JP6168731B2 - Molding material and molded product having vibration damping properties - Google Patents

Description

  The present invention provides a molding material and molding that have excellent vibration damping properties, excellent molding processability, and can be easily manufactured into a molded product without requiring complicated steps such as lamination of damping materials. Related to goods.

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, 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. Therefore, the lamination method of the damping material needs to take a method such as bonding with an adhesive or pressure-sensitive adhesive, double-sided tape, laminating or coating, adhesion by pressing, or bonding of self-adhesive damping material. It becomes complicated and leads to an increase in cost.

JP 2006-052377 A WO20008 / 018444 pamphlet International Publication No. 2009/063837 Pamphlet

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

  As a result of intensive investigations to achieve the above object, the present inventors have found that the fluidity of the damping material is mixed by mixing a damping material comprising a polyester resin and a filler and a specific modifier for improving fluidity. As a result, the present inventors have found that a molded article having vibration damping properties can be easily produced without requiring a complicated process such as lamination, thereby achieving the present invention.

That is, the present invention provides the following molding materials and molded products.
1. 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) mainly composed of a dicarboxylic acid component structural unit and a diol component structural unit, and a flow A molding material containing a modifying material (β) for improving the property , wherein the content of the damping material (α) is in the range of 90 to 98% by mass ,
(1) In all the carboxylic acid structural units of the polyester resin, 50 mol% or more is a dicarboxylic acid structural unit derived from an aromatic dicarboxylic acid, and in the dicarboxylic acid structural unit (a) derived from an aromatic dicarboxylic acid, 70 mol% The above is a dicarboxylic acid structural unit derived from isophthalic acid,
(2) Of all the diol constituent units of the polyester resin, the diol component constituent unit (b) derived from ethylene glycol is 60 mol% or more,
(3) The polyester resin contains a structural unit (c) composed of an aliphatic dicarboxylic acid having 5 or more carbon atoms, an aliphatic diol and / or an aliphatic hydroxycarboxylic acid, and the total of these structural units is 5 ~ 25 mol%,
(4) The total of the structural units (a), (b) and (c) in the polyester resin is 75 mol% or more in the total structural units of the polyester resin,
(5) Intrinsic viscosity of the polyester resin measured at 25 ° C. in a mixed solvent of tetrachloroethane / phenol = 1/1 (mass ratio) is 0.2 to 2.0 dL / g,
(6) The calorific value of the crystallization exothermic peak when the temperature of the polyester resin measured by a differential scanning calorimeter is 5
J / g or less,
(7) In the damping material (α), the content of titanium dioxide (Y) is 2 to 20% by mass, the content of mica scale (Z) is 18 to 70% by mass, and the fillers (Y) and (Z) The total amount of is 20 to 80% by mass,
(8) The modifier (β) for improving fluidity is polypropylene resin, polyethylene resin, polyisoprene resin, ethylene-vinyl acetate copolymer resin, polyvinylidene fluoride resin, polystyrene resin, acrylonitrile butadiene styrene copolymer. Resin, styrene-acrylonitrile copolymer resin, polymethyl methacrylate, polyvinyl chloride resin, chlorinated polyethylene resin, at least one selected from the group consisting of polyacetal resins,
(9) A molding material having a melt flow rate in the range of 600 to 5 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. A molded product obtained by molding the molding material of 1 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 vibration damping material resin composition 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) mainly composed of a dicarboxylic acid component structural unit and a diol component structural unit, and a flow It contains a modifier (β) for improving the performance.

  In all the structural units of the polyester resin (X) composed of the dicarboxylic acid structural unit and the diol structural unit, the total of the dicarboxylic acid structural unit and the diol structural unit is preferably 75 mol% or more, and more preferably 90 mol% or more. It is more preferable.

In the dicarboxylic acid structural unit of the polyester resin (X), the dicarboxylic acid structural unit (a) derived from the aromatic dicarboxylic acid is 50 mol% or more, preferably 60 mol% or more. When the dicarboxylic acid structural unit (a) derived from the aromatic dicarboxylic acid is less than 50 mol%, the reactivity is insufficient during resin polymerization, which is not preferable.
Furthermore, in the dicarboxylic acid structural unit (a) derived from the aromatic dicarboxylic acid, the isophthalic acid structural unit is 70 mol% or more, preferably 90 mol% or more. When the isophthalic acid structural unit is 70 mol% or more, more filler for enhancing the vibration damping performance of the resin composition can be dispersed in the polyester resin.

  As the dicarboxylic acid structural unit (a) derived from the aromatic dicarboxylic acid, other aromatic dicarboxylic acids can be used as long as isophthalic acid is 70 mol% or more. Specific examples of aromatic dicarboxylic acids other than isophthalic acid include conventionally known aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, and their alkyl, halogen, alkoxy Examples include substitution products. The dicarboxylic acid structural unit (a) derived from the aromatic dicarboxylic acid of the polyester resin used in the present invention may contain one or two or more aromatic dicarboxylic acid structural units other than isophthalic acid.

Of all the diol structural units of the polyester resin (X), the diol component structural unit (b) derived from ethylene glycol is 60 mol% or more, preferably 70 mol% or more. By setting the diol component structural unit (b) derived from ethylene glycol to 60 mol% or more, a resin composition excellent in moldability, toughness, and vibration damping performance can be obtained.

The polyester resin (X) contains a structural unit (c) composed of an aliphatic dicarboxylic acid having 5 or more carbon atoms, an aliphatic diol and / or an aliphatic hydroxycarboxylic acid, and the structural unit (c) The content is 5 to 25 mol%, preferably 10 to 20 mol%. When the content of the structural unit (c) is 25 mol% or more, sufficient performance cannot be exhibited in a temperature region higher than room temperature, and when it is less than 5 mol%, the material lacks toughness, which is not preferable.
The structural unit (c) composed of an aliphatic dicarboxylic acid having 5 or more carbon atoms, an aliphatic diol and an aliphatic hydroxycarboxylic acid is a functional group of the dicarboxylic acid component, the diol component or the hydroxycarboxylic acid component constituting the polyester resin. The total number of carbon atoms contained in the main chain and side chain existing between the groups is 5 or more. At this time, the carbon atom contained in the carboxyl group which forms an ester bond shall be contained in a dicarboxylic acid structural unit or a hydroxycarboxylic acid structural unit. The upper limit of the number of carbon atoms of the structural unit (c) composed of aliphatic dicarboxylic acid, aliphatic diol and / or aliphatic hydroxycarboxylic acid is not particularly limited, but those having 17 or less carbon atoms are preferable.

  Specific examples of the component corresponding to the structural unit (c) include 2-methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, undecanedioic acid, dodecanedioic acid, Brassylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic 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] undecane and other aliphatic dicarboxylic acids; 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6 -Hexanediol, 1,7-pentanediol, 2,5-hexanediol, 1, -Octanediol, 1,9-nonanediol, neopentyl glycol, cyclohexanediol and derivatives thereof, decahydronaphthalenediethanol and derivatives thereof, norbornene dimethanol and derivatives thereof, tricyclodecane dimethanol and derivatives thereof, pentacyclododecanedi Methanol, triethylene glycol, dipropylene glycol, dibutylene glycol, 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane, 3,9-bis (1 , 1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane; polyether compounds such as polyethylene glycol, polypropylene glycol and polybutylene glycol; - hydroxyhexadecanoic acid, and aliphatic hydroxycarboxylic acids such as 12-hydroxy stearic acid. Of these, preferably azelaic acid, sebacic acid, 3-methyl-1,5-pentanediol, 1,6-hexanediol, triethylene glycol, more preferably azelaic acid, sebacic acid, triethylene glycol, Most preferred is azelaic acid.

  The total of the structural units (a), (b) and (c) in the polyester resin (X) is 75 mol% or more, preferably 90 mol% or more of all the structural units of the polyester resin. The total of the structural units (a), (b) and (c) is 75 mol% or more of the total structural units of the polyester resin, so that the vibration damping performance, moldability, toughness and other physical properties are excellent. it can.

The polyester resin (X) has other conventionally known dicarboxylic acids, diols, hydroxys, as long as the total of the structural units (a), (b) and (c) is 75 mol% or more of the total structural units of the polyester resin Carboxylic acids, polycarboxylic acids and polyhydric alcohols can be used.
Specific examples of dicarboxylic acids, diols, hydroxycarboxylic acids, polycarboxylic acids and polyhydric alcohols other than these structural units (a), (b) and (c) include 1,2-propylene glycol, 1,3 -Aliphatic dicarboxylic acids having less than 5 carbon atoms, such as propanediol, 2-methyl-1,3-propanediol, 2-methyl-1,2-propanediol, 1,3-butylene glycol, diethylene glycol, hydroxyacetic acid; Aromatic diols and aliphatic hydroxycarboxylic acids, metaxylene glycol, tetralin dimethanol and derivatives thereof; hydroxybenzoic acid, dihydroxybenzoic acid, hydroxyisophthalic acid, 2,4-dihydroxyacetophenone, 4-hydroxyphthalic acid, 4,4′-bis (p-hydroxyl Phenyl) aromatic hydroxycarboxylic acids such as pentanoic acid; trivalent or higher polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid, glyceryl tricarbarate, trimethylolpropane, pentaerythritol, polyhydric alcohols and many And monovalent hydroxycarboxylic acid.

  The polyester resin (X) used in the present invention has an intrinsic viscosity of 0.2 to 2.0 dL / g measured at 25 ° C. in a mixed solvent of tetrachloroethane / phenol = 1/1 (mass ratio), And the calorific value of the crystallization exothermic peak at the time of cooling as measured with a differential scanning calorimeter needs to be 5 J / g or less. If the above conditions are not satisfied, the vibration damping performance is lowered, which is not preferable.

There is no restriction | limiting in particular in the method of manufacturing polyester resin (X), 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, conventionally known ones 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, a compound containing a metal such as germanium, antimony, tin, titanium, for example, 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, 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 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 material 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. In the present invention, by using titanium dioxide in particular, a molding material having high vibration damping performance can be obtained.
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), titanium dioxide (Y) and mica scale (Z) in the damping material (α) used for the molding material of the present invention is 15-40: 5-30. : 30 to 80, preferably 15 to 25: 15 to 25: 50 to 70.
If the mass ratio of the polyester resin (X) in the vibration damping material (α) is less than 15, the effect of improving the vibration damping property due to titanium dioxide and mica scales cannot be obtained sufficiently, and the moldability may be lost. When the mass ratio exceeds 40, the titanium dioxide and mica scales having a content in which the effect of improving the vibration damping properties appears remarkably cannot be dispersed.
If the mass ratio of titanium dioxide (Y) in the vibration damping material (α) is less than 5, the effect of improving the damping properties by titanium dioxide cannot be obtained. If the mass ratio of titanium dioxide (Y) exceeds 30, the titanium dioxide Despite the high content, the damping performance is not so improved.
If the mass ratio of the mica scale (Z) in the damping material (α) is less than 30, the effect of improving the damping performance cannot be obtained, and if the mass ratio exceeds 80, the damping property due to the increase in the mica content Further improvement is almost lost and there is a risk of losing moldability.
Further, in the damping material (α), the content of titanium dioxide (Y) is 2 to 20% by mass, the content of mica scale (Z) is 18 to 70% by mass, and the fillers (Y) and (Z) The total amount is preferably 20 to 80% by mass.

  The damping material (α) used in the molding material of the present invention can be obtained by mixing the polyester resin (X), titanium dioxide (Y), and mica scale (Z), and 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.
Examples of the thermoplastic resin include polypropylene resin, polyethylene resin, polyisoprene resin, ethylene-vinyl acetate copolymer resin, polyvinylidene fluoride resin, polystyrene resin, acrylonitrile butadiene styrene copolymer resin, styrene-acrylonitrile copolymer resin, poly Methyl methacrylate, polyvinyl chloride resin, chlorinated polyethylene resin, and polyacetal resin are 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 the lubricant include polyethylene wax, oxidized polyethylene wax, fluorine-modified polyethylene wax, polypropylene wax, oxidized polypropylene 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.
Moreover, the melt flow rate at the time of measuring on conditions of 200 degreeC, a load of 10 kg, and an orifice diameter of 2 mm using the molding material of the present invention and a melt indexer is 5 to 1500 g / 10 min, and 5 to 600 g / It is preferably 10 min, and more preferably 5 to 100 g / 10 min.

  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 agent, weathering agent, heat resistance agent, processing aid, brightening agent, colorant (pigment, dye), foaming agent, foaming aid, conductive material, inorganic filler, and the like that do 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 titanium dioxide (Y) and mica scale (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) Composition of structural unit of polyester resin It was calculated from the ratio of integral values of 400 MHz-1H-NMR spectrum measurement results.

(2) Intrinsic viscosity ([η]) of the polyester resin (X):
The polyester resin was dissolved in a mixed solvent of tetrachloroethane / phenol = 1/1 (mass ratio) and held at 25 ° C., and measured using an Ubbelohde viscometer.

(3) Calorific value of crystallization exothermic peak during temperature drop The calorific value of the crystallization exothermic peak during temperature fall of the polyester resin was measured using a DSC-60 type 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 (50 ml / min) at a heating rate of 10 ° C./min up to 150 ° C., held at 150 ° C. for 1 min, 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 40 ° 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) 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.
Note that “* 2” in the table indicates that measurement was not possible because the sample did not flow under the measurement conditions.

(6) 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)
In a 500 ml glass flask equipped with a heating device, a stirring blade, a condenser, a trap, a thermometer, and a nitrogen gas introduction tube, 7.2 mol% of terephthalic acid (manufactured by Mizushima Aroma Co., Ltd.), 64. A mixture of 8 mol% (manufactured by EI International Chemical Co., Ltd.) and 28 mol% azelaic acid (EMEROX 1144 manufactured by Cognis) and 0.8 mol of ethylene glycol (manufactured by Maruzen Oil Chemical Co., Ltd.) The input ratio of diol / dicarboxylic acid was 1.5.
The raw material charged was heated to 220 ° C. under an atmospheric pressure of nitrogen and subjected to esterification reaction for 2.5 hours or more. The reaction conversion of dicarboxylic acid was 90 mol% while monitoring the amount of condensed water distilled off. After the above, 50 ppm of titanium (IV) tetrabutoxide (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) was added, and the temperature was increased and the pressure was gradually reduced. The polycondensation reaction was finally performed at 240 to 250 ° C. and 1.5 kPa or less while extracting the diol component out of the system. The viscosity of the reaction mixture and the stirring torque value gradually increased, and the reaction was terminated when an appropriate viscosity was reached or when the distillation of the diol stopped.
The properties of the obtained polyester resin X were [η] = 0.92 (dL / g) and ΔHc = 0 (J / g).

<Example 1>
Polyester resin X 24.8% by mass obtained in Production Example 1, titanium dioxide powder (Ishihara Sangyo Co., Ltd., trade name: Taipei CR-80) 15% by mass, mica scale (Yamaguchi Mica Co., Ltd., trade name: CS) -060DC) 60% by mass and carbon powder (Ketjen Black International Co., Ltd .: Ketjen Black EC) 0.2% by mass were kneaded at 200 ° C. using a biaxial kneader to obtain a damping material α1. . The damping material α1 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>
Polyester resin X 24.8% by mass obtained in Production Example 1, titanium dioxide powder (Ishihara Sangyo Co., Ltd., trade name: Taipei CR-80) 15% by mass, mica scale (Yamaguchi Mica Co., Ltd., trade name: CS) -060DC) 60% by mass and carbon powder (Ketjen Black International Co., Ltd .: Ketjen Black EC) 0.2% by mass were kneaded at 200 ° C. using a biaxial kneader to obtain a damping material α1. . Table 1 shows the physical property measurement results with only the obtained vibration damping material α1.

< Reference Example 1, Examples 2 to 6>
The damping material α1 obtained in Comparative Example 1 and polypropylene (trade name: Novatec PP · MG03B, manufactured by Nippon Polypro Co., Ltd.) were mixed at the ratios shown in Tables 1 and 2 to obtain a molding material. The physical property measurement results of the obtained molding material are shown in Tables 1 and 2.

<Example 7>
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 8>
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 9>
A damping material α1 (95% by mass) and polyisoprene (NIPOL IR2200, manufactured by Nippon Zeon Co., Ltd.) (5% by mass) were mixed to obtain a molding material. Table 2 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 polystyrene (PSJ polystyrene GPPS 679, manufactured by PS Japan Ltd.) 5 mass% were mixed to obtain a molding material. Table 3 shows the physical properties of the molding material obtained.

<Example 12>
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 3 shows the physical properties of the molding material obtained.

<Example 13>
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 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.

<Example 15>
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 4 shows the physical properties of the molding material obtained.

<Example 16>
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.

<Example 17>
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.

<Comparative example 2>
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 5 shows the physical properties of the molding material obtained.

<Comparative Example 3>
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.

<Comparative example 4>
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 5>
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 6>
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：流動せず、メルトフローレートの測定は不可
*３：材料が溶融せず、評価不可

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

  As shown in Tables 1 and 2, the molding materials of Examples 1 to 6 obtained by mixing the damping material α1 and the modifier (polypropylene) for improving fluidity are the damping materials of Comparative Example 1. Compared to the material α1, the melt flow rate is high and the fluidity is good. In addition, the molding materials of Examples 1 to 6 have improved moldability (shape and mold release property) as compared with the damping material α1 of Comparative Example 1. The damping material α1 of Comparative Example 1 has no fluidity and cannot be injection-molded, but the molding materials of Examples 1 to 6 can be injection-molded, and a molded product can be easily obtained. The

  As shown in Table 2, Table 3 and Table 4, as a modifier, polyethylene resin, polyisoprene resin, ethylene-vinyl acetate copolymer resin, polyvinylidene fluoride resin, polystyrene resin, acrylonitrile butadiene styrene copolymer It can be seen that excellent moldability can be obtained in the same manner as the polypropylene resin when a resin, styrene-acrylonitrile copolymer resin, polymethyl methacrylate, polyvinyl chloride resin, chlorinated polyethylene resin, or polyacetal resin is used.

  From Comparative Example 2 in Table 5, 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 1% by mass or less. In addition, it can be seen from Comparative Examples 3 to 6 in Table 5 that good moldability cannot be obtained with polycarbonate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyamide resin.

  The molding material of the present invention has excellent vibration damping properties over a wide range of temperatures, is excellent in molding processability, and can be easily obtained without requiring complicated processes such as lamination of vibration damping materials. Therefore, as molded products, personal computers, OA equipment, AV equipment, electric / electronic equipment such as mobile phones, optical equipment, precision equipment, toys, home / office electrical products and other parts and housings, automobiles, aircraft, ships, etc. As a part, it can be suitably used in a place where vibration occurs.

Claims (2)

A damping material (α) comprising a resin composition 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, and improvement in fluidity A molding material containing a modifying material (β) for the content of the damping material (α) in the range of 90 to 98% by mass ,
(1) In all the carboxylic acid structural units of the polyester resin, 50 mol% or more is a dicarboxylic acid structural unit derived from an aromatic dicarboxylic acid, and in the dicarboxylic acid structural unit (a) derived from an aromatic dicarboxylic acid, 70 mol% The above is a dicarboxylic acid structural unit derived from isophthalic acid,
(2) Of all the diol constituent units of the polyester resin, the diol component constituent unit (b) derived from ethylene glycol is 60 mol% or more,
(3) The polyester resin contains a structural unit (c) composed of an aliphatic dicarboxylic acid having 5 or more carbon atoms, an aliphatic diol and / or an aliphatic hydroxycarboxylic acid, and the total of these structural units is 5 ~ 25 mol%,
(4) The total of the structural units (a), (b) and (c) in the polyester resin is 75 mol% or more in the total structural units of the polyester resin,
(5) Intrinsic viscosity of the polyester resin measured at 25 ° C. in a mixed solvent of tetrachloroethane / phenol = 1/1 (mass ratio) is 0.2 to 2.0 dL / g,
(6) The calorific value of the crystallization exothermic peak at the time of cooling of the polyester resin measured with a differential scanning calorimeter is 5 J / g or less,
(7) In the damping material (α), the content of titanium dioxide (Y) is 2 to 20% by mass, the content of mica scale (Z) is 18 to 70% by mass, and the fillers (Y) and (Z) The total amount of is 20 to 80% by mass,
(8) The modifier (β) for improving fluidity is polypropylene resin, polyethylene resin, polyisoprene resin, ethylene-vinyl acetate copolymer resin, polyvinylidene fluoride resin, polystyrene resin, acrylonitrile butadiene styrene copolymer. Resin, styrene-acrylonitrile copolymer resin, polymethyl methacrylate, polyvinyl chloride resin, chlorinated polyethylene resin, at least one selected from the group consisting of polyacetal resins,
(9) A molding material having a melt flow rate in the range of 5 to 1500 g / 10 min when measured using a melt indexer at 200 ° C., a load of 10 kg, and an orifice diameter of 2 mm. A molded product obtained by molding the molding material according to claim 1 .