JP2012149126A - Method for manufacturing damping film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a damping film being light and exhibiting excellent damping property and being high in versatility, in a stable manufacturing condition.SOLUTION: A method for manufacturing a damping film makes the temperature of a feed portion of a screw to be ≥5°C and ≤50°C in extrusion of a damping film of 20 to 200 μm in thickness from a resin composition in which a titanium dioxide (Y) and a mica scale (Z) are dispersed in a polyester resin (X) composed of a dicarboxylate component structural unit and a diol component structural unit, and which satisfies the following condition (I) to (III). (I): The ratios of the polyester resin (X), the titanium dioxide (Y) and the mica scale (Z) in the resin composition are in the ranges of 40 to 60 mass%, 5 to 15 mass%, and 30 to 55 mass%, respectively. (II): The average particle diameter of the mica scale (Z) is 5 to 80 μm. (III): The elongation at break of a test specimen composed of the resin composition as measured according to JIS K7127 is 30 to 70%. In the extrusion of a film shape composed of the resin composition, making the temperature of a feed portion of a screw to be ≥5°C and ≤50°C can provide a damping film of 20 to 200 μm easily and stably.

Description

The present invention relates to a method for producing a vibration damping film mainly composed of a polymer material.

Conventionally, vibration-damping materials have been used as materials to absorb vibration energy in places where vibrations occur, such as vehicles, railways, aircraft, home appliances / OA equipment, precision equipment, construction machinery, civil engineering buildings, shoes, and sports equipment. Generally used.

As a material that absorbs vibration energy such as a damping material, a polyester resin composition having a portion where the number of carbon atoms between ester bonds in the main chain is an odd number is disclosed (Patent Document 1). This polyester resin composition is excellent in vibration damping performance near room temperature, and is a promising material as a vibration damping material. However, when carbon powder or mica powder, which is a conductive material, is dispersed in a polyester resin, it is difficult to manufacture the damping material with a thickness of less than 200 μm, and it cannot be used as a damping material for film applications. There's a problem.

In addition, rubber materials such as butyl rubber and NBR, which are excellent in terms of workability, mechanical strength, and material cost, are often used as vibration damping materials. However, these rubber materials have the most excellent damping properties (vibration energy transmission insulation performance or transmission relaxation performance) among general polymer materials, but rubber materials alone can be used as damping materials. Since the vibration damping property (property of absorbing vibration energy) is low, sufficient vibration damping performance cannot be exhibited even when used as a vibration damping material for film applications, for example.

JP 2006-052377 A

An object of the present invention is to stably manufacture a vibration damping film that is lightweight, exhibits excellent vibration damping properties, and has high versatility from the above situation.

As a result of intensive investigations to achieve such an object, the present inventors have identified a resin composition in which titanium dioxide and mica scales are dispersed in a polyester resin composed of a dicarboxylic acid component constituent unit and a diol component constituent unit. It was found that a vibration-damping film meeting the above-mentioned purpose can be obtained by extrusion molding under the above-described extrusion molding conditions.

The resin composition satisfies the following conditions (I) to (III) in which titanium dioxide (Y) and mica scale (Z) are dispersed in a polyester resin (X) composed of a dicarboxylic acid component structural unit and a diol component structural unit. .
(I) The ratio of the polyester resin (X), titanium dioxide (Y), and mica scale (Z) in the resin composition is in the range of 35 to 60% by mass, 5 to 15% by mass, and 30 to 55% by mass, respectively. It is.
(II) The average particle size of the mica scale (Z) is 5 to 80 μm.
(III) The elongation at break when a test piece made of the resin composition is measured in accordance with JISK7127 is 30 to 70%.

In the film-like extrusion molding made of the resin composition, a damping film having a thickness of 20 to 200 μm can be obtained easily and stably by setting the temperature of the supply part of the screw to 5 ° C. or more and 50 ° C. or less.

According to the method for producing a vibration damping film of the present invention, a vibration damping film having a thickness of 20 to 200 μm can be obtained easily and stably.
The vibration damping film obtained by the method of the present invention is lightweight and exhibits excellent vibration damping properties.
Further, the vibration-damping film obtained by the method of the present invention is one in which titanium dioxide and mica flakes are added, and since there is no need to use carbon powder or the like, it can be used in applications and places where various color tones are required. High versatility.
Therefore, the vibration damping film obtained by the method of the present invention can be used for vibration of vehicles, railways, aircraft, ships, home appliances / OA equipment, precision equipment, construction machinery, civil engineering buildings, housing equipment, medical equipment, shoes, sports equipment, and the like. It can be widely used in places where it occurs. It can also be applied as a vibration-damping label for cassette tape labels, hard disks, handy cameras, digital cameras, and the like.

The present invention is described in detail below.
The resin composition used in the present invention comprises a resin composition in which titanium dioxide (Y) and mica scale (Z) are dispersed in a polyester resin (X) composed of a dicarboxylic acid component structural unit and a diol component structural unit. It is a requirement that the elongation at break measured in accordance with JISK7127 of the composition is 30 to 70%.
The elongation at break was adjusted by adjusting the strip-shaped test piece of 10 mm × 150 mm × 1.0 mmt made of the resin composition at 23 ° C./50% RH for 80 hours or longer. It is a value obtained by conducting a tensile test 5 times under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 50 mm, and calculating an average value of elongation.
When the elongation at break of the resin composition used for the vibration damping film is 30% or more, film breakage hardly occurs at the time of extrusion molding, and when the elongation at break is 70% or less, the resin composition is sticky. And the adhesion to the cooling roll during extrusion molding can be reduced. As a result, a film having a thickness of 20 to 200 μm can be formed.

The polyester resin (X) as the resin component of the resin composition used in the present invention is composed of a dicarboxylic acid component structural unit and a diol component structural unit, the total number of dicarboxylic acid component structural units (A ₀ ) and the total diol component structural unit. the number (B ₀₎ of the total amount the dicarboxylic acid constitutional unit number carbon atoms in the main chain is odd for (a ₁₎ and the diol constitutional units number an odd number of carbon atoms in the backbone (B ₁ ) In the total amount ratio [(A ₁ + B ₁ ) / (A ₀ + B ₀ )] is preferably in the range of 0.5 to 1.0.
Here, “the number of carbon atoms in the main chain of the dicarboxylic acid component structural unit (or diol component structural unit)” is sandwiched between one ester bond [—C (═O) —O—] and the next ester bond. The number of carbon atoms existing on the shortest path along the main chain of the polyester resin in the monomer unit. In addition, the number of structural units of each component can be calculated from a ratio of integrated values of ¹ H-NMR spectrum measurement results described later.

In the present invention, the dicarboxylic acid component in which the number of carbon atoms in the main chain is an odd number with respect to the total amount of the total number of dicarboxylic acid component structural units (A ₀ ) and the total number of diol component structural units (B ₀ ) of the polyester resin (X) The ratio [(A ₁ + B ₁ ) / (A ₀ + B ₀ )] of the total amount of the number of structural units (A ₁ ) and the number of diol component structural units (B ₁ ) having an odd number of carbon atoms in the main chain is 0 The range is from 0.5 to 1.0, and the range from 0.7 to 1.0 is preferable. The number of carbon atoms in the main chain of the dicarboxylic acid component constituent unit and the number of carbon atoms in the main chain of the diol component constituent unit are preferably 1, 3, 5, 7, and 9, which are odd numbers.

Examples of the dicarboxylic acid component structural unit having an odd number of carbon atoms in the main chain of the polyester resin (X) include isophthalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, undecanedioic acid, brassylic acid, 1 , 3-cyclohexanedicarboxylic acid and the like. Among these, structural units derived from isophthalic acid and 1,3-cyclohexanedicarboxylic acid are preferable, and structural units derived from isophthalic acid are more preferable. The polyester resin (X) may contain one or more structural units derived from the dicarboxylic acid. Moreover, when 2 or more types of structural units are included, it is preferable to include a structural unit derived from isophthalic acid and azelaic acid.

Examples of diol component structural units having an odd number of carbon atoms in the main chain of the polyester resin (X) include 1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol. 1,3-pentanediol, 1-methyl-1,3-butanediol, 2-methyl-1,3-butanediol, neopentyl glycol, 1,3-hexanediol, 3-methyl-1,3-butane Diol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,5-hexanediol, 2-ethyl-1,5-pentanediol, 2 -Propyl-1,5-pentanediol, metaxylene glycol, 1,3-cyclohexanediol, 1,3-bis (hydroxymethyl) cyclohexane It includes structural units derived from at etc.. Among them, derived from 1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, metaxylene glycol and 1,3-cyclohexanediol The structural unit derived from 1,3-propanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,3-butanediol and neopentyl glycol is more preferable. The polyester resin (X) may contain one or more structural units derived from the diol.

Furthermore, the ratio (A ₁ / A ₀ ) of the number of dicarboxylic acid component constituent units (A ₁ ) in which the number of carbon atoms in the main chain is odd to the total number of dicarboxylic acid component constituent units (A ₀ ) of the polyester resin (X). Is preferably in the range of 0.5 to 1.0, more preferably the ratio (A ₁ / A ₀ ) is in the range of 0.7 to 1.0.
Further, the ratio (B ₁ / B ₀ ) of the number of structural units (B ₁ ) derived from the diol having an odd number of carbon atoms in the main chain to the total number of structural units (B ₀ ) of the diol component of the polyester resin (X). Is preferably in the range of 0.5 to 1.0, more preferably the ratio (B ₁ / B ₀ ) is in the range of 0.7 to 1.0.

The polyester resin (X) of the present invention has (1) an intrinsic viscosity of 0.2 to 2.0 dL / g measured at 25 ° C. in a mixed solvent having a trichloroethane / phenol mass ratio of 40/60, and (2 ) It is preferable that the calorific value of the crystallization exothermic peak during cooling as measured by a differential scanning calorimeter is 5 J / g or less. By satisfying the above (1) and (2), higher vibration damping can be obtained.

The polyester resin (X) used in the present invention may contain other structural units to the extent that the effects of the present invention are not impaired in addition to the above-described dicarboxylic acid component structural units and diol component structural units. There are no particular restrictions on the type, and all dicarboxylic acids and esters thereof that can form polyester resins (referred to as "other dicarboxylic acids"), diols (referred to as "other diols") or The structural unit derived from hydroxycarboxylic acid and its ester (this is called "hydroxycarboxylic acids") can be included.

Examples of other dicarboxylic acids include terephthalic acid, orthophthalic acid, 2-methylterephthalic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid Acid, decalin dicarboxylic acid, norbornane dicarboxylic acid, tricyclodecane dicarboxylic acid, pentacyclododecanedicarboxylic acid, isophorone dicarboxylic acid, 3,9-bis (2-carboxyethyl) -2,4,8,10-tetraoxaspiro [ 5.5] Dicarboxylic acid or dicarboxylic acid ester such as undecane; trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid, tricarballylic acid, or derivatives thereof.

There is no restriction | limiting in particular in the method of manufacturing polyester resin (X) used by this invention, A conventionally well-known method is applicable. In general, it can be produced by polycondensing monomers as raw materials. For example, a melt polymerization method such as a transesterification method or a direct esterification method or a solution polymerization method can be used. As the transesterification catalyst, esterification catalyst, etherification inhibitor, polymerization catalyst used in the polymerization, various stabilizers such as a heat stabilizer and a light stabilizer, polymerization regulators and the like can be used. Compounds containing metals such as manganese, cobalt, zinc, titanium and calcium as transesterification catalysts, compounds containing metals such as manganese, cobalt, zinc, titanium and calcium as esterification catalysts, and amines as etherification inhibitors Examples thereof include compounds. As the polycondensation catalyst, compounds containing metals such as germanium, antimony, tin, titanium, such as germanium (IV) oxide; antimony (III) oxide, triphenylstibine, antimony (III) acetate; tin (II) oxide; titanium ( Examples thereof include titanic acid esters such as IV) tetrabutoxide, titanium (IV) tetraisopropoxide, and titanium (IV) bis (acetylacetonato) diisopropoxide. It is also effective to add various phosphorus compounds such as phosphoric acid, phosphorous acid, and phenylphosphonic acid as heat stabilizers. In addition, a light stabilizer, an antistatic agent, a lubricant, an antioxidant, a release agent, and the like may be added. In addition to the dicarboxylic acid from which the dicarboxylic acid component structural unit is derived, the dicarboxylic acid component used as a raw material may be a dicarboxylic acid derivative such as a dicarboxylic acid ester, a dicarboxylic acid chloride, an active acyl derivative, or a dinitrile. it can.

The vibration-damping film obtained by the method of the present invention comprises a resin composition in which titanium dioxide (Y) and mica scale (Z) are dispersed in the polyester resin (X) for the purpose of improving vibration energy absorption.
The form of titanium dioxide (Y) dispersed in the polyester resin (X) is not particularly limited, and titanium dioxide containing only rutile type or anatase type, or titanium dioxide mixed with rutile type and anatase type can be used. Examples of the surface coating treatment for suppressing the photocatalytic activity of titanium dioxide include surface treatment agents such as aluminum oxide, silicon oxide, zirconium oxide, and zinc oxide. Moreover, the titanium dioxide which has electroconductivity by including electroconductive powder can also be used for the damping film of this invention. Titanium dioxide (Y) preferably has an average particle size (volume average particle size) of 0.01 to 0.5 μm determined by a laser-diffraction method.
Although it does not specifically limit to the kind of mica scale (Z) disperse | distributed to polyester resin (X), White mica which is a scale-like mica with a high vibration energy absorption effect is preferable. Moreover, since the dispersed mica is easily oriented inside the vibration damping film, the average particle size of mica in the resin composition used for the vibration damping film of the present invention is 5 to 80 μm, more preferably 20 to 60 μm. More preferably, it is 25-50 micrometers. By making the average particle diameter of mica 5 μm or more, an effect of improving vibration damping can be obtained, and when the average particle diameter is 80 μm or less, a film having a thickness of 20 to 200 μm can be easily formed. In addition, an average particle diameter shows the volume average particle diameter calculated | required by the laser-diffraction method.

The ratios of the polyester resin (X), titanium dioxide (Y) and mica scale (Z) in the resin composition used for the vibration damping film obtained by the method of the present invention are 35 to 60% by mass and 5 to 15% by mass, respectively. 30 to 55% by mass, preferably 38 to 55% by mass, 5 to 12% by mass, and 40 to 55% by mass, more preferably 40 to 55% by mass, and 5 to 10% by mass. It is the range of 45-55 mass%.
By setting the ratio of the polyester resin (X) in the resin composition used for the vibration damping film to 35% by mass or more, a film having a thickness of 20 to 200 μm can be formed, and by setting the ratio to 60% by mass or less. It becomes possible to disperse titanium dioxide and mica flakes with a content in which the effect of improving vibration damping is noticeable.
In addition, when the ratio of titanium dioxide (Y) in the resin composition used for the vibration damping film is 5% by mass or more, the effect of improving the vibration damping property by titanium dioxide becomes noticeable, and titanium dioxide (Y) When the ratio is set to 15% by mass or less, a film having a thickness of 20 to 200 μm can be easily formed.
Furthermore, the effect of improving the damping property can be obtained by setting the ratio of mica scale (Z) in the resin composition used for the damping film to 30% by mass or more, and by setting the ratio to 55% by mass or less, 20 A film having a thickness of ˜200 μm can be easily formed.

The vibration damping film obtained by the method of the present invention is composed of the above polyester resin (X), titanium dioxide (Y), and mica scale (Z), but if necessary, other than titanium dioxide and mica scale Other inorganic fillers and one or more additives such as dispersants, compatibilizers, surfactants, antistatic agents, lubricants, plasticizers, flame retardants, crosslinkers, antioxidants, anti-aging agents, Weathering agents, heat-resistant agents, processing aids, brighteners, foaming agents, foaming aids and the like can be added as long as the effects of the present invention are not impaired. Also, blending with other resins or surface treatment after molding can be performed within a range that does not impair the effects of the present invention.

  The vibration damping film obtained by the method of the present invention can be obtained by mixing polyester resin (X), titanium dioxide (Y) and mica scale (Z), and further forming a film. A known method can be used as the mixing method, and examples thereof include a method of melt-mixing using a device such as a hot roll, a Banbury mixer, a twin-screw kneader, an extruder. In addition, a method in which a polyester resin is dissolved or swollen in a solvent and titanium dioxide and mica flakes are mixed and then dried, and a method in which each component is mixed in a fine powder form can also be employed. In addition, the addition method of titanium dioxide, mica scales, an additive, etc., an addition order, etc. are not specifically limited.

  The method for producing a vibration damping film using the mixture of the present invention is a method in which the mixture is melted using an extruder, the mixture melted from a T-die is formed into a film, and cooled by a cooling roll. The screw of an extruder is generally divided into three areas: a supply unit, a compression unit, and a metering unit. The supply unit transports solid resin pellets and flakes, and the compression unit compresses and melts the resin. Has an effect of stabilizing the discharge amount. There may be a mixing in the measuring section for the purpose of kneading.

When the mixture is molded using the extruder, the polyester resin in the mixture may melt at the screw supply portion of the extruder. When the resin is melted in the supply unit, the mixture is wound around the screw and is not conveyed, and the film cannot be manufactured.
In order to avoid this and obtain a good vibration damping film, it is necessary to control the barrel temperature of the extruder within a certain range. Specifically, it is preferable that the temperature of the portion corresponding to the screw supply part of the barrel is 5 ° C. or more and 50 ° C. or less. In the case of 5 ° C. or lower, condensation may occur in a hot and humid environment. When the temperature is 50 ° C. or higher, the mixture is wound around the screw in the extruder, and as a result, the resin cannot be fed, and a film or sheet cannot be produced.
By controlling the temperature of the portion corresponding to the screw supply section of the extruder within the range of 5 ° C. to 50 ° C., it becomes possible to easily and stably produce the vibration damping film.

In the vibration damping film obtained by the method of the present invention, with the above-described configuration, the thickness ratio of the aluminum alloy 5052 material as the substrate (the thickness of the vibration damping film / the thickness of the substrate) is 1.0. When the restraint type test piece is measured by the central vibration method under the condition where the measurement temperature range is 0 to 80 ° C., the maximum value of the loss coefficient at 500 Hz can be 0.15 or more.
Moreover, since the damping film obtained by the method of the present invention is mainly composed of a polyester resin component, titanium dioxide, and mica scale pieces, it is lightweight and provides excellent damping properties.
Furthermore, the present invention is particularly characterized in that a damping film having a thickness of 20 to 200 μm can be easily formed. By adding titanium dioxide together with mica flakes to the resin component at a predetermined mass ratio, a damping material having high damping performance can be obtained. In addition to obtaining a vibration material, a method for easily producing a vibration-damping film that could not be considered in the past is disclosed.
In addition, the vibration-damping film obtained by the method of the present invention is obtained by adding titanium dioxide together with mica flakes to the resin component, and it is not necessary to use carbon powder or the like. Can be used and is highly versatile.
Thus, the vibration damping film obtained by the method of the present invention is molded or processed into a constrained vibration damping film, an unconstrained vibration damping film, a label, a tape, an injection molded product, a fiber, a container, a foam, an adhesive, a paint, or the like. Anti-vibration materials, vibration-damping materials, and absorbing materials applicable to vehicles, railways, aircraft, ships, home appliances / OA equipment, precision equipment, construction machinery, civil engineering buildings, housing equipment, medical equipment, shoes, sports equipment, etc. It can be widely used as a sound insulating material. It can also be applied as a vibration-damping label for cassette tape labels, hard disks, handy cameras, digital cameras, and the like. Moreover, the damping film used for the use which improves the damping property of a laminated body by laminating | stacking with the sheet-like prepreg which impregnated the uncured thermosetting resin to the reinforcement fiber which consists of this inorganic fiber and / or organic fiber Can be used particularly preferably.

Examples are shown below, but the present invention is not limited to the following examples.
The polyester resin and the damping film were evaluated by the following method.
(1) Molar ratio of each structural unit of the polyester resin: [(A ₁ + B ₁ ) / (A ₀ + B ₀ )], (A ₁ / A ₀ ), (B ₁ / B ₀ ):
400 MHz- ¹ was calculated from the ratio of the integrated value of the H-NMR spectrum measurement.

(2) Intrinsic viscosity of polyester resin ([η]):
The intrinsic viscosity ([η]) of the polyester resin was measured by using a Canon Fenceke viscometer after dissolving the polyester resin in a mixed solvent of trichloroethane / phenol = 40/60 (mass ratio) and maintaining at 25 ° C. .

(3) Calorific value (ΔHc) of crystallization exothermic peak during temperature drop of polyester resin:
The calorific value (ΔHc) of the crystallization exothermic peak when the polyester resin was cooled was measured using a DSC / TA-50WS differential scanning calorimeter manufactured by Shimadzu Corporation. About 10 mg of a sample is put in an aluminum non-sealed container, heated in a nitrogen gas stream (30 ml / min), heated to 280 ° C. at a heating rate of 20 ° C./min, held at 280 ° C. for 1 minute, and then 10 ° C./min. It calculated | required from the area of the exothermic peak which appears when it falls at the temperature fall rate.

(4) Elongation at break:
In accordance with JISK7127, a strip-shaped test piece having a size of 10 mm × 150 mm × 1.0 mm is left to stand for 80 hours or more at 23 ° C./50% RH, and then the tension is adjusted to 50 mm / min. Tensile tests were performed five times under the condition of a distance of 50 mm, and the average value of elongation was calculated.

(5) Film molding thickness:
The vibration damping film obtained using the extrusion molding equipment was measured using a micrometer, and the average of 5 points was used as a representative value.

(6) Release property:
Each material was kneaded at 200 ° C. for 15 minutes with a 60 cc kneader, and then the release property was evaluated by whether or not the kneaded material remained in the blade or the kneading tank when discharged from the kneading tank using a brass cast spatula. The case where there was little adhesion of the material to a braid | blade or a kneading tank and it can be judged that there is no problem as an industrial manufacturing method was evaluated as “good”, and the others were evaluated as “poor”.

(7) Loss coefficient of damping film:
The vibration-damping film obtained by using the extrusion molding equipment was cut into 10 mm x 150 mm to make a test piece, which was bonded to a 1 mm-thick substrate (aluminum alloy 5052 material) by hot pressing with a hot press, and was not restrained. A material was prepared. Using the loss factor measuring device (manufactured by Ono Sokki Co., Ltd.), the loss factor at 500 Hz was measured by the central excitation method for the obtained unconstrained damping material using a loss factor measuring device (manufactured by Ono Sokki Co., Ltd.). The damping performance was evaluated by comparing the maximum value of the loss coefficient obtained in the above measurement temperature range. Note that the greater the loss factor, the higher the damping performance.

Example 1
A polyester production apparatus with an internal volume of 30 liters (L) equipped with a packed tower type rectification tower, a stirring blade, a partial condenser, a full condenser, a cold trap, a thermometer, a heating device, and a nitrogen gas introduction pipe was mixed with isophthalic acid ( A. G. International Chemical Co., Ltd., 10834 g (65.3 mol), azelaic acid (Cognis, trade name: EMEROX 1144), this product contains 93.3 mol% azelaic acid, the total amount of dicarboxylic acid is 99.97%.) 5854 g (32.3 mol), 2-methyl-1,3-propanediol (manufactured by Dalian Chemical Industry Co., Ltd.) 11683 g (129.6 mol) were added, and the mixture was subjected to normal pressure and nitrogen atmosphere. The temperature was raised to 230 ° C. and the esterification reaction was carried out for 3.5 hours. After the reaction conversion rate of isophthalic acid and azelaic acid is 85 mol% or more while monitoring the amount of condensed water distilled off, 14.9 g of titanium (IV) tetrabutoxide monomer (manufactured by Wako Pure Chemical Industries, Ltd.) (The concentration of titanium with respect to the total mass of the initial condensation reaction product excluding the mass of condensed water from the total charged raw material mass is 67.4 ppm), gradually increasing the temperature and reducing the pressure, and then 2-methyl-1,3-propane The polycondensation reaction was finally performed at 240 to 250 ° C. and 0.4 kPa or less while extracting the diol out of the system. The reaction was terminated when the viscosity of the reaction mixture and the stirring torque gradually increased and reached an appropriate viscosity or when distillation of 2-methyl-1,3-propanediol was stopped.
Properties of the obtained polyester resin are [η] = 0.72 (dL / g), ΔHc = 0 (J / g), ¹ H-NMR [400 MHz, CDCl ₃ , internal standard TMS): δ (ppm) = _{7.5~8.9 (Ph- H, 4H);} 3.5~4.6 (-C H 2 -CH (CH 3) -C H 2 -, 6H); 1.0~2.6 ( _{-CH 2 C H (CH 3)} CH 2 -, - CH 2 CH (C H 3) CH 2 -, - CO (C H 2) 7 CO-, was 13H].
45% by mass of this polyester resin [(A ₁ + B ₁ ) / (A ₀ + B ₀ ) = 1.0; (A ₁ / A ₀ ) = 1.0; (B ₁ / B ₀ ) = 1.0] Biaxially 5% by mass of titanium dioxide powder (Ishihara Sangyo Co., Ltd., trade name: Taipei CR-80) and 50% by mass of mica scale (Yamaguchi Mica Co., Ltd., trade name: SYA-21R, average particle size: 27 μm) Using a kneader, the mixture was kneaded at 200 ° C. to obtain pellets of the mixture.
A damping film was produced from the obtained pellets using a film extrusion molding equipment equipped with a single-screw extruder, a T die, a roll take-up machine, and a film winder. The temperature control of the barrel of the extruder is divided into five parts, C1 and C2 from the resin charging port respectively contact the screw supply part, C3 corresponds to the compression part, and C4 and C5 correspond to the measurement part. Each temperature was set to 10 ° C, 40 ° C, 90 ° C, 120 ° C, and 130 ° C. As a result, a vibration damping film could be obtained stably. The physical properties of the obtained vibration damping film are shown in Table 1.

Comparative Example 1
A vibration-damping film was prepared from pellets of the mixture similar to Example 1 using a film extrusion equipment equipped with a single screw extruder, a T die, a roll take-up machine, and a film winder. The temperature control of the barrel of the extruder was set to 30 ° C., 90 ° C., 90 ° C., 120 ° C., and 130 ° C. from the resin charging port, respectively. As a result, several minutes after the pellets were put, the mixture was wound around the screw supply section of the extruder, and a vibration damping film could not be obtained.

Comparative Example 2
A vibration-damping film was prepared from pellets of the mixture similar to Example 1 using a film extrusion equipment equipped with a single screw extruder, a T die, a roll take-up machine, and a film winder. The temperature control of the barrel of the extruder was set to 40 ° C., 100 ° C., 130 ° C., 130 ° C., and 130 ° C. from the resin charging port, respectively. As a result, several minutes after the pellets were put, the mixture was wound around the screw supply section of the extruder, and a vibration damping film could not be obtained.

From Table 1, the damping film of the present invention has a high loss factor, excellent damping properties, and can form a film with a thickness of 200 μm or less when the elongation at break is in the range of 30 to 70%. It turns out that it is.
It can be seen from Table 2 that a damping film having a thickness of 20 to 200 μm can be obtained easily and stably by setting the temperature of the screw supply section to 5 ° C. or more and 50 ° C. or less.

The vibration damping film obtained by the method of the present invention can be formed into a thickness of 20 to 200 μm, is lightweight, and exhibits excellent vibration damping properties. Further, the vibration-damping film of the present invention adds titanium dioxide and mica flakes, and does not require the use of carbon powder. Therefore, it can be used for applications and places where various color tones are required and is highly versatile. . Therefore, the vibration-damping film of the present invention is applied to a place where vibration occurs in vehicles, railways, aircraft, ships, home appliances / OA equipment, precision equipment, construction machinery, civil engineering buildings, housing equipment, medical equipment, shoes, sports equipment, and the like. Can be widely used. It can also be applied as a vibration-damping label for cassette tape labels, hard disks, handy cameras, digital cameras, and the like.

Claims (10)

20 comprising a resin composition satisfying the following conditions (I) to (III) in which titanium dioxide (Y) and mica scale (Z) are dispersed in a polyester resin (X) comprising a dicarboxylic acid component constituting unit and a diol component constituting unit. A method for producing a vibration damping film, characterized in that, in extrusion molding of a vibration damping film having a thickness of ˜200 μm, the temperature of a screw supply section is set to 5 ° C. or more and 50 ° C. or less.
(I) The ratio of the polyester resin (X), titanium dioxide (Y), and mica scale (Z) in the resin composition is in the range of 35 to 60% by mass, 5 to 15% by mass, and 30 to 55% by mass, respectively. It is.
(II) The average particle size of the mica scale (Z) is 5 to 80 μm.
(III) The elongation at break when a test piece made of the resin composition is measured in accordance with JISK7127 is 30 to 70%. Number of dicarboxylic acid component constituent units (A ₁ ) having an odd number of carbon atoms in the main chain relative to the total amount of all dicarboxylic acid component constituent units (A ₀ ) and all diol component constituent units (B ₀ ) of the polyester resin And the ratio [(A ₁ + B ₁ ) / (A ₀ + B ₀ )] of the total amount of diol component structural units (B ₁ ) having an odd number of carbon atoms in the main chain is 0.5 to 1.0 The method for producing a vibration damping film according to claim 1, which is within a range. The structural unit of the dicarboxylic acid component having an odd number of carbon atoms in the main chain of the polyester resin (X) is isophthalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, undecanedioic acid, brassic acid and 1,3- The method for producing a vibration-damping film according to claim 2, which is a structural unit derived from a dicarboxylic acid selected from the group consisting of cyclohexanedicarboxylic acid. The method for producing a vibration-damping film according to claim 2, wherein the dicarboxylic acid component structural unit having an odd number of carbon atoms in the main chain of the polyester resin (X) is a structural unit derived from isophthalic acid and / or azelaic acid. . The ratio (A ₁ / A ₀ ) of the number of dicarboxylic acid component structural units (A ₁ ) in which the number of carbon atoms in the main chain is odd in the total number of dicarboxylic acid component structural units (A ₀ ) of the polyester resin (X) is The method for producing a vibration damping film according to claim 2, which is in the range of 0.5 to 1.0. The diol component structural unit having an odd number of carbon atoms in the main chain of the polyester resin (X) is 1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl The method for producing a vibration-damping film according to claim 2, which is a structural unit derived from a diol selected from the group consisting of glycol, 1,5-pentanediol, metaxylene glycol, and 1,3-cyclohexanediol. The diol component structural unit having an odd number of carbon atoms in the main chain of the polyester resin (X) is 1,3-propanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1, The method for producing a vibration damping film according to claim 2, which is a structural unit derived from a diol selected from the group consisting of 3-butanediol and neopentyl glycol. The ratio (B ₁ / B ₀ ) of the number of diol component structural units (B ₁ ) in which the number of carbon atoms in the main chain in the total number of diol component structural units (B ₀ ) of the polyester resin (X) is an odd number is 0. The method for producing a vibration damping film according to claim 2, which is within a range of 5 to 1.0. The polyester resin (X) has an intrinsic viscosity of 0.2 to 2.0 dL / g measured at 25 ° C. in a mixed solvent of (1) trichloroethane / phenol mass ratio 40/60, and (2) differential scanning. The method for producing a vibration damping film according to claim 1, wherein the calorific value of the falling temperature crystallization exothermic peak measured with a calorimeter is 5 J / g or less. An unconstrained specimen having a plate thickness ratio (thickness of damping film / thickness of substrate) of 1.0 using aluminum alloy 5052 as a substrate was measured by a central vibration method under a measurement temperature range of 0 to 80 ° C. The method for producing a vibration damping film according to claim 1, wherein the maximum value of the loss coefficient at 500 Hz is 0.15 or more.