JPH0335072A - Damping coating material - Google Patents

Abstract

PURPOSE:To obtain the subject coating material having excellent resistance to water, weatherability and damping properties by reacting polyester polyol derived from polycondensation of specific diol and dicarboxylic acid and polyisocyanate. CONSTITUTION:(A) polyester polyol obtained by polycondensation of diol composed of single or mixture of at least two species of 2,2-dialkyl-1,3-propanediol expressed by the formula (R1 and R2 are 2-4C alkyl) and dicarboxylic acid [preferably aliphatic saturated dicarboxylic acid expressed by the formula HOOC(CH2)nCOOH (n is 2-8)] is reacted with (B) polyisocyanate (e.g. hexamethylene diisocyanate or isophorone diisocyanate) to afford the aimed coating material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a vibration-damping paint that is water resistant, weather resistant, and has extremely excellent vibration damping performance.

[Prior art and its problems]

BACKGROUND ART In the fields of vehicles, boat bottoms, automobiles, equipment, machinery, and even architecture, various efforts have been made for the purpose of soundproofing and damping vibrations, and the most commonly used of these is damping paint.

In other words, in order to prevent vibrations on the surfaces of structural members such as the above-mentioned equipment and building materials, and the accompanying noise, it is necessary to make the members thicker, improve the equipment, or attach vibration-damping materials to the surfaces of the members. are doing. Furthermore, vibration and noise are often prevented by applying or spraying a damping material.

Up to now, many paints with vibration damping performance and methods for producing the same have been provided. For example, rubber, asphalt, various synthetic resins, etc., which utilize the viscoelastic properties of polymers themselves, and these polymers are mixed with crushed inorganic substances such as mica, talc, and calcium carbonate to reduce mechanical hysteresis and internal friction. There are some that are larger.

Unfortunately, however, many of these are designed to be used at around room temperature, and even though they have high vibration damping performance at around room temperature, when the temperature range of use is expanded, they become softer. There was a tendency for vibration damping performance to decline due to a decline in mechanical properties.

In addition, although water-based vibration damping resin compositions are advantageous in terms of safety in terms of the working environment, they have limitations in water resistance and weather resistance.
Therefore, it has the disadvantage that its range of use is limited.

Generally, in the case of a single-layer structure type, the larger the Young's modulus of the coating film, the more effectively a good damping effect (high loss coefficient) can be obtained with a thin film, and the standard value of the loss coefficient η when showing a good damping effect is 0
．． It is said to be more than 0.05 to 0.1.

In view of the above-mentioned current situation, the present inventors have conducted extensive research to further improve vibration damping performance, and have surprisingly found that when using a paint containing a specific polyester polyol, water resistance and weather resistance The present inventors have discovered that the present invention has excellent vibration damping performance, and has completed the present invention.

As is clear from the above description, an object of the present invention is to provide a coating material that is excellent in water resistance and weather resistance, and has extremely excellent vibration damping performance.

[Means for solving problems]

The configuration of the present invention will be described in detail below.

That is, the present invention provides a coating material obtained by reacting a polyester polyol obtained by condensation polymerization of a diol and a dicarboxylic acid with a polyisocyanate, in which the diol component is 2,2-dialkyl-1 represented by the following formula.
, 3-propanediol alone or in a mixture of 21E1 or more.

Further, it is a vibration-damping paint consisting of a saturated dicarboxylic acid represented by the following formula (n) as a dicarboxylic acid component, either alone or in a mixture of two or more.

The diol of the present invention is a single or a mixture of two or more 2,2-dialkyl-1,3-propanediols represented by
It is a diol containing mol% or more.

If a diol having an alkyl group having less than 2 carbon atoms or hydrogen in the R+ and R symbols is used, the resin will become hard, the resulting coating film will become brittle, and the damping performance will also deteriorate. On the other hand, if a diol having an alkyl group with more than 4 carbon atoms in R1 and R2 is used, the esterification reaction with dicarboxylic acid is extremely slow and it takes an extremely long time to obtain a polyester polyol, making it difficult to use as an industrial method. It's difficult. Examples of diols other than the specific diol include ethylene glycol, glopyresi glycol, butanediol, hexane diol, neopentyl glycol, and polycaprolacto-7 diol, and one or two of these diols may be used. More than one species can be used in combination with the diol.

The dicarboxylic acid of the present invention may be an aliphatic carboxylic acid or an aromatic carboxylic acid, but among them, an aliphatic carboxylic acid is preferable, and a saturated dicarboxylic acid represented by the following formula % formula %) It preferably contains at least 40 mol% or more, and more preferably 50 mol% or more, of either one or a mixture of two or more. Examples of dicarboxylic acids other than the specific dicarboxylic acid include brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, isophthalic acid, terephthalic acid, and 5-methylisophthalic acid. Or 28! The above can be used in combination with the dicarboxylic acid.

The polyester polyol of the present invention can be obtained by esterifying a diol and a dicarboxylic acid using a known method.

According to the present invention, the molecular weight of the polyester polyol is preferably 1000 to 1000G, more preferably 2
000 to 5ooo. If it is less than 1000, the resin becomes too hard, the coating film becomes brittle, and the scratch resistance decreases. If it exceeds too much, the coating film will be too flexible and its toughness will be impaired.

On the other hand, any known polyisocyanate can be used in the present invention. For example, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2.4-) lylene diisocyanate), 2.6-
) lylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc., and one or more of these can be used.

The vibration-damping coating material of the present invention is obtained by reacting a polyester polyol and a polyinsyanate, and at this time, a chain extender may be used as necessary. In addition, as chain extenders, hydrazine, ethylene diamine, tetramethylene diamine, hexamethylene diamine, heavy,
Diamines such as 4-cyclohexanediamine can be mentioned, and one or more of these can be used.

In the present invention, it is preferable to carry out the urethanization reaction of the transferred isocyanate and the polyester polyol at an NGO10H ratio of around 1. This makes it possible to obtain a high-molecular-weight polyurethane resin composition, and as a result, a resin that maintains the hydrolysis resistance, heat resistance, and weather resistance characteristic of polyurethane resins, and also has extremely excellent vibration damping performance. I was able to do something.

The damping paint according to the present invention is synthesized using each of the above components, and at this time, the IIco index is usually about 0.9.
-1.2, preferably about 0.95-1.10. The manufacturing method may be any of the well-known methods such as the Wanshirobuto method and the prepolymer method. At this time, if necessary (urethane conversion)
A catalyst may also be used.

The vibration-damping paint of the present invention may include vinyl chloride resin, vinyl chloride/vinyl chloride/vinyl acetate copolymer resin, vinyl chloride/vinyl acetate/vinyl alcohol J [polymer I
Resins such as oil, nitrocellulose, polyvinyl butyral resin, polyvinyl acetal resin, alkyd resin, and epoxy resin can be blended. Further, in the present invention, additives such as antistatic agents may be added as necessary.

The damping paint of the present invention preferably uses a solvent,
The good solvent includes ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,
Examples include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and tetrahydrofuran.

Various methods can be used to apply the damping paint thus obtained to the member (support). For example, impregnated coat,
Reverse roll coating, cast coating, spray coating, etc. can be used. After coating, dry at room temperature to about 100°C. Drying time is 10 minutes or more, preferably 1
A drying time of about 0 minutes to 24 hours is good.

Although the reason why it has excellent vibration damping performance is not necessarily clear, the vibration damping diol component of the present invention has two components as described above.
, 2-dialkyl-1,3-propanediol, and this diol has a so-called quaternary carbon, which does not have hydrogen at the 2-position carbon, so it exhibits distinctive properties. It can be assumed that this is involved in the excellent vibration damping performance.

In addition, the alkyl groups of R1 and Re bonded to this quaternary carbon become so-called side chains, which form the main chain (straight chain).
It has a unique feature of having larger molecules than the other two, and these are thought to be involved in its excellent vibration damping performance.

〔Effect of the invention〕

The present invention is a vibration damping paint obtained by reacting a polyester polyol, which is made by condensation polymerization of a specific diol and a dicarboxylic acid, with a polyisocyanate, so it has excellent vibration damping performance over a wide temperature range, and at the same time has water resistance and heat resistance. , has excellent weather resistance. For this reason, vehicles, boat bottoms, automobiles, equipment,
It can be used for soundproofing and vibration damping purposes in the mechanical and even architectural fields.

〔Example〕

EXAMPLES The present invention will be described in detail below with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited by these examples. The physical properties of the vibration-damping paint of the present invention were measured by the following method.

■ Loss coefficient (η) Two ends of the obtained test piece (rectangular shape) were fixed, vibration of 600 Hz was applied to the test piece, and the loss coefficient was determined from the resonance curve to evaluate the damping performance.

■ When the water resistance test pieces were immersed in running water (at room temperature) for one week, those with no change in the state of the paint film compared to before immersion were marked 0, and those with some leakage were marked Δ. The marks and x marks indicate what was mostly leaked.

■ When the heat resistance test piece was left standing vertically for 1 hour at a temperature of 200°C, those that showed no change in the state of the coating film compared to before heating were marked 0, and some were marked 0. Those in which sagging or the like was observed were marked with a Δ, and those with significant sagging or swelling were marked with an X.

■ A weather resistance test piece was held in a Sunshine Weatherometer for 600 hours and compared with a blank, a 0 mark indicates that no change was observed in the state of the coating film, and a Δ mark indicates that some leakage was observed. , the ones that were mostly leaked are marked with an x.

Example 1 L equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser
146 g of adipic acid (
1,24 g (1,24 mol), 2-butyl-2-ethyl-1,3-propanediol (hereinafter abbreviated as DMII)
mol), antimony dioxide 0.1 as esterification catalyst
Put 5g in, under normal pressure while passing N2 gas, 195~
Esterification reaction was carried out at 220°C for 6 hours.

During the reaction, produced water was distilled off, and by 6 hours of reaction, 35
．． 7 g of produced water was distilled off. Next, the pressure of the 11 reaction system was reduced using a vacuum pump at ambient temperature, and 22.9 g of excess diol in the reaction system was distilled off to obtain 285 g of polyester polyol having a number average molecular weight of about 2,000.

Subsequently, after cooling the reaction solution to room temperature, 480 g of cyclohexanone and 35 g of 4,4'-diphenylmethane diincyanate (hereinafter abbreviated as MDI) were added, and the mixture was heated to 80°C.
Reacted for 2 hours, solid content 40%, viscosity 9400cps
(Nite at 25°C) to obtain a vibration damping paint having a number average molecular weight of 2500G.

Example 2 Azelaic acid 1 was placed in a separable flask similar to Example 1.
Add 88 g (1.0 mol), 80 g (0°5 mol) of DIIH, 98 g (0.74 mol) of 2,2-diethyl-1,3-propanediol (hereinafter abbreviated as DMP), and 0.15 g of antimony dioxide, Esterification reaction temperature of 200-230°C and distillation amount of excess diol 15.4g
Except for the same method as in Example 1, the number average molecular weight was about 2.
000 polyester polyol was obtained.

Subsequently, the reaction solution was cooled to room temperature, and cyclohexanone 5
05g12.4-) 22g of lylene diisocyanate was added, and the solid content was 40% by the same method as in Example 1.
A damping coating solution with a viscosity of 10,500 cps (at 25° C.) and a number average molecular weight of about 24,000 was obtained.

Comparative Example 1 Adipic acid 73g (0.5 mol), isophthalic acid 83g
(0.5 mol), neopentyl glycol 79.8 g (
0,77 mol), ethylene glycol 29.1 g (0,
47 mol) and 0.15 g of antimony dioxide, 225 g of a polyester polyol having a number average molecular weight of about 2000 was obtained in the same manner as in Example 2.

Next, cyclohexanone 400g 1MDI 14g
was added, and the solid content was reduced to 40% by the same method as in Example 2.
A vibration damping paint having a number average molecular weight of about 21,000 was obtained.

Comparative Example 2 As Comparative Example 2, a polyamide epoxy resin and a thickening agent were added to a styrene-acrylic acid ester copolymer emulsion, and then mica was gradually added and mixed to form a vibration-damping coating composition. Obtained. This composition is a styrene-di-functional tylhexyl acrylate copolymer emulsion (
To 100 parts by weight of copolymer composition 1:1), 5 parts by weight of polyamide epoxy resin (Sumirate Resin-650: manufactured by Sumitomo Chemical), mica (StlZORITE MIC)
A vibration damping paint was obtained, which contained 800 parts by weight of &605 (weight average flake diameter 280 μm) and 1031 parts by weight of a thickener (polyvinyl alcohol), and had a solid content of 62% by weight. These were compared with Examples.

Test Example The coating resin composition solutions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 above were applied onto a cold-rolled steel plate with a thickness of 0.8wm, 1300mm, and 50i+m using a spray gun, and the solution was applied at room temperature for a full day.
After drying the painted surface, it was further dried for 2 hours in hot air dryer 4 at 100°C. The coating thickness when completely dry is 0.4
+l1m.

The obtained test piece was evaluated by the method described above.

The evaluation results are shown in Table 1.

As is clear from these tables, the vibration damping paint of the present invention not only has good water resistance, heat resistance and weather resistance when formed into a film, but also has excellent properties in the low to high temperature range. Has vibration damping performance.

No. table that's all

Claims (2)

[Claims] (1) In a paint obtained by reacting a polyester polyol made by condensation polymerization of a diol and a dicarboxylic acid with a polyisocyanate, the diol component has the following formula (I)▲Mathematical formula, chemical formula, table, etc.▼・・・( I) A vibration-damping paint consisting of 2,2-dialkyl-1,3-propanediol represented by (R_1 and R_2 represent an alkyl group having 2 to 4 carbon atoms) alone or in a mixture of two or more. (2) As the dicarboxylic acid component according to the first claim, the following (
II) Formula HOOC(CH_2)_nCOOH...(II) (n=
2-8) A vibration-damping paint consisting of a saturated dicarboxylic acid represented by the following or a mixture of two or more thereof.