds, and fillers having different shapes may be combined. Among them, from the viewpoint of increasing the flexural modulus of elasticity and suppressing the reduction of the loss coefficient, it is preferably one or two or more selected from the group consisting of a plate-shaped filler, a needle-shaped filler, and a fibrous filler. Preferably, it is one or two or more selected from the group consisting of a plate-shaped filler and a needle-shaped filler, and more preferably one or two or more of the plate-shaped filler. Specifically, mica, talc and glass fiber are preferably used, mica and talc are more preferably used, and mica is more preferably used. It is presumed that the plate-shaped filler is aligned in the injection molded body by the flow direction. Therefore, compared with other fillers, the tensile elastic modulus in the alignment direction or the bending elastic modulus in the direction perpendicular to the alignment direction is significantly improved. In addition, there are many interfaces that affect the friction generated when the formed body vibrates, and therefore, the reduction of the loss coefficient is further suppressed. From the viewpoint of suppressing a reduction in the loss coefficient, 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 even more preferably 90% by mass or more.

From the viewpoint of improving rigidity, the content of the inorganic filler (C) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and more preferably 20 parts by mass relative to 100 parts by mass of the thermoplastic polyester resin (A). It is more preferably 30 parts by mass or more. From the viewpoint of suppressing a reduction in the loss coefficient, it is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less. In addition, the content of the inorganic filler refers to the total mass of the inorganic filler used, and when it contains a plurality of compounds, it means the total content.

From the viewpoint of improving rigidity, the content of the inorganic filler in the polyester resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and even more preferably It is 20% by mass or more, and more preferably 23% by mass or more. From the viewpoint of suppressing a reduction in the loss coefficient, it is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.

In the present invention, the mass ratio of the component (B) to the inorganic filler (C) (component (B) / inorganic filler (C)) is preferably 10 in terms of increasing the elastic modulus and increasing the loss coefficient. / 90 to 60/40, more preferably 25/75 to 50/50, and even more preferably 40/60 to 47/53.

[Organic Crystal Nucleating Agent (D)]
In addition, the polyester resin composition in the present invention may contain an organic crystal nucleating agent from the viewpoints of increasing the crystallization speed of the polyester resin, improving the crystallinity of the polyester resin, and increasing the flexural modulus.

As the organic crystal nucleating agent, known organic crystal nucleating agents can be used, and organic carboxylic acid metal salts, organic sulfonates, carboxamides, phosphorus compound metal salts, rosin metal salts, and metal alkoxides can be used. Salts, and organic nitrogen compounds. Specifically, for example, those listed in paragraph 0074 of Japanese Patent Laid-Open No. 2016-89148 can be cited.

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

The polyester resin composition in the present invention may contain a lubricant, an inorganic crystal nucleating agent, a hydrolysis inhibitor, a flame retardant, an antioxidant, a hydrocarbon wax or an anionic interfacial activity within a range not impairing the effects of the present invention. Lubricants, UV absorbers, antistatic agents, anti-fog agents, light stabilizers, pigments, antifungal agents, antibacterial agents, foaming agents, etc. are used as other components other than the above. In the same manner, other polymer materials or other resin compositions may be contained within a range that does not inhibit the effects of the present invention.

The polyester resin composition in the present invention can be prepared without particular limitation as long as it contains a thermoplastic polyester resin (A), a component (B) as a plasticizer and / or an elastomer, and an inorganic filler (C). . For example, a well-known kneading machine such as a closed kneader, a uniaxial or biaxial extruder, an open-drum type kneader can be used to contain a thermoplastic polyester resin, a plasticizer and / or an elastomer, and an inorganic filler, Furthermore, if necessary, the raw materials of various additives are melt-kneaded and prepared. After the melt-kneading, the melt-kneaded material may be dried or cooled according to a known method. In addition, the raw materials may be uniformly mixed in advance using a Henschel mixer, a high-speed mixer, or the like, and then subjected to melt-kneading. Furthermore, in the case of melt-kneading, in order to promote the plasticity of the polyester resin, a supercritical gas may also be present for melt-mixing.

The melt-kneading temperature depends on the type of the thermoplastic polyester resin used, and cannot be set uniformly. From the viewpoint of improving the moldability and the prevention of deterioration of the polyester resin composition, it is preferably 220 ° C or higher, more preferably 225 ° C or higher, further preferably 230 ° C or higher, and further preferably 300 ° C or lower, more preferably 290 ° C or lower, still more preferably 280 ° C or lower, still more preferably 260 ° C or lower, and still more preferably 250 ° C Hereinafter, it is more preferably 240 ° C or lower. Melt-kneading time depends on the melt-kneading temperature and the type of kneading machine. It cannot be generalized, but it is preferably 15 to 900 seconds.

2. Manufacturing method of laminated sheet Next, the manufacturing method of the laminated sheet of this invention is demonstrated.
The laminated sheet of the present invention can be produced by a previously known method. For example, a method in which each layer is separately formed in advance and laminated or thermocompression-bonded, and a method in which other layers are formed by coating on the upper or lower surface of the previously formed layer, and each of them is co-extruded. The method of resin lamination. Hereinafter, as an example of the manufacturing method, a method in which each layer is separately formed in advance and each layer is stacked and then subjected to thermocompression bonding and pressing will be described more specifically.

＜ Production of polycarbonate layer ＞
The sheet-shaped molded body formed from the polycarbonate resin composition used as the polycarbonate layer can be obtained by a known method such as inflation molding, extrusion sheet molding, pressure molding, and casting molding. thickness.

＜ Manufacturing of vibration damping layer ＞
The melt-kneaded product of the polyester resin composition prepared as described above is supplied to, for example, a known extruder or an extruder to be stretched, whereby a vibration-controlling layer having a desired thickness can be produced.

＜ Conditions for thermocompression and pressurization ＞
The layers manufactured in the above manner are overlapped in a specific order. It is set in a press and pressed under the conditions of a pressure of 1 to 7 MPa, a temperature of 160 to 190 ° C, and a pressing time of 0.5 to 2.0 minutes, followed by cooling to normal temperature to obtain a specific laminated sheet. When a laminated sheet is produced by thermocompression bonding, the change in the thickness of the polycarbonate layer or the vibration-damping layer before and after the pressing is almost negligible.

Regarding the above embodiment, the present invention further discloses the following laminated sheet.

<1> A laminated sheet, which is formed by laminating a vibration damping layer and a polycarbonate, and the vibration damping layer exists on the surface and / or near the surface of the laminated sheet,
A sheet-shaped molded body of the vibration-controlling layer-based polyester resin composition containing a thermoplastic polyester resin (A) composed of a component including a dicarboxylic acid component and a diol component, and plasticized And / or an elastomer component (B) and an inorganic filler (C).

<2> The laminated sheet according to the above <1>, wherein the relative position (%) of the vibration damping layer from the upper surface of the laminated sheet is preferably within 40%, more preferably within 33%, and even more preferably 30 % Or less, further preferably 25% or less, further preferably 20% or less, still more preferably 15% or less, further preferably 10% or less, and preferably 0.05% or more, more preferably 0.25% or more It is further preferably 0.5% or more, further preferably 1.0% or more, still more preferably 5.0% or more, and still more preferably 10% or more.
<3> The laminated sheet according to the above <1> or <2>, wherein the ratio of the vibration-controlling layer in the laminated sheet is in volume fraction, preferably 1% or more, more preferably 5% or more, and further It is preferably 10% or more, more preferably 70% or less, more preferably 50% or less, still more preferably 34% or less, and still more 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.
The <5> laminated sheet as described in any one of said <1> to <4> whose inorganic filler (C) contains a plate-shaped 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>, in which at least one layer of the vibration damping layer is at a position ratio of 10 to 40%.
<8> The laminated sheet according to any one of <1> to <7>, wherein the thickness of each polycarbonate layer is preferably 0.05 mm or more, more preferably 0.10 mm or more, and even more preferably 0.15 mm. The above is more preferably 10 mm or less, more preferably 5.0 mm or less, and still more preferably 3.5 mm or less.
<9> The laminated sheet according to any one of the above <1> to <8>, wherein the thickness of each vibration-controlling layer is preferably 0.05 mm or more, more preferably 0.2 mm or more, and even more preferably 0.4 mm or more Moreover, it is preferably 10 mm or less, more preferably 5.0 mm or less, and still more preferably 1.0 mm or less.
<10> The laminated sheet according to any one of the above <1> to <9>, wherein the thickness of the entire laminated sheet is preferably 0.3 mm or more, more preferably 1.0 mm or more, and further preferably 1.5 mm or more It is further preferably 2.0 mm or more, further preferably 2.5 mm or more, and further preferably 30 mm or less, more preferably 10 mm or less, and still more preferably 5.0 mm or less.
<11> The laminated sheet according to any one of <1> to <10>, in which the total thickness of the polycarbonate layer is preferably 100 when the total thickness of the vibration-controlling layer is set to 100%. % Or more, more preferably 200% or more, further preferably 300% or more, and more preferably 2000% or less, and more preferably 1000% or less.
<12> The laminated sheet according to any one of the above <1> to <11>, wherein the thermoplastic polyester resin (A) is preferably polybutylene terephthalate; the plasticizer is preferably selected from the group consisting of Polyester plasticizer, polyol ester plasticizer, polycarboxylic acid ester plasticizer, and bisphenol plasticizer; more preferably, the elastomer is selected from the group consisting of polystyrene -Isoprene block copolymer (SIS), polystyrene-polybutadiene copolymer (SEBS), polystyrene-hydrogenated polybutadiene copolymer (SEBS), polystyrene-hydrogenated polyisoprene Diene-polystyrene block copolymer (SEPS), polystyrene-ethylene-polyisoprene-polystyrene block copolymer (SHIVS), polystyrene-hydrogenated polybutadiene-hydrogenated polyisoprene One or more styrene-based elastomers in the group consisting of a pentadiene-polystyrene block copolymer and a polystyrene-hydrogenated polybutadiene-polyisoprene-polystyrene block copolymer And the inorganic filler (C) is preferably a plate-shaped filler, more preferably mica and / or talc.

<13> The laminated sheet according to any one of the above <1> to <12>, wherein the content of the thermoplastic polyester resin (A) in the polyester resin composition is preferably 50% by mass or more, more preferably 55 mass% or more, further preferably 60 mass% or more, and more preferably 90 mass% or less, more preferably 80 mass% or less, still more preferably 75 mass% or less, and still more preferably 70 mass% or less; 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, and further preferably 25% by mass or less, more preferably 20% by mass or less, more preferably 15% by mass or less; 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 further preferably 9.5% by mass or more, In addition, the content is preferably 30% by mass or less, more preferably 25% by mass or less, and 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, and more 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 On, and preferably 40 mass% or less, more preferably 35 mass% or less, preferably 30 mass% or less.
<14> The laminated sheet according to any one of the above <1> to <13>, wherein the total content of the plasticizer and the elastomer when used in combination is preferably relative to 100 parts by mass of the thermoplastic polyester resin (A) It is 15 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more, and still more preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 40 parts by mass or less.
<15> The laminated sheet according to any one of <1> to <14>, in which the mass ratio (plasticizer / elastomer) of the plasticizer and the elastomer when used in combination is preferably 10/90 ~ 90/10, more preferably 30/70 ~ 70/30.
<16> The laminated sheet according to any one of <1> to <15>, wherein the mass ratio of the component (B) to the inorganic filler (C) (component (B) / inorganic filler (C)) It is preferably 10/90 to 60/40, more preferably 25/75 to 50/50, and even more preferably 40/60 to 47/53.
<17> The laminated sheet according to any one of the above <1> to <16>, wherein each layer in the laminated sheet is preferably selected from a polycarbonate layer (PC) / vibration layer (PBT) , PC / PBT / PC, PC / PBT / PC / PBT / PC, and PBT / PC / PBT.
<18> The laminated sheet according to any one of the above <1> to <17>, in which the loss coefficient is preferably 0.04 or more, more preferably 0.05 or more, still more preferably 0.06 or more, and still more preferably 0.07 or more .
<19> The laminated sheet according to any one of the above <1> to <18>, wherein the bending elastic modulus is preferably 2.7 or more, more preferably 2.8 or more, still more preferably 2.9 or more, and even more preferably 3.1 or more.
[Example]

The following examples illustrate the invention. In addition, this embodiment is merely an illustration of the present invention, and does not mean any limitation. Unless otherwise stated, parts in the examples are parts by mass. In addition, "normal pressure" means 101.3 kPa, and "normal temperature" means 25 ° C.

<Mass average molecular weight of thermoplastic polyester resin (A)>
0.6 mg of granule sample was completely dissolved in HFIP (1,1,1,3,3,3-Hexafluoro-2-propanol (1,1,1,3,3,3-hexafluoro-2-propanol) and light pure 2 g), and measured the molecular weight using a gel permeation chromatography (manufactured by TOSOH: EcoSEC HLC-8320GPC). The measurement conditions were performed at an eluent of HFIP / 0.5 mM sodium trifluoroacetate, a flow rate of 0.2 mL / min, and a measurement temperature of 40 ° C. As a standard polymer used to prepare a calibration curve, polystyrene (manufactured by Tosoh Co., Ltd.) was used. When a plurality of peaks or shoulders are confirmed, a single peak is used as the molecular weight distribution of the polyester resin.

<Absolute crystallinity (Xc) of polyester resin composition>
The XRD (MiniFlex II DESKTOP X-ray DIFFRACTOMETER) manufactured by a flat test piece (127 mm × 12.7 mm × 1.6 mm) obtained by press-forming a polyester resin composition was used to measure the X-ray incident angle 2θ. Diffraction light at 5 ° ~ 40 °, the absolute crystallinity is calculated according to the intensity of the wave peak and 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 formed body or elastomer of a polyester resin composition prepared in the same manner as described below was prepared. Next, using a DMA (dynamic mechanical analyzer) device (manufactured by SII Corporation, EXSTAR6000), the measurement frequency was set to 1 Hz, and the temperature was raised from -50 ° C to 250 ° C at a temperature increase rate of 2 ° C / min. The peak temperature of the lossy elastic modulus obtained is used as the glass transition point.

＜ Enthalpy of crystallization of thermoplastic polyester resin ＞
Approximately 7 mg of a thermoplastic polyester resin sample was weighed, and a DSC (differential scanning calorimeter) device (manufactured by PerkinElmer, DSC8500) was used. According to JIS K 7122 (1999), the temperature was increased at a rate of 20 ° C / min. The resin was heated from 25 ° C. to 300 ° C. and held in this state for 5 minutes, and then cooled at -20 ° C./min to 25 ° C. or less, and the crystallization enthalpy was calculated from the exothermic peak accompanying crystallization at this time.

<Styrene content of styrene elastomer>
The elastomer was dissolved in deuterochloroform, and the H-NMR spectrum of the sample solution was measured within an observation range of 15 ppm. In addition, a calibration curve was obtained in advance based on the peak areas and concentrations of styrene in the H-NMR spectra of three concentrations of polystyrene / deuterochloroform solution, and the calibration curve was used to calculate benzene based on the peak areas of styrene in the sample solution. Content of ethylene.

＜ MFR of polycarbonate ＞
Calculated in accordance with ASTM D1238 under the conditions of a test temperature of 300 ° C and a test load of 1.2 kgf.

Manufacturing example 1 and manufacturing example 3 (manufacturing of a sheet-shaped molded article of a polyester resin composition)
The raw materials of the polyester resin composition shown in Table 1 were melt-kneaded at 240 ° C. using a co-rotating twin-screw extruder (TEX-28V manufactured by Japan Steel Manufacturing Co., Ltd.) to perform wire cutting to obtain a resin. Composition of particles. Furthermore, the obtained pellets were dehumidified and dried at 110 ° C. for 3 hours, so that the moisture content was 500 ppm or less.

Then, the obtained pellets were supplied to a 50 mm uniaxial extruder, and melt-kneaded at 240 ° C, and the melt-kneaded product was formed into a sheet shape by a roll whose roll temperature was controlled to 90 ° C and a cooled roll. , A sheet having a width of 450 mm and a thickness of 0.5 mm is rolled up to form a sheet-shaped formed body of a polyester resin composition (referred to as "PBT sheet").

[Table 1]

The details of the raw materials in Table 1 are as follows.
[Thermoplastic polyester resin]
PBT (700FP): Polybutylene terephthalate resin, Duranex 700FP (manufactured by Polyplastics, unreinforced, 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 (manufactured by Daba Chemical Industry Co., Ltd.); 5% mass reduction temperature: 235 ° C
[Elastomer]
Styrene / isoprene block copolymer: HYBRAR 5127 (manufactured by Kuraray Plastics, glass transition temperature: 8 ° C, styrene content: 20% by mass)
Polystyrene-hydrogenated polybutadiene copolymer: SOE S1605 (manufactured by Asahi Kasei Corporation, glass transition temperature: 8 ° C, styrene content: 67% by mass)
[Inorganic filler]
Mica: A-21S (made by Yamaguchi Mica, the length of the longest side in the largest surface: 23 μm, the thickness of the largest surface: 0.33 μm, aspect ratio: 70)

Manufacturing example 2 (manufacturing of polycarbonate resin composition sheet)
On one side, pellets of a polycarbonate resin (manufactured by SABIC, trade name: LEXAN, MFR: 7 g / 10 minutes (300 ° C, 1.2 kgf)) were supplied to a die having a width of 500 mm and a film winding device mounted on the front end. A uniaxial extruder with a diameter of 50 mm was film-formed at a barrel temperature of 260 to 300 ° C to obtain a PC sheet with a thickness of 0.5 mm.

Manufacturing example 4 (manufacturing of polycarbonate resin composition sheet)
On one side, pellets of a polycarbonate resin (manufactured by SABIC, trade name: LEXAN, MFR: 7 g / 10 minutes (300 ° C, 1.2 kgf)) were supplied to a die having a width of 500 mm and a film winding device mounted on the front end. One side of the uniaxial extruder with a diameter of 50 mm was formed into a film at a cylinder temperature of 260 to 300 ° C to obtain a PC sheet with a thickness of 0.25 mm.

Example 1 (manufacturing of laminated sheet)
One PBT sheet manufactured in Manufacturing Example 1 and two PC sheets manufactured in Manufacturing Example 2 were prepared. Two PC sheets are layered on the surface area of one PBT sheet. Then, using a press set with a pressure heating temperature of 165 ° C, the three laminates were heated and compressed for one minute under a pressure of 0.2 to 3 MPa to integrate them, and then cooled and pressurized. Cool to room temperature. In this way, a laminated sheet having a thickness of 1.5 mm was produced.

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

Example 2 (manufacturing of laminated sheet)
One PBT sheet manufactured in Manufacturing Example 1 and eight PC sheets manufactured in Manufacturing Example 2 were prepared. One PC sheet was layered on the surface area of one PBT sheet, and seven PC sheets were layered on the surface area of the PBT sheet. Then, using a press set with a pressure heating temperature of 165 ° C, the 9 pieces of the laminate were heated and compressed under the condition of a pressure of 0.2 to 3 MPa for 2 minutes to integrate them, and then, the temperature was increased by cooling. Press and cool to room temperature. In this way, a laminated sheet having a thickness of 4.5 mm was manufactured.

The manufactured laminated sheet is a PC sheet as the polycarbonate layer 2 on the surface area of the PBT sheet as the vibration damping layer 1 and a polycarbonate layer 3 as the surface area on the lower surface of the vibration damping layer 1. The structure of the PC sheet has a cross-section equivalent to the cross-sectional view of FIG. 2B.

Example 3 (manufacturing of laminated sheet)
One PBT sheet manufactured in Manufacturing Example 1 and fourteen 0.25 mm thick PC sheets manufactured in Manufacturing Example 4 were prepared. One PC sheet was layered on the surface area of one PBT sheet, and 13 PC sheets were layered on the surface area below the PBT sheet. Then, using a press with a pressure heating temperature set to 165 ° C, the 15 pieces of the laminate were heated and compressed for 2 minutes under a pressure of 0.2 to 3 MPa to integrate them, and then, the temperature was increased by cooling. Press and cool to room temperature. In this way, a laminated sheet having a thickness of 4.0 mm was manufactured.

The manufactured laminated sheet is a PC sheet as the polycarbonate layer 2 on the surface area of the PBT sheet as the vibration damping layer 1 and a polycarbonate layer 3 as the surface area on the lower surface of the vibration damping layer 1. The structure of the PC sheet has a cross-section corresponding to the cross-sectional view of FIG. 4A.

Comparative example 1 (manufacturing of laminated sheet)
One PBT sheet manufactured in Manufacturing Example 1 and two PC sheets manufactured in Manufacturing Example 2 were prepared. A PC sheet is layered on the surface area above the PBT sheet, and a PC sheet is layered on the surface area below the PBT sheet. Next, using a press set with a pressure heating temperature of 165 ° C, the three laminates were heated and compressed for 1.5 minutes under a pressure of 0.2 to 3 MPa to integrate them, and then, the temperature was increased by cooling. Press and cool to room temperature. In this way, a laminated sheet having a thickness of 1.5 mm was manufactured.

The manufactured laminated sheet is a PC sheet as the polycarbonate layer 2 on the surface area of the PBT sheet as the vibration damping layer 1 and a polycarbonate layer 3 as the surface area on the lower surface of the vibration damping layer 1. The structure of the PC sheet has a cross-section equivalent to the cross-sectional view of FIG. 3A.

Comparative example 2 (manufacturing of laminated sheet)
One PBT sheet manufactured in Manufacturing Example 1 and eight PC sheets manufactured in Manufacturing Example 2 were prepared. Four PC sheets are layered on the surface area above one PBT sheet, and four PC sheets are layered on the surface area below the PBT sheet. Then, using a press set with a pressure heating temperature of 165 ° C, the 9 pieces of the laminate were heated and compressed under a pressure of 0.2 to 3 MPa for 1.5 minutes to integrate them, and then, cooled and applied. Press and cool to room temperature. In this way, a laminated sheet having a thickness of 4.5 mm was manufactured.

The manufactured laminated sheet is a PC sheet as the polycarbonate layer 2 on the surface area of the PBT sheet as the vibration damping layer 1 and a polycarbonate layer 3 as the surface area on the lower surface of the vibration damping layer 1. The structure of the PC sheet has a cross-section equivalent to the cross-sectional view of FIG. 3B.

Comparative Example 3 (manufacturing of a laminated sheet formed of only a vibration-damping layer)
Four PBT sheets produced in Production Example 1 were prepared. Four PBT sheets were laminated, and then a four-layer laminate was heated and compressed at a pressure of 0.2 to 3 MPa for 1.5 minutes using a press set with a pressure heating temperature of 225 ° C to integrate them. And then cooled to normal temperature by cooling and pressurizing. In this way, a laminated sheet having a thickness of 2.0 mm was manufactured.
The produced laminated sheet is a laminated sheet formed only of the PBT sheet as the vibration-damping layer 1.

Comparative example 4 (manufacturing of laminated sheet)
One PBT sheet manufactured in Manufacturing Example 1 and seven PC sheets manufactured in Manufacturing Example 2 were prepared. Four PC sheets were laminated on the surface area of one PBT sheet, and three PC sheets were laminated on the surface area below the PBT sheet. Then, using a press set with a pressure heating temperature of 165 ° C, the 8 pieces of the laminate were heated and compressed for 1.5 minutes under a pressure of 0.2 to 3 MPa to integrate them, and then, the temperature was increased by cooling. Press and cool to room temperature. In this way, a laminated sheet having a thickness of 4.0 mm was manufactured.
The manufactured laminated sheet is a PC sheet as the polycarbonate layer 2 on the surface area of the PBT sheet as the vibration damping layer 1 and a polycarbonate layer 3 as the surface area on the lower surface of the vibration damping layer 1. The structure of the PC sheet has a cross-section corresponding to the cross-sectional view of FIG. 4B.

The characteristics of each of the obtained laminated sheets were evaluated according to the following test examples. The results are shown in Table 2. The description of the evaluation results of Example 2, Comparative Example 2, and Comparative Example 3 is omitted.

Test example 1 [loss factor]
Each laminated sheet was cut into a size of 127 mm × 12.7 mm × thickness (2.0 to 4.5) mm (thickness based on the thickness of the laminated sheet obtained in each example and comparative example) to prepare a flat test piece.
For the flat test piece, based on JIS K 7391, the loss coefficient was calculated by the half-width method based on the second resonance peak of the frequency response function measured by the central vibration method. A system consisting of a 3160-type oscillator, a 2718-type amplifier, a 4810-type exciter, and a 8001-type acceleration sensor (all manufactured by B & K) was used, and the loss coefficient measurement software MS18143 was used. The measurement environment was controlled by a thermostatic bath (manufactured by Espec, PU-3J), and the measurement was performed at 23 ° C. The higher the loss coefficient of the laminated sheet, the faster the attenuation of the vibration can be determined, that is, the higher the damping effect of the laminated sheet.

Test example 2 [rigidity]
Each laminated sheet was cut into a size of 30 mm × 25 mm × thickness (2.0 to 4.5) mm (thickness based on the thickness of the laminated sheet obtained in each example and comparative example) to prepare a flat test piece. For the flat test piece, based on JIS K 7171, a bending test was performed using a Tensilon universal material testing machine (RTC-1250A, manufactured by Orientec, Inc.), the distance between the fulcrum points was set to 24 mm, and the test speed was set to 1 mm / min. Flexural modulus of elasticity. When the bending elastic modulus is 2.0 GPa or more, it can be judged that the bending elastic modulus is high and has good rigidity.

[Table 2]

It is known that the laminated sheet (example of the present invention) of the present invention has a higher loss coefficient and a higher elastic modulus, and is excellent in both independence and vibration damping effect. Furthermore, it is predicted to have sufficient rigidity and high impact strength. On the other hand, it was found that the laminated sheet (Comparative Examples 1, 2 and 4) in which the vibration damping layer does not exist at a specific position has a low loss coefficient, and therefore lacks a vibration damping effect. The laminated sheet formed only of the vibration damping layer ( Comparative Example 3) Since the elastic modulus is low, the rigidity is low. Furthermore, it was found that even when a laminated sheet composed of a polycarbonate layer and a vibration damping layer does not have the multilayer structure of the present invention, it cannot satisfy both rigidity and vibration damping effects (Comparative Examples 1, 2 And 4).

Example 4 (manufacturing of laminated sheet)
Two PBT sheets manufactured in Manufacturing Example 1 and six PC sheets manufactured in Manufacturing Example 2 were prepared. One PC sheet is layered on the surface area under one PBT sheet, four PC sheets are layered on the surface area above the PBT sheet, and one PBT sheet is layered on the surface area above the PC sheet, on the PBT sheet 1 PC sheet on the surface area of the substrate. Then, using a press set with a pressure heating temperature of 165 ° C, the 8 pieces of the laminate were heated and compressed for 2 minutes under a pressure of 0.2 to 3 MPa to integrate them, and then, the temperature was increased by cooling. Press and cool to room temperature. In this way, a laminated sheet having a thickness of 4.0 mm was manufactured.

The manufactured laminated sheet is made of a polycarbonate layer 2, a damping layer 4 and a polycarbonate layer 5 on the surface area above the vibration damping layer 1 and a polycarbonate layer 3 on the surface area below the vibration damping layer 1. The structure has a cross-section equivalent to the cross-sectional view of FIG. 5A.

Example 5 (manufacturing of laminated sheet)
Two PBT sheets manufactured in Manufacturing Example 1 and six PC sheets manufactured in Manufacturing Example 2 were prepared. Six PC sheets were layered on the surface area of one PBT sheet, and one PBT sheet was layered on the surface area of the PC sheet. Then, using a press set with a pressure heating temperature of 165 ° C, the 8 pieces of the laminate were heated and compressed for 2 minutes under a pressure of 0.2 to 3 MPa to integrate them, and then, the temperature was increased by cooling. Press and cool to room temperature. In this way, a laminated sheet having a thickness of 4.0 mm was manufactured.
The produced laminated sheet has a structure in which a polycarbonate layer 2 and a vibration-damping layer 4 are layered on the surface area above the vibration-damping layer 1, and its cross-section corresponds to the cross-sectional view of FIG. 5B.

Example 6 (manufacturing of laminated sheet)
Two PBT sheets manufactured in Manufacturing Example 1 and 12 PC sheets having a thickness of 0.25 mm manufactured in Manufacturing Example 4 were prepared. A PC sheet is layered on the surface area under one PBT sheet, 10 PC sheets are layered on the surface area above the PBT sheet, and one PBT sheet is layered on the surface area above the PC sheet, on the PBT sheet 1 PC sheet on the surface area of the substrate. Then, using a press with a pressure heating temperature set to 165 ° C, the 14 laminates were heated and compressed under the condition of a pressure of 0.2 to 3 MPa for 2 minutes to integrate them, and then, cooled and added. Press and cool to room temperature. In this way, a laminated sheet having a thickness of 4.0 mm was manufactured.

The manufactured laminated sheet is made of a polycarbonate layer 2, a damping layer 4 and a polycarbonate layer 5 on the surface area above the vibration damping layer 1 and a polycarbonate layer 3 on the surface area below the vibration damping layer 1. The structure has a cross-section equivalent to the cross-sectional view of FIG. 5C.

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

[table 3]

According to Examples 4 to 6, it is known that even if the laminated sheet has a plurality of vibration damping layers, as long as the conditions of the present invention are satisfied, it is a higher loss coefficient and a higher elastic modulus, that is, independence and vibration damping. Both effects are excellent. It was also found that even if the PC sheet is set relatively thick, sufficient vibration damping properties can be ensured. Furthermore, it turns out that the laminated sheet obtained using a polystyrene-hydrogenated polybutadiene copolymer as an elastomer (Example 7) shows a laminated sheet obtained using a styrene-isoprene block copolymer (Example 1) A loss coefficient and an elastic modulus of the same degree. That is, it turns out that a polystyrene-hydrogenated polybutadiene copolymer can also be used suitably as an elastomer.
[Industrial availability]

Since the laminated sheet of the present invention has a polycarbonate layer, it not only has sufficient rigidity and impact strength, but also has a high loss coefficient, so it has excellent vibration damping effect. Therefore, it can be used as a speaker, a television, a radio cassette recorder, or a headphone , Audio components, microphones and other audio equipment materials or electrical products, vehicles, buildings, industrial machinery and other products, or their parts, vibration damping materials for the frame.

1‧‧‧ Vibration layer

2‧‧‧ polycarbonate layer

3‧‧‧ polycarbonate layer

4‧‧‧ Vibration layer

5‧‧‧ polycarbonate layer

S‧‧‧upper surface

S'‧‧‧ another surface

FIG. 1 is a schematic view showing a cross-sectional structure of one aspect of a laminated sheet according to the present invention.

FIG. 2 is a schematic diagram (A) and (B) showing the cross-sectional structure of various aspects of the laminated sheet of this invention.

FIG. 3 is a schematic diagram (A) and (B) showing the cross-sectional structure of the aspect of the laminated sheet which is a comparison target.

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 comparison target.

Fig. 5 is a schematic view showing a cross-sectional structure of various aspects of the laminated sheet of the present invention.

Claims (9)

A laminated sheet, which is obtained by laminating a vibration damping layer and a polycarbonate, and The vibration damping layer exists on the surface and / or near the surface of the laminated sheet, A sheet-shaped molded body of the vibration-controlling layer-based polyester resin composition containing a thermoplastic polyester resin (A) composed of a component including a dicarboxylic acid component and a diol component, and plasticized And / or an elastomer component (B) and an inorganic filler (C). For example, the laminated sheet of claim 1, wherein the relative position (%) of the vibration damping layer from the upper surface of the laminated sheet is within 30%. For example, the laminated sheet of claim 1 or 2, wherein the ratio of the vibration damping layer in the laminated sheet is 1% or more and 70% or less by volume fraction. The laminated sheet according to any one of claims 1 to 3, wherein the thermoplastic polyester resin (A) contains polybutylene terephthalate. The laminated sheet according to any one of claims 1 to 4, wherein the inorganic filler (C) contains a plate-like filler. 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. For example, the laminated sheet according to any one of claims 1 to 6, wherein at least one layer of the vibration damping layer exists at a position ratio of 10 to 40%. 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. The laminated sheet according to any one of claims 1 to 8, wherein the thickness of each vibration damping layer is 0.05 mm or more and 10 mm or less.