JPH05279443A - Urethane resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of a specific mixed polyol and a polyisocyanate compound and giving a vibration-damping material having excellent vibration-damping performance over a wide temperature range from normal temperature to high temperature and free from generation of ill odor and volatile component even at high temperature. CONSTITUTION:The objective composition is composed of two liquid components consisting of (A) a liquid containing a mixed polyol having a hydroxyl value of 200-300mgKOH/g and produced by mixing 30-70wt.% of castor oil with 70-30wt.% of a polyfunctional ricinolate-type polyol and (B) a liquid containing a polyisocyanate compound. The equivalent ratio of the hydroxyl group of the component A to the NCO group of the component B is 0.6-1.2. The polyfunctional ricinolate-type polyol can be produced by modifying castor oil with a polyhydric alcohol such as glycerol. The component B is preferably an aromatic polyisocyanate compound such as diphenylmethane diisocyanate. The above composition is molded usually at a temperature between room temperature and 100 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a two-pack type urethane resin composition.

[0002]

2. Description of the Related Art Conventionally, as a damping material, a material in which a filler or the like is added to an asphalt material is known. However, such a material has a drawback that it softens and produces a bad odor at a high temperature of about 40 to 70 ° C. Further, a foam obtained by mixing a polyol and a polyisocyanate compound with a foaming agent, a catalyst, a foam stabilizer and other additives is also used as a vibration damping material. Not satisfactory.

By the way, it is generally known that a damping material made of a cured resin has a large loss coefficient at the glass transition point. Therefore, it has been attempted to add a plasticizer to the resin composition to adjust the glass transition point so as to exhibit appropriate vibration damping performance. However, when such a material is used at a high temperature, the plasticizer volatilizes and the vibration damping performance is changed.

[0004]

It is an object of the present invention to have excellent vibration damping performance in a wide temperature range from room temperature to high temperature, and to have excellent vibration damping without generating an offensive odor or volatile component even at high temperature. To provide the material.

[0005]

Means for Solving the Problems The present inventor has conducted extensive studies to solve the above problems. As a result, a urethane molding obtained by using a mixed polyol composed of castor oil and a polyfunctional ricinoleate-based polyol as a polyol component and mixing the same with a polyisocyanate compound was excellent in a wide temperature range from normal temperature to high temperature. It has been found that the vibration damping performance can be exhibited, and the present invention has been completed here.

That is, the present invention is a mixed polyol comprising (I) castor oil and a polyfunctional ricinoleate type polyol, which comprises 30 to 70% by weight of the former and 70 to 30% by weight of the latter. , Hydroxyl value is 20
A liquid A containing a mixed polyol of 0 to 300 mgKOH / g and a liquid B containing a (II) polyisocyanate compound. /OH=0.6 to 1.2 The present invention relates to a two-pack type urethane resin composition.

In the urethane resin composition of the present invention, a mixed polyol composed of castor oil and a polyfunctional ricinolate type polyol is used as the polyol component.

Castor oil is a triglyceride containing ricinoleic acid (12-hydroxyoleic acid) as a main component, and about 90% by weight of its constituent fatty acids is ricinoleic acid, and most of the remaining fatty acids have no hydroxyl group. And is a ricinoleate-based polyol having a hydroxyl group of about 2.7 in the molecule. As a specific example of castor oil, Yulic H-30 (trade name, manufactured by Ito Oil Co., Ltd., hydroxyl value 1)
60 mg KOH / g, viscosity 700 cP / 25 ° C.) and the like.

The polyfunctional ricinolate type polyol is obtained by modifying castor oil with a polyhydric alcohol, and is preferably a polyfunctional ricinoleate polyol having a functionality of about 4 to 5. Examples of the polyhydric alcohol used for modification include glycerin, trimethylolpropane, pentaerythritol, and sorbitol. Specific examples of the polyfunctional ricinoleate-based polyol suitable for use in the present invention include Yulic H-105 (trade name, manufactured by Ito Oil Co., Ltd.).

The compounding ratio of castor oil and polyfunctional ricinoleate-based polyol is based on the total amount of both and the former 30
˜70% by weight, the latter 70 to 30% by weight, and the hydroxyl value of the mixed polyol is 200 to 300 mg.
It should be about KOH / g. Hydroxyl value is 200m
If it is less than gKOH / g, the temperature at which the maximum vibration damping performance is obtained, that is, the temperature at which the loss coefficient (η) becomes maximum becomes extremely low, and the vibration damping performance at high temperature becomes insufficient, which is not preferable. Further, when the hydroxyl value exceeds 300 mgKOH / g, the temperature at which the loss coefficient becomes maximum becomes too high, and the vibration damping performance at low temperature becomes insufficient, which is not preferable.

In the urethane resin composition of the present invention, the temperature at which the loss coefficient becomes maximum is in the range from room temperature to high temperature by appropriately adjusting the compounding ratio of the castor oil and the polyfunctional ricinolate type polyol within the above range. It can be appropriately adjusted, and a material having excellent vibration damping performance in all temperature ranges from normal temperature to high temperature can be easily obtained.

The polyisocyanate compound used in the present invention is preferably an aromatic polyisocyanate compound, for example, the following general formula:

[0013]

[Chemical 1]

An isocyanate compound represented by the formula (wherein n is 0 to 2) can be mentioned. The polyisocyanate compound can be used alone or in combination of two or more. Specific examples of the polyisocyanate compound include diphenylmethane diisocyanate with n = 0 in the above general formula, and polymeric MDI (polymethylene polyphenyl polyisocyanate) with n = 0-2.

The urethane resin composition of the present invention is a two-part type composed of solution A containing the above-mentioned mixed polyol and solution B containing the polyisocyanate compound.
Further, if necessary, the liquid A may contain a foam stabilizer such as a silicon-based surfactant, an antifoaming agent, an organometallic compound such as dibutyltin dilaurate, a curing catalyst such as silanes, a valve stem, yellow lead, carbon black, or an oxidation agent. Organic or inorganic coloring pigments such as titanium, silica, calcium carbonate, clay, talc, mica, ferrite, barium sulfate, inorganic fillers such as graphite, fine silica powder, red phosphorus, aromatic bromine compounds, tri Flame retardants such as cresyl phosphate and aluminum hydroxide can be blended, and surface-treated calcium carbonate obtained by treating light calcium carbonate with a fatty acid, a resin acid or the like can be blended as a thixotropic agent.

Further, if necessary, a phthalic acid ester such as dioctyl phthalate, diisononyl phthalate, diundecyl phthalate, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, etc. may be added to the liquid A or the liquid B as a plasticizer. It is also possible to add the phosphoric acid ester of the above.

In the urethane resin composition of the present invention, the mixing ratio of the liquid A and the liquid B is such that the equivalent ratio of the hydroxyl group of the polyol in the liquid A and the isocyanate group of the polyisocyanate compound in the liquid B is NCO / OH = 0. It may be 6 to 1.2.

The method for molding the urethane resin composition of the present invention is not particularly limited and may be a conventional method, but it is preferable to use an automatic casting machine for mixing two liquids. Further, urethane foam may be prepared by adding a blowing agent or by forcibly mixing air into the urethane resin composition using an automatic casting machine without adding a blowing agent.

The molding temperature may be usually room temperature to about 100 ° C.

[0020]

According to the urethane resin composition of the present invention,
It is possible to provide an excellent vibration damping material that has excellent vibration damping performance in a wide temperature range from room temperature to high temperature and that does not generate a bad odor or a volatile component even at a high temperature.

[0021]

EXAMPLES The present invention will be described in more detail with reference to examples.

Examples 1 to 3 Urethane resin compositions having the respective formulations (parts by weight) shown in Table 1 below were well mixed and stirred, and cured at 60 ° C. for 16 hours to obtain urethane cured products. Obtained sample (30 mm x
3 mm x 2 mm), using a high-frequency viscoelasticity spectrometer (manufactured by Iwamoto Seisakusho), measuring frequency 110H
z, the loss coefficient (η) of the urethane cured product was measured in the measurement temperature range of −50 to 100 ° C. Table 1 shows the loss coefficient at 4 ° C and 73 ° C, the maximum value of the loss coefficient and the temperature thereof.

[0023]

[Table 1]

(* 1) Trade name: Yurick H-30, manufactured by Ito Oil Co., Ltd. (* 2) Trade name: Yurick H-105, Ito Oil Co., Ltd.
(* 3) Polyphenylmethane polyisocyanate, trade name: Millionate MR-200, Nippon Polyurethane Industry Co., Ltd. As can be seen from the above results, the vibration damping material obtained from the urethane resin composition of the present invention is at a low temperature. It has excellent vibration damping performance from high to high temperature.

Comparative Example 1 100 parts by weight of polypropylene glycol (PPG-2000, Sanyo Kasei Co., Ltd.) was used for crude MDI (*).
3) 17 parts by weight were mixed and the loss coefficient of the material obtained by curing at 60 ° C. for 16 hours was measured by the same method as in the example. As a result, the maximum loss coefficient was 0.60 at −70 ° C., and the loss coefficient was reduced to 0.05 at −50 ° C., and only vibration damping performance was obtained at very low temperatures.

Comparative Example 2 100 parts by weight of polybutadiene-based polyol (R-45HT, manufactured by Idemitsu Petroleum Co., Ltd.) was added to crude MDI (*).
3) 11 parts by weight were mixed, and the loss coefficient of the material obtained by curing at 60 ° C. for 16 hours was measured by the same method as in the example. As a result, the maximum loss coefficient was 0.80 at −60 ° C., and the loss coefficient was reduced to 0.05 at −50 ° C., and only vibration damping performance was obtained at very low temperatures.

Comparative Example 3 27 parts by weight of diaminodiphenylmethane (DDM, Mitsui Toatsu Kagaku Co., Ltd.) was mixed with 100 parts by weight of an epoxy resin (Epicoat 828, Oil Shell Epoxy Co., Ltd.), and the mixture was mixed at 16 ° C. at 100 ° C. The loss coefficient of the material obtained by time-curing was measured by the same method as in the example. As a result, the maximum loss coefficient was 0.80 at 155 ° C,
At 0 ° C., the loss factor decreased to 0.05, and only vibration damping performance was obtained at very high temperatures.

Comparative Example 4 40 parts by weight of asphalt having a softening temperature of 50 ° C. was added to 200 ° C.
Talc 4 with a weight average flake diameter of 10 μm
The loss coefficient of the material obtained by mixing 5 parts by weight and 15 parts by weight of white mica having a weight average flake diameter of 340 μm and pouring the mixture into a mold was measured in the same manner as in the example. As a result, the maximum value of the loss factor becomes 0.5 at 50 ° C,
Above 0 ° C, it softened and the loss factor could not be measured, and it could be used as a damping material only in the low temperature range.

Loss factor measurement test On a 400 mm × 25 mm × 0.8 mm iron diaphragm,
The damping material of each of Examples 1 to 3 and Comparative Examples 1 to 4 (40
(0 mm x 25 mm x 1.6 mm) is adhered to the test piece, and the part 25 mm from the end is used as a gripping margin, and at a frequency of 300 Hz, at 23 ° C and 40 ° C by a vibration lead method.
And the loss factor at 60 ° C. were measured. The results are shown in Table 2.

[0030]

[Table 2]

From the above results, it is understood that the damping material of the present invention has excellent damping performance in a wide temperature range from normal temperature to high temperature.

Claims (1)

[Claims] 1. A mixed polyol comprising (I) castor oil and a polyfunctional ricinoleate-based polyol, the former 30 to 70% by weight and the latter 70 to 70% by weight based on the total amount of both.
30% by weight, with a hydroxyl value of 200-300 mgK
It is composed of a liquid A containing a mixed polyol of OH / g and a liquid B containing a (II) polyisocyanate compound, and the equivalent ratio of the hydroxyl group of the polyol to the isocyanate group of the polyisocyanate compound is NCO / OH.
= 0.6 to 1.2, a two-component urethane resin composition.