JP2001342234A - Urethane composition for damping and vibration isolation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane composition for damping and vibration isolation that is suitable for buildings, motor vehicles, railways, vessels, aircraft, industrial equipment, household electrical appliances, and the like of which the structures require the damping and vibration isolation properties. SOLUTION: The objective damping and vibration isolation urethane composition is produced by mixing the composition (I) that mainly comprises polyisocyanate in which the equivalent ratio of the isocyanate group in the polyisocyanate (A) to the hydroxyl group in the polyol (B) is 0.1-1.3 (NCO/OH equivalent ratio) with the composition (II) that mainly comprises polyol (B) and allowing them to react with each other wholly or partially. In this case, the composition (I) includes 0.1-100 pts.wt. of inorganic filler per 100 pts.wt. of the component (A) and the composition (II) does 0.1-100 pts.wt. of inorganic filler per 100 pts.wt. of the component (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane-based composition for vibration damping / vibration control, and more particularly to buildings, automobiles, railways, ships, and the like, which require structural damping / vibration control. The present invention relates to a urethane-based composition suitable for vibration control and vibration isolation suitable for aircraft, industrial equipment, home electric appliances and the like.

[0002]

2. Description of the Related Art Various types of rubber-like substances, bituminous substances, thermoplastic resins, and the like include, for example, mica,
Some include inorganic fillers such as carbon black, calcium carbonate, and barium sulfate, and various fibers. However, these have many processing steps and construction steps, and
There are many limitations such as complexity, and there is a problem in practical use. Also, some urethane-based materials have entered the testing stage, but they have not yet reached a satisfactory level in terms of vibration damping and vibration isolation, and there are obstacles in terms of cost. Therefore, a material having low elasticity (60 or less in type D durometer hardness) and high loss factor (tan δ) is desired.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and has a low elasticity and a high loss coefficient (tan δ) excellent in vibration damping and vibration proof performance. An object of the present invention is to provide a urethane-based composition. In addition,
The loss coefficient (tan δ) described here is a value obtained from the ratio of the storage elastic modulus and the loss elastic modulus obtained by the dynamic viscoelasticity measurement, and is used as one measure of the vibration damping and vibration isolation performance.

[0004]

According to the present invention, the equivalent ratio of the isocyanate group in the polyisocyanate compound (A) to the hydroxyl group in the polyol compound (B) is from 0.1 to 0.1.
1.3 (NCO / OH equivalent ratio), and a composition (I) containing a polyisocyanate compound (A) as a main component and a composition (II) containing a polyol compound (B) as a main component are mixed. A part or all of the isocyanate group in the composition (I) and a part or all of the hydroxyl group in the composition (II). The composition (I) is an isocyanate compound (A)
100 parts by weight, inorganic filler (C) 0.1 to 100
It is preferable to use a mixture of parts by weight. Further, the composition (II) is preferably a composition in which 0.1 to 100 parts by weight of the inorganic filler (D) is blended with respect to 100 parts by weight of the polyol compound (B).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The polyisocyanate compound (A) used in the present invention includes, for example, aliphatic,
Examples thereof include aromatic and alicyclic polyisocyanate compounds. This polyisocyanate compound (A)
Specific examples of xylylene diisocyanate, polyphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, water Examples include isocyanate compounds such as added xylylene diisocyanate and dicyclohexylmethane diisocyanate, and polymers thereof. These compounds can be used alone or in combination of two or more.
The use of an aliphatic or alicyclic polyisocyanate as the polyisocyanate compound (A) is suitable for lowering the elasticity and lowering the hardness of the urethane composition for vibration damping and vibration damping of the present invention.

The polyisocyanate compound (A)
Can be used in the form of a prepolymer having an isocyanate group at a terminal obtained by reacting the above isocyanate compound with an active hydrogen compound such as a polyamine compound. This prepolymer is obtained by reacting the above isocyanate compound with an active hydrogen compound such as a polyamine compound at a normal reaction temperature, for example, 20 to 90 ° C. for 1 to 6 hours. Here, examples of the polyamine compound include ethylenediamine, hexamethylenediamine, and the like. Further, a compound having an allophanate bond, an isocyanurate bond, a carbodiimide bond, or the like in the molecule and having an isocyanate group at a terminal, for example, a condensate of diphenylmethane diisocyanate can be used as the polyisocyanate compound (A). Further, a part of the polyisocyanate compound (A) may be preliminarily reacted with the polyol compound (B) and used in the form of a prepolymer having an isocyanate group at a terminal. As the number of functional groups of the polyisocyanate compound (A), those having two or more functional groups are preferably used.

Next, the polyol compound (B) used in the present invention includes, for example, ethylene glycol, propylene glycol, polypropylene glycol, trimethylolpropane, diethylene glycol,
Triethylene glycol, hexamethylene glycol,
Polyhydric alcohols such as glycerin, 1,3-butylene glycol, 1,4-butanediol, hexanetriol, pentaerythritol, sorbitol, neopentyl glycol; and the above polyhydric alcohols and alkylene oxides such as ethylene oxide and propylene oxide Polyether polyols such as compounds obtained by addition polymerization; polyesters obtained by a condensation reaction of the above polyhydric alcohols with polybasic acids such as maleic acid, succinic acid, adipic acid, sebacic acid, tartaric acid, terephthalic acid and isophthalic acid Polyol compounds; polyester polyols obtained by ring-opening polymerization with lactones such as ε-caprolactone and γ-valerolactone; hydroxyethyl acrylate, hydroxybutyl acrylate, trimethylolpropane A polymerizable monomer having a hydroxyl group such as an acrylic acid monoester is polymerized alone, or a monomer copolymerizable therewith, for example, acrylic acid, methacrylic acid, styrene, acrylonitrile, obtained by copolymerizing α-methylstyrene and the like. Castor oil or a derivative thereof; an epoxy polyol compound obtained by reacting an epoxy resin having epoxy groups at both ends with monoethanolamine, diethanolamine, or the like. The above polyol compound (B)
Can be used singly or as a mixture of two or more. Further, a part of the polyol compound (B) can be reacted with the polyisocyanate compound (A) in advance and used in the form of a prepolymer having a hydroxyl group at a terminal.

As the number of functional groups of the polyol compound (B), those having 2 or more functional groups are preferably used.
Monools having one functional group are also used as necessary to reduce the elasticity of the composition. In the polyol compound (B), the ratio of the hydroxyl group contained in the high molecular weight polyol compound having an average molecular weight per hydroxyl group of 500 or more is preferably 10 to 100 equivalent% of all the hydroxyl groups, more preferably 20 to 100%. 100 equivalent%, particularly preferably 3
0 to 80 equivalent%. If it is less than 10 equivalent%, the elastic modulus and hardness of the urethane composition are undesirably high.

A primary or secondary amine compound can be added to the urethane composition of the present invention in order to prevent the composition from sagging when applied to an adherend. This primary or secondary amine compound is usually added to the composition (II) containing the polyol compound (B) as a main component. Specific examples of the primary or secondary amine compound include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenehexamine, and pentaethylenehexamine; and fatty acids such as cyclohexylenediamine, dicyclohexylmethanediamine, and isophoronediamine. Cyclic polyamines; aromatic polyamines such as phenylenediamine, tolylenediamine, xylylenediamine, diphenylmethanediamine, and polyphenylmethanepolyamine; and heterocyclic polyamines such as piperazine and aminoethylpiperazine. The above amine compounds can be used alone or in combination of two or more.
The addition amount of these amine compounds is preferably 0 to 5 parts by weight based on 100 parts by weight of the polyol compound (B).

Further, a curing catalyst may be added to the urethane composition of the present invention in order to accelerate the curing of the composition. This curing catalyst is usually added to the composition (II) containing the polyol compound (B) as a main component.
Examples of the curing catalyst include stannous carboxylate such as stannous acetate, stannous octoate, stannous laurate, and stannous oleate; dibutyltin acetate;
Dialkyltin salts of carboxylic acids such as dibutyltin dilaurate, dibutyltin diacetate and dioctyltin diacetate; trialkyltin hydroxides such as trimethyltin hydroxide, tributyltin hydroxide and trioctyltin hydroxide; dibutyltin oxide and dioctyltin oxide;
Dialkyltin oxides such as dilauryltin oxide; dialkyltin chlorides such as dibutyltin dichloride and dioctyltin dichloride; tertiary amines such as triethylamine, benzyldimethylamine, triethylenediamine, tetramethylbutanediamine, 2-methyl-triethylenediamine; , 8-diaza-bicyclo (5.4.0) undecenyl-7 (hereinafter also referred to as "DBU"), such as phenol salts, stearates, oleates, and formate salts
U salt and the like. The curing catalyst may be used alone or as a mixture of two or more. The amount of the curing catalyst used is preferably 0 to 1 part by weight based on 100 parts by weight of the polyol compound (B).

The composition (I) and the composition (II) of the present invention
The equivalent ratio of the isocyanate group in the polyisocyanate compound (A) to the hydroxyl group in the polyol compound (B) (equivalent ratio of NCO group / OH group) is 0.1 to
1.3, preferably 0.2 to 1.2, more preferably 0.2 to 0.7. If it is less than 0.1, the loss factor of the urethane-based composition decreases, which is not preferable.
If the ratio exceeds 1.3, physical properties of the urethane composition change with time, which is not preferable in practical use.

Next, as the inorganic fillers (C) and (D) used in the present invention, those well-known as reinforcing fillers for rubber and plastic are used. The shape is not limited as long as it is solid, and may be in the form of powder, fibrous powder, fiber, whisker, balloon, or the like. However, in consideration of economy and the like, powder is preferable. Specifically, clay, calcined clay, talc, catalbo, silica, alumina, magnesium oxide, calcium silicate, asbestos, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, aluminum hydroxide, calcium hydroxide , Barium sulfate, potassium sulfate, alum, sodium alum, iron alum, shirasu balloon, glass balloon, carbon black, coke please, zinc oxide, antimony trioxide, boric acid, borax, zinc borate, metal powder, metal whisker, Mica, graphite, titanium oxide, carbon fiber,
Examples include glass fiber, glass fiber powder, glass beads, calcium carbonate, zinc carbonate, hydrotalcite, iron oxide, and zeolite. The above-mentioned inorganic fillers can be used alone or in combination of two or more. Also, inorganic fillers (C) and (D)
May be the same or different. Examples of these inorganic fillers (C) to (D) include those subjected to various surface treatments in order to further enhance the effects of the present invention.

In the urethane composition of the present invention, the amount of the inorganic filler (C) used is preferably from 0 to 100 parts by weight, more preferably from 0.1 to 100 parts by weight, based on 100 parts by weight of the polyisocyanate compound (A). 100 parts by weight, particularly preferably 0.1 to 80 parts by weight, and the amount of the inorganic filler (D) used is preferably 0 to 100 parts by weight, more preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the polyol compound (B). 1 to 1
00 parts by weight, particularly preferably 0.1 to 80 parts by weight. The amount of the inorganic filler (C) or (D) used is (A)
If the amount exceeds 100 parts by weight based on 100 parts by weight of the component or the component (B), the viscosity of the system increases and the mixing coating processability is impaired. The ratio of the total amount of the components (C) to (D) to the total composition is preferably 50% by weight or less, more preferably 40% by weight or less. (C) ~
When the total amount of the component (D) exceeds 50% by weight, the viscosity of the system increases, and the mixing coating processability is impaired.

In the present invention, a composition (I) containing a polyisocyanate compound as a main component and a composition (II) containing a polyol compound (B) as a main component are produced in advance, respectively, and these are applied. It is used for.
If the components (A) to (D) are mixed at once, poor dispersion is likely to occur, and if mixed sufficiently to disperse, the components (A) and (B) will react and harden, making it impossible to apply. turn into. Urethane composition for vibration damping and vibration isolation of the present invention, for example, by a gun with a dispenser,
The composition (I) and the composition (II) can be mixed, preferably immediately before the application, or the composition (I) and the composition (II) can be applied to a predetermined portion in a laminated form. As a method of construction, for example, methods such as direct bead coating, non-contact shot coating, and non-contact spray coating can be used. Furthermore, it is also possible to carry out injection molding into a mold or molding into a sheet.

Thus, the composition (I) and the composition (II)
Is mixed and reacted, the hardness of the urethane composition of the present invention obtained by a type D durometer is preferably 60
Below, more preferably below 50 (hardness is one measure of elasticity). If the hardness exceeds 60 in a type D durometer, the peak of the loss coefficient is shifted to a high temperature side, which is not preferable. Here, in order to adjust the hardness and the elastic modulus, an aliphatic isocyanate is used as the polyisocyanate compound (A), or a monol having a functional group number of 1 is used as necessary as the polyol compound (B). . Further, in the polyol compound (B),
The proportion of hydroxyl groups in the high molecular weight polyol compound having an average molecular weight of 500 or more per hydroxyl group is preferably 10 to 100 equivalent% of all hydroxyl groups in order to adjust hardness and elastic modulus.

The urethane composition of the present invention can be applied to an arbitrary site by a coating machine such as a gun with a dispenser,
Alternatively, it can be easily injected into a formwork, or can be formed into a sheet shape, and can take advantage of the features of low elasticity and high loss factor (tan δ) to make it possible to use the inside and walls of floor materials of buildings. Materials, ceiling materials, etc., car engine peripherals, floors, doors, trunks, tire houses, ceilings, pillars, etc., or train interiors, ship interiors, road noise barriers, railway tracks Can be widely used for applications such as sound insulation walls.

[0017]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but it should not be construed that the invention is limited thereto. In the examples, parts and% are by weight unless otherwise specified.

Examples 1-2 Preparation of the first component (1) A polyether polyol "Exenol 3020" having an average molecular weight of 3,000 (manufactured by Asahi Glass Co., Ltd.) was mixed with 45 parts of 4,4'-diphenylmethane diisocyanate polymer. Sumidur 44V-20 "(manufactured by Sumitomo Bayer Urethane Co., Ltd., average functionality 2.5) 10 parts and hydrogenated xylylene diisocyanate" Takenate 600 "(manufactured by Takeda Pharmaceutical Co., Ltd., average functionality 2) 10 And the temperature is 8
The mixture was reacted at 0 ° C. for 3 hours to synthesize a polyisocyanate prepolymer. To this, 35 parts of an inorganic filler was added to obtain a first component containing 6.2% of isocyanate groups. This was designated as "I-1".

(2) Polyether polyol "Exenol 1020" having an average molecular weight of 1,000 [Asahi Glass Co., Ltd.]
35 parts, 20 parts of 4,4'-diphenylmethane diisocyanate polymer "Sumidur 44V-20" [manufactured by Sumitomo Bayer Urethane Co., Ltd., average functionality 2.5].
20 parts of carbodiimide-modified 4,4'-diphenylmethane diisocyanate "Isonate 143L" (manufactured by Kasei Upjohn Co., Ltd., average functionality 2) was added, and the temperature was 80 ° C.
For 3 hours to synthesize a polyisocyanate prepolymer, to which 25 parts of an inorganic filler was added to obtain a first component containing 9.1% of isocyanate groups. This is called "I-
2 ".

Preparation of Second Component (1) 35 parts of polyether polyol "Exenol 823" (manufactured by Asahi Glass Co., Ltd.) having an average molecular weight of 5,000;
A mixture of 35 parts of polyether polyol "Exenol 3020" having an average molecular weight of 3,000 (manufactured by Asahi Glass Co., Ltd.) and 10 parts of polyether polyol "Exenol 220" having an average molecular weight of 250 (manufactured by Asahi Glass Co., Ltd.) 0.1 part of triethylenediamine "DABCO" (manufactured by Sankyo Air Products Co., Ltd.) and 20 parts of an inorganic filler were added to obtain a second component. This was designated as "II-1".

(2) Exenol 823, a polyether polyol having an average molecular weight of 5,000 [Asahi Glass Co., Ltd.]
40 parts) and 20 parts of a polyether polyol "Exenol 330" having an average molecular weight of 330 (manufactured by Asahi Glass Co., Ltd.), and triethylenediamine "DABC"
O "(manufactured by Sankyo Air Products Co., Ltd.) and 0.1 part of inorganic filler were added to obtain a second component. This is called "II-
2 ".

The inorganic filler used in the first and second components is calcium carbonate (trade name: NS # 600) manufactured by Nitto Powder Chemical Industry Co., Ltd.

Preparation of urethane composition The first component and the second component obtained as described above were mixed at a predetermined ratio (weight ratio) shown in Table 1 to obtain a urethane composition. Table 1 shows the evaluation results obtained by the following methods. As is clear from Table 1, the urethane-based composition for vibration damping and vibration damping of the present invention (Examples 1 and 2) has excellent vibration damping and vibration damping properties.

Preparation of Test Specimens for Measurement (Measurement of Vibration Suppression / Vibration Isolation Performance)
For use) The first component and the second component of the examples were mixed at a predetermined ratio, and an aluminum mold (a hollow product, 1 mm thick)
And cured at room temperature for 3 days to obtain a sheet-like cured product. The sheet-like cured product thus obtained was used as a test piece having a width of 5 mm and a length that could be measured at a distance between chucks of 20 mm.

In the case of hardness measurement type D durometer, JIS K6253
The values were read within 1 second using a durometer hardness tester type D in accordance with (Method of testing hardness of vulcanized rubber and thermoplastic rubber). In the case of a type FP durometer, the end of the pressing surface of the hardness tester is 1 mm from the end of the test piece.
JIS K6 except for measurement at a distance of 2 mm or more
253, Durometer hardness tester type FP
(Manufactured by Kobunshi Keiki) was used. Vibration Suppression / Vibration Isolation Performance Measurement (Loss Coefficient) Vibration suppression / vibration isolation performance (hereinafter referred to as “loss coefficient (tan δ)”) was measured by dynamic viscoelasticity (tensile test) using Rheogel-E4000 from UBM. From 20 ° C
Was obtained.

[0026]

[Table 1]

[0027]

The urethane composition of the present invention can be optimally used as a cushioning material having a low elasticity and a low hardness, so that it is deformed at a low stress, has excellent deformation follow-up properties, and has vibration damping and vibration damping properties. . Further, the urethane-based composition of the present invention can be easily applied to an arbitrary portion by an applicator such as a gun with a dispenser, or can be easily injected into a mold, or can be formed into a sheet. Utilizing the characteristics of low elasticity and high loss factor (tan δ), the interior of building floor materials, wall materials, ceiling materials, etc., engine periphery of automobiles, floor parts, door parts, trunk parts, tire houses Part, ceiling part, pillar part, etc., or train interior part,
It can be widely used for interior parts of ships, sound insulation walls of roads, and sound insulation walls of railway tracks.

Claims (3)

[Claims] The polyisocyanate compound (A) has an equivalent ratio of isocyanate groups in the polyisocyanate compound (A) to hydroxyl groups in the polyol compound (B) of 0.1 to 1.3 (NCO / OH equivalent ratio). ) Is mixed with the composition (II) containing the polyol compound (B) as a main component, and a part or all of the isocyanate groups in the composition (I) are mixed with the composition (I). A urethane composition for vibration damping and vibration control obtained by reacting a part or all of the hydroxyl groups in the product (II). 2. The composition (I) is composed of 100 parts by weight of the isocyanate compound (A) and 0.1 part of an inorganic filler (C).
2. The vibration damper according to claim 1, wherein 1 to 100 parts by weight is blended.
Urethane-based compositions for vibration isolation. 3. The composition (II) is used in an amount of from 0.1 to 100 parts by weight of the polyol compound (B) to the inorganic filler (D).
The urethane-based composition for vibration damping and vibration isolation according to claim 1 or 2, which is blended with 100 parts by weight.