JP2013010929A - Molding material and molded article having vibration-damping properties and sound insulating properties - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material from which a molded article is easily produced without the need of complicated steps, such as lamination of a vibration-damping material, and which exhibits excellent vibration-damping properties and sound insulating properties.SOLUTION: The molding material contains: a vibration-damping material (α) comprising a resin composition in which barium sulfate (Y) and mica flakes (Z) are dispersed in a polyester resin (X) comprising a constituent unit of a dicarboxylic acid component and a constituent unit of a diol component; and a reforming material (β) for improving flowability, wherein the ratio of the total amount of a constituent unit number (A) of the dicarboxylic acid component in which the number of a carbon atom in the main chain is odd and a constituent unit number (B) of the diol component in which the number of a carbon atom in the main chain is odd relative to the total amount of the constituent unit number (A) of the total dicarboxylic acid components and the constituent unit number (B) of the total diol components in the polyester resin (X), [(A+B)/(A+B)], is within the range of 0.5-1.0.

Description

  The present invention provides a molding material having excellent vibration damping and sound insulation properties, excellent molding processability, and capable of easily producing a molded product without requiring a complicated process such as lamination of damping materials. Regarding molded products.

Molding used for parts and housings of personal computers, OA equipment, AV equipment, mobile phones and other electrical / electronic equipment, optical equipment, precision equipment, toys, home and office electrical appliances, as well as automobile, aircraft and ship parts In addition to general material properties such as impact resistance, heat resistance, strength, and dimensional stability, the material is required to have vibration damping properties (a property of absorbing vibration energy).
This vibration damping property depends largely on the shape of the molded product, but also depends on the elastic modulus and vibration damping property of the material used. It is extremely difficult to satisfy all of these required performances with a single material, so multiple materials can be combined, such as blends of various polymers, composites of organic and inorganic materials, and stacking of different materials. By doing so, a molding material having vibration damping properties is manufactured.
However, in particular, since the elastic modulus and the vibration damping property are mutually contradictory properties, the molding material having the vibration damping property needs to be combined with a material having a high elastic modulus and the vibration damping material.

  Conventionally, a soft vinyl chloride resin in which a plasticizer is added to a vinyl chloride resin is known as a material that absorbs vibration energy such as a vibration damping material. In this soft vinyl chloride resin, vibration energy is consumed as frictional heat inside the resin, so that vibration energy is attenuated. However, vibration energy is not sufficiently absorbed or attenuated.

Further, rubber materials such as butyl rubber and NBR butadiene acrylonitrile rubber are often used as vibration damping materials that are excellent in terms of workability, mechanical strength, and material cost. 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. Vibration control is low. For example, a vibration-damping structure for buildings and equipment is combined with a laminate of rubber material and steel plate, or a lead core and oil damper that absorbs vibration energy by plastic deformation. It is used in a composite form called a damping structure.
Such a rubber material as a vibration damping material cannot be used alone as described above, and has been forced to be compounded. Therefore, the vibration damping structure is inevitably complicated. The material itself and the rubber material itself are required to have high vibration damping properties.

  As a damping material different from the soft vinyl chloride resin and rubber material as described above, a polyester resin composition having a portion where the number of carbon atoms between the ester bonds of the main chain is an odd number is disclosed (Patent Document 1, (See Patent Document 2 and Patent Document 3). This polyester resin composition is excellent in vibration damping performance in a wide range of temperatures, and is a promising material as a vibration damping material. However, these vibration damping materials have a drawback that they are difficult to use as molding materials due to poor fluidity during molding. For this reason, the lamination method of the damping material requires complicated methods, such as bonding with adhesives and adhesives, double-sided tape, laminating and coating, adhesion by pressing, or lamination of self-adhesive damping materials. Leads to an increase in cost.

  In addition, this polyester resin composition is excellent in vibration damping performance near room temperature and is a promising material as a vibration damping material, but it does not have sound insulation and suppresses vibrations that contain both solid vibration and air vibration. Has a problem that it is difficult to use.

On the other hand, it has been disclosed that sound insulation can be imparted by mixing inorganic substances such as high specific gravity metals and metal oxides (see Patent Document 4). This sound insulating material uses an inorganic substance having a specific gravity of 4.0 or more and has an excellent sound insulating performance, but has a problem that the loss factor is low and the vibration damping performance is inferior.
An object of the present invention is to provide a vibration damping and sound insulating material that exhibits excellent vibration damping and sound insulating properties.

JP 2006-052377 A International Publication No. 2008/018444 Pamphlet International Publication No. 2009/063837 Pamphlet JP 58-90700 A

  The object of the present invention is that, from the above situation, a molded product is easily manufactured without requiring complicated processes such as lamination of vibration damping materials, and exhibits excellent vibration damping, sound insulation and moldability. It is to provide a molding material and a molded product.

As a result of intensive studies to achieve the above object, the present inventors blend a specific polyester resin with an inorganic substance having a large specific gravity for improving sound insulation and a specific modifier for improving fluidity. As a result, it has been found that a moldable vibration-damping and sound-insulating material having excellent vibration-damping properties, sound-insulating properties and moldability can be obtained.

That is, the present invention provides the following molding materials and molded products.
1. A damping material (α) comprising a resin composition in which barium sulfate (Y) and mica scale (Z) are dispersed in a polyester resin (X) comprising a dicarboxylic acid component constitutional unit and a diol component constitutional unit, and improvement in fluidity A molding material containing a modifying material (β) for
(1) Dicarboxylic acid component constitution in which the number of carbon atoms in the main chain is an odd number with respect to the total amount of all dicarboxylic acid component constitutional units (A ₀ ) and all diol component constitutional 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 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. Within the range of 5-1.0,
(2) The mass ratio (X: Y: Z) of the polyester resin (X), barium sulfate (Y) and mica scale (Z) in the vibration damping material (α) is 5-40: 30-90: 5. A range of 40,
(3) The content of the vibration damping material (α) is 50 to 97% by mass,
(4) The modifier (β) for improving fluidity is selected from the group consisting of polypropylene resin, polyethylene resin, polyisoprene resin, ethylene-vinyl acetate copolymer resin, and styrene-acrylonitrile copolymer resin. At least one
(5) A molding material having a melt flow rate of 3 to 500 g / 10 min when measured using a melt indexer at 200 ° C., a load of 10 kg, and an orifice diameter of 2 mm.
2. Said 1 molding material whose content of damping material ((alpha)) is 90-97 mass%.
3. A molded product obtained by molding the molding material 1 or 2 above.

  The molding material of the present invention has excellent vibration damping properties, excellent molding processability, and can easily produce molded products having vibration damping properties without requiring complicated steps such as lamination. Therefore, it can be suitably used in parts where vibrations occur, such as parts and housings such as electrical / electronic equipment, optical equipment, precision equipment, toys, home / office electrical appliances, and parts such as automobiles, airplanes, and ships.

The present invention is described in detail below.
The molding material of the present invention is a vibration damping material (α comprising a resin composition in which barium sulfate (Y) and mica scale (Z) are dispersed in a polyester resin (X) comprising a dicarboxylic acid component constituent unit and a diol component constituent unit. ) And a modifier (β) for improving fluidity.
First, the polyester resin (X) in the vibration damping material (α) 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 number of diol component structural units (B _0). ) The total number of dicarboxylic acid component structural units (A ₁ ) having an odd number of carbon atoms in the main chain and the number of diol component structural units (B ₁ ) having an odd number of carbon atoms in the main chain. The ratio [(A ₁ + B ₁ ) / (A ₀ + B ₀ )] is 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 damping material (α), the number of carbon atoms in the main chain with respect to the total amount of the total number of dicarboxylic acid component constituent units (A ₀ ) and the total number of diol component constituent units (B ₀ ) of the polyester resin (X) is odd. Ratio of the total amount of a certain number of dicarboxylic acid component constituent units (A ₁ ) and the number of diol component constituent units (B ₁ ) having an odd number of carbon atoms in the main chain [(A ₁ + B ₁ ) / (A ₀ + B ₀ )] Is in the range of 0.5 to 1.0, preferably in the range of 0.7 to 1.0. The number of carbon atoms in the main chain of the dicarboxylic acid component structural unit and the number of carbon atoms in the main chain of the diol component structural unit in the polyester resin (X) are preferably 1, 3, 5, 7, 9. .

Examples of the dicarboxylic acid component constituting 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, azelaic 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, and 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. 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.

The damping material (α) is a ratio of the number of dicarboxylic acid component structural units (A ₁ ) having an odd number of carbon atoms in the main chain to the total number of dicarboxylic acid component structural units (A ₀ ) of the polyester resin (X) ( A ₁ / A ₀ ) is preferably in the range of 0.5 to 1.0, and the ratio (A ₁ / A ₀ ) is more preferably in the range of 0.7 to 1.0.
Further, in the vibration damping material (α), the ratio (B ₁ / B ₀ ) of the number of structural units (B ₁ ) derived from the diol to the total number of structural units (B ₀ ) of the diol component of the polyester resin (X) is 0. is preferably in the range of 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) in the vibration damping material (α) has (1) an intrinsic viscosity of 0.2 to 2.0 dL / g measured at 25 ° C. in a mixed solvent of 40/60 mass ratio of trichloroethane / phenol. And (2) it is preferable that the calorie | heat amount of the crystallization exothermic peak at the time of temperature measurement measured with the 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) in the vibration damping material (α) includes other structural units to the extent that the effects of the present invention are not impaired in addition to the dicarboxylic acid component structural unit and the diol component structural unit. Also good. 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.

  Examples of other diols include ethylene glycol, 1,2-propylene glycol, 2-methyl-1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, 2,5- Aliphatic diols such as hexanediol, diethylene glycol, and triethylene glycol; polyether compounds such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalene diethanol, 1,3-decahydronaphthalene diethanol, 1,4-decahydronaphthalene diethanol, 1,5- Big Dronaphthalene diethanol, 1,6-decahydronaphthalene diethanol, 2,7-decahydro naphthalene diethanol, tetralin dimethanol, norbornane dimethanol, tricyclodecane dimethanol, 5-methylol-5-ethyl-2- ( 1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane, pentacyclododecanedimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10- Alicyclic diols such as tetraoxaspiro [5.5] undecane; 4,4 ′-(1-methylethylidene) bisphenol, methylenebisphenol (bisphenol F), 4,4′-cyclohexylidenebisphenol (bisphenol Z) 4,4′-sulfonylbisphenol (bisphenol) S) and other alkylene oxide adducts of bisphenols; alkylene oxide addition of aromatic dihydroxy compounds such as hydroquinone, resorcin, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylbenzophenone Such as things.

  Examples of hydroxycarboxylic acids include hydroxybenzoic acid, dihydroxybenzoic acid, hydroxyisophthalic acid, hydroxyacetic acid, 2,4-dihydroxyacetophenone, 2-hydroxyhexadecanoic acid, 12-hydroxystearic acid, 4-hydroxyphthalic acid, 4,4 Examples include '-bis (p-hydroxyphenyl) pentanoic acid and 3,4-dihydroxycinnamic acid.

The method for producing the polyester resin (X) used in the vibration damping material (α) is not particularly limited, and conventionally known methods can be applied. 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.
The transesterification catalysts, esterification catalysts, etherification inhibitors used in these melt polymerization methods or solution polymerization methods, various stabilizers such as polymerization catalysts, heat stabilizers and light stabilizers, polymerization regulators and the like are also known in the past. Things 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.
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 other than the dicarboxylic acid from which the dicarboxylic acid component structural unit is derived. it can.

The damping material (α) used for the molding material of the present invention is filled with a high specific gravity filler barium sulfate (Y) and mica scale (Z) for the purpose of improving the sound insulation of the polyester resin (X).
The barium sulfate (Y) dispersed in the polyester resin (X) preferably has an average particle diameter of 3 to 300 μm. Here, the average particle diameter is a value measured by an X-ray transmission type particle size distribution measuring device Sedigraph.
When the content ratio of the inorganic substance having a specific gravity of 3.5 or more in the vibration damping and sound insulating material of the present invention is increased, the sound insulating property is also increased. In the present invention, the content of barium sulfate is 30 to 90% by mass, preferably 40 to 80% by mass, and more preferably 50 to 75% by mass from the balance of physical properties as a vibration damping and sound insulating material.

  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 material, it is preferable that the average particle diameter of mica in the vibration damping material of the present invention is 25 to 500 μm.

The mass ratio (X: Y: Z) of the polyester resin (X), barium sulfate (Y) and mica scale (Z) in the vibration damping material (α) used for the molding material of the present invention is 5-40: 30-90. : 5 to 40, preferably 10 to 30:40 to 80:10 to 30.
If the mass ratio of the mica scale (Z) in the damping material (α) is less than 5, the effect of improving the damping performance cannot be obtained, and if the mass ratio exceeds 40, the damping property due to the increase in the mica content There is almost no further improvement and the moldability may be lost.

  The damping material (α) used in the molding material of the present invention can be obtained by mixing the polyester resin (X), barium sulfate (Y) and mica scale (Z), but the mixing method should be a known method. Can do. For example, the method of melt-mixing using apparatuses, such as a hot roll, a Banbury mixer, a biaxial kneader, an extruder, is mentioned. 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.

Next, examples of the modifier (β) for improving fluidity contained in the molding material of the present invention include thermoplastic resins and lubricants.
As the thermoplastic resin, at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyisoprene resin, ethylene-vinyl acetate copolymer resin and styrene-acrylonitrile copolymer resin is used. Of these, polyethylene resins and polypropylene resins are more preferable, and polypropylene resins are particularly preferable. Note that these thermoplastic resins may be thermoplastic resins reinforced with glass fibers, carbon fibers, or the like.
Examples of lubricants include polyethylene wax, polyethylene oxide wax, fluorine-modified polyethylene wax, polypropylene wax, polypropylene oxide wax, polyolefin wax such as vinyl acetate-ethylene copolymer wax, organosilicone wax, higher fatty acid ester wax, carnauba wax, and montan. Acid ester wax, zinc stearate, calcium stearate, magnesium stearate and the like can be mentioned, but not limited thereto. Particularly preferred is montanic acid ester wax. The modifier may be a single type or a mixture of two or more types.

When the content ratio of the damping material (α) in the molding material is increased, the damping property is also increased, but the fluidity is lowered. In particular, when the content ratio of the vibration damping material (α) is 50 to 97% by mass, the balance between the vibration damping property, the fluidity, and the release property is good and the moldability is good. The content ratio of the damping material (α) is preferably 90 to 97% by mass, and more preferably 94 to 97% by mass.
Further, the melt flow rate when measured under the conditions of 200 ° C., load of 10 kg, orifice diameter of 2 mm using the molding material and melt indexer of the present invention is 3 to 500 g / 10 min, and 50 to 300 g / 10 min is preferred.

  The molding material of the present invention comprises a vibration damping material (α) comprising a resin composition in which titanium dioxide (Y) and mica scale (Z) are dispersed in a polyester resin (X), and a modifier for improving fluidity ( β), and optionally one or more additives such as dispersants, compatibilizers, surfactants, antistatic agents, plasticizers, flame retardants, crosslinking agents, antioxidants. Anti-aging agents, weathering agents, heat-resistant agents, processing aids, brighteners, colorants (pigments, dyes), foaming aids, foaming aids, conductive materials, inorganic fillers and the like within a range that does not impair the effects of the present invention. Can be added.

  The molding material of the present invention comprises a vibration damping material (α) comprising a resin composition in which barium sulfate (Y) and mica scales (Z) are dispersed in a polyester resin (X), and a modifier for improving fluidity ( It can be obtained by mixing β) and, if necessary, other additives. A known method can be used as the mixing method. For example, the method of melt-mixing using apparatuses, such as a hot roll, a Banbury mixer, a biaxial kneader, an extruder, is mentioned. In addition, addition methods, such as other additives, addition order, etc. are not specifically limited.

  The molded product of the present invention is formed by molding the above-described molding material and is preferably injection molding, but may be obtained by molding by other known methods such as extrusion molding and press molding. The molded article of the present invention includes parts and housings such as personal computers, OA equipment, AV equipment, mobile phones, and other electrical / electronic equipment, optical equipment, precision equipment, toys, home / office electrical products, automobiles, airplanes, and ships. It can utilize suitably for components, such as. The molded product of the present invention can be easily manufactured without requiring a complicated process such as lamination of damping materials, and can exhibit excellent damping properties.

Examples are shown below, but the present invention is not limited to the following examples.
In addition, evaluation of the polyester resin (X) obtained by the Example and the comparative example and molding material was performed with the following method.
(1) Molar ratio of each structural unit of the polyester resin (X): [(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 ([η]) of the polyester resin (X):
The polyester resin was dissolved in a mixed solvent of trichloroethane / phenol = 40/60 (mass ratio) and maintained at 25 ° C., and measurement was performed using a Canon Fenceke viscometer.
(3) Calorific value (ΔHc) of the crystallization exothermic peak when the temperature of the polyester resin (X) is lowered:
This 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) Loss coefficient of molding material:
The molding materials obtained in Examples and Comparative Examples were formed into a sheet having a thickness of about 1 mm by hot pressing at 200 ° C., and cut into 10 mm × 150 mm to obtain test pieces.
The test piece is bonded to a 1 mm-thick substrate (aluminum alloy 5052 material) by hot pressing with a hot press or a two-component curable epoxy adhesive (trade name: Cemedine SG-EPO, EP008). Thus, an unconstrained vibration damping material was produced.
The obtained unconstrained damping material was measured for a loss factor at a 500 Hz antiresonance point by a central excitation method under a measurement temperature of 20 ° C. using a loss factor measuring device (manufactured by Ono Sokki Co., Ltd.). Note that the greater the loss factor, the higher the damping performance.

(5) Sound transmission loss:
The sheet obtained in the same manner as in (4) was cut out to 300 mm × 300 mm to form a test piece, and a two-component curable epoxy adhesive (trade name, manufactured by Cemedine Co., Ltd.) on a 1 mm thick substrate (aluminum alloy 5052 material). : Cemedine SG-EPO, EP008) to prepare a test piece, and the sound transmission loss (dB) of 125 Hz to 16 KHz was measured. The measurement temperature is 23 ° C. In addition, sound insulation property is so high that sound transmission loss is large.
(6) Flowability of molding material:
The melt flow rate was measured under the conditions of 200 ° C., a load of 10 kg, and an orifice diameter of 2 mm using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd., melt indexer TYPE C-5059D). The higher the melt flow rate, the higher the fluidity.

(7) Moldability of molding material:
The mold material was molded with an injection molding machine (SE130DU-HP, manufactured by Sumitomo Heavy Industries, Ltd.), and the mold shape and mold release properties were observed and evaluated.
In addition, the case where both the shape of the molded product and the releasability from the mold are good, ○, the case where the shape of the molded product is good and the releasability from the mold is poor, or the releasability from the mold is good The case where the shape of the molded product is bad is indicated by Δ, and the case where both the shape of the molded product and releasability from the mold are bad is indicated by “X”.

Production Example 1 (Production of polyester resin X)
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 ( 9950 g (60.3 mol), manufactured by AG International Chemical Co., Ltd., azelaic acid (manufactured by Cognis, trade name: EMEROX 1144, azelaic acid content: 93.3 mol%, total amount of dicarboxylic acid: 99 .97%) 5376 g (29.7 mol) and 2-methyl-1,3-propanediol (manufactured by Dalian Chemical Industry Co., Ltd.) 14600 g (162 mol) were added, and the temperature was raised to 225 ° C. under normal pressure and nitrogen atmosphere. Then, the esterification reaction was performed for 3.0 hours. After the reaction conversion rate of isophthalic acid and azelaic acid reached 85 mol% or more while monitoring the amount of condensed water distilled off, 14.3 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 mass of charged raw materials is 70.5 ppm) is added, and the temperature is gradually increased and the pressure is reduced, whereby 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 X are [η] = 0.71 (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].
The ratio of the dicarboxylic acid component constituent unit and the diol component constituent unit of this polyester resin X is (A ₁ + B ₁ ) / (A ₀ + B ₀ ) = 1.0; (A ₁ / A ₀ ) = 1.0; _{B 1} / B 0) a = 1.0.
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] 14.80 mass %, Mica scales (manufactured by Yamaguchi Mica Co., Ltd., trade name: CS-060DC; average particle size 200 μm, specific gravity 2.7 to 3.1), 17.25% by mass, carbon powder (manufactured by Ketjen Black International Co., Ltd .: Ket CHEN BLACK EC300J) 0.25% by mass, barium sulfate (manufactured by Nippon Solvay Co., Ltd .: G grade; average particle size 4.0 μm, specific gravity 4.4) 63.5% by mass, ethane-1,2-pentabromophenyl 3.00 mass% and antimony trioxide 1.20% were kneaded using a kneader to obtain a vibration damping and sound insulating material α1.

<Examples 1-5>
The damping material α1 obtained in Production Example 1 and polypropylene (trade name: Novatec PP · MG03B, manufactured by Nippon Polypro Co., Ltd.) were mixed at a ratio shown in Table 1 to obtain a molding material. The physical property measurement results of the obtained molding material are shown in Table 1.

<Comparative example 1>
Table 1 shows the physical property measurement results obtained only with the vibration damping material α1 obtained in Production Example 1.

<Example 6>
A damping material α1 of 95% by mass and polyethylene (Novatech PE LJ803 manufactured by Nippon Polyethylene Co., Ltd.) of 5% by mass were mixed to obtain a molding material. Table 2 shows the physical properties of the molding material obtained.

<Example 7>
A damping material α1 (95% by mass) and ethylene vinyl acetate copolymer (Evaflex V5773W, Mitsui / DuPont Chemical Co., Ltd.) (5% by mass) were mixed to obtain a molding material. Table 2 shows the physical properties of the molding material obtained.

<Example 8>
A damping material α1 of 95% by mass and polyisoprene (NIPOL IR2200, manufactured by Nippon Zeon Co., Ltd.) of 5% by mass were mixed to obtain a molding material. Table 2 shows the physical properties of the molding material obtained.

<Example 9>
A damping material α1 95% by mass and 5% by mass of a styrene acrylonitrile copolymer (Sanlex SAN-R (S20), manufactured by Technopolymer Co., Ltd.) were mixed to obtain a molding material. Table 3 shows the physical properties of the molding material obtained.

<Example 10>
A damping material α1 (95% by mass) and polyvinylidene fluoride (Kureha KF Polymer # 1000, manufactured by Kureha Corporation) (5% by mass) were mixed to obtain a molding material. Table 3 shows the physical properties of the molding material obtained.

<Example 11>
A damping material α1 (95 mass%) and polycarbonate (Iupilon H-3000R, manufactured by Mitsubishi Engineering Plastics) (5 mass%) were mixed to obtain a molding material. Table 5 shows the physical properties of the molding material obtained.

<Example 12>
A damping material α1 of 95% by mass and polyacetal (Iupital F30-03, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) of 5% by mass were mixed to obtain a molding material. Table 4 shows the physical properties of the molding material obtained.

<Example 13>
A damping material α1 (95% by mass) and polymethyl methacrylate (Acrypet MF001, manufactured by Mitsubishi Rayon Co., Ltd.) (5% by mass) were mixed to obtain a molding material. Table 4 shows the physical properties of the molding material obtained. A damping material α1 95% by mass and 5% by mass of a styrene acrylonitrile copolymer (Sanlex SAN-R (S20), manufactured by Technopolymer Co., Ltd.) were mixed to obtain a molding material. Table 3 shows the physical properties of the molding material obtained.

<Example 14>
A damping material α1 (95% by mass) and chlorinated polyethylene (Elaslene 303B, Showa Denko KK) (5% by mass) were mixed to obtain a molding material. Table 4 shows the physical properties of the molding material obtained.

<Comparative example 2>
Polyester resin X 22.2% by mass, mica scales (manufactured by Yamaguchi Mica Co., Ltd., CS-060DC) 60% by mass, carbon powder (manufactured by Ketjen Black International Co., Ltd .: Ketjen Black EC300J) 0.3% by mass, titanium oxide (CR-80 manufactured by Ishihara Sangyo Co., Ltd.) 17.5% by mass was kneaded using a kneader to obtain a vibration damping and sound insulating material α2. Table 4 shows the physical properties of the obtained vibration damping material .

<Comparative Example 3>
Polyester resin X 36% by mass, mica scales (Yamaguchi Mica Co., Ltd., CS-060DC) 60% by mass, carbon powder (Ketjen Black International Co., Ltd .: Ketjen Black EC300J) 4% by mass were kneaded using a kneader. Thus, a vibration damping and sound insulating material α3 was obtained. Table 4 shows the physical properties of the obtained vibration damping material.

<Comparative example 4>
A damping material α1 99% by mass and polypropylene (manufactured by Nippon Polypro Co., Ltd., trade name: Novatec PP · MG03B) 1% by mass were mixed to obtain a molding material. Table 4 shows the physical properties of the molding material obtained.

<Comparative Example 5>
A damping material α1 99% by mass and polypropylene (manufactured by Nippon Polypro Co., Ltd., trade name: Novatec PP · MG03B) 1% by mass were mixed to obtain a molding material. Table 4 shows the physical properties of the molding material obtained.

<Comparative Example 6>
A damping material α1 95 mass% and polystyrene (PSJ polystyrene GPPS 679, manufactured by PS Japan Ltd.) 5 mass% were mixed to obtain a molding material. Table 4 shows the physical properties of the molding material obtained.

<Comparative Example 7>
A damping material α1 (95% by mass) and acrylonitrile butadiene styrene copolymer (UMG-ABS Fu23, manufactured by UMG-ABS Co., Ltd.) (5% by mass) were mixed to obtain a molding material. Table 5 shows the physical properties of the molding material obtained.

<Comparative Example 8>
A damping material α1 (95% by mass) and polyvinyl chloride (KVC 938U-H05, Showa Kasei Kogyo Co., Ltd.) (5% by mass) were mixed to obtain a molding material. Table 5 shows the physical properties of the molding material obtained.

<Comparative Example 9>
A damping material α1 (95% by mass) and polybutylene terephthalate (Novaduran 5010R5, manufactured by Mitsubishi Engineering Plastics) were mixed to obtain a molding material. Table 5 shows the physical properties of the molding material obtained.

<Comparative Example 10>
A damping material α1 (95% by mass) and polyphenylene sulfide (Fortron 0220A9, manufactured by Polyplastics Co., Ltd.) (5% by mass) were mixed to obtain a molding material. Table 5 shows the physical properties of the molding material obtained.

<Comparative Example 11>
A damping material α1 (95% by mass) and polyamide (Novamid 3010N5-SL4, manufactured by Mitsubishi Engineering Plastics) (5% by mass) were mixed to obtain a molding material. Table 5 shows the physical properties of the molding material obtained.

*１：材料が溶融せず、評価不可
*２：材料が溶融せず、評価不可
*３：流動せず、メルトフローレート測定不可
*４：材料が溶融せず、評価不可

* 1: Evaluation is not possible because the material does not melt.
* 2: The material does not melt and cannot be evaluated.
* 3: Does not flow and cannot measure melt flow rate
* 4: Evaluation is not possible because the material does not melt.

  As shown in Table 1, the molding materials of Examples 1 to 5 obtained by mixing a damping material α1 and a modifier (polypropylene) for improving fluidity are compared with the damping material α1 of Comparative Example 1. High melt flow rate and good fluidity. In addition, the molding materials of Examples 1 to 5 have improved moldability (shape and mold release) as compared with the vibration damping material α1 of Comparative Example 1. Therefore, it turns out that the molding material of Examples 1-5 can be injection-molded, and a molded product can be obtained easily.

  As shown in Tables 2 and 3, as modifiers, polyethylene resin, polyisoprene resin, ethylene-vinyl acetate copolymer resin, polyvinylidene fluoride resin, styrene-acrylonitrile copolymer resin, polycarbonate resin, polyacetal resin It can be seen that, when polymethyl methacrylate and chlorinated polyethylene resin are used, excellent moldability can be obtained as with polypropylene resin.

  Comparative Example 2 and Comparative Example 3 in Table 4 are obtained by changing the composition of the damping material of Comparative Example 1. These compositions are poor in fluidity and moldability and cannot be used as molding materials. Further, the damping materials of Comparative Example 2 and Comparative Example 3 have a smaller sound insulation (sound transmission loss) than other examples and comparative examples.

From Comparative Example 4 and Comparative Example 5 in Table 4, it can be seen that when a polypropylene resin or the like is used as a modifier, good moldability cannot be obtained when the content is 2% by mass or less. Further, from Comparative Examples 6 to 11 in Table 4 and Table 5, good moldability with polystyrene resin, acrylonitrile butadiene styrene copolymer resin, polyvinyl chloride resin, polybutylene terephthalate resin, polyphenylene sulfide resin and polyamide resin, etc. It turns out that cannot be obtained.

Claims (3)

A damping material (α) comprising a resin composition in which barium sulfate (Y) and mica scale (Z) are dispersed in a polyester resin (X) comprising a dicarboxylic acid component constitutional unit and a diol component constitutional unit, and improvement in fluidity A molding material containing a modifying material (β) for
(1) Dicarboxylic acid component constitution in which the number of carbon atoms in the main chain is an odd number with respect to the total amount of all dicarboxylic acid component constitutional units (A ₀ ) and all diol component constitutional 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 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. Within the range of 5-1.0,
(2) The mass ratio (X: Y: Z) of the polyester resin (X), barium sulfate (Y) and mica scale (Z) in the vibration damping material (α) is 5-40: 30-90: 5. A range of 40,
(3) The content of the vibration damping material (α) is 50 to 97% by mass,
(4) The modifier (β) for improving fluidity was selected from the group consisting of polyethylene resin, polypropylene resin, polyisoprene resin, ethylene-vinyl acetate copolymer resin, and styrene-acrylonitrile copolymer resin. At least one,
(5) A molding material having a melt flow rate of 3 to 500 g / 10 min when measured using a melt indexer at 200 ° C., a load of 10 kg, and an orifice diameter of 2 mm.   The molding material according to claim 1, wherein the content of the damping material (α) is in the range of 90 to 97 mass%. A molded product obtained by molding the molding material according to claim 1.