JPH04202316A - Resin composition for vibration-damping steel plate - Google Patents

Abstract

PURPOSE:To provide the subject composition containing saturated polyesters having respective specific glass transition temperatures and a glass transition temperature difference falling within a specific temperature range and a specific polycyanate, having excellent vibration-damping performance and coating property and useful for automobile, etc. CONSTITUTION:The objective composition contains (A) a saturated polyester having a glass transition temperature of <=-10 deg.C, (B) a saturated polyester having a glass transition temperature of >=0 deg.C and (C) a polycyanate (e.g. 1,3- dicyanatobenzene) selected from polyfunctional cyanic acid ester having >=2 cyanato groups in the molecule and a prepolymer of the polyfunctional cyanic acid ester. The difference between the glass transition temperatures of the component B and the component A is 10-150 deg.C. The weight ratio of A/B is preferably 20/80 to 80/20 and the weight ratio of (A+B)/C is preferably 80/20 to 99/1.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition for vibration-damping steel plates. More specifically, the present invention relates to a resin composition for damping steel plates that can be suitably used as a damping material in fields where structural vibration is a problem, such as electric washing machines, vacuum cleaners, automobiles, and bridges.

[Conventional technology]

In fields where vibration is a structural problem, damping materials are generally used. Conventionally, polyester-urethane resin compositions have been mainly used for such vibration damping materials (Japanese Patent Application Laid-Open No. 63-207809, Japanese Patent Application Laid-Open No. 63-1989).
-2021313, JP 63-48321, JP 62-295949).

However, polyester-urethane resin compositions have a short pot life, which is the time during which they can maintain an appropriate viscosity during coating, and the viscosity of the system increases, resulting in poor coating workability. However, there are problems in that the resulting coating film has uneven coating and a decrease in surface smoothness.

[Problem to be solved by the invention]

The present invention has been made in view of the above-mentioned prior art,
The object of the present invention is to provide a resin composition for vibration-damping steel plates that has excellent coating workability, has a wide distribution temperature range which is important as a vibration-damping material, and has excellent adhesiveness to a base material.

[Means to solve the problem]

The present invention comprises (A) a saturated polyester having a glass transition temperature of 110°C or lower; (B) a saturated polyester having a glass transition temperature of 0°C or higher;
B), and (C) a polycyanato selected from a polyfunctional cyanate ester containing two or more cyanato groups in the molecule and a prepolymer of the polyfunctional cyanate ester, and the saturated polyester ( The present invention relates to a resin composition for vibration-damping steel plates in which the difference between the glass transition temperature of B) and the glass transition temperature of the saturated polyester (A) is 10 to 150°C.

[Function and Examples]

As mentioned above, the resin composition for damping steel sheets of the present invention comprises: (A) a saturated polyester having a glass transition temperature of -IO°C or lower; (B) a saturated polyester having a glass transition temperature of 0°C or higher;
B) and (C) contain a polycyanato selected from a polyfunctional cyanate ester containing two or more cyanato groups in the molecule and a prepolymer of the polyfunctional cyanate ester.

As described above, since the resin composition for damping steel sheets of the present invention is a blended resin composition of polyester and cyanato compound, its viscosity is close to that of polyester, and it has good coating workability. The resulting damping material has physical properties comparable to those of conventional materials.

In addition, in the present invention, since two types of saturated polyesters having different glass transition temperatures and being incompatible are used, namely saturated polyester (A) and saturated polyester (B), the resulting damping material can be One of its characteristics is that the swing area is extremely wide.

The saturated polyester (A) has a glass transition temperature of -1
The temperature is below 0°C. Such a glass transition temperature is -1
If the temperature is higher than 0°C, vibration damping characteristics near room temperature will be insufficient. The preferred glass transition temperature is -80 to -10°C
, and <-70 to -10°C. In addition, if the number average molecular weight of the saturated polyester (A) is too large, the coating properties will be poor, and if it is too small, it will be difficult to obtain sufficient vibration damping properties. 1000~50000, especially 2000~
Preferably, it is aoooo.

The saturated polyester (A) can be obtained, for example, by reacting a dicarboxylic acid and a polyol.

Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1.5-naphthalenedicarboxylic acid, 2.6-naphthalenedicarboxylic acid, and 4.4'
- Aromatic dicarboxylic acids such as biphenyldicarboxylic acid and 5-sodium sulfoisophthalic acid; Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1.2-cyclohexanedicarboxylic acid: Examples include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and dimer acid; oxycarboxylic acids such as p-oxybenzoic acid, and these dicarboxylic acids may be used alone or in combination with two It is used by mixing more than one species.

In addition, examples of the polyol include neopentyl glycol, neopentyl glycol hydroxypivalate, ethylene glycol, propylene glycol,
, 3-butanediol, 1,4-butanediol, ■,
5-bentanediol, 3-methylbentanediol,
l, 6-hexanediol, 1,9-nonanediol,
Aliphatic glycols such as diethylene glycol; l, 4
-Alicyclic diols such as cyclohexane dimetatool and tricyclodecane dimethylol; ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol S, propylene oxide of bisphenol S Examples include aromatic ring-containing glycols such as adducts,
These polyols may be used alone or in combination of two or more.

The molar ratio of the dicarboxylic acid to the polyol is usually 1. [l: LO~LO: 3.0, nakandzu < 1
．． 0: 1.05-1. 〇 It is preferable to adjust it so that it becomes 2.0.

The saturated polyester (B) has a glass transition temperature of 0°C.
That's all. If the glass transition temperature is lower than 0°C, it becomes difficult to change the allocation characteristics at temperatures above room temperature. The preferred glass transition temperature is 0 to 100
°C, <10 to 100 °C. In addition, if the number average molecular weight of the saturated polyester (B) is too large, the coating properties will be poor, and if it is too small, it will not be possible to obtain sufficient vibration damping properties. ~50000, Nakakan<1000
It is preferably 30,000 to 30,000.

The saturated polyester (B) can be obtained, for example, by reacting a dicarboxylic acid and a polyol.

Examples of the dicarboxylic acid and polyol include those used when preparing the saturated polyester (A) described above.

The molar ratio of the dicarboxylic acid to the polyol is usually 1.0:1, 0-1.0:3.0, <1.0:L, 05-1.0+2.0. It is preferable to adjust so that

Glass transition temperature (TB) of the saturated polyester (B)
and the glass transition temperature (T
) The difference (TB-TA) is adjusted to be 10 to 150°C. If this difference (T - TA) is smaller than 10°C, the temperature range showing damping properties tends to become narrower, and if it exceeds 150°C, the damping properties in that temperature range tend to become narrower. descend. In addition, the above difference (
T-TA) is preferably 20-120°C, preferably <20-100°C.

The saturated polyester (A) and the saturated polyester (
The blending ratio of B) is usually 0.5:995 to 99 by weight.
．． 5+ 0.5, preferably 10:90-90・IO
The ratio is more preferably 20:80 to 80:20.

If the proportion of the saturated polyester (A) is outside the above range, it is not possible to expect a wider temperature range that exhibits vibration damping properties.

As a representative example of the polyfunctional cyanate ester containing two or more cyanato groups in the molecule, for example,
): % Formula %( ) (wherein R is an aromatic organic group, m is an integer of 2 or more, preferably 2 or 3). Specific examples of the polyfunctional cyanate ester include:
For example, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3゜5-tricyanatobenzene, 1
．． 3-dicyanatonaphthalene, 1.4-dicyanatonaphthalene, 1.6-dicyanatonaphthalene, 1.8-dicyanatonaphthalene, 2.6-dicyanatonaphthalene, 2
．． 7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4゜4'-dicyanatobiphenyl, bis(4-cyanatophenyl)methane, 2,2-bis(4-
cyanatophenyl)propane, 2,2-bis(3,5-
dichloro-4-cyanatophenyl)propane, 2.2-
Bis(3゜5-bromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis(
4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulpone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate, reaction products of novolak and cyanogen halide, etc. can give.

Further, the polyfunctional cyanate ester can be used as a prepolymer obtained by polymerization in the presence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, or a phosphate ester such as tributylphosphine. can. These prepolymers generally have in their molecules a 5yl-triazine ring formed by trimerization of the cyanide groups in the cyanate ester. In the present invention, it is preferable to use the prepolymer having a number average molecular weight of 300 to eooo.

Moreover, the polyfunctional cyanate ester can also be used in the form of a prepolymer with an amine. Examples of amines that can be suitably used include meta- or para-phenylene diamine, meta- or para-xylylene diamine,
．． 4- or 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4'-diaminobiphenyl, bis(4-aminophenyl)methane, bis(4-
aminophenyl) ether, bis(4-aminophenyl) sulfone, bis(4-amino-3-methylphenyl)
Methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-aminophenyl)cyclohexane, 2.2-bis(4-aminophenyl)propane, 2,
2-bis(4-amino-3-methylphenyl)propane, 2.2-bis(4-amino-3-chlorophenyl)propane, bis(4-amino-3-chlorophenyl)methane, 2.2-bis(4 -Amino-3゜5-dibromophenyl)propane, bis(4-aminophenyl)phenylmethane, 3.4-diaminophenyl-4-aminophenylmethane, ■, 1-bis(4-aminophenyl)-1-
Examples include phenylethane.

The polyfunctional cyanate esters, their prepolymers and prepolymers with amines can be used as mixtures.

The saturated polyester (A) and the saturated polyester (
B) and polycyanato are usually 70': 30-99.
They are mixed at a weight ratio of 5:0.5, preferably 80:20 to 99:1. In addition, if the ratio of the saturated polyester (A) and the saturated polyester (B) is smaller than the above range, sufficient vibration damping properties cannot be obtained.
Moreover, if it is larger than the above range, the adhesive strength with the base material and heat resistance tend to decrease.

The saturated polyester (A) and the saturated polyester (
B) and by blending the polycyanato,
The resin composition for vibration-damping steel plates of the present invention can be obtained, but when used, the resin composition for vibration-damping steel plates is usually dissolved in a solvent. When the resin composition for vibration-damping steel plates of the present invention is dissolved in a solvent and used, the concentration is usually 10 to 80% (weight %, the same shall apply hereinafter), especially 20 to 80%.
It is adjusted to 70%. Examples of the solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isophorone, and cyclohexanone.

In addition, various fillers, coupling agents, leveling agents, colorants, etc. may be appropriately blended into the resin composition for damping steel plates of the present invention, if necessary.

Next, the resin composition for damping steel plates of the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1 055 mol of isophthalic acid, 0.45 mol of sehanic acid, 0.52 mol of ethylene glycol, 0.25 mol of neopentyl glycol and 0.23 mol of triethylene glycol.
mol of saturated polyester (A) (glass transition temperature: 20°C, number average molecular weight: 20,000), 0.8 mol of terephthalic acid, 0.2 mol of isophthalic acid, 0.75 mol of ethylene glycol and tricyclodecane dimethylol. Saturated polyester (B
) (Glass transition temperature: 90°C, number average molecular weight: 100
00) in a weight ratio of 50:50.

The saturated polyester (A) and the saturated polyester (
2.2-bis(4-cyanatophenyl)propane (manufactured by Mitsubishi Gas Chemical, BT2000) was added to 95 parts by weight of resin solids in the 40% cyclohexanone solution of the mixture B)
) were mixed together in an amount of 5 parts by weight to obtain a coating liquid for a resin composition for damping steel plates.

First, the stability of the coating solution was investigated, and then the obtained coating solution was applied onto a steel plate using a roll coater so that the thickness of the coating after drying was 50 μm, and then the coating solution was dried in a hot air dryer. and dried at 180° C. for 3 minutes. The condition of the coating film at this time was examined. Furthermore, a steel plate without a coating film was placed on top of the coating film on this steel plate, and heat treated with a pressure horn of 10 kg/cm2 at a temperature of 230°C for 3 minutes. ．． A composite steel plate with a resin layer formed between two steel plates was obtained.

As physical properties of the obtained composite steel plate, the damping characteristics of the damping peak temperature, maximum loss coefficient, temperature range of loss 0.1 or more, T-peel strength, and shear strength were investigated.

The results are shown in Table 1.

The methods for measuring various physical properties are as shown below.

(a) Stability of coating solution The coating solution was left at 40° C., and the time until gelation occurred was measured.

(b) Coating unevenness It is expressed as the difference (μm) between the target coating film thickness and the actual coating film thickness.

(c) Painted surface condition Visually observe the condition of the painted surface.

(d) Damping characteristics B & using an automatic vibration damping measurement system manufactured by
Measurement is performed by determining the loss coefficient at various temperatures at 50117.

(i) The damping peak temperature is the temperature at which the maximum loss coefficient is exhibited.

(ii) The temperature range where the loss is 0.1 or more is the loss coefficient or 0.1
The range of temperatures within which the temperature remains is shown.

(iii) Ttll separation strength (kgf/25+nm)
: According to JISK-Ef854 (sample width is 25a++n, tensile speed is 10mm/ff1in).

(iv) Shear strength (kgr/cm2): JISK
- According to 6850 (the vertical width of the sample piece is 10+n
m, the width is 35+nm, and the tensile speed is 5 mm/min).

Example 2 Saturated polyester (A) consisting of 0.5 mol of terephthalic acid, 0.5 mol of isophthalic acid, 0.45 mol of ethylene glycol and 0.55 mol of triethylene glycol (
Glass transition temperature: 10℃, number average molecular weight: 2000
0 ), isophthalic acid 055 mol, sebacic acid 0.4 mol
Saturated polyester (B) consisting of 5 mol, 0.85 mol of ethylene glycol and 0.15 mol of tricyclodecane dimethylol (glass transition temperature 0°C, number average molecule j
i: 20000) at a weight ratio of 50:50.

The saturated polyester (A) and the saturated polyester (
5 parts by weight of 2,2-bis(4-cyanatophenyl)propane is mixed with 95 parts by weight of the resin solid content in the 40% cyclohexanone solution of the mixture B) to coat the resin composition for damping steel sheets. I got the industrial fluid.

A composite steel plate was obtained in the same manner as in Example 1 using the obtained coating liquid.

Various physical properties of the obtained coating liquid and composite steel plate were investigated in the same manner as in Example 1. The results are shown in Table 1.

Example 3 0.7 moles of isophthalic acid, 03 moles of sebacic acid, 02 moles of ethylene glycol, and 0 moles of triethylene glycol
．． 8 mol of saturated polyester (A) (glass transition temperature: 60°C, number average molecular weight + 2000), 0.5 mol of terephthalic acid, 0.55 mol of isophthalic acid, 0.75 mol of ethylene glycol and 0 mol of tricyclodecane dimethylol. Saturated polyester (B) consisting of .25 mol
(Glass transition temperature = 90°C, number average molecular weight: 1500
0) and were mixed at a weight ratio of 40:fiO.

The saturated polyester (A) and the saturated polyester (
To 90 parts by weight of the resin solid content in the 40% cyclohexanone solution of the mixture B), 10 parts by weight of (1),6-dicyanatonaphthalene was mixed to obtain a coating liquid of a resin composition for vibration-damping steel plates.

A composite steel plate was obtained in the same manner as in Example 1 using the obtained coating liquid.

Various physical properties of the obtained coating liquid and composite steel plate were investigated in the same manner as in Example 1. The results are shown in Table 1.

Example 4 0.55 mol of isophthalic acid, 0.45 mol of sebacic acid,
0.52 mol of ethylene glycol, 0.25 mol of neopentyl glycol and 0.2 mol of triethylene glycol
3 moles of saturated polyester (A) (glass transition temperature: 20°C, number average molecular weight: 20,000), 0.25 moles of terephthalic acid, 0.5 moles of isophthalic acid, 0.25 moles of sebacic acid, 0.25 moles of ethylene glycol. 5 mol, neopentyl glycol 0.25 mol and tricyclodecane dimethylol 0.25 mol saturated polyester (B) (glass transition temperature: 30°C, number average molecular weight: 15000) in a weight ratio of 60:40. mixed in proportion.

The saturated polyester (A) and the saturated polyester (
20 parts by weight of 1,4-dicyanatobenzene was mixed with 80 parts by weight of the resin solid content in the 40% cyclohexanone solution of the mixture B) to obtain a coating liquid of a resin composition for vibration-damping steel plates.

A composite steel plate was obtained in the same manner as in Example 1 using the obtained coating liquid.

Various physical properties of the obtained coating liquid and composite steel plate were investigated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 95 parts by weight of the same polyester as used in Example 1 and polyisocyanate compound (Coronet) L, manufactured by Nippon Polyurethane Co., Ltd., resin solid content = 70%, isocyanate concentration: 11.5%)7. 1 part by weight was mixed to obtain a coating liquid of a resin composition for damping steel plates.

Next, a composite steel plate was produced in the same manner as in Example 1 using the obtained coating liquid, and its physical properties and various physical properties of the coating liquid were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 100 mol of adipic acid and 1 mol of neopentyl glycol
Polyester diol (hydroxyl value:
5f3KOt1mg/g, number average molecular weight: 2000
) was prepared.

In a reaction vessel equipped with a thermometer, stirrer, and reflux condenser, 50 parts by weight of toluene and 50 parts by weight of methyl ethyl ketone were added.
parts by weight, and then the polyester diol 10
0 parts by weight was added and dissolved.

Next, 16.5 parts by weight of isophorone diisocyanate and 0.02 parts by weight of dibutyltin dilaurate were added, and 70 parts by weight of
After reacting at -80°C for 3 hours, 5 parts by weight of 4,4-diaminodiphenylmethane was added, and the reaction was further carried out at 70-80°C for 4 hours. During this time, as the viscosity increased, 94 parts by weight of toluene and 94 parts by weight of methyl ethyl ketone were added to adjust the resin solid content concentration to 30%.

A composite steel plate was produced in the same manner as in Example 1 using the obtained polyurethane (glass transition temperature: 32°C, number average molecular weight: 52,000), and its physical properties and various physical properties of the coating liquid were the same as in Example 1. I looked it up. The results are shown in Table 1.

[Margin below]

As is clear from the results shown in Table 1, the resin composition for vibration-damping steel plates of the present invention obtained in the examples exhibits uneven damping properties over a wide temperature range, and also has excellent vibration damping characteristics with the base material. The adhesive strength and coating properties are good, so it can be seen that it is suitable for use as a vibration damping material.

[Effects of the invention] The resin composition for damping steel plates of the present invention has better damping properties and coatability than conventional resin compositions for damping steel plates, so it is suitable as a vibration damping material. It is used by Uruchino.

Patent applicant Nippon Gosei Kagaku Gyokugyo Co., Ltd. Teitouri Nehosho (self-proposal) February 12, 1992 Case 1 Indication 1990 Patent Application No. 334411 Name of the invention Resin composition for vibration-damping steel plates 3 Relationship with the case of the person making the amendment Patent Applicant Address 9-6 Nozaki-cho, Kita-ku, Osaka Name (410) Nippon Gosei Kagaku Kogyo Co., Ltd. Representative Masaru Ohashi - 4 Agent 540 Address Chuo, Osaka City 2-2-22, Tanimachi, Ward 5 Subject of amendmentfl) Contents of the sleeve correction in column 6 of “Detailed Description of the Invention
” he corrected.

that's all

Claims (1)

[Claims] 1 (A) A saturated polyester having a glass transition temperature of -10°C or lower (B) A saturated polyester having a glass transition temperature of 0°C or higher (
B), and (C) a polycyanato selected from a polyfunctional cyanate ester containing two or more cyanato groups in the molecule and a prepolymer of the polyfunctional cyanate ester, and the saturated polyester ( The difference between the glass transition temperature of B) and the glass transition temperature of the saturated polyester (A) is 10 to
A resin composition for vibration-damping steel plates having a temperature of 150°C.