JP2016044234A - Nonaqueous vibration damper composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous vibration damper composition which does not cause cracks on a coated film, does not need rust preventive treatment of a facility, and has sufficient vibration damping performance, when the coated film applied by coating means is baked.SOLUTION: There is provided a nonaqueous vibration damper composition in which 1.0-3.3 pts.mass of a latent curing agent for an epoxy resin, 50-100 pts.mass of a plasticizer, and 25.0-66.7 pts.mass of a filler are added to 100 pts.mass of a main agent in which an acrylic resin and an epoxy resin are mixed at a mass ratio of 1:0.5-1.SELECTED DRAWING: None

Description

  The present invention relates to a vibration damping composition used for automobile floors and the like, and more particularly, to a non-aqueous vibration damping composition used by applying to automobile floors.

Conventionally, the following are known as damping materials provided on the floor of an automobile.
(1) There is a damping material of a type in which a material mainly composed of a bitumen substance such as asphalt and an inorganic filler such as calcium carbonate is formed into a sheet shape, and is heat-sealed and molded after the vehicle is installed (see Patent Document 1). ).
Since this damping material is manually attached, it takes time. Moreover, the molded product according to an attachment site | part will exist, and management man-hours will start. Furthermore, since a molded sheet is pasted, only a shape having a predetermined design can be used.
(2) There is a water-based damping material mainly composed of a water-based emulsion, which is applied to the floor by a painting robot.
However, since water is used, it is necessary to carry out rust prevention work on tanks and pipes in blending equipment and coating equipment, which entails enormous costs.

JP 63-141731 A JP 2005-126644 A

In order to solve the problems (1) and (2), a non-aqueous system that can be applied by a coating means such as a painting robot and does not need to be subjected to a rust prevention treatment such as a tank or piping in a blending facility or coating facility. There is a need for vibratory compositions.
In order to solve such a problem, it is conceivable to use a conventional non-aqueous composition as a vibration damping material. However, there is a risk that cracking and swelling may occur during baking after spray application.
Therefore, the present invention provides a non-aqueous vibration damping material having sufficient vibration damping performance that does not cause cracks in the coating film and does not require rust prevention construction of the equipment when the coating film applied by the application means is baked. An object is to provide a composition.

  The non-aqueous vibration damping composition of the present invention is a latent curing agent 1.0 for epoxy resin with respect to 100 parts by mass of the main agent obtained by mixing acrylic resin and epoxy resin at a mass ratio of 1: 0.5-1. -3.3 parts by mass, plasticizers 50-100 parts by mass, and fillers 25.0-66.7 parts by mass were added.

  In the non-aqueous vibration damping composition according to the present invention, the coating film is not cracked during baking of the coating film applied by the application means, and there is no need for rust prevention construction of equipment, sufficient vibration damping performance Can have.

1. The non-aqueous vibration damping composition of the present invention is a latent curing agent 1.0 for epoxy resin with respect to 100 parts by mass of the main agent obtained by mixing acrylic resin and epoxy resin at a mass ratio of 1: 0.5-1. It is comprised by adding -3.3 mass parts, 50-100 mass parts of plasticizers, and 25-66.7 mass parts of fillers.
In the said composition, when the mass ratio of the epoxy resin with respect to an acrylic resin will be less than 0.5, since a surface layer part will not fully harden | cure after a predetermined | prescribed hardening process, vibration damping property will run short. On the other hand, when the mass ratio exceeds 1, the film is excessively cured and the coating film is easily cracked by physical impact.
In addition, when the plasticizer is less than 50 parts by mass with respect to 100 parts by mass of the main agent, the viscosity is high and there is no sufficient dispersibility, and the efficiency becomes extremely poor when coating using a robot. On the other hand, when the plasticizer exceeds 100 parts by mass, a decrease in the vibration damping property due to a decrease in the resin concentration and a shift of the glass transition point to a low temperature range (less than 20 ° C.) occur. I can't get it.
If the latent curing agent for the epoxy resin is less than 1.0 part by mass, the reaction of the epoxy resin becomes insufficient and the vibration damping performance is lowered. If the amount exceeds 3.3 parts by mass, the material after baking becomes brittle, which is not preferable.
When the filler is less than 25 parts by mass, it is difficult to maintain the shape after coating due to low viscosity, and sagging (liquid dripping) is likely to occur. When the amount exceeds 66.7 parts by mass, the resin concentration decreases. Damping performance decreases.
According to said composition, it can be used as a damping material only by apply | coating to the predetermined site | part of a vehicle body by application means, such as a spray gun. In addition, since the composition is a non-aqueous material, it can be easily introduced into an automobile application line configured on the premise that an existing non-aqueous material is applied. Moreover, since this damping material can form a strong film with an epoxy resin after application and after curing such as baking, cracking and swelling during baking can be suppressed. Furthermore, this damping material can adjust a glass transition point in the normal temperature range (20 to 60 degreeC) assumed to be application part temperature by using the main ingredient of the said mass ratio. Furthermore, sagging of the composition applied by the application means can be prevented. Moreover, the said composition prevents that a glass transition point becomes a low temperature range (less than 20 degreeC), it becomes easy to set to a normal temperature range, and it becomes easy to exhibit the damping effect in this temperature range.

  As the acrylic resin, for example, a single polymer or copolymer of a monomer selected from alkyl acrylate, alkyl methacrylate and the like can be used. Specific examples of the monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, ter-butyl acrylate, cyclohexyl acrylate, benzyl acrylate, Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, ter-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and the like can be used. Moreover, styrene, (alpha) -methylstyrene, methacrylic acid, acrylic acid, itaconic acid, crotonic acid etc. can also be used as a copolymerization component.

  Examples of the epoxy resin include cyanamide type, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin and other glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and aliphatic epoxides. -Type epoxy resin, alicyclic epoxide-type epoxy resin, rubber-modified epoxy resin such as rubber-modified epoxy resin modified with butadiene-acrylonitrile copolymer, urethane-modified epoxy resin, etc. can be used, and bisphenol A type epoxy resin should be used Is preferred.

  As the latent curing agent for epoxy resins, for example, polyamines and modified products, aromatic amines and modified products, hydrazides, etc. can be used, which are inert at room temperature, but are particularly activated by heating and react with isocyanates. Any can be used.

  As the plasticizer, dialkylene glycol dibenzoate, phosphorylated triaryl isopropylate or alkylbenzyl phthalate can be used, and any one of them can be used alone or in combination of two or more.

  As the filler, for example, inorganic fillers such as mica, calcium carbonate, barium sulfate, clay, diatomaceous earth, silica, talc, wollastonite, alumina, calcia, magnesia, sericite, etc. can be used. Species can be used alone or in combination of two or more. Preferably mica is good. Further, if necessary, hollow particles such as a glass balloon, a resin balloon, or a resin balloon that expands when heated can be blended.

2. In the composition described in the above “1.”, a mixture of a foaming agent and a foaming aid at a mass ratio of 1.5: 0.5 to 1.0 with respect to 100 parts by mass of the main agent is 17.5 to You may add 70.0 mass parts.
When the mass ratio of the foaming aid to the foaming agent is less than 0.5, the decomposition temperature of the foaming agent is not sufficiently lowered, resulting in insufficient foaming. On the other hand, even if the mass ratio exceeds 1.0, the decomposition temperature reduction effect obtained when the mass ratio is 1.0 cannot be obtained.
With the above composition, since the thermal decomposition can be promoted using the foaming aid, the foaming agent is sufficiently foamed before the epoxy resin is cured, and the vibration damping performance by the foaming agent can be enhanced.

  A well-known thing can be used as a foaming agent, and azodicarbonamide (ADCA) can be used. Further, although ADCA alone has a decomposition temperature exceeding 180 ° C., the decomposition temperature can be adjusted to 130 to 180 ° C. by using it together with a foaming aid.

  As the foaming aid, known ones can be used, and various metal oxides (for example, zinc oxide and magnesium oxide), metal soap (for example, zinc stearate), urea compounds, amines and the like can be used. In addition, such a foaming auxiliary agent can be blended for other purposes at the same time. For example, metal soap can be used as a surface treatment agent for inorganic fillers such as calcium carbonate, and metal soap used as such a surface treatment agent can also be used here as long as the decomposition temperature of the foaming agent is lowered. Included in the agent.

3. In the composition described in the above “1.” or “2.”, the latent curing agent for epoxy resin can be used in an amount of 1.0 to 3.3 parts by mass, particularly cyanamide and 1 The mass ratio of cyanamide: primary amine containing 1: 1 amine is 1: 1 to 1: 3, which shows a particularly good vibration damping effect. When the mass ratio of the primary amine to cyanamide 1 is less than 1, the reaction is slowed, so that the vibration damping property is low. When it exceeds 3, the vibration damping property is also low due to the decrease in rigidity.

4). In the composition described in the above “3.”, the latent curing agent for the epoxy resin may be dicyandiamide and a primary amine.
Thereby, the hardening state of an epoxy resin can be made into an optimal state. Moreover, it is easy to set the glass transition point to a suitable temperature within a normal temperature range (20 ° C. to 60 ° C.) where damping is required for both low temperature baking of about 140 ° C. and high temperature baking of about 170 ° C. Become.

5. In the composition described in the above “1.” to “4.”, the plasticizer is dialkylene glycol dibenzoate, triaryl isopropylate phosphate, or alkylbenzyl phthalate, and any one of them is used alone or in combination. More than one species can be used in combination. By sufficiently gelling the acrylic resin by low-temperature baking at about 140 ° C., the performance of the resin can be maximized and the vibration damping effect can be enhanced.

6). In the non-aqueous vibration damping composition described in the above “1.” to “5.”, the glass transition point may be 20 to 60 ° C. Thereby, it can be set as the damping material with the high damping performance in a normal temperature range.

According to the damping material composition described in “1.” to “6.”, the damping material such as an automobile floor is simply applied to a predetermined part of the vehicle body by an application means such as a spray gun. It can be a material.
In addition, the conventional line for applying paint to the body of an automobile has a facility configuration based on non-aqueous materials, so the damping material composition is a non-aqueous material mainly composed of acrylic resin and epoxy resin. According to the product, it is not necessary to apply rust prevention treatment to the equipment as compared with the case of introducing a water-based material into the line, and it can be introduced at a very low cost.
Moreover, according to this damping material composition, since a firm film | membrane can be formed with an epoxy resin after application | coating hardening, the crack and swelling at the time of baking can be suppressed.
Furthermore, according to this damping material composition, the sagging after application | coating can be prevented by adding the predetermined amount of filler with respect to the main ingredient. Moreover, it becomes easy to set the room temperature range by preventing the glass transition point from becoming a low temperature range of less than 20 ° C., and the vibration damping effect in this temperature range is easily exhibited.
Furthermore, according to this damping material composition, since the thermal decomposition can be promoted using a foaming aid, the foaming agent foams sufficiently before the epoxy resin is cured, and the damping performance by the foaming agent is improved. Can be increased.
Moreover, according to this damping material composition, it is possible to make it easier to set the glass transition point in the normal temperature range by using dicyandiamide and a primary amine as the latent curing agent for the epoxy resin. Furthermore, not only low temperature baking (140 ° C.) but also high temperature baking (170 ° C.) can easily set the glass transition point in the normal temperature range.
Further, according to the present invention, as the plasticizer, dialkylene glycol dibenzoate, triaryl isopropylate phosphate, or alkylbenzyl phthalate, any one of which can be used alone or in combination of two or more. Even with low-temperature baking, the vibration damping performance with acrylic resin can be enhanced.

  Hereinafter, although the non-aqueous vibration damping composition according to the present invention will be described more specifically with reference to examples, the present invention is not limited to the following examples unless it exceeds the gist.

[Non-aqueous damping material composition]
In the following Examples and Comparative Examples, the main ingredients of the non-aqueous vibration damping composition are acrylic acid alkyl ester (ZF Kasei Co., Ltd., KF301) as an acrylic resin, and bisphenol A type epoxy resin (Dow Chemical Japan) as an epoxy resin. DER331J) was used.
For the first additive (additive 1), dicyandiamide (manufactured by Mitsubishi Chemical Corporation, DISY-7) as a latent curing agent for epoxy resin, primary amine (manufactured by AC Japan Ltd., K37Y) ), Dialkylene glycol dibenzoate (manufactured by Dainippon Ink and Chemicals, PB10) as a plasticizer, and mica (manufactured by Lebco, mica 200HG) as a filler. The mass ratio of dicyandiamide: primary amine was 1: 2.
For the second additive (Additive 2), ADCA (manufactured by Eiwa Chemical Industry Co., Ltd., VINYHALL AC # R) is used as a foaming agent, and metal oxide (manufactured by Eiwa Chemical Industry Co., Ltd., cell paste 101) is used as a foaming aid. did.

[Test piece]
In the evaluation test, each composition obtained as each example and comparative example was applied to a steel plate having a thickness of 0.8 mm. Application was performed by a robot, and test pieces were prepared so that the surface density of the composition was 4.5 kg / m ² when dried. Curing conditions were low temperature baking 140 ° C., high temperature baking 170 ° C., and baking time 30 minutes.

[Testing and evaluation methods]
<Use of existing facilities>
The availability of the dependent equipment was evaluated using a holoplate pump. When the pumping was possible, “○” was evaluated, and when it was not possible, “X” was evaluated.
<Bulging and cracking>
The presence or absence of swelling was evaluated by visual inspection. When there was no swelling, it was evaluated as “◯”, and when there was swelling, it was evaluated as “x”. Moreover, the presence or absence of the crack was evaluated by visual recognition. When there was no crack, it was evaluated as “◯”, and when there was a crack, it was evaluated as “x”.
<Robot application>
The applicability of slit coating was evaluated by robot coating. When the application was possible, “◯” was evaluated, and when the application was impossible, “×” was evaluated.
<Sauce>
Sagging was evaluated by slit coating. When the sagging was 10 mm or less, it was evaluated as “◯”, and when it was larger than 10 mm, it was evaluated as “x”.
<Vibration control at room temperature>
The vibration damping property of the test piece was measured by the impedance method at a frequency of 200 Hz and a measurement temperature of 20 ° C. (normal temperature range). When the loss coefficient was 0.38 or more, “◯” was evaluated, and when it was less than 0.38, “X” was evaluated.

(Example 1)
50 parts by mass (mass ratio 1: 0.5) of epoxy resin was mixed with 100 parts by mass of acrylic resin to obtain a main agent. To 100 parts by mass of the main agent, 1.5 parts by mass of a latent curing agent for epoxy resin, 50 parts by mass of a plasticizer, and 25.0 parts by mass of a filler are added as an additive 1, and a non-aqueous vibration damping material is added. It was set as the composition.
(Example 2)
An epoxy resin was mixed in an amount of 75 parts by mass (mass ratio 1: 0.75) with respect to 100 parts by mass of the acrylic resin to obtain a main agent. To 100 parts by mass of the main agent, 1.0 part by mass of a latent curing agent for epoxy resin, 100 parts by mass of a plasticizer, and 25.0 parts by mass of a filler are added as additive 1, and a non-aqueous vibration damping composition It was a thing.

(Example 3)
100 parts by mass (1: 1 by mass) of epoxy resin was mixed with 100 parts by mass of acrylic resin to obtain a main agent. To 100 parts by mass of the main agent, 3.3 parts by mass of a latent curing agent for epoxy resin, 75 parts by mass of a plasticizer, and 66.7 parts by mass of a filler are added as an additive 1, and a non-aqueous vibration damping composition It was a thing.

(Examples 4 to 7)
The non-aqueous vibration damping composition of Example 2 was further mixed as additive 2 at a mass ratio of 1.5: 0.5 (Example 4) and 1.5: 1.0 (Example 5). 17.5 parts by mass of the foaming agent and the foaming assistant were added to 100 parts by mass of the main agent.
Moreover, with respect to the non-aqueous vibration damping composition of Example 2, the additive 2 has a mass ratio of 1.5: 0.5 (Example 6) and 1.5: 1.0 (Example 7). 70.0 parts by mass of the mixed foaming agent and foaming aid were added to 100 parts by mass of the main agent.

(Comparative Examples 1-4)
The epoxy resin was changed in an amount of 0 to 120 parts by mass (mass ratio 1: 0 to 1.2) with respect to 100 parts by mass of the acrylic resin, and mixed to obtain a main agent (Comparative Examples 1 to 3). Moreover, only 100 mass parts of epoxy resins were used as the main agent (Comparative Example 4). To 100 parts by mass of the main agent, 2 parts by mass of a latent curing agent for epoxy resin, 75 parts by mass of a plasticizer, and 50 parts by mass of a filler are added as additive 1 to obtain a non-aqueous vibration damping composition. .

  Table 1 shows the evaluation results for the vibration damping composition of each example and comparative example.

  As shown in Table 1, for Examples 1 to 7, good results were obtained in all evaluations. On the other hand, in Comparative Examples 1 and 2, since the mass ratio of the epoxy resin to the acrylic resin 1 was less than 0.5, the surface layer portion was not sufficiently cured after the curing treatment, and the vibration damping property was insufficient. Further, in Comparative Example 3, when the mass ratio of the epoxy resin to the acrylic resin 1 exceeded 1, the liquid became highly viscous, so that slit coating by robot coating could not be performed, and sagging increased. Further, in Comparative Example 4, since the main agent is only epoxy resin, the viscosity is higher than Comparative Example 3 and slit coating by robot coating is not possible, the sagging is large, and the state after baking is hard, resulting in vibration suppression. Lack of sex.

Claims (6)

  With respect to 100 parts by mass of the main agent obtained by mixing an acrylic resin and an epoxy resin in a mass ratio of 1: 0.5 to 1, a latent curing agent for epoxy resin is 1.0 to 3.3 parts by mass, and a plasticizer is 50 to 100. A non-aqueous vibration-damping material composition, characterized by adding 2 parts by mass and 25.0 to 66.7 parts by mass of a filler.   A total of 17.5 to 70.0 parts by mass of a mixture of a foaming agent and a foaming auxiliary agent in a mass ratio of 1.5: 0.5 to 1.0 is added to 100 parts by mass of the main agent. The non-aqueous vibration damping composition according to claim 1.   The latent curing agent for the epoxy resin contains cyanamide and a primary amine, and the mass ratio of cyanamide: primary amine is 1: 1 to 1: 3. A non-aqueous vibration damping composition.   The non-aqueous vibration damping composition according to claim 3, wherein the latent curing agent for the epoxy resin is dicyandiamide and a primary amine.   The plasticizer is dialkylene glycol dibenzoate, triaryl isopropylate, or alkylbenzyl phthalate, and one of these is used alone or in combination of two or more. 5. The non-aqueous vibration damping composition according to any one of 4 above.   The non-aqueous vibration damping composition according to any one of claims 1 to 5, wherein the glass transition point is 20 to 60 ° C.