JP2007262220A - Method for producing damping coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a damping coating easy to enhance the damping of the coating film therefrom compounded with an inorganic filler. <P>SOLUTION: The method for producing the damping coating comprises the first mixing step of mixing an aqueous resin dispersion with an epoxy-based silane coupling agent and the second mixing step of mixing the resultant mixed liquid with the inorganic filler; wherein resin particles dispersed in the aqueous resin dispersion are constituted of at least one polymeric material selected from an acrylic resin and an acrylic/styrene-based resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an attenuating coating material that exhibits a damping performance for attenuating energy such as vibration energy and impact energy.

Conventionally, for example, a compound having a benzothiazyl group is known as an attenuating component that imparts attenuating properties to various 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 this damping paint exhibits damping performance by the action of the damping imparting component. On the other hand, it is known that the adhesion between the resin material and the metal material is improved by blending various coupling agents into the resin material (see Patent Document 4).
International Publication No. 97/42844 Pamphlet International Publication No. 99/28394 Pamphlet International Publication No. 01/40391 Pamphlet JP-A-5-329980

  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. In such an attenuating paint in which an inorganic filler is blended with an aqueous paint, the damping of the coating film is imparted by blending the inorganic filler. And as the compounding amount of the inorganic filler is increased, the attenuation of the coating film tends to be further increased. However, an increase in the blending amount of the inorganic filler decreases the fluidity of the water-based paint, so that it is difficult to sufficiently obtain the applicability as a paint with such an attenuating paint. Moreover, since the increase of the compounding quantity of an inorganic filler will reduce the dispersibility of the inorganic filler in a coating material, it will become difficult to exhibit the attenuation performance corresponding to the compounding quantity. As described above, while the inorganic filler is an effective component for imparting attenuation to the coating film, in the case of an aqueous coating material, to increase the attenuation by increasing the blending amount of the inorganic filler. There was a limit.

  The present invention has been made in view of such conventional circumstances, and an object of the present invention is to provide a method for producing an attenuating paint that can easily enhance the attenuating property of a coating film containing an inorganic filler. is there.

  In order to achieve the above object, the invention according to claim 1 is characterized in that an attenuation property obtained by blending an inorganic filler in an aqueous resin dispersion in which resin particles forming a coating film are dispersed in an aqueous dispersion medium. A method for producing a paint, wherein the resin particles dispersed in the aqueous resin dispersion are composed of at least one polymer material selected from an acrylic resin and an acrylic / styrene resin, and the aqueous resin dispersion and the epoxy resin The gist includes a first mixing step of mixing the silane coupling agent, and a second mixing step of mixing the mixed liquid obtained by the first mixing step and the inorganic filler.

  The invention according to claim 2 is the invention according to claim 1, wherein the epoxy-based silane coupling agent is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxy. The gist is to use at least one selected from silane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.

  The invention according to claim 3 is the invention according to claim 1 or 2, wherein the amount of the epoxy silane coupling agent is the total amount of the epoxy silane coupling agent and the inorganic filler. The content is 0.1 to 5% by mass with respect to the content.

The gist of the invention according to claim 4 is that, in the invention according to any one of claims 1 to 3, mica is used as the inorganic filler.
The invention according to claim 5 is the invention according to any one of claims 1 to 4, wherein as the attenuating agent, a normal phosphate ester compound, an aromatic secondary amine compound, and The gist is to further mix at least one selected from halogenated ester compounds.

  According to the present invention, it is easy to increase the attenuation of a coating film containing an inorganic filler.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The damping paint in the present embodiment is produced by mixing an inorganic filler with an aqueous resin dispersion in which resin particles forming a coating film are dispersed in an aqueous dispersion medium. In this method for producing an attenuating coating, a first mixing step of mixing an epoxy-based silane coupling agent with an aqueous resin dispersion, and a mixed solution obtained by the first mixing step and an inorganic filler are mixed. A second mixing step is included.

  The resin particles dispersed in the aqueous resin dispersion are composed of at least one polymer material selected from acrylic resins and acrylic / styrene resins. Examples of the acrylic resin include a homopolymer having acrylic acid, acrylic ester, methacrylic acid and methacrylic ester as monomers, a mixture of these homopolymers, and a copolymer obtained by polymerizing these monomers. Can be mentioned. Examples of acrylic acid esters and methacrylic acid esters include methyl esters, ethyl esters, propyl esters, 2-ethylhexyl esters, ethoxyethyl esters, and the like. Examples of the acrylic / styrene resin include a copolymer of a monomer that forms the acrylic resin and a styrene monomer. The resin particles may be formed of a single type of polymer material or may be formed of a plurality of types of polymer material. Furthermore, the aqueous resin dispersion may contain resin particles composed of these polymer materials alone, or may contain a plurality of types of resin particles.

  Examples of the aqueous dispersion medium include water and a mixed liquid of water and alcohol. Examples of the alcohol include methanol and ethanol. The aqueous resin dispersion can be 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.

  In the first mixing step, an epoxy silane coupling agent is mixed with the aqueous resin dispersion. The epoxy silane coupling agent is an organic compound in which a reactive group having an epoxy group and an alkoxy group having hydrolyzability are bonded to a single silicon atom. And the hydroxyl group and silanol group are formed in the molecule | numerator of the silane coupling agent by hydrolyzing the alkoxy group of the epoxy silane coupling agent mixed with the aqueous resin dispersion. Further, the epoxy group of the silane coupling agent and the polymer constituting the resin particle are bonded to each other, so that the resin particle is surrounded by the hydroxyl group of the molecule of the silane coupling agent. It is estimated that the affinity with the aqueous dispersion medium is increased.

  Examples of the epoxy silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycol. Preference is given to at least one selected from sidoxypropyltriethoxysilane. Among the epoxy-based silane coupling agents, 3-glycidoxypropyltrimethoxysilane is more preferable from the viewpoint that the ability to modify the surface of the resin particles is high, and the attenuation of the coating film is more likely to increase. .

  The compounding amount of the epoxy silane coupling agent is preferably 0.1 to 5.0% by mass, more preferably relative to the total amount of the coupling agent and the inorganic filler mixed in the second mixing step. Is 0.1 to 3.0% by mass, more preferably 0.1 to 1.0% by mass. When the compounding amount of the epoxy silane coupling agent is less than 0.1% by mass, there is a possibility that it is difficult to remarkably obtain the effect of increasing the attenuation. On the other hand, if the blending amount exceeds 5.0% by mass, the improvement rate of the damping property tends to decrease, which may be uneconomical.

  For the mixing operation in the first mixing step, a known method such as stirring, shaking, ultrasonic vibration or the like can be used. What is necessary is just to set the mixing time in a 1st mixing process suitably with temperature etc., for example, is set to about 30 to 60 minutes on 20 degreeC temperature conditions.

  In the second mixing step, the mixed liquid obtained in the first mixing step and the inorganic filler are mixed. In this second mixing step, the inorganic filler is dispersed in the aqueous dispersion medium. At this time, it is presumed that the inorganic filler can easily approach the resin particles whose affinity with the aqueous dispersion medium is increased by the first mixing step. That is, it is presumed that the miscibility between the resin particles and the inorganic filler is increased by mixing the inorganic filler into the mixed liquid after the first mixing step.

  Examples of the inorganic filler include mica, talc, clay, barium sulfate, magnesium carbonate, glass, silica, alumina, aluminum, aluminum hydroxide, iron, asbestos, titanium oxide, iron oxide, diatomaceous earth, zeolite, and ferrite. An inorganic filler may mix | blend single seed | species and may mix | blend multiple types in combination. Among inorganic fillers, mica is preferred from the viewpoint that it is presumed to have excellent miscibility with the resin particles modified by the first mixing step, and it is easy to further enhance the attenuation of the coating film.

  The blending amount of the inorganic filler is preferably 10 to 80% by mass, more preferably 30 to 60% by mass, and further preferably 35 to 45% by mass with respect to the total amount of the inorganic filler and the resin particles. . When the blending amount of the inorganic filler is less than 10% by mass, it may be difficult to provide excellent attenuation. On the other hand, if it exceeds 80% by mass, it becomes difficult to ensure the dispersibility of the inorganic filler in the attenuating paint. As a result, it becomes difficult to exhibit the attenuating performance commensurate with the blending amount, and the fluidity of the attenuating paint decreases. As a result, it may be difficult to obtain sufficient coating properties as a paint.

  For the mixing operation in the second mixing step, a known method such as stirring, shaking, ultrasonic vibration or the like can be used. What is necessary is just to set the mixing time in a 1st mixing process suitably according to the dispersion state of an inorganic filler, for example, is set to about 10 minutes to 30 minutes.

  In the damping paint, as other components, damping agent, gelling agent, foaming agent, foaming aid, dispersing agent, viscosity modifier, thickener, flow improver, antifoaming agent, film-forming aid In addition, it is possible to add an anti-settling agent or the like as necessary. Other components can be mixed in the pre-process, the post-process, the post-process of the second mix process, the first mix process, or the second mix process of the first mixing process. These components are preferably blended after the second mixing step is completed from the viewpoint of sufficiently exerting the effects of the first and second mixing steps. Moreover, it is suitable to mix | blend a damping property imparting agent with a damping paint from a viewpoint of improving damping performance. Examples of the attenuating agent include at least one selected from a regular phosphate ester compound, an aromatic secondary amine compound, and a halogen-containing ester compound.

  Examples of the orthophosphate compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (butoxyethyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl Examples thereof include at least one selected from diphenyl phosphate and 2-ethylhexyl diphenyl phosphate.

  Examples of the aromatic secondary amine compound include p- (p-toluenesulfonylamide) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine, and N, N′-diphenyl-p-phenylenediamine. N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated Examples thereof include at least one selected from diphenylamine and 4,4′-bis (α, α-dimethylbenzyl) diphenylamine.

  Examples of the halogen-containing phosphate compound include at least one selected from tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, and tris (tribromoneopentyl) phosphate.

Among the attenuating agents, the phosphoric acid ester compound is preferable, and triphenyl phosphate is more preferable because it has an excellent effect of enhancing the attenuation performance of the coating film.
The blending amount of the attenuating agent is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less with respect to the total amount of the resin particles and the attenuating agent. When the blending amount of the damping property-imparting agent exceeds 20% by mass, the improvement rate of the damping performance tends to decrease, which may be uneconomical. Furthermore, the blending amount of the attenuating agent 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 agent. When the blending amount of the attenuating agent is less than 1% by mass, it may be difficult to impart excellent attenuating properties.

  The damping performance of such a damping paint, that is, the damping performance of the coating film obtained from the damping paint is indicated by the loss factor of the coating film. That is, the higher the loss coefficient of the coating film, the better the 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.

  This damping paint can be used as a vibration-damping paint that attenuates vibration energy, an impact-absorbing paint that attenuates impact energy, and the like. Examples of the application field of the vibration-damping paint include automobiles, building materials, home appliances, and industrial machines. Examples of the application field of the impact absorbing paint include 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, various cushioning materials, There are various interior materials.

  In order to use a damping paint, a coating film is formed by applying the damping paint to an application site and then drying the damping paint. For this application, it is possible to use an application means such as an air spray gun, an airless spray gun, or a brush application in addition to a method of discharging an attenuating paint from a slit or the like and applying it to an application site.

  At this time, in the attenuating paint obtained by the above-described manufacturing method, the miscibility between the resin particles and the inorganic filler is enhanced by the epoxy silane coupling agent. It is presumed that the interaction between the polymer and the inorganic filler increases. As a result, when energy (excluding light energy and electric energy) such as vibration energy, impact energy, and sound energy is transmitted to the coating film, such energy is easily converted into thermal energy.

The effects exhibited by this embodiment will be described below.
(1) After carrying out the first mixing step of mixing a specific silane coupling agent with respect to the aqueous resin dispersion in which specific resin particles are dispersed, the mixture obtained by the first mixing step is inorganic. A second mixing step of mixing the filler is performed. In the damping paint manufactured in this way, it is presumed that a coating film with increased miscibility between the resin component and the inorganic filler is formed. For this reason, the attenuation | damping function by the mixing | blending of an inorganic filler can be exhibited more. For this reason, when blending the inorganic filler, even if the blending amount is reduced in consideration of the coating property as a paint, the dispersibility of the inorganic filler, etc., the attenuation of the coating film is easily maintained. Therefore, according to this manufacturing method, it is easy to increase the attenuation of the coating film containing the inorganic filler.

  (2) 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycine as an epoxy-based silane coupling agent It is preferable to use at least one selected from sidoxypropyltriethoxysilane. In particular, 3-glycidoxypropyltrimethoxysilane is presumed to have a high ability to modify the surface of resin particles composed of at least one polymer material selected from acrylic resins and acrylic / styrene resins. This is more preferable because the attenuation of the film is more likely to increase.

  (3) By setting the blending amount of the epoxy silane coupling agent to 0.1 to 5% by mass with respect to the total amount of the silane coupling agent and the inorganic filler, the effect of increasing the attenuation is sufficient. And an increase in cost due to the compounding of the epoxy silane coupling agent can be suppressed.

  (4) Among inorganic fillers, mica is presumed to be excellent in miscibility with the resin particles modified by the first mixing step. For this reason, the use of mica as the inorganic filler makes it easier to increase the attenuation of the coating film.

  (5) The damping property of the coating film is further enhanced by mixing at least one selected from a regular phosphate ester compound, an aromatic secondary amine compound, and a halogen-containing ester compound as an attenuating agent. be able to.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
(Examples 1-3)
Epoxy to acrylic emulsion (resin particles: 52.5% by mass of polymer obtained by polymerizing monomers including methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate, 47.5% by mass of water, etc.) 3-glycidoxypropyltrimethyoxysilane as a silane coupling agent was blended, and the acrylic emulsion and the epoxy silane coupling agent were mixed by stirring with a stirrer (first mixing step). Mixing mica (made by Kuraray Co., Ltd., wet 300W, 200HK) as an inorganic filler into the liquid mixture obtained in the first mixing step, mixing the mica into the liquid mixture by stirring with a stirrer, and damping A second paint was prepared (second mixing step). In addition, a dispersing agent etc. are mix | blended with the predetermined | prescribed mixing | blending rate in the damping paint of each Example. The compounding amount of the epoxy-based silane coupling agent shown in Table 1 is expressed by mass% with respect to the total amount of the inorganic filler and the coupling agent, and the compounding amount of the inorganic filler shown in the table is resin particles and inorganic filler. It is expressed in mass% with respect to the total amount with the agent.

  Example 3 was attenuated in the same manner as in Example 1 except that after completion of the second mixing step, triphenyl phosphate as a damping property-imparting agent was blended and mixed with triphenyl phosphate by stirring with a stirrer. An adhesive paint was prepared. In addition, in the damping paint of Example 3, a dispersant or the like is blended at a predetermined blending rate. The compounding amount of the attenuating agent shown in Table 1 is mass% with respect to the total amount of the resin particles and the attenuating agent.

(Comparative Example 1)
As shown in Table 2, in Comparative Example 1, an attenuating paint was prepared in the same manner as in Example 1 except that the first mixing step was not performed.

(Comparative Examples 2 and 3)
In Comparative Example 2, a mica surface treatment was performed by impregnating an aqueous solution of a silane coupling agent with mica (manufactured by Kuraray Co., Ltd., wet 300W, 200HK) and then leaving it in a thermostatic bath at 80 ° C. for 12 hours. did. Next, the surface-treated mica was treated with an acrylic emulsion (resin particles: 52.5% by mass of a polymer obtained by polymerizing monomers including methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate, water, etc. 47.5%. In addition, the acrylic emulsion and the surface-treated mica were mixed by stirring with a stirrer to prepare a damping paint. In addition, a dispersing agent etc. are mix | blended with the predetermined | prescribed mixing | blending rate in the attenuating coating material of each comparative example.

(Comparative Example 4)
In Comparative Example 4, after completion of the second mixing step, attenuation was performed in the same manner as in Comparative Example 1, except that triphenyl phosphate as a damping property-imparting agent was blended and mixed with triphenyl phosphate by stirring with a stirrer. An adhesive paint was prepared.

<Evaluation of damping performance>
After applying the damping paint of each 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 used as test pieces. In addition, the coating amount was adjusted so that the thickness of the coating film with respect to a steel plate might become the same. About the test piece of each example, the loss coefficient in each temperature shown in Table 1 and Table 2 was measured using the central excitation method loss coefficient measuring apparatus (CF5200 type, Ono Sokki Co., Ltd. product). The loss factor at each temperature is also shown in Tables 1 and 2.

各表及び図１に示す結果から明らかなように、実施例１における損失係数は、比較例１における損失係数よりも高い値を示していることから、第１及び第２の混合工程により、減衰性能がより発揮されることがわかる。さらに、図２に示す結果から明らかなように、実施例１における損失係数は、比較例２における損失係数よりも高い値を示している。そして、比較例２の損失係数の値は、比較例１の損失係数の値と同等である。この結果から、比較例２のように、エポキシ系シランカップリング剤で処理した無機充填剤を、第２の混合工程によって混合しても、実施例１のような効果が得られないことがわかる。加えて、図３に示す結果から明らかなように、実施例１における損失係数は、比較例３における損失係数よりも高い値を示している。そして、比較例３の損失係数の値は、比較例１の損失係数の値と同等である。この結果から、比較例３のように、アミノ系シランカップリング剤を用いて第１の混合工程を実施しても、実施例１のような効果が得られないことがわかる。さらに、図４に示す結果から明らかなように、実施例３における損失係数は、比較例４における損失係数よりも高い値を示している。この結果から、減衰性付与剤を配合した減衰性塗料においても、第１及び第２の混合工程による効果が発揮されることがわかる。

As is clear from the results shown in the tables and FIG. 1, the loss factor in Example 1 shows a higher value than the loss factor in Comparative Example 1, so that the first and second mixing steps attenuate the loss factor. It can be seen that the performance is more exhibited. Further, as is apparent from the results shown in FIG. 2, the loss factor in Example 1 is higher than the loss factor in Comparative Example 2. The loss factor value of Comparative Example 2 is equivalent to the loss factor value of Comparative Example 1. From this result, it can be seen that, as in Comparative Example 2, even if the inorganic filler treated with the epoxy silane coupling agent is mixed in the second mixing step, the effect as in Example 1 cannot be obtained. . In addition, as is apparent from the results shown in FIG. 3, the loss factor in Example 1 is higher than the loss factor in Comparative Example 3. The value of the loss factor in Comparative Example 3 is equivalent to the value of the loss factor in Comparative Example 1. From this result, it can be seen that, as in Comparative Example 3, even if the first mixing step is performed using an amino silane coupling agent, the effect as in Example 1 cannot be obtained. Furthermore, as is clear from the results shown in FIG. 4, the loss factor in Example 3 is higher than the loss factor in Comparative Example 4. From this result, it can be seen that the effects of the first and second mixing steps are exhibited even in the damping paint containing the damping imparting agent.

The graph which shows the relationship between the temperature and loss factor in Example 1 and Comparative Example 1. The graph which shows the relationship between the temperature and loss factor in Example 1 and Comparative Example 2. The graph which shows the relationship between the temperature and loss factor in Example 1 and Comparative Example 3. The graph which shows the relationship between the temperature and loss factor in Example 3 and Comparative Example 4.

Claims (5)

A water-based resin dispersion in which resin particles forming a coating film are dispersed in an aqueous dispersion medium, a method for producing an attenuating paint comprising an inorganic filler,
The resin particles dispersed in the aqueous resin dispersion are composed of at least one polymer material selected from acrylic resins and acrylic / styrene resins,
A first mixing step of mixing the aqueous resin dispersion and the epoxy silane coupling agent;
A method for producing an attenuating paint, comprising: a second mixing step of mixing the mixed liquid obtained in the first mixing step and the inorganic filler. As the epoxy silane coupling agent, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycid The method for producing an attenuating paint according to claim 1, wherein at least one selected from xylpropyltriethoxysilane is used. The compounding quantity of the said epoxy-type silane coupling agent is 0.1-5 mass% with respect to the total amount of this epoxy-type silane coupling agent and the said inorganic filler, The Claim 1 or Claim 2 A manufacturing method of a damping paint. The method for producing an attenuating paint according to any one of claims 1 to 3, wherein mica is used as the inorganic filler. 5. The system according to claim 1, wherein at least one selected from a regular phosphate ester compound, an aromatic secondary amine compound, and a halogen-containing ester compound is further mixed as an attenuating agent. A method for producing an attenuating paint as described in 1.

Images