JP2003327846A - Viscoelastic resin composition and composite damping material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a viscoelastic resin composition having excellent damping performance, adhesion strength and heat resistance. <P>SOLUTION: This viscoelastic resin composition comprises A component of a thermoplastic resin, B component of a curing agent forming a crosslink by reacting with the A component and C component of a phenolic compound, wherein the C component is contained at a rate of 2-25 mass% based on the mass total of the A, B and C components. The B component of 3-50 pts.mass is preferably contained in 100 pts.mass A component. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a viscoelastic resin composition. More specifically, the present invention is used as an intermediate layer and / or a surface layer of a composite vibration damping material used as a structural member of various structures such as industrial machinery, transportation machinery, and buildings, or as a part thereof. The present invention relates to a viscoelastic resin composition which exhibits high vibration damping performance and excellent adhesive strength and also has excellent heat resistance.

The present invention also relates to a composite damping material. More specifically, the present invention is used as a structural member of a variety of structures such as industrial machinery, transportation machinery, household equipment, audio equipment, electronic equipment, information equipment, and buildings, or a part thereof having high control. The present invention relates to a composite vibration damping material that exhibits vibration performance and excellent adhesive strength, and that also has excellent workability and heat resistance.

[0003]

2. Description of the Related Art In recent years, noise and vibration have become a social problem as pollution due to the development of transportation facilities and the approach to residential factories. In many industrial fields including manufacturing and transportation, improvement of the working environment of the workplace is required, and the level of noise and vibration is being regulated more strictly as a part of this. Further, as the standard of living is improved, the demand level of consumers for electric products and mechanical products is also increasing, and such products also tend to be required to be quiet during operation.

Further, in the industrial field of audio equipment and the like, there is a strong demand for suppression of extra vibration that may cause noise in order to obtain higher quality sound. Further, in the industrial field of information equipment and the like, with the increase in the speed of CD-ROMs and the increase in recording density in large-capacity recording media such as DVDs and MOs, reduction of vibration noise and reduction of reading errors due to vibrations are becoming important issues. is there.

Corresponding to such a tendency, it is socially strongly to add vibration damping performance to metal materials and the like, which often become noise sources or vibration sources, and further improve the functions of the metal materials and the like. It has been demanded.

Conventionally, as one of vibration damping materials used for preventing noise and vibration, a composite vibration damping material having a multilayer structure in which an intermediate layer made of a viscoelastic resin composition is sandwiched between metal layers has been proposed. . Such a composite type damping material,
By absorbing the vibration energy of the member itself that generates noise,
It has a function of converting the vibration energy into heat energy by shear deformation of the intermediate layer having viscoelasticity accompanying bending vibration of the composite type vibration damping material, attenuating the vibration velocity and vibration amplitude, and reducing acoustic radiation.

Such a composite type vibration damping material exerts its vibration damping performance most by being brought into direct contact with the vibration source or used as a part of the vibration source body including the cover. Therefore, such composite type damping material is used for automobiles such as automobile oil pans, engine head covers, engine room shielding plates, dash panels, floor panels, gear covers, chain covers, muffler covers, mufflers, floor housings, motorcycles, Agricultural machinery parts, motor covers, compressor covers, evaporator covers and other refrigeration temperature control device parts, portable cassette tape recording and / or reproducing machines, CD recording and / or reproducing machines, MD recording and / or reproducing machines, computers It is actually used in applications such as cases, hard disk cases, acoustic electronic parts such as speaker frames, outdoor equipment parts such as chainsaw covers, generator covers, and mower covers, and building materials such as stairs, doors, flooring and roofing materials. ing. The use of such composite damping material is also being considered for many other products that require damping performance.

Generally, the damping performance of such a composite damping material depends on the performance of the viscoelastic resin composition forming the intermediate layer, and the damping performance can be represented by a loss coefficient. . Here, the loss coefficient is a coefficient indicating a scale by which vibration energy from the outside is converted into heat energy by internal friction, and is a quantity related to mechanical hysteresis loss due to vibration.

When a viscoelastic resin composition is used as an intermediate layer of such a composite type damping material, the damping performance of this resin composition exhibits peak characteristics of damping performance in the glass transition region, It is known that use in the vicinity of this peak characteristic temperature is most effective in terms of vibration damping performance. Therefore, generally, in developing a composite vibration damping material, an intermediate layer made of an appropriate viscoelastic resin composition is selected according to the temperature range of use and the adhesiveness to a substrate.

Many viscoelastic resins or viscoelastic resin compositions are known as the viscoelastic resin or viscoelastic resin composition used for the intermediate layer of such a composite type vibration damping material. Resin (Japanese Patent Laid-Open No. 50-143
880) or a resin composition obtained by adding a plasticizer to a polyester resin (JP-A-52-93770),
A resin composition in which a plurality of polyester resins are combined (JP-A-62-295949, JP-A-63-2024).
46), polyurethane resin foam (JP-A-51)
No. 91981), polyamide resin (Japanese Patent Laid-Open No. 56-
159160), ethylene-vinyl acetate copolymer (JP-A-57-34949), polyvinyl butyral resin, or a mixed resin of polyvinyl butyral resin and polyvinyl acetate resin, and a plasticizer and a tackifier. Compositions (JP-A-55-27975), isocyanate prepolymers and vinyl monomer copolymers (JP-B-55-27975), polyvinyl acetal resins (JP-A-60-88149) and the like are known. .

Here, the viscoelastic resin composition used as the intermediate layer in the composite type vibration damping material exhibits excellent vibration damping performance, and at the same time, has a high adhesive strength with a substrate such as a metal. Required. However, in the viscoelastic resin composition that has been used for the intermediate layer of the conventional composite type vibration damping material, for example, a glass transition temperature (also referred to as Tg in the present specification) having a peak of vibration damping performance at room temperature. Generally, a viscoelastic resin composition having a low viscosity has a problem that the cohesive force at room temperature is small and the adhesive strength to a substrate such as a metal is low. Therefore, the composite vibration damping material using such a viscoelastic resin composition cannot withstand molding processes such as pressing and bending, and has no heat resistance that can withstand heat treatment such as baking coating after the process. was there. On the other hand, a viscoelastic resin composition having a high adhesive strength to a substrate such as a metal at room temperature and a high glass transition temperature does not have a peak of vibration damping performance around room temperature, so There was a problem that the damping performance was insufficient.

In addition, although a viscoelastic resin composition using a thermoplastic crystalline resin generally has high adhesive strength, the desired vibration damping performance is low, and the resin melts at a temperature above the crystal melting point. There was also a problem with heat resistance.

That is, the composite type vibration damping material produced by using the above-mentioned conventional viscoelastic resin or viscoelastic resin composition as the intermediate layer cannot sufficiently satisfy the requirements concerning the vibration damping performance and the adhesive strength at the same time. Also, the heat resistance was not sufficiently satisfactory.

Therefore, conventionally, there has been a strong demand for a viscoelastic resin or a viscoelastic resin composition that exhibits excellent vibration damping performance and adhesive strength and is also excellent in heat resistance. In fact, many research and development efforts have been made in various fields in order to meet such requirements, and in order to maintain high vibration damping performance and adhesive strength, use of a cross-linking agent, Methods such as a viscoelastic resin composition composed of a mixture and a laminated composite of a plurality of viscoelastic resin compositions have been studied.

As a specific example, as a method using a cross-linking agent, viscoelasticity including a specific amorphous block copolymerized polyester resin composed of a high glass transition temperature segment and a low glass transition temperature segment such as a lactone component. Resin composition (JP-A-1-198622), viscoelastic resin composition containing polyester resin synthesized from dimer acid or hydrogenated dimer acid and glycol having a side chain (JP-A-6-329770) ,
A viscoelastic resin composition containing a copolyester resin having an aromatic ring in a side chain (JP-A-6-329771), a viscoelastic resin composition containing a copolyester resin having a side chain of 5 or more carbon atoms (special (Kaihei 7-179735 gazette)
It is also known that vibration damping performance, adhesive strength, and heat resistance can be achieved at a certain level by using such as. However, it is also true that there is room for further improvement of vibration damping performance, adhesive strength and heat resistance in order to sufficiently satisfy the above demands.

As a method of using a mixture of a plurality of viscoelastic resins, a resin composition containing a polyester resin, an addition polymerization block copolymer, a polyester block copolymer and a polypropylene resin and / or a tackifying resin ( JP-A-9-227766), an acrylic acid ester-based copolymer having a specific glass transition temperature,
Thermoplastic resin composition containing other copolymer having a specific glass transition temperature (JP 2000-212373 A)
It is also known that vibration damping performance, adhesive strength, and heat resistance can be achieved at a certain level by using such as. However, it is also true that there is room for further improvement of vibration damping performance, adhesive strength and heat resistance in order to sufficiently satisfy the above demands.

Further, a viscoelastic resin composition obtained by blending a viscoelastic resin with an inorganic filler having a specific particle size and specific properties (JP-A-5-222239), and an inorganic powder subjected to a specific surface treatment. Although a viscoelastic resin composition (JP-A-7-91490) containing the above is known, all of them mainly achieve vibration damping performance, adhesive strength and heat resistance at sufficiently satisfactory levels. Not intended.

Further, there is known a method of improving vibration damping performance by blending a viscoelastic resin with a specific additive. For example, a damping material in which a polymer is blended with an active component that increases the dipole moment (Japanese Patent Laid-Open No. 10-7845), or a damping material in which an organic dielectric or ferroelectric is dispersed in a polymer (special Kaihei 11-68190, JP 2
000-273435), or a composite vibration-damping composition comprising a resin having a polar atomic group in its side chain and an organic filler (JP 2001-131422 A). However, in these technologies, although the damping performance has been studied, the bonding strength and heat resistance to the base material made of metal have not been studied. It cannot be said that it is a technology that realizes the nature at a satisfactory level.

A resin composition (Japanese Unexamined Patent Publication No. 2002-12848) in which a polyhydric phenol in which a lower alkyl group may be substituted is blended with a polymer is also known. Although the damping performance and heat resistance of the flexible molded body have been studied, the bonding strength to a metal base material, which is important when used as a composite damping material, has not been studied. As for heat resistance, since it is a study using a thermoplastic resin as a base material as is clear from the examples, it is a technology that realizes vibration damping performance, adhesive strength and heat resistance at a sufficiently satisfactory level. I can't.

Further, in the resin composite type vibration-damping metal plate excellent in peeling resistance (JP-A-11-277671), an amorphous polyester having a specific property is thermally cured to form a base material made of a metal. Have been studied to improve the adhesive strength of. However, the vibration damping performance is not mentioned, and it is also true that there is room for further improvement of the vibration damping performance, the adhesive strength and the heat resistance in order to sufficiently satisfy the above demands.

[0021]

As described above, a viscoelastic resin composition that achieves vibration damping performance, adhesive strength, and heat resistance at a sufficiently satisfactory level at the same time in spite of great research and development efforts in various fields. At present, there is no known technology that can provide a product. Therefore, based on the above-mentioned current situation, an object of the present invention is to provide a viscoelastic resin composition which exhibits high vibration damping performance and excellent adhesive strength and is also excellent in heat resistance.

Another object of the present invention is to provide a composite vibration damping material which exhibits high vibration damping performance and excellent adhesive strength, and is excellent in workability and heat resistance.

[0023]

Means for Solving the Problems The inventors of the present invention have the idea that in order to solve the above problems, an additive for improving vibration damping performance and adhesive strength should be added to a resin. The inventors have made intensive studies on such combinations of resins and additives. Then, after investigations, the present inventors have found that a viscoelastic resin composition having excellent vibration damping performance can be obtained by adding a large amount of a specific phenolic compound to a specific thermoplastic resin.

At the same time, the present inventors have found that when a large amount of a phenolic compound is added to a thermoplastic resin, the adhesive strength of the viscoelastic resin composition is significantly reduced. That is, it has been found that the above viscoelastic resin composition cannot be suitably used as an intermediate layer of the composite vibration damping material as it is.

Therefore, the present inventors have made further studies in order to prevent the adhesive strength of the viscoelastic resin composition from being lowered by adding a large amount of a phenolic compound to the thermoplastic resin. At the end of the study, the present inventors have found that in a viscoelastic resin composition containing a large amount of a phenolic compound and a thermoplastic resin that have a function as an antioxidant and thus tend to inhibit a polymerization reaction or a crosslinking reaction. In addition, even if a curing agent capable of reacting with the thermoplastic resin to form crosslinks is added, three-dimensional network crosslinks are formed in the thermoplastic resin by heating and curing, and the adhesive strength of the viscoelastic resin composition is increased. It has been found to be improved.

In addition, the present inventors also provided a large amount of a phenolic compound in a viscoelastic resin composition containing a thermoplastic resin in which a three-dimensional network crosslink is formed and a large amount of a phenolic compound. It was found that excellent vibration damping performance was maintained.

Further, the present inventors have found that the composite type vibration damping material obtained by forming the above-mentioned viscoelastic resin composition and the base material in multiple layers exhibits high vibration damping performance and excellent adhesive strength, and has excellent processability and workability. They have found that they also have excellent heat resistance and have completed the present invention.

That is, the viscoelastic resin composition of the present invention is
As the component A, a thermoplastic resin, as the component B, a curing agent capable of reacting with the component A to form crosslinks, and as the component C,
A viscoelastic resin composition containing a phenolic compound and containing C component in the range of 2 to 25% by mass with respect to the total value of the masses of A component, B component and C component.

The viscoelastic resin composition of the present invention is A
It is preferable to contain the component B in the range of 3 to 50 parts by mass with respect to 100 parts by mass of the component.

The component A is preferably an amorphous copolyester resin. Furthermore, it is recommended that the component B is one or more selected from the group consisting of polyepoxy compounds, acid anhydrides and polyisocyanate compounds.

When the viscoelastic resin composition of the present invention is heat-cured while being sandwiched between metal base materials as an intermediate layer, it has a T-peel strength of 8 after heat-curing.
It is preferably at least kgf / 25 mm and the gel fraction after heat curing is in the range of 50 to 98%.

The present invention also includes a composite vibration damping material having a multilayer structure in which the viscoelastic resin composition is sandwiched as an intermediate layer between base materials made of metal.

In the composite type vibration damping material of the present invention, the viscoelastic resin composition is applied to at least one surface of the substrate made of metal, the coating film is crosslinked, and the crosslinked coating film obtained is applied to the inside. It is preferable that the composite type vibration damping material is obtained by bonding the base materials to each other and then thermocompression bonding.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by showing embodiments.

The viscoelastic resin composition of the present invention comprises an amorphous copolyester resin as the A component and A as the B component.
It is characterized by containing a curing agent capable of reacting with the components to form crosslinks and a phenolic compound as the C component as essential components in a specific ratio.

<Amorphous Copolymerized Polyester Resin> Amorphous copolymerized polyester resin (component A) used in the viscoelastic resin composition of the present invention (in this specification, the amorphous copolymerized polyester used in the present invention is used). (Also called resin)
Polycarboxylic acid bond unit, polyol bond unit and /
Alternatively, it is an amorphous copolyester resin containing a polyhydroxycarboxylic acid block bonding unit.

In the present invention, the term "amorphous" means a differential scanning calorimeter (DSC), and a clear crystal melting peak is obtained by raising the temperature from -100 ° C to 300 ° C at a heating rate of 20 ° C / min in a nitrogen atmosphere. Is not indicated. Since it is an amorphous polyester resin, the vibration damping performance is improved, and the phenomenon such as a decrease in adhesive strength over time due to the progress of crystallization often observed in crystalline polyester resins is not observed.

The polycarboxylic acid bond unit of the amorphous copolyester resin used in the present invention is not particularly limited in kind and amount as long as the copolyester resin is amorphous, but the polycarboxylic acid bond unit is not limited. Of these, 40 mol% or more is preferably an aromatic dicarboxylic acid unit, and particularly 5
It is preferably 0 mol% or more. The upper limit of the content of the aromatic dicarboxylic acid bond unit is not particularly limited and may be 100 mol%. When the content of the aromatic dicarboxylic acid bond unit is less than 40 mol%,
The viscoelastic resin composition may have insufficient adhesive strength and heat resistance.

As the monomer forming the aromatic dicarboxylic acid bond unit of the amorphous copolyester resin used in the present invention (also referred to herein as the aromatic dicarboxylic acid used in the present invention), terephthalic acid , Isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 2,2′-biphenyldicarboxylic acid, diphenylmethanedicarboxylic acid, phenylindenedicarboxylic acid, Mention may be made of aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid and their ester-forming derivatives.

Among these aromatic dicarboxylic acids and their ester-forming derivatives, it is preferable to use aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid from the viewpoints of vibration damping and easy availability. Further, these aromatic dicarboxylic acids and their ester-forming derivatives may be used alone or in combination of two or more kinds.

Further, as the monomer forming a polycarboxylic acid bond unit other than the aromatic dicarboxylic acid bond unit used in the present invention (also referred to as other polycarboxylic acid in the present invention in the present specification), Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid and ester-forming derivatives thereof, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3, 8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9, 2-dimethyl-eicosane diacid, dimer acid, and hydrogenated dimer acid, octenyl succinic anhydride,
Alkenyl succinic acids such as dodecenyl succinic anhydride, pentadecenyl succinic anhydride, octadecenyl succinic anhydride, fumaric acid, maleic acid, itaconic acid, 8,12
Mention may be made of aliphatic dicarboxylic acids such as eicosadiene dicarboxylic acid and their ester-forming derivatives. These polycarboxylic acids and their ester-forming derivatives may be used alone or in combination of two or more.

Among these polycarboxylic acids and their ester-forming derivatives, adipic acid, azelaic acid, sebacic acid, dimer acid, hydrogenated dimer acid, alkenyl succinic acid, from the viewpoint of vibration damping performance and practicality. Acids and the like are preferable, and sebacic acid, dimer acid, hydrogenated dimer acid, alkenylsuccinic acid and the like are more preferable.

Further, the polycarboxylic acid unit formed by using sebacic acid, dimer acid, hydrogenated dimer acid, and alkenylsuccinic acid as raw materials has the following properties in terms of vibration damping performance and adjustment of the glass transition temperature of the resin. The content of the polycarboxylic acid bond unit used in the present invention is preferably 2 mol% or more, more preferably 5 mol% or more.

The content of these polycarboxylic acid bond units is preferably 60 mol% or less, more preferably 50 mol% or less. When the content of these polycarboxylic acid bond units is less than 2 mol%, the vibration damping performance may be insufficient or it may be difficult to adjust the glass transition temperature of the resin to a predetermined value. . If the content of these polycarboxylic acid bond units exceeds 60 mol%, the adhesive strength may be insufficient.

The polycarboxylic acid-bonding unit-forming monomer used in the present invention may have a trimerit, if necessary, in a small amount so as not to impair the properties of the viscoelastic resin composition of the present invention. A trifunctional or higher polycarboxylic acid such as an acid or pyromellitic acid may be used.

Here, the content of the trifunctional or higher polycarboxylic acid in the monomer forming the polycarboxylic acid bond unit used in the present invention is preferably 0.5 mol% or more, preferably 1 mol. % Or more is more preferable. The content of these trifunctional or higher polycarboxylic acids is preferably 10 mol% or less, more preferably 5 mol% or less. When the content of these trifunctional or higher polycarboxylic acids is less than 0.5 mol%, curability and vibration damping performance may be insufficient. When the content of these trifunctional or higher polycarboxylic acids exceeds 10 mol%, gelation may occur during the production of the amorphous copolyester resin.

The polyol bonding unit of the amorphous copolyester resin used in the present invention is not particularly limited in kind and amount as long as the copolyester resin is amorphous, but 30 mol of the polyol bonding unit is contained. % Or more is preferably a glycol bond unit having an alkyl group in the side chain and having 4 or more carbon atoms, and particularly preferably 50 mol% or more. The upper limit of the content of the glycol bond unit is not particularly limited and may be 100 mol%.
When the content of the glycol bond unit having an alkyl group in the side chain and having 4 or more carbon atoms is less than 30 mol%, the vibration damping performance may be insufficient.

The amorphous copolyester resin used in the present invention is a monomer forming a glycol bond unit having an alkyl group in the side chain and having 4 or more carbon atoms (in the present specification, the side chain used in the present invention is an alkyl group). (Also referred to as a glycol having 4 or more carbon atoms having a group), 2-methylpropanediol, 1,3-butanediol, neopentyl glycol, 3-methylpentanediol, trimethylpentanediol, 2-methyl-1,8. -Octanediol, 3,3'-dimethylolpentane, 3,3'-dimethylolheptane, 8,13-methyleicosanediol, a reduced product of dimer acid, neopentylglycol hydroxypivalate and the like can be mentioned.

Among these glycol-bonding units having an alkyl group in the side chain and having 4 or more carbon atoms, 2-methylpropanediol, neopentylglycol and 3-methyl are preferred from the viewpoints of vibration damping and easy availability. Pentanediol and 3,3′-dimethylolheptane are preferred. These glycols having an alkyl group on the side chain and having 4 or more carbon atoms may be used alone or in combination of two or more.

Further, a monomer forming a polyol bond unit other than the glycol bond unit having an alkyl group in the side chain used in the present invention and having 4 or more carbon atoms (in the present specification,
(Also referred to as other polyols used in the present invention), ethylene glycol, propylene glycol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, eicosanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, polycarbonate diol, etc. Examples thereof include alicyclic diols such as aliphatic glycol, 1,4-cyclohexanedimethanol and tricyclodecanedimethanol, and aromatic diols such as ethylene oxide adducts or propylene oxide adducts of bisphenol A or bisphenol S. . These polyols may be used alone or in combination of two or more.

As the monomer for forming the polyol bond unit used in the present invention, trimethylolpropane, if necessary, in a small amount so as not to impair the properties of the viscoelastic resin composition of the present invention, You may use trifunctional or more than trifunctional polyols, such as glycerin and pentaerythritol.

Here, the content of the trifunctional or higher-functional polyol in the monomer forming the polyol bond unit used in the present invention is preferably 0.5 mol% or more, and 1
More preferably, it is at least mol%. However, if the content of the above-mentioned trifunctional or higher polycarboxylic acid is 0.5 mol% or more, this is not the case. The content of these trifunctional or higher functional polyols is preferably 10 mol% or less, and more preferably 5 mol% or less. The content of these trifunctional or higher functional polyols is 0.5
If it is less than mol%, the curability and vibration damping performance may be insufficient. When the content of these trifunctional or higher functional polyols exceeds 10 mol%, gelation may occur during the production of the amorphous copolyester resin.

There are many combinations of compositions of the amorphous copolyester resin obtained from such a polycarboxylic acid bond unit and a polyol bond unit, and they are appropriately selected depending on the desired resin cohesive strength, adhesive strength, vibration damping performance and the like. From the viewpoint of vibration damping performance, for example, 40 mol% or more of the polycarboxylic acid bond units are aromatic dicarboxylic acid units, and 30 mol% or more of the polyol bond units are side chains. It is a glycol-bonding unit having 4 or more carbon atoms having an alkyl group, and the content of the trifunctional or higher polycarboxylic acid is preferably 0.5 mol% or more, which is a preferable combination. 50 mol% or more is an aromatic dicarboxylic acid unit, and 50 mol% or more of the polyol bonding unit has 4 or more carbon atoms having an alkyl group in a side chain. A glycol bonding units, the content of the trifunctional or higher polycarboxylic acid, is the most preferred combination is at least 1 mol%.

Further, as described above, the glass transition temperature of the amorphous copolyester resin obtained from the polycarboxylic acid bond unit and the polyol bond unit is adjusted, and the adhesiveness or the reactivity with the curing agent is improved. From this point of view, it is possible to add a polyhydroxycarboxylic acid block bond unit by ring-opening addition polymerization of a cyclic ester at the molecular chain end using a known method. The polyhydroxycarboxylic acid block bond unit of the amorphous copolyester resin used in the present invention is not particularly limited in kind and amount as long as the copolyester resin is amorphous, but polyhydroxycarboxylic acid is a block copolymer unit. It must be polymerized. Cyclic esters that give a polyhydroxycarboxylic acid block bonding unit include β-propiolactone,
Examples include β-2,2-dimethylpropiolactone, δ-valerolactone, δ-3-methylvalerolactone, ε-caprolactone, and enanthlactone.

<Method for producing amorphous copolyester resin> The amorphous copolyester resin (A
The manufacturing method of the component) is not particularly limited, and a known manufacturing method can be used. For example, in a container under a nitrogen atmosphere, a polycarboxylic acid and a polyol component are charged and allowed to undergo an esterification and / or transesterification reaction under a constant temperature condition for a constant time, and then under a constant temperature condition for a constant time. A production method in which the polycondensation reaction is carried out under high vacuum over a period of time.

In the above production method, the temperature condition for the esterification and / or transesterification reaction is 1
The temperature is preferably 40 ° C. or higher, and more preferably 160 ° C. or higher. In addition, this temperature condition is 26
It is preferably 0 ° C. or lower, and particularly preferably 240 ° C. or lower. When this temperature condition is lower than 140 ° C., the reaction rate tends to decrease, and when this temperature condition exceeds 260 ° C., the decomposition of the product tends to become remarkable.

In the above production method, the reaction time of the esterification and / or transesterification reaction is 0.
It is preferably 5 hours or more, and particularly preferably 1 hour or more. Further, this reaction time is preferably 24 hours or less, and more preferably 12 hours or less. When the reaction time is less than 0.5 hours, the esterification and / or transesterification reaction tends not to proceed sufficiently, and the reaction time exceeding 24 hours is not preferable from the economical point of view.

In the above production method, the temperature condition of the polycondensation reaction is preferably 180 ° C. or higher, and more preferably 200 ° C. or higher. Further, the temperature condition is preferably 300 ° C. or lower, and more preferably 280 ° C. or lower. When this temperature condition is less than 180 ° C., polycondensation tends not to proceed at a practically sufficient rate, and this temperature condition is 30
If it exceeds 0 ° C, the molecular weight of the amorphous copolyester resin tends to be insufficient due to the decomposition of the product.

In the above production method, the reaction time of the polycondensation reaction is preferably 0.5 hours or longer, and more preferably 1 hour or longer. Also,
The reaction time is preferably 5 hours or less, and more preferably 3 hours or less. If the reaction time is less than 0.5 hours, the polycondensation of the amorphous copolyester resin tends not to proceed until a sufficient molecular weight is obtained, and if the reaction time exceeds 5 hours, the product Decomposition tends to be noticeable.

In the above production method, the pressure inside the vessel during the polycondensation reaction is preferably 660 Pa or less, and more preferably 130 Pa or less.
When the pressure in the container exceeds 660 Pa, there is a tendency that polycondensation of the amorphous copolyester resin does not proceed until a sufficient molecular weight is obtained.

Further, in the above production method, the polycondensation reaction can proceed without a catalyst, but it is generally preferable to add a catalyst to carry out the polycondensation reaction. The type of this catalyst is not particularly limited, and a known catalyst for polymerization of an amorphous copolyester resin can be preferably used. Specific examples include calcium acetate, zinc acetate,
Examples thereof include dibutyltin oxide, dibutyltin dilaurate, germanium oxide, antimony trioxide and tetrabutyl titanate. These catalysts may be used alone or in combination of two or more.

Further, in the above production method, the content of the catalyst in the polycondensation reaction solution is preferably 1 ppm or more, and more preferably 30 ppm or more. The content of this catalyst is preferably 5000 ppm or less, and more preferably 2000 ppm or less. When the content of this catalyst is less than 1 ppm, the reaction rate tends to decrease, and when the content of this catalyst exceeds 5000 ppm, decomposition and coloring of the product tend to be remarkable.

<Number average molecular weight of amorphous copolyester resin> The number average molecular weight of the copolyester resin (component A) used in the present invention measured by GPC (gel permeation chromatography) is 5000 or more. Is preferable, and more preferably 8000 or more. Also,
The number average molecular weight is not particularly limited, but from the viewpoint of workability in the production process of the viscoelastic resin composition, it is preferably 50,000 or less, particularly 400.
It is more preferably 00 or less.

When the number average molecular weight is less than 5,000, there is a problem that both the vibration damping performance and the adhesive strength of the viscoelastic resin composition decrease. Further, from the viewpoints of vibration damping performance and adhesive strength of the viscoelastic resin composition, the higher the number average molecular weight, the more preferable, and it is preferable to determine the value to be the most practical value. However, when the number average molecular weight exceeds 50,000, workability in the production process of the viscoelastic resin composition tends to be deteriorated.

<Glass Transition Temperature of Amorphous Copolyester Resin> The temperature at which the vibration damping performance is maximized is mainly determined by the glass transition temperature of the amorphous copolyester resin (component A). In selecting the polycopolymerized polyester resin, a resin having an optimum glass transition temperature may be selected so that a desired vibration damping temperature peak can be obtained.

For example, when the composite damping material using the viscoelastic resin composition containing the amorphous copolyester resin of the present invention is used at around room temperature, the glass transition of the amorphous copolyester resin is performed. The point temperature is preferably −60 ° C. or higher, and more preferably −40 ° C. or higher. Further, the glass transition temperature is preferably 0 ° C or lower, and more preferably -10 ° C or lower.
If the glass transition temperature is lower than -60 ° C or higher than 0 ° C, depending on the type and amount of the curing agent, the vibration damping performance may not be exhibited near room temperature. Here, the glass transition temperature of the amorphous copolyester resin can be measured by a known method using a differential scanning calorimeter (DSC) or the like.

<Curing Agent> The viscoelastic resin composition of the present invention comprises
A curing agent (component B) capable of reacting with the amorphous copolyester resin (component A) to form crosslinks (in the present specification,
It is also referred to as a curing agent used in the present invention) as an essential component.

Here, as the curing agent used in the present invention,
The compound is not particularly limited, and any compound capable of reacting with the amorphous copolyester resin used in the present invention to form crosslinks can be suitably used. For example, polyepoxy compounds, polyisocyanate compounds and acid anhydrides can be used. It is preferable to use one or more curing agents selected from the group consisting of: That is, the curing agent used in the present invention may be a polyepoxy compound, a polyisocyanate compound or an acid anhydride alone, but a polyisocyanate compound and a polyepoxy compound, a polyepoxy compound and an acid anhydride, a polyepoxy compound and You may mix and use in combination, such as an acid anhydride and a polyisocyanate compound.

By blending the amorphous copolyester resin (component A) used in the present invention with the curing agent (component B) used in the present invention and then heat curing to form crosslinks,
Since the adhesion of the viscoelastic resin composition of the present invention is improved, the moldability and processability of the composite vibration damping material of the present invention are improved,
The heat resistance after molding or processing is also improved. Similarly, since the hydrolysis resistance of the viscoelastic resin composition of the present invention is also improved, it is considered that the durability of the composite vibration damping material of the present invention is also improved.

<Polyepoxy compound> Here, the polyepoxy compound used in the present invention is not particularly limited, but epibis type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, glycidyl ether resin. Polyepoxy compounds such as glycidyl ester-based resin, glycidylamine-based resin, novolac type epoxy resin, and heterocyclic epoxy resin can be preferably used.
Further, among these polyepoxy compounds, a polyepoxy compound having two or more glycidyl groups in one molecule is particularly preferable from the viewpoint of curability.

Specific examples of the polyepoxy compound used in the present invention include bisphenol A diglycidyl ether, bisphenol A dibetamethyl glycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and tetrahydroxyphenylmethane tetraglycidyl. Ether, resorcinol diglycidyl ether, brominated bisphenol A diglycidyl ether, novolac glycidyl ether, sorbitol glycidyl ether, polyalkylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A alkylene oxide adduct diglycidyl ether, epoxy Urethane resin, glycerol triglycidyl ether, trimethylolpropanate Glycidyl ether, pentaerythritol tetraglycidyl ether, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, acrylic acid diglycidyl ester, dimer acid diglycidyl ester, diglycidyl-p-oxybenzoic acid Esters, diglycidyl propylene urea, tetraglycidyl diaminodiphenylmethane, triglycidyl isocyanurate, epoxidized polybutadiene, epoxidized soybean oil and the like can be mentioned. These polyepoxy compounds may be used alone or in combination of two or more.

Among these polyepoxy compounds, from the viewpoint of the balance of vibration damping performance and adhesive strength,
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether and novolac glycidyl ether are particularly preferable.

<Polyisocyanate Compound> Here, the polyisocyanate compound used in the present invention is not particularly limited, but, for example, an aliphatic, alicyclic or aromatic bifunctional or more polyisocyanate compound is used. The compound can be preferably used. Among these polyisocyanate compounds, trifunctional or higher polyisocyanate compounds are particularly preferable from the viewpoint of volatility, adhesiveness and durability.

Specific examples of the polyisocyanate compound used in the present invention include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TD
I), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HD
I), isophorone diisocyanate (IPDI), phenylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and other diisocyanate compounds, trimers of these isocyanate compounds, and isocyanate compounds of these. Excess amount and low molecular weight active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine or various polyester polyols, polyether polyols, polyamides, etc. Terminal isocyanate group-containing compounds obtained by reacting with other polymer active hydrogen compounds And the like. These polyisocyanate compounds may be used alone or in combination of two or more.

The polyisocyanate compound used in the present invention may be a blocked isocyanate compound. Among these polyisocyanate compounds, a trimer of TDI or HDI or a reaction product of TDI or HDI and trimethylolpropane is particularly preferable from the viewpoint of vibration damping performance.

<Acid Anhydride> An acid anhydride is blended with the polyepoxy compound in the viscoelastic resin composition of the present invention. In this case, the polyepoxy compound reacts with the acid end and acid anhydride of the polyester,
The H-terminal reacts with an acid anhydride to become an acid terminal, and the acid-terminal reacts with an epoxy compound to promote a crosslinking reaction. Therefore, the acid anhydride promotes a crosslinking reaction of the viscoelastic resin composition of the present invention. It can be said that there is an effect.

Here, the acid anhydride used in the present invention is not particularly limited, but, for example, among aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, etc.,
Those having one or more acid anhydride groups in one molecule are mentioned. Among these acid anhydrides, those having two or more acid anhydride groups in one molecule are particularly preferable from the viewpoint of curability.

Specific examples of the acid anhydride used in the present invention include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylnasic anhydride, chlorendecic anhydride, trimellitic anhydride, and hyromellitic anhydride. Examples thereof include benzophenone tetracarboxylic acid anhydride, dodecenyl succinic anhydride, polyadipic acid anhydride, and polyazelaic acid anhydride.

The amorphous copolyester resin (component A) used in the present invention was mixed with an epoxy compound and an acid anhydride as a curing agent (component B) used in the present invention and then heat-cured to form crosslinks. In this case, the terminal functional group of the amorphous copolyester resin is more reactive with a carboxyl group than a hydroxyl group, so that the adhesiveness of the viscoelastic resin composition of the present invention is further improved, and as a result, the composite of the present invention is It is considered that the durability of the mold damping material is further improved.

<Amount of Curing Agent> The amount of the curing agent (component B) in the viscoelastic resin composition of the present invention is the type and amount of the amorphous copolyester resin (component A) to be incorporated together. , The amorphous copolyester resin (A
Component) The amount is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass. The compounding amount of this curing agent (component B) is preferably 50 parts by mass or less, and particularly preferably 35 parts by mass or less.

When the amount of the curing agent is less than 3 parts by mass, the curability of the viscoelastic resin composition is lowered and the adhesive strength tends to be lowered. The amount of the curing agent is 50 parts by mass. If it exceeds, the compatibility of the both generally decreases, and both the adhesive strength and the vibration damping performance tend to decrease.

<Phenolic Compound> The viscoelastic resin composition of the present invention contains a phenolic compound (component C) (also referred to as a phenolic compound used in the present invention in the present specification) as an essential component. Contains in proportion.

The phenolic compound used in the present invention is not particularly limited, and any compound having a phenolic hydroxyl group can be preferably used, but heat resistance,
From the viewpoint of volatility and adhesive strength of the viscoelastic resin composition of the present invention, a phenolic compound which is solid at room temperature and has a molecular weight of 300 or more is preferable. Furthermore, it is solid at room temperature,
A hindered phenol having a molecular weight of 500 or more and a lower alkyl group substituted on the aromatic ring is more preferable. Moreover,
Most preferred is a hindered phenol which is solid at room temperature and has a molecular weight of 700 or more and in which a lower alkyl group is substituted with an aromatic ring.

By blending the phenolic compound in a specific amount, the vibration damping performance is improved without impairing the adhesive strength and heat resistance of the viscoelastic resin composition of the present invention. Also,
For the same reason, the vibration damping performance of the composite type vibration damping material of the present invention is improved.

Specific examples of the phenolic compound used in the present invention include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl. -4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tri-tert-butylphenol, 2-tert-butyl-4-methoxyphenol,
3-methyl-4-isopropylphenol, 2,6-di-tert-butyl-4-hydroxymethylphenol, 2,2-bis (4-hydroxyphenyl) propane, bis (5-tert-butyl-4-hydroxy-2)
-Methylphenyl) sulfide, bis (5-tert-)
Butyl-4-hydroxy-3-methylphenyl) sulfide, 2,5-di-tert-amylhydroquinone,
2,5-di-tert-butylhydroquinone, 1,1-
Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) butane, bis (3-tert-butyl-
2-hydroxy-5-methylphenyl) methane, bis (3-tert-butyl-2-hydroxy-5-ethylphenyl) methane, 2,6-bis (2-hydroxy-3)
-Tert-butyl-5-methylbenzyl) -4-methylphenol, 2,6-bis (2-hydroxy-3,5
-Di-tert-butylbenzyl) -4-methylphenol, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis (3-tert-butyl-4-hydroxy-5-methylbenzyl) sulfide, Bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane, bis (3-tert-butyl-2-hydroxy-5)
-Methylphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) cyclohexane, ethylenebis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate], bis [2- (2-hydroxy) -3-Tert-butyl-5-methylbenzyl) 4-
Methyl-6-tert-butylphenyl] terephthalate, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, styrenated phenol, 4-methoxyphenol, cyclohexylphenol, p-phenylphenol , Catechol, hydroquinone, 4-tert-butylpyrocatechol, ethyl gallate, propyl gallate, octyl gallate, lauryl gallate, cetyl gallate, β-naphthol, 2,
4,5-trihydroxybutyrophenone, tris (3,3
5-di-tert-butyl-4-hydroxybenzyl)
Isocyanate, tris (2,6-dimethyl-4-te
rt-Butyl-3-hydroxybenzyl) isocyanate, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl) -4-hydroxybenzyl) benzene, 1,6-bis [3- (3,5-di-t
ert-Butyl-4-hydroxyphenyl) propionyloxy] hexane, tetrakis [3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, N, N′-bis [3-
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, bis [3- (3,5-di-tert-). Butyl-4-
Hydroxyphenyl) propionyloxyethyl] sulfide, n-octadecyl-3- (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionate,
Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionylamino] hexane, triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] , 2,6-bis (3-tert-butyl-2-hydroxy-5-methylphenyl) -4-methylphenol, bis [S- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)] Thioterephthalate, tris [3- (3,5-di-tert-butyl-4]
-Hydroxyphenyl) propionyloxyethyl] isocyanurate, 1,1,3-tris (3-tert-
Butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris [4- [3- (3,5-di-t
ert-Butyl-4-hydroxyphenyl) propionyloxy] -2-methyl-5-tert-butylphenyl] butane, 2,4-bis (octylthio) -6-
(3,5-Di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -6-methylphenol, 3,9
-Bis [1,1-dimethyl-2- [β- (3-tert
-Butyl-4-hydroxy-5-methylphenyl) propionyloxyethyl] 2,4,8,10-tetraoxospiro- [5,5] -undecane and 2-tert-
Butyl-4- [1- (3-tert-butyl-4-hydroxyphenyl) isopropyl] phenyldi (p-nonylphenyl) phosphite, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, bis Phosphorus-containing phenolic compounds such as (3,5-di-tert-butyl-4-hydroxybenzylphosphonate) calcium and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) ) -5-Methylphenyl] -benzotriazole,
2- (2-hydroxy-5-methylphenyl) -benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -benzotriazole, 2- (2-hydroxy-3) -Tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-
Butylphenyl) -benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl)-
5-chlorobenzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -benzotriazole, 2- (2-hydroxy-3,5-di-tert-
Pentylphenyl) -benzotriazole, methyl-3
Condensate with-[3-tert-butyl-5- (benzotriazol-2-yl) -4-hydroxyphenyl] propionate-PEG, 2- [2-hydroxy-3-
(Linear and side chain dodecyl) -5-methylphenyl] -benzotriazole, bis [3- (benzotriazole-
Examples thereof include benzotriazole group-containing phenolic compounds such as 2-yl) -5-tert-octyl-2-hydroxyphenyl] methane. These compounds may be used alone or in combination of two or more.

<Amount of Phenolic Compound> The amount of the phenolic compound (component C) in the viscoelastic resin composition of the present invention is the same as that of the amorphous copolymerized polyester resin (component A) and the curing agent. The amorphous copolymerized polyester resin (A component) and the curing agent in the viscoelastic resin composition of the present invention vary depending on the type and amount of the (B component) and the properties required for the composite damping material of the present invention. 2 mass% of the phenolic compound (C component) based on the total mass of the (B component) and the phenolic compound (C component).
It is preferably at least the above, and more preferably at least 5% by mass. In addition, this phenolic compound (C
The blending amount of the component) is preferably 25% by mass or less, and particularly preferably 20% by mass or less.

The compounding ratio of this phenolic compound is 25
When the content exceeds 2% by mass, the curability of the viscoelastic resin composition decreases as compared with the improvement of the vibration damping performance, so that both adhesive strength and heat resistance tend to decrease. There is a tendency that no improvement in vibration damping performance due to the phenolic compound is observed.

Here, the phenolic compound (component C) used in the present invention includes many compounds generally used as an antioxidant for the purpose of increasing physical properties such as heat resistance by being added to a resin composition. There is. When these are used as antioxidants, usually, with respect to 100% by mass of the resin composition,
It is often used in the range of about 0.05 to 1% by mass.

Generally, when a large amount of a low-molecular weight compound is added to the resin composition, the cohesive force of the resin is lowered, and many physical properties, particularly when applied to the present invention, immediately after production and after aging, This is because it is easily expected to sacrifice the adhesiveness. Further, in a resin composition composed of a combination of a thermoplastic resin and a curing agent, it is intended to improve the physical properties by three-dimensionally crosslinking the resin to increase the cohesive force of the entire resin. One of the reasons was that it was generally believed that the addition of a large amount of a low-molecular compound would result in a decrease in the functional group concentration in the molecule involved in the reaction and the suppression of the crosslinking reaction. is there.

In particular, it has hitherto been considered that the addition of a large amount of a hindered phenol type antioxidant which can serve as a radical scavenger tends to hinder the above curing reaction itself. The present invention is not limited to the conventional common sense as described above, and the conventional technique (for example, Japanese Unexamined Patent Application Publication No.
002-12848, JP 2000-273435.
In addition to the thermoplastic resins and phenolic compounds disclosed in the publications, etc., by further compounding a curing agent not described in these, the adhesive strength, which is an important characteristic as a composite vibration damping material, is put into practical use. It was possible to raise it to a possible level. As a result, according to the present invention, it has become possible to achieve both excellent vibration damping performance and adhesive strength, which have not been realized with conventional viscoelastic resin compositions.

<Other Components> In addition to the above components, the viscoelastic resin composition of the present invention contains modified rosin, gum rosin and coumarone indene resin for the purpose of enhancing the vibration damping property of the viscoelastic resin composition. If necessary, a tackifier such as a xylene resin (also referred to as a tackifier in the present specification) may be appropriately selected and blended as long as the characteristics of the viscoelastic resin composition of the present invention are not impaired. it can.

Further, in the viscoelastic resin composition of the present invention, various fillers, plasticizers, antioxidants, and ultraviolet absorbers may be added, if necessary, within a range not impairing the properties of the viscoelastic resin composition of the present invention. Agents, antistatic agents, flame retardants, etc. may be added. Specific examples include glass fibers, polyester fibers, polyethylene fibers, various fibers such as carbon fibers, calcium carbonate, magnesium carbonate, for the purpose of increasing resin strength.
Various inorganic particles such as mica, talc and kaolin may be blended, and for the purpose of further enhancing vibration damping performance at low temperature, phthalic acid diester, sebacic acid diester, trimellitic acid triester, triphenyl phosphate, You may mix various plasticizers such as chlorinated paraffin,
For the purpose of improving heat resistance, a phenol-based antioxidant, a hindered amine-based antioxidant or the like may be blended, and for the purpose of enhancing the adhesiveness between other mixed inorganic substances and the resin, various coupling agents may be blended. Well, various leveling agents may be blended for the purpose of improving the coatability, and various metals such as iron, stainless steel, nickel, aluminum, and copper may be powdered or flaked for the purpose of imparting point contact weldability. ,
A fibrous material, a conductive filler such as carbon black, graphite, or carbon fiber may be added. It is preferable that one or more of these components be appropriately selected and blended according to the purpose.

In addition, the viscoelastic resin composition of the present invention may have a known vibration damping property other than that of a phenolic compound, if necessary, within a range not impairing the properties of the viscoelastic resin composition of the present invention. You may mix a component. Specifically, N,
N-diphenylthiourea, N, N-diethylthiourea,
Urea-based compounds such as trimethylthiourea, N-cyclohexyl-2-benzothiazolylsulfenamide, Nt
Sulfenamide compounds such as ert-butyl-2-benzothiazolyl sulfenamide, N-oxydiethylene-2-benzothiazolyl sulfenamide, N, N-dicyclohexyl-2-benzothiazolyl sulfenamide, 2 -Mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole cyclohexylamine salt, 2- (N, N-diethylthiocarbamoylthio) benzothiazole, 2- (4'-morpholino Examples thereof include thiazole compounds such as dithio) benzothiazole. It is preferable that one or more of these components be appropriately selected and blended according to the purpose.

<Adhesiveness, Gel Fraction and Heat Resistance> The viscoelastic resin composition of the present invention has a T peel strength after curing of 8 kgf / when sandwiched between metal base materials as an intermediate layer.
It is preferably 25 mm or more and the gel fraction thereof can be 50 to 98%. T peel strength is 8kgf / 25m
If it is less than m, it tends to be peeled off by bending and unbending, so that workability cannot be obtained when the composite vibration damping material is used. Also, if the gel fraction is 50% or more, the three-dimensional network of polymer chains required for flow prevention at high temperature is formed, and the adhesive strength and heat resistance are obtained, but the gel fraction is 50%.
If it is less than the above range, the amount of uncrosslinked polymer chains is large and the flow at a high temperature cannot be completely suppressed, so that the adhesive strength and the heat resistance are insufficient. The theoretical gel fraction does not exceed 98% when a phenolic compound is added.

Further, the viscoelastic resin composition of the present invention is sandwiched as an intermediate layer between base materials made of metal, and has a T peel strength retention rate of 80% before and after heating at 240 ° C. for 0.5 hours.
It is preferably at least 80%, more preferably at least 85%. If the retention rate is less than 80%, the workability after treatment such as baking coating and vulcanization after sealing is deteriorated.
Similarly, the viscoelastic resin composition of the present invention preferably has a shear adhesive strength after curing of 80 kgf / cm ² or more when sandwiched between metal substrates as an intermediate layer.
If the shear adhesive strength is less than 80 kgf / cm ² , peeling is likely to occur due to bending and unbending, so that workability cannot be obtained when the composite vibration damping material is used. Further, the viscoelastic resin composition of the present invention is preferably sandwiched as an intermediate layer between base materials made of metal and has a shear adhesive strength retention rate of 80% or more before and after heating at 240 ° C. for 1 hour, 85
% Or more is more preferable. If the retention rate is less than 80%, the workability after treatment such as baking coating and vulcanization after sealing is deteriorated.

<Loss Factor of Viscoelastic Resin Composition and Composite Damping Material> The loss coefficient, which is an index showing the vibration damping performance of the viscoelastic resin composition of the present invention, is dissipated as heat by the material during elastic deformation. It is a numerical value that is an index of the amount of energy and is one of the important material properties. In general, a material having a large loss coefficient is characterized in that it generates a small amount of sound because the vibration energy is converted into heat at a high rate. Further, in general, the loss coefficient of the viscoelastic resin composition (in the present specification, ta
nδ is also a maximum value (tanδ in the present specification) in the vicinity of the glass transition temperature of the viscoelastic resin composition.
(Also referred to as the maximum value of). Therefore, it is most effective in terms of vibration damping performance to use the viscoelastic resin composition in the temperature region near the temperature at which tan δ shows the maximum value. Here, t of the present invention
The higher the an δ, the more preferable.

The loss coefficient of the composite damping material of the present invention including the damping steel sheet using the viscoelastic resin composition of the present invention is measured by a known measurement method such as mechanical impedance method. It is possible. The higher the loss coefficient of the composite vibration damping material of the present invention, the more preferable. The maximum value of the loss coefficient of the composite type vibration-damping steel sheet of the present invention is preferably 0.4 or more when measured by the mechanical impedance method and converted to 500 Hz.
In particular, it is preferably 0.5 or more.

The viscoelastic resin composition of the present invention obtained as described above exhibits high vibration damping performance, excellent adhesive strength, and excellent heat resistance. It is preferably used as an intermediate layer and / or a surface layer of a composite type vibration damping material used as a structural member of various structures or a part thereof in a wide range of fields such as machinery and buildings.

<Composite Damping Material> The composite damping material of the present invention is a composite damping material obtained by laminating the viscoelastic resin composition of the present invention and a substrate.

Here, the composite type vibration damping material of the present invention may have a structure in which the viscoelastic resin composition of the present invention is laminated on the surface of the base material. It is preferable to have a structure sandwiching the viscoelastic resin composition. Further, the composite type vibration damping material of the present invention may have a multilayer structure of another resin composition and the viscoelastic resin composition of the present invention, if necessary, within a range that does not impair the characteristics thereof.

The material of the base material used in the composite vibration damping material of the present invention is not particularly limited, but metal (including alloy) is preferable. The shape of the base material is not particularly limited, but a plate shape is preferable. Specifically, various materials such as a steel plate, an aluminum plate, a titanium plate, and a copper plate can be used, but among these, a steel plate is generally particularly preferable. Also, the type of the steel sheet is not particularly limited, but for example, a surface-treated steel sheet such as a phosphate-treated steel sheet, a chromate-treated steel sheet, a zinc-treated steel sheet, a stainless steel sheet, an organic coated steel sheet, or a resin surface. A steel plate having is also suitably used.

The method for laminating the viscoelastic resin composition of the present invention on a substrate is not particularly limited, and a known method can be used according to the purpose. For example, the viscoelastic resin of the present invention can be used. The composition is dissolved in an organic solvent, coated on a substrate in a mixed state, a method of removing the organic solvent by heating, or the viscoelastic resin composition of the present invention is formed into a film by a known method. , A method of laminating with a substrate using a known method, a method of directly extruding the viscoelastic resin composition of the present invention onto a substrate, or a spatula, iron, or roll of the viscoelastic resin composition of the present invention Examples of the method include a method of directly coating on the substrate using

The composite type vibration damping material of the present invention is obtained by coating the viscoelastic resin composition of the present invention on at least one surface of a base material made of a metal, crosslinking the coating film, and then applying the obtained crosslinked coating film to the inside. It is preferable that the base material is bonded to the base material and then thermocompression bonded.

The composite vibration damping material of the present invention obtained as described above exhibits high vibration damping performance and excellent adhesive strength in a wide temperature range including normal temperature, and has excellent workability and heat resistance. Since it is also excellent, it is suitable for use as a structural member of various structures or a part of it in a wide range of fields such as industrial machinery, transportation machinery, household equipment, audio equipment, electronic equipment, information equipment, and buildings. To be done.

[0105]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

<Polymerization Example 1 of Amorphous Copolymerized Polyester Resin (Component A)> In a reaction vessel equipped with a thermometer, a stirrer and a distillate condenser, 215 parts by mass of isophthalic acid,
222 parts by mass of sebacic acid, 9 parts by mass of trimellitic anhydride, 264 parts by mass of 2-methyl-1,3-propanediol, 313 parts by mass of 3,3′-dimethylolheptane and 300 ppm of tetrabutyl titanate were charged. Then, the reaction system was transesterified in the temperature range of 175 to 235 ° C. for 6 hours. Then, this reaction system was pressure-reduced to 40 Pa over 30 minutes, and it heated up to 250 degreeC during this. Further, in this reaction system, a polycondensation reaction was performed for 1 hour under the conditions of 250 ° C. and 40 Pa to obtain an amorphous copolyester resin of Polymerization Example 1. The obtained amorphous copolyester resin had a molecular weight of 25,000 and a glass transition temperature of -23 ° C. The composition and characteristic analysis values of the obtained copolyester resin are shown in Table 1.

<Polymerization Example 2 of Amorphous Copolyester Resin (Component A)> The same as Polymerization Example 1 of the amorphous copolyester resin except that the raw materials having the compositions shown in Table 1 were used. By the method, an amorphous copolyester resin of Polymerization Example 2 was obtained. The composition and characteristic analysis values of the obtained amorphous copolyester resin are shown in Table 1.

<Polymerization Example 3 of Amorphous Copolyester Resin (Component A)> Dimethyl terephthalate 11 was placed in a reaction vessel equipped with a thermometer, a stirrer and a distillate condenser.
3 parts by mass, 113 parts by mass of dimethyl isophthalate, 117 parts by mass of adipic acid, 124 parts by mass of ethylene glycol, 208 parts by mass of neopentyl glycol and 300 ppm of tetrabutyl titanate were charged. Then, the reaction system was transesterified in the temperature range of 165 to 220 ° C. for 4 hours. Then, 8 parts by mass of trimellitic anhydride was added to this reaction system under a temperature condition of 190 ° C., and the temperature was raised to 230 ° C. while esterifying for 2 hours. Then, the reaction system was depressurized to 40 Pa over 30 minutes, and the pressure was reduced to 25
The temperature was raised to 0 ° C. Furthermore, in this reaction system,
The polycondensation reaction was carried out for 1 hour at 0 ° C. and 40 Pa to obtain the amorphous copolyester resin of Polymerization Example 3.
The composition and characteristic analysis values of the obtained amorphous copolyester resin are shown in Table 1.

<Polymerization Example 4 of Amorphous Copolyester Resin (Component A)> The same as Polymerization Example 3 of the amorphous copolyester resin except that the raw materials having the compositions shown in Table 1 were used. By the method, an amorphous copolyester resin of Polymerization Example 4 was obtained. The composition and characteristic analysis values of the obtained amorphous copolyester resin are shown in Table 1.

<Polymerization Example 5 of Amorphous Copolyester Resin (Component A)> In a reaction vessel equipped with a thermometer, a stirrer and a distillate condenser, 168 parts by mass of isophthalic acid,
141 parts by mass of sebacic acid, 7 parts by mass of trimellitic anhydride, 157 parts by mass of 2-methyl-1,3-propanediol, 181 parts by mass of neopentyl glycol and 300 ppm of tetrabutyl titanate were charged. Next, this reaction system was subjected to an esterification reaction in the temperature range of 175 to 230 ° C. for 8 hours. After that, this reaction system is used for 4 minutes in 4 minutes.
The pressure was reduced to 0 Pa, and the temperature was raised to 250 ° C during this period. Further, in this reaction system, a polycondensation reaction was carried out at 250 ° C. and 40 Pa for 1 hour.

Then, the vacuum is broken with nitrogen gas, and 21
139 parts by mass of ε-caprolactone was charged at 0 ° C., and the mixture was heated with stirring for 1 hour to carry out a ring-opening addition reaction to obtain an amorphous block copolymerized polyester resin of Polymerization Example 5. The composition and characteristic analysis values of the obtained copolyester resin are shown in Table 1.

<Polymerization Example 6 of Amorphous Copolyester Resin (Component A)> The same as Polymerization Example 5 of the amorphous copolyester resin except that the raw materials having the compositions shown in Table 1 were used. The polycondensation reaction was carried out by the method described above, and further the ring-opening addition reaction of ε-caprolactone was carried out to obtain the amorphous block copolymerized polyester resin of Polymerization Example 6. The composition and characteristic analysis values of the obtained copolyester resin are shown in Table 1.

<Polymerization Example 7 of Amorphous Copolyester Resin (Component A)> The same as Polymerization Example 3 of the amorphous copolyester resin except that the raw materials having the compositions shown in Table 1 were used. The polycondensation reaction was carried out by the above method, and further the ring-opening addition reaction of ε-caprolactone was carried out to obtain the amorphous block copolymerized polyester resin of Polymerization Example 7. The composition and characteristic analysis values of the obtained copolyester resin are shown in Table 1.

<Polymerization Example 8 of Amorphous Copolyester Resin (Component A)> Polymerization Example of Amorphous Copolyester Resin (Component A), except that the raw materials having the compositions shown in Table 1 were used. In the same manner as in 3, an amorphous copolyester resin of Polymerization Example 8 was obtained. Table 1 shows the raw material composition and characteristic analysis values of the obtained amorphous copolyester resin.

<Polymerization Example 9 of Amorphous Copolyester Resin (Component A)> Polymerization Example of Amorphous Copolyester Resin (Component A), except that the raw materials having the compositions shown in Table 1 were used. In the same manner as in 1, an amorphous copolyester resin of Polymerization Example 9 was obtained. Table 1 shows the raw material composition and characteristic analysis values of the obtained amorphous copolyester resin.

<Polymerization Example 10 of Crystalline Copolyester Resin> 194 parts by mass of dimethyl terephthalate was placed in a reaction vessel equipped with a thermometer, a stirrer and a distillate condenser.
180 parts by mass of 1,4-butanediol and 300 ppm of tetrabutyl titanate were charged. Then, the reaction system was transesterified in the temperature range of 165 to 220 ° C. for 4 hours. Then, the reaction system was heated to 40 Pa for 30 minutes.
The pressure was reduced to 250 ° C., and the temperature was raised to 250 ° C. during this period. further,
In this reaction system, the polycondensation reaction was carried out for 1 hour under the conditions of 250 ° C. and 40 Pa.

Then, the vacuum is broken with nitrogen gas, and 22
114 parts by mass of ε-caprolactone was charged at 0 ° C., and the mixture was heated with stirring for 1 hour to carry out a ring-opening addition reaction to obtain an amorphous block copolymerized polyester resin of Polymerization Example 7. The composition and characteristic analysis values of the obtained amorphous copolyester resin are shown in Table 1.

[0118]

[Table 1]

Here, the abbreviations in Table 1 indicate the following compounds. TPA; terephthalic acid IPA; isophthalic acid DiA; dimer acid SA; sebacic acid AA; adipic acid TMA; trimellitic anhydride NPG; neopentyl glycol 2MG; 2-methyl-1,3-propanediol DMH; 3,3'- Dimethylol heptane EG; ethylene glycol HD; 1,6-hexanediol BD; 1,4-butanediol CL; ε-caprolactone <Example 1> Amorphous copolymer polyester resin blend Copolyester resin 10
Cyclohexanone / Solvesso 100 containing 0 parts by mass
(Exxon Co., aromatic hydrocarbon solvent) = 1/1 solution (solid concentration 40%), 4 parts by mass of benzophenone tetracarboxylic acid anhydride (BTDA) as an acid anhydride, and Epotote YD8125 (as an epoxy resin) Epibis epoxy resin, manufactured by Tohto Kasei Co., Ltd., in this specification, Y
13 parts by mass of Irganox 1010 (tetrakis [3- (3,5-di-tert))
-Butyl-4-hydroxyphenyl) propionyloxymethyl] methane, manufactured by Ciba Specialty Chemicals) 15 parts by mass (corresponding to 11.4% by mass), and triphenylphosphine (TPP) 0.35 parts by mass as a curing accelerator. did.

This solution was applied to a chromate-treated steel sheet having a thickness of 0.5 mm so that the thickness after drying would be 25 μm.
After drying with hot air for 2 minutes at 0 ° C, overlap the coated surfaces and
A composite type vibration damping material was obtained by pressure bonding at 20 ° C. for 30 seconds. Table 2 shows the composition and the evaluation results of the obtained composite vibration damping material.

<Examples 2 to 7> Formulation of various amorphous copolyester resins As shown in Table 2, except that the amorphous copolyester resins produced in Polymerization Examples 2 to 7 were used, respectively. In the same manner as in Example 1, composite vibration damping materials of Examples 2 to 7 were obtained. Table 2 shows the composition and the evaluation results of the obtained composite vibration damping material.

Example 8 Blend Polymerization of Amorphous Copolyester Resins Amorphous Copolyester Resin 65 Produced in Example 6
Parts by mass, copolymerized polyester resin 3 produced in Polymerization Example 2
Cyclohexanone / Solvesso 100 = including 5 parts by mass
B solution as an acid anhydride in 1/1 solution (solid concentration 40%)
4 parts by mass of TDA, 13 parts by mass of YD8125, 15 parts by mass of Irganox 1010 (corresponding to 11.4% by mass), and triphenylphosphine (TP) as a curing accelerator.
0.35 part by mass of P) was blended. The obtained solution was transparent and the two kinds of amorphous copolyesters were compatible with each other. Table 2 shows the composition and evaluation results of the composite damping material obtained from this solution in the same manner as in Example 1.

<Examples 9 to 10> Control of amount of phenolic compound As shown in Table 2, 10 parts by mass (corresponding to 7.9% by mass) of Irganox 1010 and 25 parts by mass (17.6% by mass). (Comparative) A composite vibration damping material of Examples 9 to 10 was obtained in the same manner as in Example 6 except that it was compounded. Table 3 shows the composition and the evaluation results of the obtained composite vibration damping material.

<Examples 11 to 19> Mixing of various curing agents and phenolic compounds As shown in Table 3, various amorphous copolyester resins were used, and various kinds of BTDA and YD8125 were used in place of BTDA and YD8125. Composite type vibration damping materials of Examples 11 to 19 were performed in the same manner as in Example 1 except that an epoxy resin or an isocyanate compound was used as a curing agent, and various phenolic compounds were used instead of Irganox 1010. Got Table 3 shows the results relating to Examples 11 to 16 among the compositions and evaluation results of the obtained composite type vibration damping material.
Table 4 shows the results of Examples 17 to 19.

Comparative Example 1 Presence / Absence of Phenolic Compound Amorphous Copolyester Resin 10 Produced in Polymerization Example 1
Cyclohexanone / Solvesso 100 = 0 parts by weight
Benzophenone tetracarboxylic acid anhydride (BTDA) as an acid anhydride was added to a 1/1 solution (solid concentration 40%).
13 parts by weight of YD8125 and 0.23 parts by weight of triphenylphosphine (TPP) as a curing accelerator were added.

This solution was applied to a chromate-treated steel sheet having a thickness of 0.5 mm so that the thickness after drying would be 25 μm.
After drying with hot air for 2 minutes at 0 ° C, overlap the coated surfaces and
A composite type vibration damping material was obtained by pressure bonding at 20 ° C. for 30 seconds. Table 5 shows the composition and the evaluation results of the obtained composite vibration damping material.

<Comparative Examples 2 to 6> Presence or absence of phenolic compound As shown in Table 4, various amorphous copolymerized polyester resins were used, Irganox 1010 was not added at all, and Phenylphosphine (TP
Composite type damping materials of Comparative Examples 2 to 6 were obtained in the same manner as in Example 1 except that 0.23 part by mass of P) was blended. Table 5 shows the composition and the evaluation results of the obtained composite vibration damping material.

Comparative Example 7 Excessive Amount of Phenolic Compound As shown in Table 4, the same procedure as in Example 6 was carried out except that 50 parts by mass (corresponding to 29.9% by mass) of Irganox 1010 was blended. A composite vibration damping material of Comparative Example 7 was obtained. Table 5 shows the composition and the evaluation results of the obtained composite vibration damping material.

<Comparative Example 8> Formulation of sulfenamides As shown in Table 4, instead of Irganox 1010, Sansera DZ (N, N-dicyclohexyl-2-benzothiazolyl sulfenamide, Sanshin Chemical Industry Co., Ltd.) was used. (stock)
A composite type vibration damping material of Comparative Example 8 was obtained in the same manner as in Example 1 except that 20 parts by mass of (produced) was blended. Table 5 shows the composition and the evaluation results of the obtained composite vibration damping material.

<Comparative Example 9> Presence or absence of curing agent As shown in Table 4, the composite vibration damping material of Comparative Example 9 was prepared in the same manner as in Example 8 except that BTDA and YD8125 were not compounded at all. Obtained. Table 6 shows the composition and the evaluation results of the obtained composite vibration damping material.

Comparative Example 10 Blending with Crystalline Polyester Crystalline Copolyester Resin 1 Produced in Polymerization Example 10
15 parts by mass of Irganox 1010 was mixed with 00 parts by mass, and the mixture was put into a biaxial kneader set to 200 ° C. The obtained sheet was pressed to a thickness of 50 μ, sandwiched between chromate-treated steel sheets having a thickness of 0.5 mm, and pressure-bonded at 200 ° C. for 10 seconds to obtain a composite vibration damping material. Table 6 shows the composition and the evaluation results of the obtained composite vibration damping material.

<Comparative Example 11> Acrylic rubber compounded with acrylic rubber (AR-15, manufactured by Nippon Zeon Co., Ltd.) 10
20 parts by mass of Irganox 1010 was mixed with 0 parts by mass, and the mixture was put into a kneading roll set at 160 ° C. The obtained sheet was pressed to a thickness of 50 μ, sandwiched between chromate-treated steel sheets having a thickness of 0.5 mm, and pressure-bonded at 200 ° C. for 10 seconds to obtain a composite vibration damping material. Table 6 shows the composition and the evaluation results of the obtained composite vibration damping material.

[0133]

[Table 2]

[0134]

[Table 3]

[0135]

[Table 4]

[0136]

[Table 5]

[0137]

[Table 6]

The abbreviations in Tables 2 to 6 represent the following compounds. BTDA; Benzophenone tetracarboxylic acid anhydride PMA; Hiromellitic acid anhydride YD8125; Evotote YD8125, EP-1001 manufactured by Toto Kasei Co., Ltd .; Ebicoat 1001, Coronate HX manufactured by Yuka Shell Epoxy Co., Ltd .; Aliphatic polyisocyanate, Japan I-1010 manufactured by Polyurethane Industry Co., Ltd .; Irganox 1010 (tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, manufactured by Ciba Specialty Chemicals) AO-330; ADEKA STAB 330 (1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-
Butyl-4-hydroxybenzyl) benzene, manufactured by Asahi Denka Co., Ltd. S-WXR; Sumilizer-WX-R (bis (5-te
rt-Butyl-4-hydroxy-2-methylphenyl)
Sulfide, Sumitomo Chemical Co., Ltd. I-1222; Irganox 1222 (3,5-di-
tert-Butyl-4-hydroxybenzylphosphonate diethyl ester, manufactured by Ciba Specialty Chemicals) TIN-234: Tinuvin 234 (2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -benzotriazole MBTBC: methylene bis-tert-butyl-p-cresol (bis (3-tert-butyl-2-hydroxy-5-methylphenyl) methane, manufactured by Tokyo Kasei) SD
Z; Sunceller DZ (N, N-dicyclohexyl-2
-Benzothiazolylsulfenamide, manufactured by Sanshin Chemical Industry Co., Ltd. <Analysis method and evaluation method> Amorphous copolyester obtained in the above polymerization example, obtained in the above examples or comparative examples The characteristic analysis and performance evaluation of the viscoelastic resin composition and the composite vibration damping material were performed based on the following analysis method or evaluation method.

(1) Analysis of Composition of Amorphous Copolymerized Polyester Resin The composition of the amorphous copolyester resin was determined by a Varian nuclear magnetic resonance spectrometer (NMR) in a heavy chloroform solvent.
Determined by ¹ H-NMR analysis using Gemini-200.

(2) Analysis of number average molecular weight of amorphous copolyester resin The number average molecular weight of the amorphous copolyester resin is 150c of gel filtration permeation chromatography (GPC) manufactured by Waters Co. using tetrahydrofuran as an eluent. Was calculated from the result of GPC measurement using a column temperature of 35 ° C. and a flow rate of 1 ml / min to obtain a polystyrene-converted measured value.

(3) Analysis of glass transition temperature of amorphous copolyester resin The glass transition temperature of the amorphous copolyester resin is Seiko Instruments Inc. differential scanning calorimeter (DSC) DSC-220. Temperature rise rate of 20 ° C /
It was determined by measuring in minutes.

(4) Evaluation of gel fraction of viscoelastic resin composition After producing a damping metal plate having a skin material plate thickness of 0.5 mm and a resin layer thickness of 50 μm, the damping plate was peeled off and a film was formed on one side. The remaining portion was cut into 25 × 50 mm, immersed in a liquid of methylethylketone (MEK) / toluene = 1/1 (mass ratio) for 1 hour and dried, and the weight ratio of the resin residue was M.
It was determined by measuring the weight of the sample before and after immersion in EK.

(5) Evaluation of Adhesive Strength of Viscoelastic Resin Composition Shear adhesive strength of a 25 mm × 10 mm overlapping portion of a vibration-damping metal plate having a skin material plate thickness of 0.5 mm and a resin layer thickness of 50 μm, and the same vibration damping property. A T-peeling strength when a test piece having a width of 25 mm and a length of 150 mm was sampled from the metal plate and the front and back steel plates at the end of the test piece were pulled in a 180 ° direction was measured by a tensile tester (manufactured by Shimadzu Corporation, Autograph AG- 10 KNE)
Measured at a pulling speed of 50 mm / min and a measurement temperature of 23 ° C.,
The adhesive strength was evaluated.

(6) Evaluation of vibration damping performance of composite type vibration damping material A vibration damping metal plate of 30 mm × 300 mm was used as a test piece, and a noise vibration analyzer (SA-74 manufactured by Rion Co.) and a vibration exciter (Bruer) were used. The loss coefficient η at the time of 500 Hz vibration at various temperatures was measured by a mechanical impedance method using Type 4809 manufactured by KAIR. The larger the loss coefficient η, the better the vibration damping property. In the present invention, the vibration damping performance was evaluated by the temperature at which this loss coefficient η is maximum and the maximum value of this loss coefficient η.

(7) Evaluation of heat resistance of composite type vibration damping material The test piece for measuring the adhesiveness of the vibration damping metal plate and the test piece for measuring the vibration damping property were heated in a hot air dryer at 240 ° C. for 0.5 hour. , Changes in T peel strength and shear adhesive strength before and after heating,
It was evaluated according to the following criteria. ⊚: No decrease in adhesive strength is observed. ◯: A slight decrease in adhesive strength is observed. Δ: A considerable decrease in adhesive strength is observed. X: A significant decrease in adhesive strength is observed. Furthermore, using a test piece for measuring adhesiveness after heat resistance evaluation,
The adhesive strength was evaluated again based on the evaluation method of (5).

From the evaluation results of Tables 2 to 6 above, the composite type vibration damping materials of the examples of the present invention are remarkably excellent in vibration damping performance, adhesive strength and heat resistance as compared with the composite type vibration damping materials of the comparative examples. It turns out to be excellent.

The embodiments and examples disclosed this time must be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description but by the claims, and is intended to include meanings equivalent to the claims and all modifications within the scope.

[0148]

As is clear from the above results, the viscoelastic resin composition of the present inventor contains a specific thermoplastic resin and a large amount of a specific phenolic compound, and therefore has excellent vibration damping performance. It can be said to be an elastic resin composition.

Further, the viscoelastic resin composition of the present invention, in order to prevent a decrease in the adhesive strength of the viscoelastic resin composition by adding a large amount of a phenolic compound to the thermoplastic resin,
Further, since it contains a curing agent capable of reacting with the thermoplastic resin to form crosslinks, it can be said that the viscoelastic resin composition has high vibration damping performance and further excellent adhesive strength.

Furthermore, in the viscoelastic resin composition of the present invention, the addition of a curing agent forms a three-dimensional network crosslink in the thermoplastic resin, so that the adhesive strength is less likely to decrease even under high temperature conditions, and the high controllability is high. It can be said that it is a viscoelastic resin composition having excellent heat resistance in addition to vibration performance and adhesive strength.

Since the composite type vibration damping material of the present invention is obtained by laminating the viscoelastic resin composition of the present invention and a substrate, it exhibits high vibration damping performance and excellent adhesive strength, and is easy to process. It can be said that it is a composite type vibration damping material having excellent heat resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI Theme Coat (reference) F16F 15/08 F16F 15/08 D (72) Inventor Yasunobu Susuko 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd. Research Institute (72) Inventor Nobuo Kadowaki 5-3, Tokai-cho, Tokai-shi, Aichi Nippon Steel Co., Ltd. Nagoya Works (72) Inventor Ryoichi Matsuda 5--3, Tokai-cho, Tokai-shi, Aichi Address Nippon Steel Co., Ltd. Nagoya Steel Works F-term (reference) 3J048 AA01 AC03 BA08 BA24 BA25 BD04 BD07 BD08 EA03 EA36 4F100 AB01A AB01B AH02C AK01C AK41C AK51C AK53C AL07C JBJB07B07B07B07B07B02B07B02BA10 BA02 BA10 BA02 BA10 BA02 BA10 BA02 BA10 BA02 BA10 BA02 BA10 BA02 BA10 BA02 BA10 YY00C 4J002 BG072 CD012 CD022 CD042 CD052 CD062 CD072 CD082 CD092 CD112 CD122 CD132 CD142 CD192 CF011 CF031 CF041 CF051 CF061 C F081 CK033 CK043 EE058 EJ018 EJ028 EJ068 EL137 EN038 EQ028 ER006 ER008 EU178 EU198 EV078 EV098 EW068 EW128 FD010 FD020 FD078 FD110 FD142 FD143 FD146 FD147 FD340 GL00 GM00 GN00 GQ00 4J034 BA03 DA01 DB03 DD01 DF11 DF12 DF16 DF17 DF20 DF21 DF22 DF24 DF29 DF33 DG00 DL00 GA55 HA01 HA02 HA07 HB07 HB09 HC03 HC06 HC08 HC09 HC12 HC13 HC17 HC22 HC35 HC46 HC52 HC64 HC67 HC71 HC73 JA02 MA12 MA14 MA15 MA16 RA07 RA10 RA11 RA12 RA14 RA15 4J036 AB02 AB03 AB08 AB12 AB17 AC01 AC03 AD01 AD05 AD08 AD20 AF06 AG07 FA07 AH AAK FA12 FB11 FB12 JA01

Claims (7)

[Claims] 1. A thermoplastic resin as the component A, and a curing agent capable of reacting with the component A to form crosslinks as the component B.
It contains a phenolic compound as the C component, and the C component is 2 with respect to the total value of the masses of the A component, the B component and the C component.
The viscoelastic resin composition contained in the range of 25 to 25 mass%. 2. The viscoelastic resin composition according to claim 1, wherein the component B is contained in the range of 3 to 50 parts by mass with respect to 100 parts by mass of the component A. 3. The viscoelastic resin composition according to claim 1, wherein the component A is an amorphous copolyester resin. 4. The viscoelastic resin composition according to claim 1, wherein the component B is one or more selected from the group consisting of polyepoxy compounds, acid anhydrides and polyisocyanate compounds. object. 5. A T-peel strength after heat curing is 8 kgf / 25 mm or more when heat cured in a state of being sandwiched between base materials made of metal as a middle layer, and a gel fraction after heat curing. Is in the range of 50 to 98%, and the viscoelastic resin composition according to claim 1. 6. A composite vibration damping material having a multilayer structure in which the viscoelastic resin composition according to claim 1 is sandwiched as an intermediate layer between base materials made of metal. 7. A viscoelastic resin composition is applied to at least one surface of a base material made of a metal, and the coating film is crosslinked,
The composite vibration damping material according to claim 6, which is obtained by bonding the base material with the obtained crosslinked coating film inside and then thermocompression-bonding the base material.