WO2007110989A1

WO2007110989A1 - Attenuating coating

Info

Publication number: WO2007110989A1
Application number: PCT/JP2006/319975
Authority: WO
Inventors: Tatsuya Aoki; Kenichi Nagasaka; Yusuke Tahara
Original assignee: Cci Corporation
Priority date: 2006-03-27
Filing date: 2006-10-05
Publication date: 2007-10-04
Also published as: JP2007262137A; JP4221419B2

Abstract

It is intended to provide an attenuating coating capable of exerting an energy attenuation performance. This attenuating coating comprises an aqueous resin dispersion, in which resin particles capable of forming a coating film are dispersed in an aqueous dispersion medium, and an attenuation-imparting component capable of imparting attenuation properties to the coating film. This attenuation-imparting component is at least one member selected from among a normal phosphoric ester compound, an aromatic secondary amine compound and a halogen acid ester compound.

Description

Specification

Damping paint

Technical field

TECHNICAL FIELD [0001] The present invention relates to an attenuating paint that exhibits energy-attenuating performance for attenuating energy such as vibration energy and impact energy.

Background art

[0002] Conventionally, for example, a compound having a benzothiazyl group is known as an attenuating component that imparts energy attenuating properties to various types of resin materials (see Patent Document 1). Furthermore, an attenuating paint containing such an attenuating component and a resin component that forms a coating film is known (see, for example, Patent Documents 2 and 3). The coating film obtained from the damping paint cover exhibits energy damping performance by the action of the damping imparting component.

[0003] Recently, in consideration of the influence on the environment, an aqueous resin dispersion in which resin particles are dispersed in an aqueous dispersion medium, that is, an aqueous paint, has been widely used. On the other hand, there is a demand for a new attenuating paint in which the coating film formed from such a water-based paint cover exhibits energy attenuating performance.

Patent Document 1: International Publication No. 97Z42844 Pamphlet

Patent Document 2: Pamphlet of International Publication No. 99Z28394

Patent Document 3: Pamphlet of International Publication No. 01Z40391

Disclosure of the invention

[0004] The present invention has been made in view of the above-described problems, and an object thereof is to provide an attenuating paint capable of exhibiting energy attenuation performance.

In one aspect of the present invention, an attenuating coating material containing an aqueous rosin dispersion and an attenuating component is provided. In the aqueous resin dispersion, the resin particles forming the coating film are dispersed in the aqueous dispersion medium. The attenuating component imparts energy attenuating property to the coating film. The attenuating component is at least one selected from a normal phosphate ester compound, an aromatic secondary amine compound, and a halogenated ester compound. Brief Description of Drawings [0005] Fig. 1 is a graph showing the relationship between the amount of attenuating component and the peak value of loss factor in Examples 1, 6, 7 and Comparative Example 1.

FIG. 2 is a graph showing the relationship between temperature and loss factor in Examples 1 and 8.

BEST MODE FOR CARRYING OUT THE INVENTION

[0006] Hereinafter, embodiments of the present invention will be described in detail.

In the attenuating paint according to the present embodiment, the water-based resin dispersion liquid in which the resin particles forming the coating film are dispersed in the aqueous dispersion medium and the coating material imparting energy-damping properties are imparted. And ingredients. The attenuating component is at least one selected from a normal phosphate ester compound, an aromatic secondary amine compound, and a halogenated ester compound.

[0007] Examples of the orthophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (butoxy shechinole) phosphate, triphenyl phosphate, tricresyl phosphate, trixylate. And at least one selected from nyl phosphate, cresyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate.

[0008] Examples of aromatic secondary amine compounds include p- (p-toluenesulfonylamido) diphenylamine, N, Ν'-di-2-naphthyl-1-p-dirangeamine, Ν, Ν'-diphenyl. -Le ρ Hue-rangeamine, Ν—Fue-Lou Ν'—Isopropyl ρ ρ-Welen Jamine, Ν Hue-Nole Ν, — (1, 3 Dimethino Lebutinore) ρ Hue-Direnamine, Ν Hue-Lou 1 And at least one selected from naphthylamine, alkylated diphenylamine, octylated diphenylamine, and 4,4′-bis (a, a-dimethylbenzyl) diphenylamine.

[0009] The halogen-containing phosphoric acid ester compound is selected from, for example, tris (2 chloroethyl) phosphate, tris (black propyl) phosphate, tris (dichroic propyl) phosphate, and tris (tribromoneopentyl) phosphate. At least one kind.

[0010] Among the damping property-imparting components, since an excellent energy damping property can be imparted to the coating film, it is preferably a normal phosphate ester compound, and more preferably triphenyl phosphate. [0011] The content of the attenuating component in the attenuating coating is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of the resin particles and the attenuating component. More preferably 5% by mass or less. When the content of the damping component exceeds 20% by mass, the improvement rate of the energy damping performance tends to decrease, which may be uneconomical. Further, the content of the attenuating component in the attenuating coating is preferably 1% by mass or more, and most preferably 1 to 5% by mass with respect to the total amount of the resin particles and the attenuating component. is there. If the content of the attenuating component is less than 1% by mass, it may be difficult to impart excellent energy attenuating properties to the coating film.

[0012] When the attenuation imparting component is solid, it is easy to disperse in the aqueous resin dispersion, so that the attenuation imparting component is dispersed in the aqueous dispersion medium, and the resulting dispersion becomes an aqueous solution. It is preferred to be blended in a fat dispersion.

[0013] Examples of the aqueous dispersion medium in which the attenuation imparting component is dispersed include water and a mixture of water and alcohol. Examples of the alcohol include methanol and ethanol. The content of triphenyl phosphate in the dispersion is preferably 5 to 80% by mass, and more preferably 10 to 70% by mass, for example, considering the handling of the dispersion and the stability of the dispersion. %, More preferably 15 to 60% by mass.

[0014] The form of the attenuating component dispersed in the dispersion may be solid such as particles or liquid. When the shape of the attenuating component is particulate, the particle size of the attenuating component is preferably 1 to: LOO / zm because it is easy to manufacture and stable dispersibility is easily obtained. .

[0015] This dispersion can be prepared, for example, by the following methods (A) to (C).

Method (A): The particulate attenuating component obtained by pulverizing the attenuating component is dispersed in an aqueous dispersion medium using a dispersant.

Method (B): After the attenuation imparting component is blended in the aqueous dispersion medium, the attenuation imparting component in the aqueous dispersion medium is pulverized and dispersed using a dispersant.

Method (C): A solution of the attenuating component is prepared by dissolving the attenuating component in an organic solvent that is compatible with water. Then, when this solution is mixed with the aqueous dispersion medium, an attenuation imparting component is precipitated in the aqueous dispersion medium. The attenuated imparting component is dispersed in the aqueous dispersion medium using a dispersant. Examples of the organic solvent having compatibility with the aqueous dispersion medium include methanol and ethanol. The organic solvent compatible with the aqueous dispersion medium may be removed by passing steam through the dispersion.

[0017] As the dispersant used in each method, for example, various surfactants are suitably used as a dispersant as long as the dispersant is appropriately selected according to the type of the attenuating component. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Examples of the cation-based surfactant include alkyl sulfates, alkylaryl sulfates, and alkyl phosphates. Examples of the cationic surfactant include alkyl quaternary amine salts. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, and polyoxyethylene sorbitan fatty acid esters. Examples of amphoteric surfactants include those of carboxylic acid type and sulfonic acid type. The blending amount of the dispersant in the dispersion may be appropriately adjusted in consideration of, for example, the dispersion state of the attenuating component, and is preferably 0.01 to 20% by mass, for example. For example, a filler, a viscosity modifier, a thickener, a fluidity improver, and an antifoaming agent may be added to the dispersion as necessary. The dispersion can be prepared using a known stirring and dispersing apparatus such as various homogenizers.

[0018] Examples of the polymer material constituting the resin particles contained in the aqueous resin dispersion include acrylic resin, acrylic Z styrene resin, urethane resin, phenol resin, and salt resin.ビュ Bull resin, vinyl acetate resin, vinyl acetate z acrylic resin, ethylene Z vinyl acetate resin, epoxy resin, polyester resin, alkyd resin, Atari mouth-trill Z butadiene copolymer rubber, styrene z butadiene copolymer rubber, butadiene rubber, and isoprene rubber force There may be at least one selected. These polymer materials may be modified.

[0019] The resin particles may be formed from a single type of polymer material, or may be formed from a mixture of a plurality of types of polymer material. Furthermore, the water-based resin dispersion may contain only the resin particles formed from the same type of polymer material. A plurality of types of rosin particles formed by may be contained respectively.

[0020] Among these polymer materials, at least one selected from acrylic resin and acrylic Z styrene resin is preferable because excellent energy-damping performance is easily exhibited by the above-described damping component. . As acrylic resin, homopolymers containing acrylic acid, acrylate ester, methacrylic acid and methacrylic ester as monomers, mixtures of these homopolymers, and these monomers were polymerized. A copolymer may be mentioned. Examples of the acrylic acid ester and methacrylic acid ester include methyl ester, ethinoreestenole, propinoreestenole, 2-ethenorehexenoreestenole, and ethoxyethyl ester. Examples of the acrylic Z styrene resin include a copolymer of a monomer that forms the acrylic resin and a styrene monomer.

[0021] Examples of the water-based dispersion medium in which the resin particles are dispersed include water and a mixed liquid of water and alcohol. Examples of the alcohol include methanol and ethanol. The aqueous rosin dispersion is obtained according to a known method such as emulsion polymerization in which a monomer and a polymerization initiator are dropped into an aqueous solution containing an emulsifier.

[0022] In the damping paint, other components include a filler, a gelling agent, a foaming agent, a foaming aid, a dispersing agent, a viscosity modifier, a thickener, a flow improver, a curing agent, an antifoaming agent, A film-forming aid and an anti-settling agent can be blended as necessary. Preferably, a filler is further added to the damping paint because the coating film exhibits excellent energy damping performance. Examples of the filler include my strength, talc, clay, barium sulfate, magnesium carbonate, silica, diatomaceous earth, zeolite, ferrite, and carbon. Gelling agents are classified into organic gelling agents and inorganic gelling agents. Examples of the organic gelling agent include starch and starch derivatives. Examples of the inorganic gelling agent include ammonium nitrate, calcium nitrate, potassium carbonate, salt potassium, salt calcium, and salt ammonium. The blending amount of the filler is preferably 1 to 80% by mass with respect to the total amount of the resin particles and the filler.

[0023] The attenuating paint can be prepared by mixing the water-based resin dispersion and the attenuating component by a known mixing means such as a stirrer.

The energy attenuating performance of these dampening paints, i.e. coatings obtained from dampening paints. The energy attenuation performance of the film is indicated by the loss factor of the coating. That is, it is shown that the higher the loss coefficient of the coating film, the better the energy attenuation performance of the coating film. The loss factor of the coating film can be measured by a well-known central vibration method loss factor measuring device.

[0024] The damping paint can be used as, for example, a vibration-damping paint that attenuates vibration energy and an impact-absorbing paint that attenuates impact energy. Examples of the application field of the vibration-damping paint include automobiles, building materials, home appliances, and industrial machines. Applications of impact absorbing paint include, for example, sports equipment such as shoes, gloves, various armor, grips, and headgear, medical equipment such as casts, mats, and supporters, building materials such as walls, flooring, and fences, and various types of cushioning. Materials and various interior materials.

[0025] When the damping paint is used, the coating is formed by drying after the damping paint is applied to the application site. The application method of the attenuating paint may be appropriately selected according to the fluidity of the attenuating paint. For example, the attenuating paint such as a slit may be discharged and applied to the application site, as well as an air spray. Application means such as a gun, an airless spray gun, and brushing can be used.

[0026] The coating film formed from the damping paint contains the above-described damping imparting component. For this reason, when energies such as vibration energy, impact energy, and sound energy are transmitted to the coating film (excluding light energy and electrical energy), the damping component is added to the polymer that makes up the coating film. It is speculated that such energy is converted into thermal energy by interaction with the molecular chain. Thus, a coating film containing at least one selected from the group consisting of a normal phosphate ester compound, an aromatic secondary amine compound, and a halogenated ester compound compound is capable of, for example, attenuating vibration energy. To demonstrate.

[0027] The effects exhibited by this embodiment will be described below.

(1) Attenuating paint contains at least one kind of attenuating component selected from orthophosphoric acid ester compounds, aromatic secondary amine compounds, and halogenated ester compounds. Can be demonstrated.

[0028] (2) As an attenuating component, preferably a normal phosphate ester compound, more preferably By blending the phosphate phosphate, the energy attenuation performance of the coating film can be easily enhanced.

[3] (3) By reducing the content of the attenuating component in the attenuating coating to 5% by mass or less based on the total amount of the attenuating component and the resin particles, the energy attenuation of the coating film Performance can be enhanced and mechanical properties such as coating strength are easily maintained. Furthermore, an increase in cost due to the addition of the attenuating component can be minimized.

[0030] (4) In the attenuating paint in which the attenuating component is blended using a dispersion, it is presumed that the dispersibility of the attenuating component in the attenuating paint is improved, and the energy of the coating film Lugie attenuation performance can be easily increased. Further, since the energy attenuation performance commensurate with the blending amount of the attenuating component is easily exhibited, it is possible to reduce the blending amount of the attenuating component.

[0031] (5) In the case where the above-described attenuation imparting component is blended in an aqueous resin dispersion in which at least one resin particle selected from acrylic resin and acrylic Z styrene resin is dispersed. The energy attenuation performance of the coating film is easily exhibited. Furthermore, since the energy attenuation performance of the coating film is further improved, such an aqueous rosin dispersion is preferably formulated with a normal phosphate ester compound, and more preferably with triphenyl phosphate.

Example

Next, the embodiment will be described more specifically with reference to examples and comparative examples.

(Examples 1 to 5)

Attenuation-imparting ingredients shown in Table 1 were prepared by blending damping components with acrylic emulsion and mixing them with a stirrer. This acrylic emulsion is composed of 52.5% by weight of rosin particles and 47.5% by weight of water. The resin particles are composed of a polymer obtained by polymerization of monomers including methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate. For example, a filler and a dispersant are blended in the damping paint of each embodiment at a predetermined blending ratio. The abbreviations in the type column of attenuation-providing components shown in Table 1 represent the following compounds. In Table 1, the blending amount of the attenuating component in the attenuating coating is determined between the fat particles and the attenuating component. It is expressed in mass% with respect to the total amount.

[0033] A-1: Triphenyl phosphate

A-2: Tributyl phosphate

B—1: N Phenol 1 Naphthinoreamine

B-2: p- (p Toluenesulfuramide) diphenylamine

C—1: Tris (Diclonal Propinole) Phosphate

(Comparative Examples 1 to 3)

In Comparative Example 1, a coating material was prepared using the acrylic emulsion used in the above example as an aqueous resin dispersion. In Comparative Examples 2 and 3, paints were prepared in which the above-described damping component was not blended and a benzimidazole compound and a hindered phenol compound were blended as additive agents. For example, a filler and a dispersing agent are blended in the paint of each comparative example at the same blending ratio as in the above examples. The abbreviations in the additive type column shown in Table 1 represent the following compounds. In Table 1, the combined amount of the additive in the attenuating paint is expressed in mass% with respect to the total amount of the resin particles and the additive.

[0034] R—1: 2 Zinc salt of mercaptobenzoimidazole

R-2: N, Ν'-hexane-1, 6 dirubis [3— (3, 5 di-tert-butyl 4-hydroxyphenylpropionamide)]

(Examples 6, 7)

As shown in Table 2, in Examples 6 and 7, an attenuating paint was prepared in the same manner as in Example 1 except that the blending amount of the attenuating component A-1 was changed.

[0035] (Examples 8 and 9)

As shown in Table 2, in Example 8, a damping paint was prepared in the same manner as in Example 1 except that the damping property-imparting component A-1 was not blended as a powder but was blended using a dispersion. . The dispersion medium of the dispersion liquid is water, and the damping component is present as solid particles having an average particle diameter of 1. O / zm in the dispersion liquid. The concentration of the solid particles is 38% by mass, and the dispersion liquid contains about 5% by mass of a surfactant as a dispersant with respect to the solid particles.

[0036] In Example 9, the amount was reduced in the same manner as in Example 8, except that the type of the attenuating component was changed. A fading paint was prepared. The abbreviations in the type column of attenuation-providing components shown in Table 2 represent the following compounds. In Table 2, the blending amount of the attenuating component in the attenuating paint is expressed as mass% with respect to the total amount of the resin particles and the attenuating component.

[0037] B—3: 4,4′-bis (α, α-dimethylbenzyl) diphenylamine

(Example 10)

An attenuating paint was prepared in the same manner as in Example 1 except that the aqueous resin dispersion was changed to acrylic / styrene-based emulsion. This acrylic / styrene-based emulsion is composed of 52.5% by weight of rosin particles and 47.5% by weight of water. The resin particles are composed of polymer power obtained by polymerization of monomers including methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and styrene.

[0038] (Comparative Example 4)

In Comparative Example 4, a paint was prepared using the acrylic styrene emulsion used in Example 10 as a water-based resin dispersion. In the paint of Comparative Example 4, a filler, a dispersant, and the like are blended at the same blending ratio as in the above examples.

[0039] <Evaluation of damping performance>

After applying the damping paint of each example and the paint of each comparative example to a steel plate (thickness 0.8 mm), a coating film was formed by heating and drying at 140 ° C for 25 minutes, and these coating films were tested. It was a piece. The coating amount was adjusted so that the thickness of the coating film on the steel plate was the same. For each test piece, 20 ° C, 30 ° C, 40 ° C, 50 ° C and 60 ° C using a central excitation method loss factor measurement device (CF5200 type, manufactured by Ono Sokki Co., Ltd.) Loss factor and the peak value of the loss factor were measured. Tables 1 and 2 show the loss factor at each temperature, and the peak value and temperature of the loss factor.

[0040] [Table 1] 2 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example: 3 Aqueous resin dispersion Acrylic Acrylic Acrylic Acrylic Acrylic Acrylic Acrylic Acrylic Type A-1 A-2 B- 1 B-2 C— 1 ― ― ― Compounding amount

Attenuating component 5 5 5 5 5 0 0 0

[Mass%]

Formulation Powder Powder Liquid Powder Powder Powder

Type ― ― ― ― R-1 R-2

Additive 0 0 0 0 0 0 5 5

[Mass%]

Formulation ― ― Powder Powder Film thickness [mm] 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3

20 C 0.273 0.443 0.272 0.165 0.262 0.1 83 0.1 3 0.193

30. C 0.408 0.381 0.406 0.310 0.367 0.306 0.230 0.31 5 Loss factor 40. C 0.265 0.1 27 0.294 0.381 0.289 0.359 0.327 0.31 6

50 0.1 1 2 0.051 0.1 19 0.187 0.145 0.21 6 0.304 0.1 67

60 ° C 0,048 0.027 0.055 0.082 0.076 0.105 0.1 62 0.077 Peak value of loss factor 0.408 0.443 0.406 0.390 0.392 0.372 0.289 0.360 Peak temperature [] 30.0 20.0 30.0 37.5 32.5 37.5 35.0 35.0

[0041] [Table 2]

As is apparent from the results in Table 1, the peak value of the loss factor in Examples 1 to 5 is higher than the peak value in Comparative Example 1, so that the damping paint of each Example imparts damping properties. It can be seen that the damping performance is exhibited by the blending of the components. In contrast, as shown in Comparative Examples 2 and 3, when a benzimidazole compound and a hindered phenol compound are blended, the peak value of the loss factor is lower than that in Comparative Example 1. Thus, it can be seen that the damping performance is not exhibited by the blending of these compounds.

FIG. 1 shows the relationship between the blending amount of the attenuating component and the peak value of the loss coefficient for Examples 1, 6, 7 and Comparative Example 1. As is clear from the results in Fig. 1, the peak value of the loss factor increases as the blending amount increases, and the peak value is almost constant at 5% by mass. You can see that it has reached.

As is clear from the results of Examples 8 and 9 shown in Table 2, even when the damping property-imparting component is blended using a dispersion, the damping performance is exhibited. As shown in FIG. 2, the loss factor in Example 8 is higher than the loss factor in Example 1, so that the damping performance is further exhibited by blending the damping component with the dispersion. Can be made. As can be seen from the results of Example 10 and Comparative Example 4 shown in Table 2, it can be seen that the damping performance is exhibited even when the type of the aqueous resin dispersion is changed.

Claims

The scope of the claims

[1] An aqueous resin dispersion in which the resin particles forming the coating film are dispersed in an aqueous dispersion medium;

An attenuating coating comprising an attenuating component that imparts energy attenuating property to the coating film,

The attenuating component is

An attenuating paint comprising at least one selected from a normal phosphate ester compound, an aromatic secondary amine compound, and a halogen-containing ester compound.

[2] The attenuating paint according to claim 1, wherein the attenuating component is a normal phosphate ester compound.

[3] The damping paint according to claim 2, wherein the orthophosphate compound is triphenyl phosphate.

[4] The content of the attenuating property-imparting component in the attenuating paint is 5% by mass or less based on the total amount of the attenuating property-imparting component and the above-mentioned rosin particles. The damping paint according to any one of the above.

[5] The attenuating property according to any one of claims 1 to 4, which is obtained by adding a dispersion in which the attenuating property-imparting component is dispersed in an aqueous dispersion medium to the aqueous rosin dispersion. paint.

[6] The V of Claims 1 to 5, wherein the resin particles are composed of at least one polymer material selected from acrylic resin and acrylic Z styrene resin. The damping paint according to any one of the above.