JP2023039017A - Raw material composition for forming polyurethane with good vibration damping properties - Google Patents

Abstract

To provide a raw material composition with which it is possible to form polyurethane having good vibration damping properties in a wide temperature range.SOLUTION: A raw material composition for forming polyurethane includes monool whose molecular weight is 200 or less, and has an average functionality of 1.70 to 2.25.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a polyurethane-forming raw material composition, a polyurethane obtained from the polyurethane-forming raw material composition, and a method for producing a polyurethane-forming raw material composition, and in particular, to a polyurethane capable of forming a polyurethane having good damping properties over a wide temperature range. It relates to a forming raw material composition.

In order to suppress vibration and sound, damping materials, sound insulation materials, sound absorption materials, etc. are applied. Vibration damping materials are products that suppress the generation of sound by suppressing vibrations, and polyurethane materials and the like are used.

In JP-A-62-190215 (Patent Document 1), (A) as a hydroxyl group-containing compound, a polyhydroxy saturated hydrocarbon polymer having a number average molecular weight of 500 or more, or the polyhydroxy saturated hydrocarbon polymer The equivalent ratio of the hydroxyl group to the isocyanate group of the hydroxyl group-containing compound having a coalescence and molecular weight of 50 to 800 and an average number of hydroxyl groups of 2 or more and (B) the compound having an average number of isocyanate groups of 2 or more is within the range of 0.5 to 2. or a composition containing the reaction product and a plasticizer, and having a maximum loss tangent of 0.5 or more in the temperature range of -50 to 120°C. there is However, the damping composition described in Patent Document 1 is not sufficient from the viewpoint of damping properties over a wide temperature range, and there is room for improvement.

Japanese Patent Application Laid-Open No. 2009-102566 (Patent Document 2) describes (A) a conjugated diene polymer having a 1,4 bond rate of 50% or less and having a hydroxyl group at the molecular end and (B) a 1,4 bond rate of 60 % or more and a conjugated diene-based polymer having a hydroxyl group at the molecular end, and (C) a polyisocyanate compound, and a polyurethane cured product obtained by curing the composition has water resistance and moist heat resistance. It is described that there is no problem and that excellent vibration damping performance can be exhibited in a wide temperature range. However, although Patent Document 2 also describes that it has good damping properties in a wide temperature range of -40 to 100°C, the actual measured value of tan δ is described as 0.1 or more. In a wide temperature range, there is no result of having tan δ of 0.3 or more, and there is room for improvement.

JP-A-62-190215 JP 2009-102566 A

Under such circumstances, an object of the present invention is to provide a polyurethane-forming raw material composition capable of forming a polyurethane having good vibration damping properties in a wide temperature range by a technique different from that of the prior art.

As a result of intensive studies to achieve the above object, the present inventors found that by blending a monol having a molecular weight of 200 or less and setting the average functionality of the raw material composition for polyurethane formation to 1.70 to 2.25, , found that it is possible to form a polyurethane having good damping properties over a wide temperature range, and completed the present invention.

Accordingly, a first aspect of the present invention is a polyurethane-forming raw material composition comprising a monol having a molecular weight of 200 or less and having an average functionality of 1.70 to 2.25.

A preferred embodiment of the composition of the present invention comprises a polyol composition, wherein the polyol composition has an average functionality of 1.01 or greater.

Another preferred embodiment of the composition of the present invention comprises a polyisocyanate component, wherein the polyisocyanate component has an average functionality of 1.65 or greater.

A second aspect of the present invention is a polyurethane obtained from the above composition.

In a third aspect of the present invention, a polyol composition having an average functionality of 1.01 or more and a polyisocyanate component having an average functionality of 1.65 or more are mixed, and the average functionality is 1.70 to 2.25 is a method for producing a polyurethane forming raw material composition.

According to the first and third aspects of the present invention, it is possible to provide a polyurethane-forming raw material composition capable of forming a polyurethane having good damping properties over a wide temperature range. Moreover, according to the second aspect of the present invention, it is possible to provide a polyurethane having good damping properties over a wide temperature range.

tan δ measurement results of Examples 1 to 4 and Comparative Example 1 are shown. tan δ measurement results of Examples 5 to 7 and Comparative Example 4 are shown.

The present invention will be described in detail below.

One aspect of the present invention is a polyurethane forming stock composition. Such a raw material composition contains a polyol and a polyisocyanate, and by mixing them, the reaction between the polyol and the polyisocyanate proceeds to form a polyurethane. In the present specification, the raw material composition for forming polyurethane of the present invention is also referred to as the raw material composition of the present invention.

The raw material composition of the present invention contains a monool having a molecular weight of 200 or less. By blending a monol with a molecular weight of 200 or less, the average functionality of the raw material composition can be adjusted (more specifically, the average functionality can be reduced), and good damping properties can be obtained over a wide temperature range. A polyurethane having a A monol is a compound having one hydroxyl group, preferably excluding polymers.

The molecular weight of the monool is preferably 200 or less, more preferably 186 or less, still more preferably 46-158.

The hydroxyl value of the monol is preferably 302-1753 mgKOH/g, more preferably 355-1220 mgKOH/g. The definition of hydroxyl value will be described later.

Examples of monools having a molecular weight of 200 or less include primary alcohols in which the hydroxyl group is attached to the primary carbon, such as methanol, ethanol, butanol, 1-propanol, 1-pentanol, 1-hexanol, 1- Aliphatic alcohols such as butanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, and the like.

In the raw material composition of the present invention, the amount of monol is, for example, 1 to 60 parts by mass with respect to 100 parts by mass of the raw material composition. In addition, monol may be used individually and may be used in combination of 2 or more types.

The raw material composition of the present invention has an average functionality of 1.70 to 2.25, preferably 1.75 to 2.25, more preferably 1.80 to 2.25. By setting the average functionality of the raw material composition to 1.70 to 2.25, it is possible to form a polyurethane having good damping properties over a wide temperature range.

Vibration damping is expressed by converting external energy into thermal energy, but in the glass transition point (Tg) region, internal friction is large due to micro-Brownian motion, and vibrational energy is efficiently converted into thermal energy. However, outside the Tg region, the damping properties are extremely reduced. For this reason, widening the temperature range of the Tg peak has become a technical issue, and by solving this issue, good damping properties can be achieved over a wide temperature range from low to high, rather than within a specific temperature range. can get. The damping property can be measured using the loss tangent (tan δ) as an index.

Although it is possible to increase tan δ by adjusting the composition of the polyol, etc., it has been a difficult task to widen the temperature range. By adjusting the average functionality of from 1.70 to 2.25, it is possible to maintain a high tan δ (tan δ of 0.3 or more) from a low temperature range to a high temperature range, thereby achieving good performance in a wide temperature range. It became possible to make polyurethane with damping properties. This is because when the average functionality of the raw material composition of the present invention is low, the crosslink density is low, so the temperature range of the Tg peak can be widened, and a high tan δ can be maintained in a wide temperature range. guessed.

The average functionality of the raw material composition of the present invention can be adjusted to 1.70 to 2.25 by blending a monol with a molecular weight exceeding 200, but in this case, if curing failure occurs There is

As used herein, the average functionality of the raw material composition is an index indicating the proportion of functional groups involved in polyurethane formation contained in the raw material composition. It is determined from the number of active hydrogens (mainly hydroxyl groups) that react with the isocyanate groups contained in the substance. Since the raw material composition usually contains a polyol composition and a polyisocyanate component, the average functionality of the polyol composition and the average functionality of the polyisocyanate component are determined as follows.
[Average Functionality of Polyurethane Forming Raw Material Composition]
The average functionality of the polyol composition is OH-F, the average functionality of the polyisocyanate component is NCO-F, the polyol composition is defined as 100 parts by mass, and the polyisocyanate component that reacts with 100 parts by mass of the polyol composition. Using the number of parts by mass as NCOpbw, the average functionality of the polyurethane-forming raw material composition is calculated according to the following formula.
Calculation of the average functionality of the polyol composition and the average functionality of the polyisocyanate component will be described later.
(a formula)
Average functionality of polyurethane-forming raw material composition = OH-F x 100/(100 + NCOpbw) + NCO-F x NCOpbw/(100 + NCOpbw)

In a preferred embodiment of the raw material composition of the present invention, the raw material composition contains a polyol composition. The polyol composition contains a polyol and a monool, and optionally additives such as foaming agents, foam stabilizers, flame retardants and catalysts. Here, the monool contained in the polyol composition is as explained above.

The polyol used in the polyol composition is a compound having a plurality of hydroxyl groups, preferably a polymer polyol. Specific examples include polyether polyol, polyester polyol, polycarbonate polyol, polylactone polyol, polybutadiene polyol, polymer polyols, Mannich polyols, and the like.

The amount of polyol is appropriately adjusted according to the required performance, and is, for example, 0 to 95 parts by mass with respect to 100 parts by mass of the polyol composition. In addition, a polyol may be used independently and may be used in combination of 2 or more types.

Typical examples of polyether polyols include polyoxyalkylene-based polyols, and polyoxyalkylene-based polyols include hydroxyl groups, primary amino groups, secondary amino groups, compounds having two or more other active hydrogen-containing groups, and the like. can be produced by subjecting an alkylene oxide to a ring-opening addition reaction using a starting material.

Starting materials for polyoxyalkylene polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, Diglycerin, mannose, sucrose, fructose, dextrose, polyhydric alcohols such as sorbitol, alkanolamines such as ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, ethylenediamine, tolylenediamine, diethyltoluenediamine, 1,3-propane Diamine, 1,6-hexanediamine, isophoronediamine, diethylenetriamine, triethylenepentamine and other polyvalent amines, bisphenol A, bisphenol F, resorcinol, hydroquinone and other polyhydric phenols, Mannich bases (phenols, aldehydes, alkanolamines) etc.), modified products thereof, and the like. These starting materials may be used alone or in combination of two or more.

Examples of alkylene oxides to be subjected to ring-opening addition reaction in the production of polyoxyalkylene-based polyols include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and styrene oxide. These alkylene oxides may be used alone or in combination of two or more.

Examples of polymer polyols include polyoxyalkylene polyols in which polymer fine particles such as polyacrylonitrile fine particles and polystyrene fine particles are dispersed. Polymer polyols are a kind of polyether polyols because they contain polyoxyalkylene-based polyols.

Mannich polyols can be produced by condensation reaction of phenols, aldehydes, alkanolamines and the like, and optionally ring-opening addition reaction of alkylene oxides such as ethylene oxide and propylene oxide. Mannich polyols are a kind of polyether polyols because they have multiple ether bonds in the molecule.

Examples of suitable polyether polyols include (di)ethylene glycol-based polyether polyols, (di)propylene glycol-based polyether polyols, and (di)glycerin-based polyethers obtained by addition reaction of ethylene oxide and/or propylene oxide. Polyols, trimethylolpropane-based polyether polyols, pentaerythritol-based polyether polyols, sucrose-based polyether polyols, dextrose-based polyether polyols, sorbitol-based polyether polyols, mono(di, tri)ethanolamine-based polyether polyols, ethylenediamine polyoxyalkylene polyols such as polyether polyols, tolylenediamine polyether polyols, and bisphenol A polyether polyols, polymer polyols in which fine polymer particles are dispersed in polyoxyalkylene polyols, and Mannich polyols.

The polyester polyol can be produced by adjusting the polyester production conditions. Examples thereof include polyesters having hydroxyl groups at least at both ends of the main chain. Examples include branched polyester polyols. Polyester polyols can be prepared by known methods using aliphatic, cycloaliphatic or aromatic dicarboxylic acids, diols, and optionally polycarboxylic acids and/or trifunctional or higher polyols. can.

Polylactone polyols are homopolymers or copolymers of lactones, and include polylactones having hydroxyl groups at least at both ends of the main chain. Specifically, starting materials such as compounds having two or more active hydrogen-containing groups as described in the above polyoxyalkylene-based polyols, ε-caprolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ - can be produced by subjecting a lactone such as valerolactone to a ring-opening addition reaction. Polylactone polyol is a kind of polyester polyols because it has a plurality of ester bonds in its molecule.

Polycarbonate polyols can be produced by adjusting the production conditions of polycarbonate, and include polycarbonates having hydroxyl groups at least at both ends of the main chain. Examples of polybutadiene polyol include polybutadiene having hydroxyl groups at least at both ends of the main chain.

The polyol composition preferably contains a polyol having a functionality of 2-8 and a number average molecular weight of 62-10,000. By using a polyol having the above specific number of functional groups and number average molecular weight, it becomes possible to widely adjust the hardness of the resulting polyurethane. A polyol having a number of functional groups of 2 to 8 and a number average molecular weight of 62 to 10,000 is hereinafter also referred to as polyol (a).

The polyol (a) has a functional group number (fn) of 2-8, preferably 2-6, more preferably 2-4.

In the present specification, the number of functional groups (fn) per polyol molecule is obtained from the hydroxyl value (OHV) and number average molecular weight (Mn) of the polyol by the following formula.
fn = Mn (g/mol) x OHV (mg KOH/g)/56100

Polyol (a) has a number average molecular weight of 62 to 10,000, preferably 200 to 6,000, more preferably 1,000 to 4,000.

In the present specification, the number average molecular weight of polyol is the polystyrene-equivalent number average molecular weight measured by gel permeation chromatography.

Polyol (a) preferably has a hydroxyl value of 28 to 1810 mgKOH/g, more preferably 28 to 112 mgKOH/g.

As used herein, the hydroxyl value is the number of mg of potassium hydroxide required to neutralize free hydroxyl groups in 1 g of a sample after complete acetylation with acetic anhydride (see JIS K 1557 2007). .

Polyol (a) is preferably a polyether polyol.

The amount of polyol (a) is, for example, 10 to 90 parts by weight with respect to 100 parts by weight of the polyol composition. In addition, polyol (a) may be used independently and may be used in combination of 2 or more types.

The average functionality of the polyol composition is preferably 1.01 or higher, more preferably 1.20 to 1.99, even more preferably 1.30 to 1.99.

ポリオール組成物の平均官能基数の計算
ポリオール組成物の平均官能基数は以下の式より求められる。

As used herein, the average functionality of the polyol composition is defined from the number of monovalent hydroxyl groups represented by OH, and can be determined from the functionality and mass fraction of the polyol and monool as follows. Here, a monol has one hydroxyl group and its functionality is defined as one. Polyols usually have 2-8 hydroxyl groups and their functionality is defined as 2-8. The functionality of a polyol can also be translated into the number of hydroxyl groups (functional groups). In addition, when the polyol composition contains a component having a monovalent hydroxyl group represented by OH other than polyol and monool, such as water, the following formula is changed in consideration of such components as well, It can be obtained in the same manner as the following formula. For example, water is defined as having a functionality of two.
[Average functionality of polyol composition]
It is assumed that the polyol composition contains n kinds of polyols and m kinds of monools. For ^each polyol, ^the number of functional groups ^is F(a) ¹ , F(a) ² , . (a) ⁿ , and W(a) ¹ , W(a) ² , . . . , W(a) ⁿ respectively. On the other ^hand , for each monol, the functionalities ^are F(b) ¹ , F( ^b ) ² , . , M(b) ^m , and W(b) ¹ , W(b) ² , . . . , W(b) ^m respectively.
Calculation of total number of moles The total number of moles of the polyol composition is determined by the following formula.

Calculation of Average Functional Group Number of Polyol Composition The average functional group number of the polyol composition is obtained from the following formula.

Catalysts that can be used in the polyol composition include catalysts that promote the reaction between water and polyisocyanate (foaming catalyst), catalysts that promote the reaction between polyol and polyisocyanate (resinification catalyst), and trimerization of polyisocyanate. Catalysts (trimerization catalysts) that promote the reaction (that is, formation of an isocyanurate ring) and the like are included.

Examples of foaming catalysts include dimorpholine-2,2-diethyl ether, N,N,N',N'',N''-pentamethyldiethylenetriamine, bis(dimethylaminoethyl) ether, 2-(2-dimethyl aminoethoxy)ethanol, N,N,N'-trimethyl-N'-hydroxyethylbisaminoethyl ether and the like.

Examples of the resinification catalyst include triethylenediamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'',N''',N '''-hexamethyltriethylenetetramine, N-dimethylaminoethyl-N'-methylpiperazine, N,N,N',N'-tetramethylhexamethylenediamine, 1,2-dimethylimidazole, 1-isobutyl-2 -methylimidazole, N,N-dimethylaminopropylamine, amine catalysts such as bis(dimethylaminopropyl)amine, N,N-dimethylaminoethanol, N,N,N'-trimethylaminoethylethanolamine, N-(3 -dimethylaminopropyl)-N,N-diisopropanolamine, N-(2-hydroxyethyl)-N'-methylpiperazine, N,N-dimethylaminohexanol, 5-dimethylamino-3-methyl-1-pentanol metal catalysts such as alkanolamine catalysts such as stannous octoate, dibutyl stannic dilaurate, lead octylate, bismuth carboxylate, and zirconium complexes. As these amine catalysts and alkanolamine catalysts, amine carbonates synthesized by adding carbonic acid or amine carboxylates synthesized by adding carboxylic acids such as formic acid and acetic acid may be used.

Examples of trimerization catalysts include 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 2, aromatic compounds such as 4,6-tris(dimethylaminomethyl)phenol and 2,4-bis(dimethylaminomethyl)phenol; carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate; A quaternary ammonium salt of carboxylic acid, or other onium salt, and the like can be mentioned.

The amount of catalyst is, for example, 0.1 to 5 parts by weight, preferably 0.2 to 2.0 parts by weight, per 100 parts by weight of the polyol composition. In addition, a catalyst may be used individually and may be used in combination of 2 or more types.

Blowing agents that may be used in the polyol composition are generally classified as physical blowing agents and chemical blowing agents. The foaming agents may be used alone or in combination of two or more. Also, a physical foaming agent and a chemical foaming agent may be used in combination. The amount of foaming agent is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 15 parts by mass, based on 100 parts by mass of the polyol composition.

Specific examples of physical blowing agents include chlorofluorocarbons such as hydrochlorofluorocarbons (HCFC) and hydrofluorocarbons (HFC), hydrofluoroolefins (HFO), hydrocarbons such as heptane, hexane, pentane and cyclopentane, and carbon dioxide. is mentioned. On the other hand, chemical blowing agents include water and carboxylic acids such as formic acid and acetic acid.

Preferably, the polyol composition contains a hydrofluoroolefin as a blowing agent. Hydrofluoroolefin (HFO) is a foaming agent that is preferably used as a physical foaming agent that does not correspond to fluorocarbons. The use of hydrofluoroolefins can improve the adhesion of polyurethane foams. HFO is an olefin compound containing a fluorine atom, and includes those further containing a halogen atom other than fluorine (for example, a chlorine atom). Those further containing chlorine atoms are also referred to as hydrochlorofluoroolefins (HCFOs). Although HFO and HCFO are sometimes distinguished, in the present specification, HFO includes HCFO as described above.

The hydrofluoroolefin preferably has 2 to 5 carbon atoms and preferably 3 to 7 fluorine atoms. The molecular weight of HFO is preferably 100-200. Specific examples of HFO include 1,2,3,3,3-pentafluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3 ,3-tetrafluoropropene, 3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluorobutene, 1-chloro-3,3,3-trifluoropropene, 2-chloro -3,3,3-trifluoropropene, 3,3-dichloro-3-fluoropropene, 2-chloro-1,1,1,4,4,4-hexafluorobutene, 2-chloro-1,1, 1,3,4,4,4-heptafluorobutene and the like. HFO may be either a cis or trans isomer. These HFOs may be used alone or in combination of two or more.

The amount of hydrofluoroolefin is, for example, 0.5 to 30 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the polyol composition.

From the viewpoint of improving the appearance and strength of the foam, the polyol composition preferably contains water as a foaming agent. The amount of water is, for example, 0.1 to 10 parts by weight, preferably 0.3 to 6 parts by weight, per 100 parts by weight of the polyol composition.

Foam stabilizers that can be used in the polyol composition are preferably surfactants. Surfactants include ionic surfactants such as anionic, cationic and amphoteric surfactants and nonionic surfactants, and nonionic surfactants are preferred. Preferred specific examples include silicone-based surfactants and fluorine-based surfactants. The amount of the foam stabilizer is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyol composition. A foam stabilizer may be used independently and may be used in combination of 2 or more types.

Flame retardants that can be used in the polyol composition are preferably phosphorus flame retardants. Preferred specific examples include tricresyl phosphate (TCP), triethyl phosphate (TEP), tris(β-chloroethyl) phosphate (TCEP), tris(β-chloropropyl) phosphate (TCPP) and the like. Solid (powder) flame retardants such as ammonium polyphosphate and red phosphorus are also used as necessary. The amount of flame retardant is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polyol composition. A flame retardant may be used independently and may be used in combination of 2 or more types.

The polyol composition can be prepared by mixing various components appropriately selected as necessary.

In a preferred embodiment of the raw material composition of the present invention, the raw material composition contains a polyisocyanate component. The polyisocyanate component consists of polyisocyanate and may contain additives such as foaming agents and flame retardants.

A polyisocyanate is a compound having a plurality of isocyanate groups, and examples thereof include aliphatic, alicyclic, aromatic or araliphatic polyisocyanates, and modified products of these polyisocyanates are also included. Examples of modified polyisocyanates include polyisocyanates having structures such as uretdione, isocyanurate, urethane, urea, allophanate, biuret, carbodiimide, iminooxadiazinedione, oxadiazinetrione, and oxazolidone. Moreover, as the polyisocyanate of the present invention, an isocyanate group-containing prepolymer obtained by reacting a polyol and a polyisocyanate may be used. Specifically, a polyisocyanate and a monool are reacted to produce a polyisocyanate prepolymer, and the average functionality is adjusted. In addition, polyisocyanate may be used independently and may be used in combination of 2 or more types.

Among polyisocyanates, aromatic polyisocyanates include, for example, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate. be done. Examples of alicyclic polyisocyanates include cyclohexyl diisocyanate, methylcyclohexyl diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate and the like. Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.

In addition, from the viewpoint of adjusting the average functionality of the polyisocyanate component, the polyisocyanate component preferably contains a product obtained by the reaction of a monool and a polyisocyanate, preferably a compound having an isocyanate group. . Here, as the monool, the monool contained in the raw material composition of the present invention described above can be suitably used.

The polyisocyanate component preferably has an isocyanate group content of 10 to 40% by mass, more preferably 15 to 35% by mass. As used herein, the isocyanate group content is determined according to JIS K 1603.

In the raw material composition of the present invention, the amount of polyisocyanate can be indicated by, for example, the isocyanate index. In the raw material composition of the present invention, the isocyanate index is preferably 80-300, more preferably 80-250, still more preferably 80-200.

As used herein, the isocyanate index is a value obtained by multiplying 100 by the ratio of the isocyanate groups of the isocyanate compound to the total active hydrogen reacting with the isocyanate groups of the polyol, monool, foaming agent, and the like.

As the foaming agent and flame retardant that can be used in the polyisocyanate component, the foaming agent and flame retardant described in the polyol composition can be used.

The average functionality of the polyisocyanate component is preferably 1.65 or more, more preferably 1.70 to 2.67, even more preferably 1.75 to 2.67.

ポリイソシアネート成分の平均官能基数の計算
ポリイソシアネート成分の平均官能基数は以下の式より求められる。

As used herein, the average functionality of the polyisocyanate component is defined from the number of isocyanate groups (functional groups), and can be obtained from the functionality and mass fraction of the polyisocyanate and monool as follows. To illustrate a typical 4,4′ diphenylmethane diisocyanate (monomeric MDI), there are two isocyanate groups per aromatic polyisocyanate molecule and the functionality is defined as two. On the other hand, polymethylene polyphenyl polyisocyanate (polymeric MDI) is a polyisocyanate composed of polynuclear bodies of two or more nuclear bodies. The (average) functionality can be defined from the compositional ratio. Moreover, the term "monool" as used herein generally refers to a monool used in the production of such a prepolymer when using a monool-modified polyisocyanate prepolymer. When determining the average functionality of the polyisocyanate component, the polyisocyanate and the monol constituting the monool-modified polyisocyanate prepolymer are considered separately.
[Average functionality of polyisocyanate component]
It is assumed that n types of polyisocyanates and m types of monools are contained in the polyisocyanate component. ^For each polyisocyanate, ^the numbers of functional groups are F(a) ¹ , ^F (a) ² , . M(a) ⁿ and W(a) ¹ , W(a) ² , . . . , W(a) ⁿ respectively. On the other ^hand , for each monol, the functionalities ^are F(b) ¹ , F( ^b ) ² , . , M(b) ^m , and W(b) ¹ , W(b) ² , . . . , W(b) ^m respectively.
Calculation of total number of moles The total number of moles of the polyisocyanate component is obtained by the following formula.

Calculation of Average Functional Group Number of Polyisocyanate Component The average functional group number of the polyisocyanate component is obtained from the following formula.

The polyurethane-forming raw material composition of the present invention may be a raw material for foamed polyurethane (polyurethane foam) or a raw material for non-foamed polyurethane. When used as a raw material for polyurethane foam, the polyurethane-forming raw material composition of the present invention preferably contains a foaming agent. The blowing agent here may be blended in the polyol composition, may be blended in the polyisocyanate component, or may be mixed separately from the polyol composition and the polyisocyanate component. may be blended in. As the foaming agent that can be used in the polyurethane-forming raw material composition of the present invention, the foaming agents described for the polyol composition can be used. The amount of the foaming agent is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 15 parts by mass, based on 100 parts by mass of the raw material composition for forming polyurethane.

The polyurethane-forming raw material composition of the present invention contains, as other components, a coloring agent, a filler, an antioxidant, an ultraviolet absorber, a heat stabilizer, a light stabilizer, a plasticizer, an antifungal agent, an antibacterial agent, and a cross-linking agent. , a solvent, a viscosity reducing agent, a decompressing agent, an anti-separation agent, and other additives may be added as necessary. Commercially available products can be suitably used as these components.

The polyurethane-forming raw material composition of the present invention can be prepared by mixing various components appropriately selected according to need. For example, a polyol composition containing a polyol and a monool, a product obtained by reacting a polyisocyanate or a monool and a polyisocyanate appropriately blended as necessary, preferably a polyisocyanate containing a compound having an isocyanate group By mixing the components, the polyurethane-forming raw material composition of the present invention can be prepared.

Another aspect of the invention is a method of making a polyurethane forming stock composition. Hereinafter, the method for producing the polyurethane-forming raw material composition of the present invention is also referred to as the production method of the present invention.

The production method of the present invention is a method of producing a polyurethane-forming raw material composition by mixing a polyol composition and a polyisocyanate component, as described for the polyurethane-forming raw material composition of the present invention. Here, as a preferred embodiment of the production method of the present invention, a polyol composition having an average functionality of 1.01 or more and a polyisocyanate component having an average functionality of 1.65 or more are mixed, and the average functionality is It is a method for producing a polyurethane-forming raw material composition having a molecular weight of 1.70 to 2.25.

Another aspect of the invention is polyurethane. The polyurethane of the present invention can be obtained from the polyurethane-forming raw material composition of the present invention described above, and may be foamed polyurethane or non-foamed polyurethane.

The polyurethane of the present invention can have good damping properties over a wide temperature range by being produced from the raw material composition for forming the polyurethane of the present invention. Ideally, the polyurethane of the present invention should be able to maintain a tan δ of 0.3 or more in the temperature range of -40 to 140°C. tan δ of 0.3 or more can be maintained in a wide temperature range up to .

In the present specification, tan δ is measured using a viscoelasticity measuring device under conditions of a frequency of 10 Hz and a heating rate of 2.5° C./min. In the examples, the measurements were carried out in the temperature ranges of -80°C to 180°C and -80°C to 100°C.

The molding method of polyurethane is not particularly limited, and known molding means such as mold molding, slab molding, laminate molding, and on-site foam molding can be used. In the case of polyurethane foam, the foaming method is not particularly limited, and known foaming means such as hand mixing foaming, simple foaming, continuous foaming method, injection foaming method, froth injection foaming method, spray foaming method, etc. are used. can.

The polyurethane of the present invention is suitable as a damping material and a vibration isolating material. Specifically, it is suitable as a vibration-damping material or a vibration-isolating material used for transportation equipment such as automobiles, railroad vehicles, and aircraft, ceilings and inner walls of buildings, home appliances, OA equipment, and the like.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

<raw materials>
The materials used in the production of polyurethane are shown below.
1) Sumifen 3600: manufactured by Sumika Covestro Co., Ltd., polyether polyol, number of functional groups fn = 2, hydroxyl value = 56 mgKOH/g, number average molecular weight = 2000
2) SBU Polyol 0320: manufactured by Sumika Covestro Co., Ltd., polyether polyol, number of functional groups fn = 2, hydroxyl value = 28 mgKOH/g, number average molecular weight = 4000
3) Sumifen VB: manufactured by Sumika Covestro Co., Ltd., polyether polyol, number of functional groups fn = 4, hydroxyl value = 630 mgKOH/g, number average molecular weight = 360
4) Monoethylene glycol: Number of functional groups fn = 2, hydroxyl value = 1810 mgKOH/g, molecular weight = 62
5) 1-Octanol... Functional group number fn = 1, hydroxyl value = 432 mgKOH/g, molecular weight = 130
6) Ethanol... Functional group number fn = 1, hydroxyl value = 1220 mgKOH/g, molecular weight = 46
7) 1-decanol... Functional group number fn = 1, hydroxyl value = 355 mgKOH/g, molecular weight = 158
8) 2-(2-butoxy)ethoxyethanol: functional group number fn = 1, hydroxyl value = 272 mgKOH/g, molecular weight = 206
9) DABCO33LV: 33% triethylenediamine in dipropylene glycol 10) DBTDL: dibutyltin dilaurate 11) Toyocat ET: 70% solution of bis-2-dimethylaminoethyl ether in dipropylene glycol 12) SBU isocyanate 0632: manufactured by Sumika Covestro, liquid Modified MDI (NCO% = 29.0% by weight), average functionality of polyisocyanate component = about 2.1
13) Sumidur 44V20: Polymeric MDI manufactured by Sumika Covestro (NCO% = 31.5% by mass), average functionality of polyisocyanate component = about 2.7
14) Isocyanate (A): monool-modified polyisocyanate prepolymer (NCO% = 16.8% by mass), average functionality of polyisocyanate component = about 1.9

<Preparation of monool-modified polyisocyanate prepolymer as isocyanate (A)>
Sumidule 44V20 manufactured by Sumika Covestro Co., Ltd., 1000 g, was placed in a four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen gas inlet, and the liquid temperature was maintained at 40 ° C. -octanol was slowly added dropwise at a mass ratio of 44V20:1-octanol=100:30 over 30 minutes, and after the dropwise addition was completed, the mixture was stirred for 3 hours at a temperature of 60° C. to complete the reaction. Table 2 shows the theoretical functional group number and properties of the obtained 1-octanol-modified MDI prepolymer.

<Example of Polyurethane Production>
A polyol composition was prepared according to the formulation shown in Table 1. Next, the polyol composition and the polyisocyanate component were mixed in the amounts shown in Table 1 to produce non-foamed polyurethane molded articles.
Subsequently, a polyol composition was prepared according to the formulation shown in Table 2. Next, the polyol composition and the polyisocyanate component were mixed in the amounts shown in Table 2 to produce foamed polyurethane molded articles.
Although Tables 1 and 2 show the formulations in parts by mass, the amount of the polyisocyanate component in Table 1 is shown in terms of the amount per 100 masses of the polyol composition. For example, the description of "100/25.3" in Example 1 means that the amount of the polyisocyanate component is 25.3 parts by mass with respect to 100 parts by mass of the polyol composition.

<Method for measuring tan δ>
The tan δ of the obtained polyurethane sheet was measured using a dynamic viscoelasticity measuring device Rheoge-E4000 manufactured by UBM under conditions of a frequency of 10 Hz and a heating rate of 2.5°C/min. Measurements were carried out in the temperature range of -80°C to 180°C and -80°C to 100°C in the examples. In addition, when tan delta is 0.3 or more, damping property is favorable. The results are shown in Tables 1-2 and Figures 1-2.

The polyurethanes of Examples 1-7 exhibited good damping properties over a wide temperature range. On the other hand, the polyurethane of Comparative Example 1 has a high average functionality of the raw material composition for forming polyurethane of 2.28, and a narrow temperature range in which tan δ is 0.3 or more. In Comparative Example 2, the raw material composition for forming polyurethane had a low average functionality of 1.57, became a sticky substance, and could not be cured. In Comparative Example 3, although the average functionality was within the predetermined range, the raw material composition for forming polyurethane became sticky and could not be cured due to the addition of a monool having a large molecular weight. The polyurethane of Comparative Example 4 had an average functionality of the polyurethane forming raw material composition of 2.26 and a tan δ of less than 0.3.

Claims (5)

A polyurethane-forming raw material composition containing a monool having a molecular weight of 200 or less and having an average functionality of 1.70 to 2.25. 2. The composition of claim 1, comprising a polyol composition, wherein the polyol composition has an average functionality of 1.01 or greater. 3. A composition according to claim 1 or 2, comprising a polyisocyanate component, said polyisocyanate component having an average functionality of 1.65 or greater. A polyurethane obtainable from the composition according to any one of claims 1-3. A polyol composition having an average functionality of 1.01 or more and a polyisocyanate component having an average functionality of 1.65 or more are mixed to prepare a polyurethane-forming raw material composition having an average functionality of 1.70 to 2.25. How to manufacture.

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