JP6125799B2 - Resin composition for damping material - Google Patents

Description

The present invention relates to a resin composition for a vibration damping material. More specifically, a damping material resin, a damping material composition, and the like, which are useful as materials for damping materials used to prevent vibration and noise in various structures and maintain quietness, are formed by the same. Related to damping material.

The damping material is for keeping vibration and noise in various structures and keeping quiet, for example, in addition to being used under the indoor floor of an automobile, a railway vehicle, a ship, an aircraft, an electrical device, Widely used in building structures and construction equipment. As a material used for such a damping material, conventionally, a molded product such as a plate-shaped molded body or a sheet-shaped molded body made of a material having vibration absorption performance and sound absorption performance has been used. On the other hand, when the shape of the place where vibration or sound is generated is complicated, it is difficult to apply these molded products to the place where vibration is generated. Various methods for exerting the effect have been studied. For example, asphalt sheets containing inorganic powder have been used under the floors of automobiles, etc., but since there is a need for heat-sealing, improvement in workability and the like is desired. Various compositions for damping materials and polymers to be formed have been studied.

As described above, coating-type damping materials (paints) have been developed as substitute materials for molded products, and, for example, by coating films formed by spraying or applying by any method to the corresponding locations. Various vibration-damping paints that can obtain a vibration absorbing effect and a sound absorbing effect have been proposed. Specifically, for example, as a water-based vibration-damping paint with improved coating film hardness obtained by blending a synthetic resin powder with a color developing agent such as asphalt, rubber, synthetic resin, and the like suitable for indoor use in automobiles, Anti-vibration coatings in which activated carbon is dispersed as a filler in a resin emulsion have been developed. However, even with these conventional products, the vibration damping performance is still not at a sufficiently satisfactory level, and there is a need for a technique that can further exhibit the vibration damping performance.

As a resin composition used for such a damping material, it has a hydrogen bond forming ability capable of forming and controlling a hydrogen bond between a resin emulsion having a polar group and the polar group of the resin emulsion. A vibration-damping coating composition containing a specific compound as an aromatic compound having at least one hydroxyl group and further containing an inorganic filler is disclosed (for example, see Patent Document 1). Further, the specific polymer as the base material is composed of one or more selected from a compound having a benzotriazole group that increases the amount of dipole moment in the base material and a compound having a diphenyl acrylate group. An energy conversion composition containing an active ingredient is disclosed (for example, see Patent Document 2). Furthermore, in the vibration-damping paint containing an active ingredient that increases the amount of dipole moment in the paint component in the paint composition, an acrylic polymer substituted with a carboxyl group is disclosed as a coating film component ( For example, see Patent Document 3.) Further, one or two compounds selected from p- (p-toluenesulfonylamido) diphenylamine and octylated diphenylamine in a matrix phase composed of thermoplastic resin, thermoplastic elastomer, rubber, or water-based emulsion resin An organic damping material having a dispersed phase comprising: the dispersed phase is a dispersed phase in which the compound is microphase-separated in the matrix phase or a completely compatible dispersed phase, and the thermoplastic resin is An organic damping material selected from specific resins is disclosed (for example, see Patent Document 4).

Japanese Patent No. 4172536 Japanese Patent No. 3318593 International Publication No. 01/40391 Japanese Patent No. 4465023

As described above, resin compositions having various configurations have been disclosed for use in vibration damping materials, but in applications where such resin compositions are used, even better vibration damping properties are exhibited. There is a demand for a resin composition, and it has been a challenge to develop a resin composition with improved vibration damping properties that meet such requirements.

The present invention has been made in view of the above situation, and provides a resin composition for a damping material that exhibits excellent damping properties and can be suitably used in applications where a damping effect is required for a coating film. The purpose is to do.

The present inventor has made various studies on the resin composition for vibration damping materials. Assuming that the composition contains a polymer and an additive, and the additive is present in a state compatible with the polymer, the polymer and the additive are added. It has been found that such a resin composition exhibits excellent vibration damping properties due to the interaction with the agent. The inventor has also found out that the vibration damping property of the resin composition is further improved by using a specific compound as such an additive or by using a polymer having a specific structure. The inventors have arrived at the present invention by conceiving that the problem can be solved brilliantly.

That is, the present invention provides a vibration damping resin composition comprising a polymer obtained by polymerizing monomer components, wherein the vibration damping resin composition comprises an additive in a state compatible with the polymer. It is the resin composition for damping materials characterized by including.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The resin composition for a vibration damping material of the present invention includes a polymer obtained by polymerizing monomer components and an additive, but it is sufficient that each of these includes at least one kind, and two or more kinds. May be. Moreover, as long as it contains the polymer and additive which superpose | polymerize a monomer component, the other component may be included.
In addition, in this invention, the additive which the resin composition for damping materials contains is a component added in order to improve the damping property of the resin composition for damping materials.

The resin composition for vibration damping material of the present invention preferably contains 5 to 80% by mass of a polymer obtained by polymerizing monomer components with respect to 100% by mass of the total amount of the resin composition for vibration damping material. . More preferably, it comprises 10 to 80% by mass. More preferably, it contains 15 to 70% by mass, and particularly preferably 20 to 70% by mass.

The content of the additive in the resin composition for vibration damping material of the present invention is 10 to 2000% by mass with respect to 100% by mass of the polymer obtained by polymerizing the monomer component in the resin composition for vibration damping material. It is preferable. By including the additive at such a ratio, the interaction between the additive and the polymer is effectively exhibited, and the resin composition for a vibration damping material exhibits more excellent vibration damping properties. More preferably, it is 10 to 1000% by mass, and more preferably 10 to 500% by mass with respect to 100% by mass of the polymer obtained by polymerizing the monomer component. Further, it is particularly preferably 10 to 200% by mass, particularly preferably 15 to 180% by mass, and most preferably 20 to 160% by mass.

In the resin composition for vibration damping material of the present invention, the peak temperature of the loss factor (tan δ) of the coating film obtained from the resin composition for vibration damping material is preferably 0 to 60 ° C. When the peak temperature of the loss coefficient (tan δ) of the coating film is in such a range, the damping performance in the practical temperature range of the damping material can be effectively expressed. More preferably, the peak temperature of the loss factor (tan δ) of the coating film is 10 to 50 ° C., and more preferably 15 to 45 ° C.
The peak temperature of the loss factor (tan δ) of the coating film can be adjusted by appropriately selecting the glass transition temperature (Tg) of the polymer contained in the resin composition for damping material and the type of additive.
The loss factor (tan δ) of the coating film can be measured by the method described later.

The polymer contained in the resin composition for vibration damping material of the present invention preferably has a glass transition temperature of −25 to 150 ° C. When a polymer having such a glass transition temperature is used as the polymer, the damping performance in the practical temperature range of the damping material can be effectively expressed. The glass transition temperature of the polymer is more preferably -20 to 100 ° C, still more preferably -20 to 80 ° C. Especially preferably, it is -15-35 degreeC, Most preferably, it is -10-30 degreeC.
The glass transition temperature (Tg) of the polymer may be determined based on the knowledge already obtained, or may be controlled by the type and proportion of the monomer component described later, but theoretically It can be calculated from the following calculation formula (1).

In the formula, Tg ′ is Tg (absolute temperature) of the polymer. W ₁ ′, W ₂ ′,... Wn ′ are mass fractions of the respective monomers with respect to the total monomer components. Tg ₁ , Tg ₂ ,... Tgn are glass transition temperatures (absolute temperatures) of homopolymers (homopolymers) composed of the respective monomer components.

The additive contained in the resin composition for vibration damping material of the present invention interacts with the polymer contained in the resin composition for vibration damping material, thereby reducing the vibration energy applied to the polymer as described above. There is no particular limitation as long as it can promote conversion to another energy such as heat energy by friction. The interaction between the additive and the polymer includes various types such as formation and dissociation of ionic interactions, formation and dissociation of hydrogen bonds, change in direction and amount of dipole moment, and change in van der Waals force. .

The above additive is in a state compatible with the polymer in the vibration damping resin composition, but is compatible with the polymer when the vibration damping material is formed from the vibration damping resin composition. If the resin composition for vibration damping material contains other components such as pigments and fillers to be described later in addition to the polymer and additives added to improve vibration damping properties, these other What is necessary is just to include a component and to be in a state compatible with the polymer when the damping material is formed.
Such a method for producing a resin composition for a vibration damping material in which the resin composition for a vibration damping material contains a polymer and an additive and the additive is in a state compatible with the polymer is also one aspect of the present invention. It is.

The additive is not particularly limited as long as it interacts with the polymer, and p- (p-toluenesulfonylamido) diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, octylation Aromatic secondary amine additives such as diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine, a reaction product of N-phenylbenzenediamine and styrene, 2,4,4-trimethylpentane; Guanidine additives such as 1,3-diphenylguanidine, N, N′-diphenylguanidine, N, N′-diortolylguanidine; Thiourea additives such as N, N′-diphenylthiourea; α, α ′ -Aniline additives such as bis (4-aminophenyl) -1,4-diisopropylbenzene, n-butyraldehyde aniline Quinoline additives such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolylsulfur Addition of benzothiazyl compounds such as phenamide, N- (t-butyl) -2-benzothiazole sulfenamide, N, N-dicyclohexylbenzothiazole-2-sulfenamide, 2-mercaptobenzothiazole, dibenzothiazyl sulfide Agents; 2- (2′-hydroxy-5′-methylphenyl) -benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 3- [3-t-Butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxypheny Octyl propionate, 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] octyl propionate, 2- [2-hydroxy-3,5-bis ( [alpha], [alpha] -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3 '-(3,4,5,6-tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2 ′ -Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t-octylph) Enol) benzotriazole additives such as benzotriazole; diphenyl acrylate additives such as ethyl-2-cyano-3,3-diphenyl acrylate, octyl-2-cyano-3,3-diphenyl acrylate;

Benzophenone-based additives such as 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid; 1,1′-bis (4-hydroxyphenyl) cyclohexane, 2,2′-bis (4-hydroxy-3-methylphenyl) propane, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-nonylphenol), 2,2 ′ -Methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methylphenol), 2,2'-methylenebis (4-propylphenol), 2,2'-methylenebis (4- Chlorophenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2 2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-isobutylidenebis (4,6-dimethylphenol), 2,2′-thio-diethylenebis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobisphenol, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (2- Methyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-methylenebis (2,5-dimethylphenol), 4,4′-methylenebis (2 -Methyl-5-ethylphenol), 4,4'-methylenebis (2-methyl-5-propylphenol), 4,4'-ethylenebis (2,6-di-t-butylphenol) ), 4,4′-isopropylidenebis (2,6-di-t-butylphenol), 4,4′-isopropylidenebis (2,7-di-t-butylphenol), 4,4′-butylidenebis (2 , 6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-dihydroxybiphenyl, 1,3,5-trimethyl-2,4,6- Tris- (3,5-di-tert-butyl-4hydroxybenzyl) -benzene, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Butylation reaction product of p-cresol and dicyclopentadiene, 1,4-bis (4-benzoyl-3-hydroxyphenoxy) -butane, 1- [2- {3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,5-di-t-butylhydroquinone, 3,9-bis [1,1-dimethyl-2 -[(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 4-vinylphenol, tetrakis (methylene -Di-t-butyl-4-hydrohydrocinnamate), tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, pentaerythro Lityl-tetra [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], Α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, mono (or di, tri) (α-methylbenzyl) phenol, tetrakis (methylene-3,5-di-t-butyl) -4-hydrohydrocinnamate), phenolic additives such as hydroquinone;

Naphtholic additives such as 1,5-dihydroxynaphthalene, 5-amino-1-naphthol, 2-amino-6-hydroxynaphthol; ditridecyl 3,3′-thiobispropionate, 3,3′-thiobispropionic acid Organic thioacid additives such as didodecyl; tris (nonylphenyl) phosphite, diphenylisodecylphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol Phosphite additives such as diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite; triphenyl phosphate, 2 -Ethylhexyl diphenyl phosphate, tricresyl phosphate, trixylate Ruphosphate, cresyl diphenyl phosphate, cresyl-di-2,6-xylenyl phosphate, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphapyro [5 .5] Phosphate ester additives such as undecane can be preferably used.

The polymer obtained by polymerizing the monomer components preferably has a weight average molecular weight of 10,000 to 1,500,000. In order to exert vibration damping properties, it is preferable to change the energy of vibration applied to the polymer to thermal energy due to friction, and the polymer must be able to move when vibration is applied to the polymer. Necessary. When the polymer has such a weight average molecular weight, the polymer can sufficiently move when vibration is applied, and high damping properties can be exhibited. The weight average molecular weight of the polymer is more preferably 1 to 1,000,000, still more preferably 2 to 400,000, particularly preferably 30,000 to 400,000, and most preferably 40,000 to 400,000. is there.
The weight average molecular weight can be determined, for example, by GPC (gel permeation chromatography) measurement under the following measurement conditions.
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) are connected in series. Eluent: Tetrahydrofuran (THF)
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The measurement object is dissolved in THF so that the solid content is about 0.2% by mass, and the molecular weight is measured using an object obtained by filtration through a filter as a measurement sample.

The polymer obtained by polymerizing the monomer component preferably has a solubility parameter (SP value) of 7 to 10. When the SP value of the polymer is in such a range, the compatibility with the additive is excellent. The SP value is more preferably 7.3 to 9.9, and still more preferably 7.6 to 9.9.
The SP value of the polymer can be determined by the following Small formula.

In the formula, δ is the SP value of the polymer. Δe ₁ is a calculated value (kcal / mol) of the evaporation energy of each monomer component constituting the polymer, and ΣΔe ₁ is a total value of the calculated values of all the monomer components constituting the polymer. ΔV _m is the calculated value (ml / mol) of the molecular volume of each monomer component constituting the polymer, and ΣΔV _m is the sum of the calculated values of all the monomer components constituting the polymer. x is the molar distribution of each monomer component constituting the polymer.
Note that normally used calculation values can be used for the evaporation energy of the monomer component and the molecular volume of the monomer component.
Thus, the SP value of the polymer can be adjusted by adjusting the type of monomer to be constituted and the composition ratio thereof.

As long as the additive is in a state compatible with the polymer, the resin composition for vibration damping material of the present invention further contains a solvent, and the polymer obtained by polymerizing the monomer component and the additive are dissolved in the solvent. May be a solvent-based composition, wherein a polymer obtained by polymerizing monomer components is present in the form of an emulsion in an aqueous solvent, and an additive is contained in the polymer, or an emulsion in an aqueous solvent. It may be an aqueous composition existing in the form of
Such a resin composition for a vibration damping material of the present invention further contains a solvent, and a polymer obtained by polymerizing the monomer component and an additive dissolved in the solvent are It is one of the suitable embodiment of the resin composition for damping materials of this invention.
In addition, a water-based damping material in which a polymer obtained by polymerizing monomer components is present in the form of an emulsion in an aqueous solvent, and an additive is contained in the polymer, or is present in the form of an emulsion in an aqueous solvent. The resin composition for a vibration is also one of the preferred embodiments of the resin composition for a vibration damping material of the present invention.

In the present invention, the viscosity of the solution in which the polymer is dissolved in the solvent or the emulsion of the polymer is not particularly limited, but is preferably 10 to 10000 mPa · s, more preferably 15 to 8000 mPa · s, and still more preferably. 20 to 6000 mPa · s.
The viscosity can be measured using a B-type rotational viscometer under the conditions of 25 ° C. and 20 rpm.

The resin composition for a vibration damping material of the present invention preferably has a non-volatile content in the composition of 20 to 90% by mass with respect to 100% by mass of the entire resin composition for a vibration damping material. When the nonvolatile content is in such a range, the resin composition for vibration damping material can easily form a coating film by coating, and the coating film exhibits excellent vibration damping properties. The nonvolatile content in the composition is more preferably 30 to 87% by mass, and still more preferably 40 to 84% by mass.

When the resin composition for a vibration damping material of the present invention is a water-based polymer in which a polymer obtained by polymerizing monomer components is present in the form of an emulsion in an aqueous solvent, the average particle diameter of each emulsion particle is 50 to 50. It is preferable that it is 450 nm.
By using emulsion particles with an average particle size in this range, the basic properties such as heat drying properties and coating properties required for vibration damping materials will be sufficient, and vibration damping properties will be even better. It can be. The upper limit is more preferably 400 nm or less, still more preferably 350 nm or less. The lower limit is particularly preferably 100 nm or more. When the average particle diameter of the emulsion particles is within such a range, the effect of the resin composition for vibration damping material of the present invention is more effectively exhibited. Further, the lower limit of the average particle diameter is preferably 65 nm or more, more preferably 80 nm or more.
The average particle size (volume average particle size) can be determined by, for example, diluting the emulsion with distilled water, thoroughly stirring and mixing, then collecting about 10 ml in a glass cell, and measuring the particle size distribution analyzer (Particle) by the dynamic light scattering method. It can be determined by measuring with “NICOMP Model 380” manufactured by Sizing Systems.

The emulsion particles having the above average particle diameter preferably have a particle size distribution defined by a value obtained by dividing the standard deviation by the volume average particle diameter (standard deviation / volume average particle diameter × 100) of 40% or less. More preferably, it is 30% or less. If the particle size distribution exceeds 40%, the width of the particle size distribution of the emulsion particles becomes very wide, and some of the particles contain coarse particles. Therefore, the resin for damping material is affected by such coarse particles. However, there is a possibility that sufficient heat drying property cannot be exhibited.

Moreover, when the resin composition for vibration damping material of the present invention is an aqueous composition, the pH of the composition is not particularly limited, but is preferably 4 to 12, more preferably 5 to 11, More preferably, it is 6-10. The pH of the resin composition for damping material can be adjusted by adding ammonia water, water-soluble amines, alkaline hydroxide aqueous solution, and the like to the resin.
In this specification, pH can be measured with a pH meter. For example, it is preferable to measure the value at 25 ° C. using a pH meter (“F-23” manufactured by Horiba, Ltd.).

The polymer obtained by polymerizing the monomer component contained in the resin composition for vibration damping material of the present invention is not particularly limited as long as the effects of the present invention can be exhibited, but includes an unsaturated carboxylic acid monomer. It is preferably obtained from a monomer component. More preferably, it is obtained from a monomer component containing an unsaturated carboxylic acid monomer and another monomer copolymerizable with the unsaturated carboxylic acid monomer. The unsaturated carboxylic acid monomer is not particularly limited as long as it is a compound having an unsaturated bond and a carboxyl group in the molecule, but preferably contains an ethylenically unsaturated carboxylic acid monomer.

The ethylenically unsaturated carboxylic acid monomer is not particularly limited. For example, (meth) acrylic acid monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, citraconic acid, fumaric acid, maleic acid , One or more of unsaturated carboxylic acids such as maleic anhydride, monomethyl fumarate, monoethyl fumarate, monomethyl maleate, and monoethyl maleate, or derivatives thereof. Among these, a (meth) acrylic acid monomer is preferable. That is, the polymer obtained by polymerizing the monomer component is a (meth) acrylic polymer in which at least one of the monomer components is a (meth) acrylic acid monomer. This is one of the preferred embodiments.

In the (meth) acrylic polymer of the present invention, at least one of the monomer components is C (R ⁷ ) ₂ ═CH—COOR ⁸ or C (R ⁹ ) ₂ ═C (CH ₃ ) —COOR. ¹⁰ (R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group). It is preferable that it is obtained by using.
In the present specification, the (meth) acrylic acid monomer has an acryloyl group or a methacryloyl group, or a group in which a hydrogen atom in these groups is replaced with another atom or atomic group, and A monomer having —COOH group, and a (meth) acrylic monomer has an acryloyl group or a methacryloyl group, or a group in which a hydrogen atom in these groups is replaced with another atom or atomic group. And a monomer in the form in which the —COOH group is an ester or a salt, or a derivative of such a monomer.

The monomer component used as a raw material for the (meth) acrylic polymer is 0 to 20% by mass of the (meth) acrylic monomer based on 100% by mass of all monomer components, and other copolymerizable components. It is preferable to contain 20-100 mass% of an ethylenically unsaturated monomer. By including the (meth) acrylic acid-based monomer, when the resin composition for vibration damping material of the present invention includes a filler such as inorganic powder described later, the dispersibility of the filler is improved and vibration damping is achieved. Will be improved. Moreover, it becomes easy to adjust the acid value, Tg, physical properties, etc. of a polymer by including another copolymerizable ethylenically unsaturated monomer. In the monomer component, even if the (meth) acrylic acid monomer is less than 0.1% by mass or more than 20% by mass, the monomer component is hardly stably copolymerized. There is a fear. If the resin composition for vibration damping material of the present invention is formed from these monomers, it becomes possible to have excellent heat drying properties in addition to vibration damping properties.
More preferably, 0 to 5% by mass of (meth) acrylic acid monomer and 25 to 100% by mass of other copolymerizable ethylenically unsaturated monomer with respect to 100% by mass of all monomer components. It is to comprise.

The other copolymerizable ethylenically unsaturated monomers include (meth) acrylic monomers other than (meth) acrylic acid monomers, unsaturated monomers having a nitrogen atom, and aromatic rings. And other monomers copolymerizable with the (meth) acrylic acid monomer.

Examples of (meth) acrylic monomers other than the above (meth) acrylic acid monomers include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate. Butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, isoamyl acrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, octyl acrylate, Octyl methacrylate Isooctyl acrylate, isooctyl methacrylate, nonyl acrylate, nonyl methacrylate, isononyl acrylate, isononyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, Octadecyl acrylate, octadecyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, vinyl formate, vinyl acetate, vinyl propionate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, Diallyl phthalate Triallyl cyanurate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate , Diethylene glycol diacrylate, diethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, isobornyl acrylate, isobornyl methacrylate, etc .; these salts and esterified products can be used, and one or more of these should be used Is preferred.

The salt is preferably a metal salt, ammonium salt, organic amine salt or the like. Examples of the metal atom forming the metal salt include monovalent metal atoms such as alkali metal atoms such as lithium, sodium and potassium; divalent metal atoms such as alkaline earth metal atoms such as calcium and magnesium; aluminum, Trivalent metal atoms such as iron are preferred. Further, as the organic amine salt, an alkanolamine salt such as an ethanolamine salt, a diethanolamine salt, or a triethanolamine salt, or a triethylamine salt is preferable.

As a monomer component used as the raw material of the said (meth) acrylic-type polymer, it contains 20 mass% or more of (meth) acrylic-type monomers with respect to 100 mass% of all monomer components. It is preferable. More preferably, it is 30 mass% or more.

Examples of the unsaturated monomer having an aromatic ring include divinylbenzene, styrene, α-methylstyrene, vinyltoluene, and ethylvinylbenzene. Styrene is preferred.
That is, the polymer obtained by polymerizing the monomer component is also a styrene (meth) acrylic polymer obtained from a monomer component containing styrene, which is also a preferred embodiment of the present invention. It is.

When the polymer obtained by polymerizing the monomer component is a styrene (meth) acrylic polymer, the monomer component used as a raw material is a styrene monomer with respect to 100% by mass of the monomer component. It is preferable to contain 1-90 mass%. More preferably, it is 1-80 mass%, More preferably, it is 1-70 mass%. Further, it is particularly preferably 1 to 50% by mass, particularly preferably 5 to 45% by mass, and most preferably 10 to 40% by mass.

Examples of the unsaturated monomer having a nitrogen atom include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, Ni-butoxymethyl (meth) acrylamide, etc. are mentioned. Acrylonitrile is preferred.

The polymer obtained by polymerizing the monomer component is preferably obtained from a monomer component containing a polar group-containing monomer. When the polymer contained in the resin composition for a vibration damping material has a polar group, the interaction between the polymer and the additive increases, and the vibration damping performance is more fully exhibited. Further, when the resin composition for vibration damping material contains two or more polymers, the interaction between these polymers becomes larger, and the friction between the polymers becomes larger. Will be demonstrated.
The content ratio of the polar group-containing monomer is preferably 40 to 100% by mass with respect to 100% by mass of the monomer component. More preferably, it is 45-95 mass%, More preferably, it is 50-90 mass%.

The polar group in the polar group-containing monomer is not limited as long as it is generally a polar group in an organic compound, but is a group consisting of a carboxylic acid ester, a hydroxyl group, a nitrile group, a carboxyl group, an amide group, and a pyrrolidone group. It is preferable that it is at least one selected from more. More preferably, they are a carboxylic acid ester, a hydroxyl group, and / or a carboxyl group.

The monomer component forming the (meth) acrylic polymer may further contain an unsaturated monomer having a functional group. Examples of the functional group in the unsaturated monomer having the functional group include an epoxy group, a glycidyl group, an oxazoline group, a carbodiimide group, an aziridinyl group, an isocyanate group, a methylol group, a vinyl ether group, a cyclocarbonate group, and an alkoxysilane group. Is mentioned. One kind of these functional groups may be present in one molecule of the unsaturated monomer, or two or more kinds thereof may be present. Examples thereof include glycidyl group-containing unsaturated monomers such as glycidyl (meth) acrylate and acrylic glycidyl ether, and these may be used alone or in combination of two or more.
Moreover, the monofunctional unsaturated monomer which has one functional group in 1 molecule may be sufficient, and the polyfunctional unsaturated monomer which has two or more may be sufficient.

Examples of the polyfunctional unsaturated monomer include divinylbenzene, ethylene glycol di (meth) acrylate, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, Nn-butoxymethyl ( (Meth) acrylamide, Ni-butoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, diallyl phthalate, diallyl terephthalate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, tetramethylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol Di (meth) acrylate. These may be used alone or in combination of two or more.

When the resin composition for vibration damping material of the present invention contains two or more polymers obtained by polymerizing monomer components, the two polymers are used, for example, weight average molecular weight, glass transition temperature, SP value, etc. What is necessary is just to be different in any one of various physical properties such as the kind of monomer to be used and the proportion of the monomer used. Among them, it is preferable that there is a difference in at least one of the weight average molecular weight and the glass transition temperature.

When the resin composition for vibration damping materials of the present invention contains two or more polymers obtained by polymerizing monomer components, at least one of the polymers preferably has a weight average molecular weight of 500 to 1,500,000. By using a material having such a weight average molecular weight, it is possible to further improve the vibration damping property. More preferably, it is 500-1 million, More preferably, it is 500-500,000, More preferably, it is 500-300,000. Especially preferably, it is 500 to 200,000, Especially preferably, it is 1000 to 100,000, Most preferably, it is 2000 to 50,000. The weight average molecular weight of the polymer can be measured by the same method as described above.

Moreover, when the resin composition for vibration damping materials of the present invention contains two or more kinds of polymers obtained by polymerizing monomer components, two kinds of polymers having a glass transition temperature difference of 5 to 60 ° C. among them. It is preferable to contain. Thus, by providing a difference in the glass transition temperature (Tg), for example, when applied to a damping material application, it becomes possible to express higher damping properties under a wide temperature range, and in particular, a practical range. Therefore, the vibration damping property in the 20 to 60 ° C. region is remarkably improved. The difference in glass transition temperature (Tg) is more preferably 5 to 50 ° C, and further preferably 5 to 40 ° C.
However, as described later, when any one of the polymers is an emulsion having a core part and a shell part, the Tg of the polymer forming the core part and the Tg of the polymer forming the shell part are 10 ° C. or higher. When there is a sufficient difference, and thus it is possible to express high vibration damping properties under a wide temperature range, the Tg of the entire polymer forming the core-shell emulsion and the other polymers The difference from the Tg is preferably smaller, and is preferably 10 ° C. or lower.

When the resin composition for damping material of the present invention is a water-based polymer in which the polymer obtained by polymerizing the monomer component is present in the form of an emulsion in an aqueous solvent, the polymer contained in the resin composition for damping material 1 type may be sufficient and 2 or more types may be sufficient. When two or more polymers are included, they are preferably in the form of an emulsion having a core portion and a shell portion.
When the emulsion particles having a core part and a shell part are included, the core part and the shell part may be completely compatible with each other and may have a homogeneous structure in which they cannot be distinguished from each other. The core-shell composite structure or microdomain structure may be formed inhomogeneously, but among these structures, the core-shell structure must be used in order to bring out the characteristics of the emulsion sufficiently and to produce a stable emulsion. A composite structure is preferred.
An emulsion having a core-shell composite structure is excellent in vibration damping properties in a wide range within a practical temperature range. Especially in the high temperature range, it exhibits excellent vibration damping performance compared to other forms of vibration damping composition. As a result, within the practical temperature range, the vibration damping performance covers a wide range from room temperature to high temperature range. Can be demonstrated.
In the core / shell composite structure, the surface of the core part is preferably covered with the shell part. In this case, it is preferable that the surface of the core part is completely covered with the shell part, but it may not be completely covered. For example, the core part may be covered in a mesh shape or in some places. The part may be exposed.
When the resin composition for vibration damping material of the present invention includes emulsion particles having a core part and a shell part, the unsaturated carboxylic acid monomer and other monomers copolymerizable with the unsaturated carboxylic acid monomer May be contained in any of the monomer component forming the core portion of the emulsion and the monomer component forming the shell portion, and may be used in both of them.

When at least one of the polymers contained in the resin composition for an aqueous vibration damping material of the present invention is in the form of emulsion particles having a core part and a shell part, the polymer and shell obtained from the monomer component forming the core part The polymer obtained from the monomer component forming the part has various physical properties such as weight average molecular weight, glass transition temperature, SP value (solubility coefficient), the type of monomer used, and the proportion of monomer used. Any of them may be different, but among them, it is preferable that there is a difference in at least one of the weight average molecular weight and the glass transition temperature.
The difference in glass transition temperature (Tg) between the polymer obtained from the monomer component forming the core part and the polymer obtained from the monomer component forming the shell part is the glass in the case of containing two or more kinds of the above-mentioned polymers. The same as the difference in transition temperature is preferred.
Moreover, it is preferable that Tg of the polymer obtained from the total monomer component which combined the monomer component which forms a core part, and the monomer component which forms a shell part is -25-150 degreeC. . More preferably, it is -20-100 degreeC, More preferably, it is -20-80 degreeC. Among them, more preferably, it is −20 to 40 ° C., particularly preferably −15 to 40 ° C., particularly preferably −10 to 40 ° C., and most preferably −10 to 30 ° C.
The emulsion particles having the core part and the shell part can be obtained by using an emulsion polymerization method (multistage polymerization) described later.

When the resin composition for vibration damping material of the present invention is a solvent-based resin composition for vibration damping material, the solvent contained in the composition may be a polymer formed by polymerizing monomer components and additives. As long as it can be used, it is not particularly limited, and one or more of acetone, ethyl acetate, butyl acetate, methyl ethyl ketone, hexane, toluene, xylene and the like can be used.

When the polymer obtained by polymerizing the monomer component in the resin composition for vibration damping material of the present invention is an aqueous solvent in the form of an emulsion in an aqueous solvent, the aqueous solvent may be a polymer emulsion described later. The same water-based solvent as used in the above can be used.

As long as the resin composition for a vibration damping material of the present invention includes a polymer obtained by polymerizing the monomer component and an additive added to improve the vibration damping property of the resin composition for the vibration damping material, other May be included.
When other components are included, the proportion of the other components is preferably 10% by mass or less, more preferably 5% by mass or less, with respect to the entire resin composition for a vibration damping material. In addition, other components here mean the non volatile matter (solid content) which remains in a coating film after apply | coating the resin composition for damping materials, and heat-drying, and an aqueous medium and an organic solvent are Not included.
The resin composition for a vibration damping material of the present invention preferably has a solid content of 40 to 90% by mass, more preferably 50 to 80% by mass with respect to the entire resin composition for the vibration damping material. .

When the resin composition for vibration damping material of the present invention is the solvent-based resin composition for vibration damping material described above, the method for producing the polymer contained in the resin for vibration damping material of the present invention is not particularly limited. It is preferable to produce the polymer by solution polymerization in which a monomer is dissolved in an organic solvent and polymerized in the solvent.
As the organic solvent used for the solution polymerization, the same solvents as those contained in the solvent-based vibration damping resin composition described above can be used. Moreover, the polymerization initiator, the polymerization chain transfer agent, etc. which are mentioned later can be used.

When the polymer formed by polymerizing the monomer component contained in the resin composition for vibration damping material of the present invention is in the form of an emulsion, that is, the resin composition for vibration damping material of the present invention is a water-based resin for vibration damping material In the case of a composition, the polymer contained in the resin for vibration damping material of the present invention polymerizes the monomer component by emulsion polymerization in the presence of an emulsifier. For example, the polymerization can be carried out by adding a monomer component, a polymerization initiator, and an emulsifier as appropriate in an aqueous medium for polymerization. Moreover, it is preferable to use a polymerization chain transfer agent or the like for molecular weight adjustment.

When the polymer contained in the resin composition for a vibration damping material of the present invention is an emulsion having a core part and a shell part, it is preferably obtained using a normal emulsion polymerization method. Specifically, after the monomer component is emulsion-polymerized in an aqueous solvent in the presence of an emulsifier and / or protective colloid to form a core part, the monomer component is further emulsion-polymerized into an emulsion containing the core part. It is preferably obtained by multistage polymerization that forms a shell portion. Thus, the polymer contained in the resin composition for vibration damping material of the present invention is an emulsion having a core part and a shell part, and after the emulsion forms the core part, the multistage polymerization that forms the shell part The form obtained by the above is also one of the preferred forms of the present invention.

The aqueous solvent is not particularly limited. For example, water, one or two or more mixed solvents that can be mixed with water, and a mixed solvent in which water is a main component in such a solvent. Etc. Among these, water is preferable in consideration of safety and environmental impact when applying a paint containing the resin composition for vibration damping material of the present invention.

The amount of the emulsifier used is preferably 0.1 to 10% by mass with respect to 100% by mass of the total amount of compounds having a polymerizable unsaturated bond group. If it is less than 0.1% by mass, the mechanical stability cannot be sufficiently improved and the polymerization stability may not be sufficiently maintained. More preferably, it is 0.5-7 mass%, More preferably, it is 1-6 mass%.

As the emulsifier, one or more of anionic (system), cationic (system), nonionic (system), amphoteric surfactants and polymer surfactants can be used.
The anionic surfactant is not particularly limited, and examples thereof include polyoxyalkylene alkyl ether sulfate, polyoxyalkylene oleyl ether sulfate sodium salt, polyoxyalkylene alkylphenyl ether sulfate, alkyl diphenyl ether disulfonate, poly Oxyalkylene (mono, di, tri) styryl phenyl ether sulfate, polyoxyalkylene (mono, di, tri) benzyl phenyl ether sulfate, alkenyl succinate; sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium alkyl sulfate Alkyl sulfate salts such as sodium dodecyl polyglycol ether sulfate; sodium sulforicinoate; Alkyl sulfonates such as sodium salts; alkyl sulfonates such as sodium dodecylbenzene sulfonate and alkali metal sulfates of alkali phenol hydroxyethylene; high alkyl naphthalene sulfonates; naphthalene sulfonic acid formalin condensates; sodium laurate, triethanolamine oleate, tri Fatty acid salts such as ethanolamine abietate; polyoxyalkyl ether sulfate ester; polyoxyethylene carboxylic ester sulfate salt; polyoxyethylene phenyl ether sulfate ester; succinic acid dialkyl ester sulfonate salt; polyoxyethylene alkyl aryl sulfate Examples include salts. These 1 type (s) or 2 or more types can be used.

Examples of commercially available products suitable as the anionic surfactant include Latemul WX, Latemuru 118B, Perex SS-H, Emulgen A-60, B-66, Lebenol WZ (manufactured by Kao Corporation), New Coal 707SF, New Coal 707SN, New Call 714SF, New Call 714SN, AB-26S, ABEX-2010, 2020, 2030, DSB (manufactured by Rhodia Nikka Co., Ltd.) and the like.
In addition, surfactants corresponding to these nonionic types can also be used.

As the above anionic surfactants, reactive surfactants, reactive anionic surfactants, sulfosuccinate type reactive anionic surfactants, alkenyl succinate type reactive anionic surfactants, etc. 1 type (s) or 2 or more types can be used.
Commercially available sulfosuccinate-type reactive anionic surfactants include Latemul S-120, S-120A, S-180 and S-180A (all trade names, manufactured by Kao Corporation), Eleminol JS-2 (Products) Name, manufactured by Sanyo Kasei Kogyo Co., Ltd.), ADEKA rear soap SR-10, SR-20, SR-30 (manufactured by ADEKA) and the like.
As a commercial item of an alkenyl succinate type reactive anionic surfactant, Latemul ASK (trade name, manufactured by Kao Corporation) and the like can be mentioned.
Furthermore, (meth) acrylic acid polyoxyethylene sulfonate salt (for example, “Eleminol RS-30” manufactured by Sanyo Chemical Industries, “Antox MS-60” manufactured by Nippon Emulsifier Co., Ltd.), allyloxymethylalkyloxypolyoxy Sulfate ester (salt) having an allyl group such as sulfonate salt of ethylene (for example, “Aqualon KH-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ammonium polyoxyalkylene alkenyl ether sulfate (for example, “Latemul PD-” manufactured by Kao Corporation 104 "etc.) can also be used.

Further, as the anionic surfactant, the following surfactants and the like can be used as the reactive surfactant.
Sulfoalkyl (carbon number 1 to 4) ester salt type surfactant of aliphatic unsaturated carboxylic acid having 3 to 5 carbon atoms, for example, 2-sulfoethyl (meth) acrylate sodium salt, 3-sulfopropyl (meth) acrylate ammonium (Meth) acrylic acid sulfoalkyl ester salt type surfactants such as salts; sulfopropylmaleic acid alkylester sodium salt, sulfopropylmaleic acid polyoxyethylene alkylester ammonium salt, sulfoethylfumaric acid polyoxyethylene alkylester ammonium salt, etc. Aliphatic unsaturated dicarboxylic acid alkyl sulfoalkyl diester salt surfactants.

The nonionic surfactant is not particularly limited. For example, polyoxyethylene alkyl ether; polyoxyethylene alkyl aryl ether; sorbitan aliphatic ester; polyoxyethylene sorbitan aliphatic ester; aliphatic such as monolaurate of glycerol Monoglyceride; polyoxyethyleneoxypropylene copolymer; condensation products of ethylene oxide and aliphatic amines, amides or acids. Also, allyloxymethylalkoxyethylhydroxypolyoxyethylene (for example, “ADEKA rear soap ER-20” manufactured by ADEKA), polyoxyalkylene alkenyl ether (for example, “Latemul PD-420”, “Latemul PD-” manufactured by Kao Corporation) Nonionic surfactants having reactivity such as “430” and the like can also be used. These 1 type (s) or 2 or more types can be used.

The cationic surfactant is not particularly limited, and examples thereof include dialkyldimethylammonium salts, ester-type dialkylammonium salts, amide-type dialkylammonium salts, dialkylimidazolinium salts, and the like. Can be used.

The amphoteric surfactant is not particularly limited, and examples thereof include alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethylimidazolinium betaine, alkylamidopropylbetaine, alkylhydroxysulfobetaine, and the like. 1 type (s) or 2 or more types can be used.

The polymer surfactant is not particularly limited. For example, polyvinyl alcohol and a modified product thereof; (meth) acrylic water-soluble polymer; hydroxyethyl (meth) acrylic water-soluble polymer; hydroxypropyl (meth) acrylic Water-soluble polymers such as polyvinyl pyrrolidone, and one or more of them can be used.
Among the above surfactants, it is preferable to use a non-nonylphenyl type surfactant from the environmental viewpoint.

Examples of the protective colloid include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose salt; natural polysaccharides such as guar gum Etc., and one or more of these can be used. The protective colloid may be used alone or in combination with a surfactant.
The use amount of the protective colloid may be appropriately set according to use conditions and the like. For example, 5 parts by mass or less with respect to 100 parts by mass of the total amount of monomer components used to form the polymer. It is preferable that it is 3 mass parts or less.

The polymerization initiator is not particularly limited as long as it is a substance that decomposes by heat and generates radical molecules. For example, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile Azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile); organic peroxidation such as tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, di-tert-butyl peroxide Products: Hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide and Rongalite, potassium persulfate and metal salts, ammonium persulfate Redox polymerization initiators such as sodium hydrogen sulfite and the like, can be used alone or in combination of two or more thereof.
The amount of the polymerization initiator used is not particularly limited and may be set as appropriate according to the type of the polymerization initiator. For example, the total amount of monomer components used to form the polymer is 100 parts by mass. It is preferable that it is 0.1-2 mass parts with respect to this, More preferably, it is 0.2-1 mass part.

In order to accelerate the polymerization, the polymerization initiator may be used in combination with a reducing agent as necessary. Examples of the reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, and glucose; for example, reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. These 1 type (s) or 2 or more types can be used.
It does not specifically limit as the usage-amount of the said reducing agent, For example, it is preferable that it is 0.05-1 mass part with respect to 100 mass parts of total amounts of the monomer component used in forming a polymer.

The polymerization chain transfer agent is not particularly limited, for example, alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan; carbon tetrachloride , Halogenated hydrocarbons such as carbon tetrabromide and ethylene bromide; mercaptocarboxylic acid alkyl esters such as mercaptoacetic acid 2-ethylhexyl ester, mercaptopropionic acid 2-ethylhexyl ester, mercaptopyropionic acid tridecyl ester; mercaptoacetic acid methoxybutyl Mercaptocarboxylic acid alkoxyalkyl ester such as ester, mercaptopropionic acid methoxybutyl ester; carboxylic acid mercaptoal such as octanoic acid 2-mercaptoethyl ester Glycol ester or, alpha-methylstyrene dimer, terpinolene, alpha-terpinene, .gamma.-terpinene, dipentene, anisole, allyl alcohol and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, and n-tetradecyl mercaptan. As a usage-amount of a polymerization chain transfer agent, for example with respect to 100 mass parts of all the monomer components, Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less. More preferably, it is 5.0 parts by mass or less, particularly preferably 2.0 parts by mass or less, and most preferably 1.0 part by mass or less.

The polymerization may be performed in the presence of a chelating agent such as sodium ethylenediaminetetraacetate, a dispersing agent such as sodium polyacrylate, an inorganic salt, or the like, if necessary. Moreover, as addition methods, such as a monomer component and a polymerization initiator, methods, such as a batch addition method, a continuous addition method, a multistage addition method, are applicable, for example. Moreover, you may combine these addition methods suitably.

With respect to the polymerization conditions in the above production method, the polymerization temperature is not particularly limited, and is preferably, for example, 0 to 100 ° C, more preferably 40 to 95 ° C. Also, the polymerization time is not particularly limited, and is preferably 1 to 15 hours, and more preferably 5 to 10 hours, for example.
The addition method of the monomer component, the polymerization initiator, and the like is not particularly limited, and for example, a batch addition method, a continuous addition method, a multistage addition method, or the like can be applied. Moreover, you may combine these addition methods suitably.

In the method for producing a polymer contained in the aqueous vibration damping resin composition of the present invention, it is preferable to produce an emulsion by emulsion polymerization and then neutralize the emulsion with a neutralizing agent. As a result, the emulsion is stabilized.
The neutralizing agent is not particularly limited, and for example, tertiary amines such as triethanolamine, dimethylethanolamine, diethylethanolamine and morpholine; diglycolamine, aqueous ammonia; sodium hydroxide and the like can be used. These may be used alone or in combination of two or more. Among these, since the water resistance of the coating film formed from the resin composition for vibration damping materials is improved, it is preferable to use a volatile base that volatilizes when the coating film is heated. More preferably, an amine having a boiling point of 80 to 360 ° C. is preferably used because heat drying properties are improved and vibration damping properties are improved. As such a neutralizing agent, for example, tertiary amines such as triethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, and diglycolamine are preferable. More preferably, an amine having a boiling point of 130 to 280 ° C is used.
In addition, the said boiling point is a boiling point in a normal pressure.

The resin composition for a vibration damping material of the present invention can contain other components as necessary. It is also one of preferred embodiments of the present invention that the resin composition for a vibration damping material of the present invention contains a pigment, a foaming agent, and a thickener as essential components. Such a resin composition for a vibration damping material of the present invention has excellent heat drying properties, can exhibit various functions, and forms a vibration damping material that can exhibit particularly excellent vibration damping properties. It is something that can be done.

When the said damping material resin composition contains a pigment, a foaming agent, and a thickener, 20-90 mass% of solid content may be contained with respect to 100 mass% of total amounts of the resin composition for damping materials. More preferably, it is 30-90 mass%, More preferably, it is 40-90 mass%.
The blending amount of the polymer obtained by polymerizing the monomer component in the vibration damping resin composition containing the pigment, foaming agent and thickener is, for example, 100% by mass of the solid content of the vibration damping resin composition. On the other hand, it is preferable to set so that the solid content of the polymer obtained by polymerizing the monomer component is 10 to 60% by mass, and more preferably 15 to 60% by mass.

When the water-based vibration damping resin composition includes a pigment, a foaming agent, and a thickener, the pH of the vibration damping resin composition is preferably 7 to 11, more preferably 7 to 9. is there. The pH can be measured by the same method as described above.
When the water-based vibration damping resin composition includes a pigment, a foaming agent, and a thickener, the viscosity of the vibration damping resin composition is preferably 50 to 200 Pa · s. When the viscosity is such, it is suitable as a resin composition for a coating-type vibration damping material that can be easily applied to a substrate and has no dripping. More preferably, it is 60-150 Pa.s.
The viscosity of the resin composition for damping material can be measured by the same method as described above.

As said pigment, 1 type (s) or 2 or more types, such as the coloring agent mentioned later and a rust preventive pigment, can be used, for example. The blending amount of the pigment is preferably 50 to 700 parts by mass, more preferably 100 parts by mass of the solid content of the polymer obtained by polymerizing the monomer component in the resin composition for vibration damping material. 100 to 550 parts by mass.

As the foaming agent, for example, a low-boiling hydrocarbon encapsulated heated expansion capsule, an organic foaming agent, an inorganic foaming agent, and the like are suitable, and one or more of these can be used. Examples of the heated expansion capsule include Matsumoto Microsphere F-30, F-50 (manufactured by Matsumoto Yushi Co., Ltd.); EXPANSELL WU642, WU551, WU461, DU551, DU401 (manufactured by Nippon Expandcel). Examples of the organic foaming agent include azodicarbonamide, azobisisobutyronitrile, N, N-dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazine, p-oxybis (benzenesulfohydrazide), and the like. Examples of the foaming agent include sodium bicarbonate, ammonium carbonate, silicon hydride and the like.
The blending amount of the foaming agent may be 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the polymer solid content obtained by polymerizing the monomer component in the resin composition for vibration damping material. Preferably, it is 1.0 to 3.0 parts by mass.

Examples of the thickener include polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resins, and the like. As a compounding quantity of a thickener, it shall be 0.01-2 mass parts by solid content with respect to 100 mass parts of solid content of the polymer which polymerizes the monomer component in the resin composition for damping materials. Is more preferable, it is 0.05-1.5 mass parts, More preferably, it is 0.1-1 mass part.

Other components that can be blended in the resin composition for vibration damping material of the present invention include, for example, a solvent; an aqueous cross-linking agent; a filler; a dispersant; an antifoaming agent; a colorant; Stabilizers; wetting agents; antiseptics; antifoaming agents; anti-aging agents; antifungal agents; ultraviolet absorbers; antistatic agents, and the like. It can be appropriately selected and used according to the form of the product.
In addition, said other component can be mixed with the said resin composition for damping materials etc. using a butterfly mixer, a planetary mixer, a spiral mixer, a kneader, a dissolver etc., for example.

Examples of the solvent include ethylene glycol, butyl cellosolve, butyl carbitol, butyl carbitol acetate, and the like. What is necessary is just to set suitably as a compounding quantity of a solvent so that the solid content density | concentration of the polymer which polymerizes the monomer component in the resin composition for damping materials may become the range mentioned above.

Examples of the aqueous crosslinking agent include oxazoline compounds such as Epocross WS-500, WS-700, K-2010, 2020, 2030 (all trade names, manufactured by Nippon Shokubai Co., Ltd.); Adeka Resin EMN-26-60, EM- Epoxy compounds such as 101-50 (Brand name, manufactured by ADEKA); Melamine compounds such as Cymel C-325 (Brand name, manufactured by Mitsui Cytec); Block isocyanate compounds; AZO-50 (Brand name, 50% by mass) Zinc oxide compounds such as zinc oxide aqueous dispersion (manufactured by Nippon Shokubai Co., Ltd.) are preferred. As a compounding quantity of a water-system crosslinking agent, for example with respect to 100 mass parts of solid content of the polymer formed by superposing | polymerizing the monomer component in the resin composition for damping materials, 0.01-20 mass parts by solid content and More preferably, it is 0.15-15 mass parts, More preferably, it is 0.5-15 mass parts.
The water-based cross-linking agent may be added to the polymer obtained by polymerizing the monomer component before the addition of the above additives, or may be added simultaneously when other components are blended as a vibration damping resin composition. Also good. By mixing a crosslinking agent with the resin composition for a vibration damping material, the toughness of the resin is improved, and as a result, a sufficiently high vibration damping property is exhibited in a high temperature region. Among them, it is preferable to use an oxazoline compound.

Examples of the filler include inorganic fillers such as calcium carbonate, kaolin, silica, talc, barium sulfate, alumina, iron oxide, titanium oxide, glass talk, magnesium carbonate, aluminum hydroxide, talc, diatomaceous earth, and clay; glass Examples of such inorganic fillers include flakes and mica; and fibrous inorganic fillers such as metal oxide whiskers and glass fibers. As a compounding quantity of a filler, it is preferable to set it as 50-700 mass parts with respect to solid content of 100 mass parts of the polymer formed by polymerizing the monomer component in the resin composition for vibration damping materials, More preferably 100 to 550 parts by mass.

Examples of the dispersant include inorganic dispersants such as sodium hexametaphosphate and sodium tripolyphosphate, and organic dispersants such as polycarboxylic acid-based dispersants.
Examples of the antifoaming agent include silicon-based antifoaming agents.
Examples of the colorant include organic or inorganic colorants such as titanium oxide, carbon black, dial, hansa yellow, benzine yellow, phthalocyanine blue, and quinacridone red.
Examples of the rust preventive pigment include a metal phosphate, a metal molybdate, and a metal borate.

As the other component, a polyvalent metal compound may be used. In this case, the polyvalent metal compound improves the stability, dispersibility, heat drying property of the resin composition for the vibration damping material, and improves the vibration damping property of the vibration damping material formed from the resin composition for the vibration damping material. It becomes. It does not specifically limit as a polyvalent metal compound, For example, zinc oxide, zinc chloride, zinc sulfate etc. are mentioned, These 1 type (s) or 2 or more types can be used.
Examples of the form of the polyvalent metal compound may include a powder, an aqueous dispersion, an emulsion dispersion, and the like. Among them, since the dispersibility in the resin composition for an aqueous vibration damping material is improved, it is preferably used in the form of an aqueous dispersion or an emulsified dispersion, more preferably in the form of an emulsified dispersion. is there.
Moreover, it is preferable that the usage-amount of a polyvalent metal compound shall be 0.05-5.0 mass parts with respect to 100 mass parts of solid content in the resin composition for damping materials, More preferably, it is 0.05. -3.5 parts by mass.

After applying the resin composition for vibration damping material, the condition for drying to form a coating film may be heat drying or room temperature drying, but it may be heat dried for efficiency. preferable. The lower limit of the heat drying temperature is preferably 110 ° C. or higher, and more preferably 120 ° C. or higher. Moreover, as an upper limit of the temperature of heat drying, it is preferable to set it as 210 degrees C or less, More preferably, it is 170 degrees C or less.

When the above-mentioned resin composition for a vibration damping material is applied to a vibration damping material, the vibration damping property can be evaluated by measuring a loss factor of a film formed from the resin composition for a vibration damping material.
The loss factor is usually expressed by tan δ and indicates how much the vibration applied to the damping material is attenuated. The loss factor indicates that the higher the numerical value, the better the damping performance.
As a method for measuring the loss factor, a method for obtaining the loss factor tan δ by dynamic viscoelasticity measurement can be used. The dynamic viscoelasticity measurement can be performed using, for example, a rheometer (RSAIII, manufactured by TA Instruments, or ARES, manufactured by TA Instruments).
The loss factor is determined by applying a vibration damping resin composition on a Teflon (registered trademark) plate having a smooth surface so that the film thickness after drying is 0.2 mm, drying at 25 ° C. for 12 hours, and then 100 ° C. Can be measured with a sample that has been dried under reduced pressure for 30 minutes and cut into a size of 25 mm length × 5 mm width. The measurement of the loss factor is based on the peak area of the loss factor measured for the film formed from the resin component of the blank corresponding to the vibration-damping resin composition to be measured, excluding the additive. This can be done by observing the increase / decrease in the peak area of the loss factor of the coating formed from the resin composition for damping material, and measuring the area in the range of 30 ° C. before and after the peak top temperature.
Alternatively, the resin composition for vibration damping material is applied on a Teflon (registered trademark) plate having a smooth surface as described in the examples so that the film thickness after drying is 0.5 mm, and dried at 25 ° C. for 12 hours. The sample can be dried at 100 ° C. for 30 minutes under reduced pressure, and a measurement method using a shear mode using a sample cut into a size of 25 mm in diameter.

The resin composition for a vibration damping material of the present invention has the above-described configuration and has excellent vibration damping properties due to the interaction between a polymer obtained by polymerizing monomer components and an additive in a state compatible with the polymer. It is a composition that can be suitably used for various applications in which coating-type vibration damping materials such as transportation equipment such as railway vehicles, ships, and airplanes, electrical equipment, building structures, and construction equipment are used.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

Production Example 1
400 parts of butyl acetate was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Furthermore, 10% of the monomer premix weighed 250 parts of methyl methacrylate, 250 parts of n-butyl acrylate and 1.0 part of n-dodecyl mercaptan was added to the polymerizer, and the internal temperature was increased while stirring under a nitrogen gas stream. The temperature was raised to 90 ° C. The remaining 90% of the monomer premix was charged into the dropping funnel. Next, 7.3 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate to a concentration of 2.1% while maintaining the internal temperature of the polymerization vessel at 90 ° C. Was added to initiate the initial polymerization. After 10 minutes, the remaining monomer premix was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 90 ° C. At the same time, 65.7 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate so as to have a concentration of 2.1% was added dropwise uniformly over 180 minutes. 30 minutes and 60 minutes after the completion of dropping, 20 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate to a 2.1% concentration as a booster was added in two portions. . The same temperature was maintained for 90 minutes after addition of the booster, and the polymerization was terminated.
After cooling the obtained reaction liquid to room temperature, a resin solution having a nonvolatile content of 50.2%, a viscosity of 3,500 mPa · s, a weight average molecular weight of 120,000, and Tg of 3 ° C. was obtained.

Production Example 2
400 parts of butyl acetate was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Furthermore, among the monomer premixes weighed 200 parts of methyl methacrylate, 52.5 parts of styrene, 190 parts of n-butyl acrylate, 50 parts of 2-ethylhexyl acrylate, 7.5 parts of acrylic acid, and 2.5 parts of n-dodecyl mercaptan 10% was added to the polymerization vessel, and the internal temperature was raised to 90 ° C. while stirring under a nitrogen gas stream. The remaining 90% of the monomer premix was charged into the dropping funnel. Next, 7.3 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate to a concentration of 2.1% while maintaining the internal temperature of the polymerization vessel at 90 ° C. Was added to initiate the initial polymerization. After 10 minutes, the remaining monomer premix was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 90 ° C. At the same time, 65.7 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate so as to have a concentration of 2.1% was added dropwise uniformly over 180 minutes. 30 minutes and 60 minutes after the completion of dropping, 20 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate to a 2.1% concentration as a booster was added in two portions. . The same temperature was maintained for 90 minutes after addition of the booster, and the polymerization was terminated.
After cooling the obtained reaction liquid to room temperature, a resin solution having a nonvolatile content of 50.0%, a viscosity of 2,700 mPa · s, a weight average molecular weight of 60,000, and Tg of 3 ° C. was obtained.

Production Example 3
150 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, to the dropping funnel, 275 parts of methyl methacrylate, 92.5 parts of 2-ethylhexyl acrylate, 125 parts of n-butyl acrylate, 7.5 parts of acrylic acid, 2.2 parts of t-dodecyl mercaptan, Latemul PD-104 (product) (Name, Kao Corporation, 20% aqueous solution) 90 parts of monomer and 97 parts of deionized water were charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 4 parts of the above monomer emulsion, 2.5 parts of 5% potassium persulfate aqueous solution and 5 parts of 2% sodium hydrogensulfite aqueous solution were added. The initial polymerization was started. After 20 minutes, the remaining monomer emulsion was uniformly added dropwise over 240 minutes while maintaining the inside of the reaction system at 80 ° C. At the same time, 50 parts of a 5% potassium persulfate aqueous solution and 50 parts of a 2% sodium hydrogensulfite aqueous solution were uniformly added dropwise over 240 minutes, and the same temperature was maintained for 90 minutes after completion of the dropwise addition to complete the polymerization.
After cooling the obtained reaction liquid to room temperature, 1.5 parts of 25% aqueous ammonia was added, and the non-volatile content was 55.2%, pH 7.3, viscosity 250 mPa · s, average particle diameter 180 nm, weight average molecular weight 80,000. An emulsion having a Tg of 8 ° C. was obtained.

Production Example 4
150 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, 100 parts of styrene, 47.5 parts of methyl methacrylate, 95 parts of 2-ethylhexyl acrylate, 7.5 parts of acrylic acid, 0.2 part of t-dodecyl mercaptan, lebenol WZ previously adjusted to a 20% aqueous solution were added to the dropping funnel. A first stage monomer emulsion consisting of 45 parts (trade name, manufactured by Kao Corporation) and 48.5 parts deionized water was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 4 parts of the above monomer emulsion, 2.5 parts of 5% potassium persulfate aqueous solution and 5 parts of 2% sodium hydrogensulfite aqueous solution were added. The initial polymerization was started. After 20 minutes, the remaining monomer emulsion was uniformly added dropwise over 120 minutes while maintaining the inside of the reaction system at 80 ° C. At the same time, 25 parts of a 5% aqueous potassium persulfate solution and 25 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 120 minutes, and the same temperature was maintained for 60 minutes after completion of the addition.
Next, 50 parts of styrene, 47.5 parts of methyl methacrylate, 145 parts of butyl acrylate, 7.5 parts of acrylic acid, 0.2 part of t-dodecyl mercaptan, Lebenol WZ (trade name, pre-adjusted to 20% aqueous solution in a dropping funnel A second stage monomer emulsion consisting of 45 parts by Kao Corporation and 48.5 parts deionized water was charged and added dropwise uniformly over 120 minutes. At the same time, 25 parts of a 5% aqueous potassium persulfate solution and 25 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 120 minutes, and the same temperature was maintained for 90 minutes after completion of the addition to complete the polymerization.
After cooling the resulting reaction liquid to room temperature, 3 parts of 25% aqueous ammonia was added, and the non-volatile content was 55.0%, pH 7.1, viscosity 400 mPa · s, average particle diameter 220 nm, weight average molecular weight 170,000, 1 An emulsion having a Tg of 10 ° C at the second stage, a Tg-10 ° C of the second stage, and a total Tg of 0 ° C was obtained.

Production Example 5
400 parts of butyl acetate was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Furthermore, 10% of the monomer premix weighed 210 parts of methyl methacrylate, 290 parts of 2-ethylhexyl acrylate and 0.8 part of n-dodecyl mercaptan was added to the polymerization reactor, and the internal temperature was increased while stirring under a nitrogen gas stream. The temperature was raised to 90 ° C. The remaining 90% of the monomer premix was charged into the dropping funnel. Next, 7.3 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate to a concentration of 2.1% while maintaining the internal temperature of the polymerization vessel at 90 ° C. Was added to initiate the initial polymerization. After 10 minutes, the remaining monomer premix was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 90 ° C. At the same time, 65.7 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate so as to have a concentration of 2.1% was added dropwise uniformly over 180 minutes. 30 minutes and 60 minutes after the completion of dropping, 20 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate to a 2.1% concentration as a booster was added in two portions. . The same temperature was maintained for 90 minutes after addition of the booster, and the polymerization was terminated.
After cooling the obtained reaction liquid to room temperature, a resin solution having a nonvolatile content of 50.4%, a viscosity of 3,800 mPa · s, a weight average molecular weight of 160,000, and Tg-21 ° C. was obtained.

Production Example 6
150 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, 484 parts of methyl methacrylate, 8.5 parts of n-butyl acrylate, 7.5 parts of acrylic acid, 2.2 parts of t-dodecyl mercaptan, LATEMUL PD-104 (trade name, manufactured by Kao Corporation, 20) A monomer emulsion consisting of 90 parts of (% aqueous solution) and 97 parts of deionized water was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 4 parts of the above monomer emulsion, 2.5 parts of 5% potassium persulfate aqueous solution and 5 parts of 2% sodium hydrogensulfite aqueous solution were added. The initial polymerization was started. After 20 minutes, the remaining monomer emulsion was uniformly added dropwise over 240 minutes while maintaining the inside of the reaction system at 80 ° C. At the same time, 50 parts of a 5% potassium persulfate aqueous solution and 50 parts of a 2% sodium hydrogensulfite aqueous solution were uniformly added dropwise over 240 minutes, and the same temperature was maintained for 90 minutes after completion of the dropwise addition to complete the polymerization.
After cooling the resulting reaction solution to room temperature, 1.5 parts of 25% aqueous ammonia was added, and the non-volatile content was 54.9%, pH 7.1, viscosity 240 mPa · s, average particle size 180 nm, weight average molecular weight 100,000. An emulsion with a Tg of 100 ° C. was obtained.

Production Example 7
400 parts of butyl acetate was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Furthermore, 10% of the monomer premix obtained by weighing 72 parts of methyl methacrylate, 28 parts of 2-ethylhexyl acrylate, 400 parts of isobornyl methacrylate and 0.8 part of n-dodecyl mercaptan was added to the polymerization vessel, The internal temperature was raised to 90 ° C. with stirring. The remaining 90% of the monomer premix was charged into the dropping funnel. Next, 7.3 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate to a concentration of 2.1% while maintaining the internal temperature of the polymerization vessel at 90 ° C. Was added to initiate the initial polymerization. After 10 minutes, the remaining monomer premix was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 90 ° C. At the same time, 65.7 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate so as to have a concentration of 2.1% was added dropwise uniformly over 180 minutes. 30 minutes and 60 minutes after the completion of dropping, 20 parts of a 2,2′-azobis (2-methylbutyronitrile) solution dissolved in butyl acetate to a 2.1% concentration as a booster was added in two portions. . The same temperature was maintained for 90 minutes after addition of the booster, and the polymerization was terminated.
After cooling the obtained reaction liquid to room temperature, a resin solution having a nonvolatile content of 50.2%, a viscosity of 4,200 mPa · s, a weight average molecular weight of 150,000, and Tg of 140 ° C. was obtained.

Example 1
In the polymer (resin) solution of Production Example 1, 4,4′-thiobis (2-methyl-6-tert-butylphenol) is added as an additive to 20 parts in a total of 100 parts of the nonvolatile content of the polymer and the additive. The mixture was mixed with stirring and applied to a Teflon (registered trademark) plate with a smooth surface so that the film thickness after drying was 0.2 mm, dried at room temperature for 12 hours, and then dried under reduced pressure at 100 ° C. for 30 minutes. Thus, a dry coating film was obtained. A test piece was cut out from the obtained dried coating film so as to have a width of 5 mm and a length of 25 mm, and used for the test.

Examples 2 and 3
Resins and additives were blended at the ratios shown in Table 1, and test pieces were prepared in the same manner as in Example 1.

Examples 4 and 5
When blending the resin and additive in the ratios listed in Table 1, the additive is completely dissolved in ethylene glycol monobutyl ether in advance, adjusted to a 50% solution, blended, and confirmed that there is no separation after 24 hours of blending A test piece was prepared in the same manner as in Example 1 except that it was used after that.

Comparative Example 1
Test pieces were prepared in the same manner as in Example 1 except that the resins listed in Table 1 were used and no additives were added.

Comparative Example 2
Resins and additives were blended at the ratios shown in Table 1, and test pieces were prepared in the same manner as in Example 1.

Example 6
Resins and additives were blended at the ratios shown in Table 1, and test pieces were prepared in the same manner as in Example 1.

Example 7
When blending the resin and additive in the ratios listed in Table 1, the additive is completely dissolved in ethylene glycol monobutyl ether in advance, adjusted to a 50% solution, blended, and confirmed that there is no separation after 24 hours of blending A test piece was prepared in the same manner as in Example 1 except that it was used after that.

Example 8
In the polymer (resin) solution of Production Example 7, alkylated diphenylamine as an additive is blended with stirring so that the total non-volatile content of the polymer and additive is 90 parts. (Trademark) was applied to a plate so that the film thickness after drying was 0.5 mm, dried at room temperature for 12 hours, and then dried under reduced pressure at 100 ° C. for 30 minutes to obtain a dried coating film. A circular test piece having a diameter of 25 mm was cut out from the obtained dried coating film and used for the test.

<Compatible state of additives>
The appearance of the obtained dried coating film was observed. The criteria for determining the compatible state of the additive are as follows.
○: Uniform coating without precipitation of additive ×: Non-uniform coating with precipitation of additive <Measurement of loss factor (tan δ)>
The loss factors (tan δ) of Examples 1 to 7 and Comparative Examples 1 and 2 were measured with a rheometer (RSAIII, manufactured by TA instruments).
The loss factor (tan δ) of Example 8 was measured with a rheometer (ARES, manufactured by TA instruments).
In Examples 1 to 7 and Comparative Examples 1 and 2, test pieces having a thickness of 0.2 mm, a width of 5 mm, and a length of 25 mm were used. The measurement conditions were tensile mode, −40 to 80 ° C., temperature increase rate of 3 ° C./min, The measurement was performed under the condition of a frequency of 1 Hz.
In Example 8, a test piece having a thickness of 0.5 mm and a diameter of 25 mm was used, under the conditions of measurement condition deviating mode, parallel plate method with a diameter of 25 mm, −40 to 160 ° C., temperature increase rate of 3 ° C./min, and frequency of 1 Hz It was measured.
Evaluation was performed by comparing the tan δ peak top value (peak height), the tan δ peak temperature, and the tan δ area compared with the blank with no additive added. The tan δ peak area was used by measuring an area in the range of 30 ° C. before and after the peak top temperature.

In Table 1, additives (1) to (5) each represent the following.
(1): 4,4′-thiobis (2-methyl-6-tert-butylphenol) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(2): N, N-dicyclohexylbenzothiazole-2-sulfinamide (manufactured by Wako Pure Chemical Industries, Ltd.)
(3): Octylated diphenylamine (Ouchi Shinsei Chemical Co., Ltd., trade name: NOCRACK AD-F)
(4): N-cyclohexyl-2-benzothiazole sulfinamide (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sunseller CM)
(5): Alkylated diphenylamine (Ouchi Shinsei Chemical Co., Ltd., trade name: NOCRACK ODA)

Claims (7)

A resin composition for a coating type damping material comprising a polymer obtained by polymerizing a monomer component,
The coating-type vibration damping resin composition includes an additive in a state compatible with the polymer,
The polymer is obtained from a monomer component containing 0.1 to 5 % by mass of a (meth) acrylic acid monomer with respect to 100% by mass of all monomer components,
The additives, aromatic secondary amine-based additives and / or phenolic additive is a <br/> application-type of damping material for a resin composition, characterized by. The coating composition according to claim 1, wherein the coating-type vibration damping resin composition includes 10 to 200 mass% of an additive with respect to 100 mass% of a polymer obtained by polymerizing a monomer component. Resin composition for mold damping material. The resin composition for a coating type vibration damping material according to claim 1 or 2, wherein the polymer has a weight average molecular weight of 20,000 to 400,000. The resin composition for a coating type damping material according to any one of claims 1 to 3, wherein the polymer has a glass transition temperature of -25 to 150 ° C. The resin composition for a coating type vibration damping material according to any one of claims 1 to 4, wherein the polymer has a solubility parameter (SP value) of 7 to 10. The polymer is 0.1 to 5 % by mass of (meth) acrylic acid monomer with respect to 100% by mass of all monomer components, and (meth) acrylic monomer other than (meth) acrylic acid monomer. 95 to 99.9% by mass of another copolymerizable ethylenically unsaturated monomer selected from a monomer, an unsaturated monomer having a nitrogen atom, and an unsaturated monomer having an aromatic ring The resin composition for a coating type vibration damping material according to any one of claims 1 to 5, wherein the resin composition is obtained from a monomer component. The resin composition for coating type vibration damping material further comprises a solvent, and a solvent-based resin composition for coating type damping material in which a polymer obtained by polymerizing monomer components and an additive are dissolved in the solvent, or The polymer obtained by polymerizing the monomer component is any one of aqueous resin compositions for coating-type vibration damping materials in the form of an emulsion in an aqueous solvent. The resin composition for coating type damping materials according to claim 1.