JP2003026752A - Shock-absorbing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane-based shock-absorbing material satisfying both high hardness and high attenuation that are usually contradictory characteristics to each other. SOLUTION: The shock-absorbing material comprises as its ingredient a polyurethane obtained by a polyaddition reaction of a polyol compound having, as a recurring unit, a specific cyclic structure exemplified by the formula to a polyisocyanate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane shock absorbing material, and more particularly to a shock absorbing material used for absorbing a shock of a hard disk of a computer, a head of a magneto-optical disk, and the like.

[0002]

2. Description of the Related Art Conventionally, crash stops are provided on both sides of a center portion of a head rotation in order to position a magnetic head and prevent runaway of the magnetic head when a hard disk drive of a computer is operated. This crash stop is required to have a high hardness in order to reduce the amount of distortion at the time of positioning, and has a high damping property (high loss coefficient: loss tangent tan δ) in order to buffer an impact in preventing runaway. Required. As described above, the above-mentioned crash stop is required to have generally contradictory characteristics of high hardness and high damping.

Therefore, at the present time, a thermoplastic polyurethane having a high hardness and a high loss coefficient is used for the crash stop.

[0004]

The conventional thermoplastic polyurethane has an insufficient damping property and is disclosed in JP-A-5-30.
In 2027, the problem is solved by mixing a material having a high hardness and a material having a small loss coefficient, but it is difficult to achieve a balance. Accordingly, an object of the present invention is to provide a polyurethane-based shock absorber which is required to have generally inconsistent characteristics of high hardness and high damping.

[0005]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a polyaddition reaction between a polyol compound having a specific alicyclic or heterocyclic structure as a diol residue and a polyisocyanate compound. The present inventors have found that an impact absorbing material containing polyurethane as a component can solve the above-mentioned problems, and have accomplished the present invention. That is, the present invention relates to a polyurethane-based shock absorber shown in the following [1] to [17]. [1] each independently formula at both ends _{(I) -CH 2 - (CH} 2) m -OH, -CH 2 - (CH 2) n -OH (I) [m, n are independently 0-5 Wherein at least one type of repeating unit constituting the structure is represented by the general formula (II):

Embedded image (II) [wherein, R _{1 to} R ₈ each independently represent a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (two of R _{1 to} R ₈ The above may be linked to form a ring.), A cyano group, a hydroxyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a formyl group, a carboxyl group (an acid anhydride may be formed from two carboxyl groups) .) Or a silyl group. An impact-absorbing material comprising, as a component, a polyurethane obtained by a polyaddition reaction of a polyol compound containing at least one polyol (a) having a ring structure represented by the following formula: [2] At least one of the polyols (a) has a structure represented by the general formula (I) independently at both ends, and a repeating unit having a ring structure represented by the general formula (II) and a carbon number of 4 The shock-absorbing material according to [1], which is a compound comprising a repeating unit of an alkylene group of 1 to 12. [3] R ₁ to R _{1 of the} repeating unit represented by the general formula (II)
R ₈ is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (two or more of R _{1 to} R ₈ may be linked to form a ring) [1] or [2]. 2. The shock absorbing material according to 1. [4] R ₁ to R _{1 of the} repeating unit represented by the general formula (II)
The shock absorber according to [1] or [2], wherein R ₈ is a hydrogen atom. [5] R ₁ to R _{1 of the} repeating unit represented by the general formula (II)
The shock absorber according to [1] or [2], wherein R ₄ , R _{6 to} R ₈ are hydrogen atoms, and R ₅ is an ethyl group. [6] The proportion of the polyol (a) in the polyol compound constituting the polyurethane is 5 to 100 mol% [1].
-The shock absorbing material according to any one of [5]. [7] respectively to both ends independently general formula _{(III) = CH- (CH 2} ) m -OH, = CH- (CH 2) n -OH (III) [m, n are independently integers of 0 to 5 Wherein at least one type of the repeating unit constituting the structure has the general formula (IV):

Embedded image (IV) wherein R _{9 to} R ₁₆ are independently a halogen atom, a hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (R ₁₁ and R ₁₂ , and R ₁₃ and R ₁₄ may be each independently an alkylidene group, and R _{9 to} R ₁₆ Two or more of which may be linked to form a ring), a cyano group, a hydroxyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a formyl group, a carboxyl group (form an acid anhydride from two carboxyl groups) Or a silyl group. An impact-absorbing material comprising, as a component, a polyurethane obtained by a polyaddition reaction between a polyol compound containing at least one polyol (b) having a ring structure represented by the formula (I) and a polyisocyanate compound. [8] at least one of the polyols (b) has a structure represented by the general formula (III) at both terminals independently of each other,
The shock absorbing material according to [7], wherein a compound consisting of a repeating unit having a ring structure represented by the general formula (IV) and a repeating unit of a hydrocarbon having 4 to 12 carbon atoms. [9] R ₉ to R _{9 of the} repeating unit represented by the general formula (IV)
R ₁₆ is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ may be independently an alkylidene group in each group, and R _{9 to} R ₁₆
And two or more of them may be linked to form a ring. ) The shock absorber according to [7] or [8]. [10] R _{9 of the} repeating unit represented by the general formula (IV)
Shock absorber according to to R ₁₆ is a hydrogen atom [7] or [8]. [11] R _{9 of the} repeating unit represented by the general formula (IV)
The impact absorbing material according to [7] or [8], wherein -R ₁₂ and R ₁₅ -R ₁₆ are hydrogen atoms, and R ₁₃ and R ₁₄ are both an ethylidene group. [12] The polyurethane impact absorber according to any one of [7] to [11], wherein the proportion of the polyol (b) in the polyol compound constituting the polyurethane is 5 to 100 mol%. [13] A composition for producing an impact absorbing material, comprising, as a component, a polyurethane comprising the polyol (a) according to [1] and a polyisocyanate compound as essential components. [14] A composition for producing an impact absorbing material, comprising, as a component, a polyurethane comprising the polyol (b) according to [7] and a polyisocyanate compound as essential components. [15] A composition for producing an impact absorbing material, comprising, as components, the polyol (a) according to [1], the polyol (b) according to claim 7, and a polyurethane having a polyisocyanate compound as an essential component. [16] An impact absorbing material obtained by a polyaddition reaction of the composition for producing an impact absorbing material according to any one of [13] to [15]. [17] The shock absorbing material according to any one of [1] to [11] and [16], wherein the peak temperature of the loss tangent at 110 Hz at a hardness of 85 A or more is 10 ° C. or more.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The shock absorbing material of the present invention is a shock absorbing material containing, as a component, a polyurethane having in its repeating unit a diol residue derived from a polyol compound comprising a repeating unit having an alicyclic or heterocyclic skeleton having a specific structure. It is.

The polyol compound comprising a repeating unit having a specific ring structure used in the present invention has at least one kind of a repeating unit having a ring structure represented by the general formula (II) or (IV). It is a polyol. Here, the polyol (a) according to claim 1, which contains a repeating unit represented by the general formula (II),
The hydrogenated carbon-carbon double bond of the polyol (b) according to claim 7, which comprises the repeating unit represented by V).

Specifically, R _{1 to} R ₈ in the general formula (II)
Will be described below as an example. The following general formula (V) is an example of the polyol (a) according to claim 1, and is a case where only the both ends of the general formula (I) and the repeating unit of the general formula (II) are included.

[0009]

Embedded image

(V) wherein R _{1 to} R ₈ are each independently a halogen atom, a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (of R _{1 to} R ₈ ) Two or more may be linked to form a ring), a cyano group, a hydroxyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a formyl group, a carboxyl group (an acid anhydride is formed from two carboxyl groups) Or a silyl group. m and n are independently 0 to 5
And k is an arbitrary natural number. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the optionally substituted hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t
ert- butyl, amyl, hexyl, octyl, decyl, dodecyl, alkyl octadecyl, cyclopentyl, the cycloalkyl group such as cyclohexyl, phenyl, tolyl, mesityl, an aryl group of naphthyl, R ₁
Two Examples or linked rings, substituents attached to one carbon atom of the common to R _8, i.e. R ₁ and R _2, R
_{A 3-} to 6-membered spiro ring in which ₃ and R ₄ or R ₅ and R ₆ are linked, a 5- to 8-membered condensed ring sharing a carbon atom represented by α or β in the general formula (V), hydroxy And substituted alkyl groups such as methyl, hydroxyethyl, chloromethyl, methoxymethyl, and acetoxymethyl.

Furthermore, examples of R _{1 to} R ₈ include a cyano group; methoxy, ethoxy, propoxy, isobutoxy,
alkoxyl groups such as tert-butoxy; acetoxy;
Acyl groups such as propionyloxy; formyl groups; carboxyl groups or their esters (alkoxycarbonyl groups) such as methyl, ethyl, propyl, butyl and phenyl or acid anhydrides formed from two carboxyl groups; silyl such as trimethylsilyl And the like.

Of these R _{1 to} R _8, a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable. A in the general formula (II) is a hydrocarbon group having substituents R ₁ and R ₂ or an oxygen atom, but is preferably a hydrocarbon group, and more preferably a methylene group.

Next, R _{9 to} R ₁₆ in the general formula (IV)
Will be described below with specific examples. The following general formula (V
I) is an example of the polyol (b) according to claim 7 and is a case where the polyol (b) comprises only both ends of the general formula (III) and a repeating unit of the general formula (IV).

[0014]

Embedded image

(VI) wherein R _{9 to} R ₁₆ are independently a halogen atom, a hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (R ₁₁ and R ₁₂ , and R ₁₃ and R ₁₄ may be each independently an alkylidene group, and R _{9 to} R ₁₆ Two or more of which may be linked to form a ring), a cyano group, a hydroxyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a formyl group, a carboxyl group (form an acid anhydride from two carboxyl groups) Or a silyl group. m and n each independently represent an integer of 0 to 5, and k represents any natural number. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t
alkyl groups such as tert-butyl, amyl, hexyl, octyl, decyl, dodecyl and octadecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, mesityl and naphthyl; R ₁₁ and R ₁₂ , R An alkylidene group independently formed from each pair of ₁₃ and R ₁₄ includes methylene (= C
H _2), ethylidene, propylidene, alkylidene group isopropylidene, The ring or two are linked in R ₉ to R _{1 6,} substituent bonded to one carbon atom in common, namely R ₉ and R ₁₀ , R ₁₁ and R ₁₂ or R ₁₃ and R ₁₄
Is a 3- to 6-membered spiro ring, a 5- to 8-membered condensed ring sharing a carbon atom represented by α or β in formula (VI), hydroxymethyl, hydroxyethyl, chloromethyl, methoxymethyl And substituted alkyl groups such as acetoxymethyl.

Further, examples of R _{9 to} R ₁₆ include a cyano group; methoxy, ethoxy, propoxy, isobutoxy,
alkoxyl groups such as tert-butoxy; acetoxy;
Acyl groups such as propionyloxy; formyl groups; carboxyl groups or their esters (alkoxycarbonyl groups) such as methyl, ethyl, propyl, butyl and phenyl or acid anhydrides formed from two carboxyl groups; silyl such as trimethylsilyl And the like.
Of these R _{9 to} R _16, a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms is preferable, and a hydrogen atom or an alkyl group or an alkylidene group having 1 to 6 carbon atoms is more preferable. A in the general formula (IV) is a hydrocarbon group or an oxygen atom having the substituents R ₉ and R ₁₀ , but is preferably a hydrocarbon group, and more preferably a methylene group.

The polyol (b) (for example, the general formula (VI)) according to claim 7 of the present invention has the general formula (VI)
Using a catalyst, a cyclic unsaturated compound (c) containing at least one compound represented by I) and a chain unsaturated compound (d) having a functional group (hydroxyl group, acyloxy group, etc.) at both terminals are used. It is produced by performing a ring polymerization and, if necessary, an operation of converting a functional group into a hydroxyl group.

At least one of the cyclic unsaturated compounds (c) has the general formula (VII):

Embedded image

(VII) wherein R _{9 to} R ₁₆ are independently a halogen atom, a hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ may be independently an alkylidene group in each group, and R _{9 to} R ₁₆ Two or more of which may be linked to form a ring or a double bond.),
Represents a cyano group, a hydroxyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a formyl group, a carboxyl group (an acid anhydride may be formed from two carboxyl groups) or a silyl group. And a norbornene-based compound represented by the formula: These norbornene compounds can be used alone or in combination of two or more.

Specific examples of the monomer compound forming the repeating unit represented by the general formula (VII) include norbornene, 2,5-norbornadiene and 5-ethylidene-2-yl.
Norbornene, 2-methyl-5-norbornene, 2-hexyl-5-norbornene, 2-cyclohexyl-5
Norbornenes formed only from hydrocarbons such as norbornene, dicyclopentadiene, benzonorbornadiene, 5-norbornene-2-carbonitrile, 5-norbornene-2-carbaldehyde, 5-norbornene-
2,3-dicarboxylic anhydride, 2-trimethylsilyl-
5-norbornene, 2-chloro-5-norbornene, 2
-Methoxycarbonyl-5-norbornene, 2-methyl-5-norbornene-3-carbaldehyde, 2-methyl-5-norbornene-3-methanol and the like, norbornenes having a substituent other than a hydrocarbon group, 8-ethylidenetetra Cyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.} 1 ^{7, 10]} -3-norbornene compounds such as norbornenes having a condensed ring such as dodecene.

As the heterocyclic compound, benzooxanorbornadiene, 2,3-bis (methoxymethyl)
Oxanorbornenes such as -7-oxa-5-norbornene and 2,3-trifluoromethyl-7-oxa-5-norbornene.

These norbornene compounds may be used alone or in combination of two or more. Among these norbornene-based compounds, preferred are norbornenes formed of only hydrocarbons, and more preferred are norbornene and 5-ethylidene-2-norbornene.

As the cyclic unsaturated compound (c), a norbornene compound represented by the general formula (VII) is indispensable, but other cyclic unsaturated compounds can also be used in combination. However, the cyclic unsaturated compound must not inhibit ring-opening polymerization of the norbornene-based compound. Examples include cycloalkenes such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, substituted cycloalkenes such as 4-methyl-1-cyclohexene, cyclopentadiene, methylcyclopentadiene, 1,5-
Cycloalkadienes such as cyclooctadiene, 3-cyclohexene-1-methanol, 3-cyclohexene-
Cyclic unsaturated compounds such as cycloalkenes having a hydroxyl group such as 1,1-dimethanol and 6-methyl-3-cyclohexene-1,1-dimethanol, and halogenated cycloalkenes such as 3-bromocyclohexene. .

These cyclic unsaturated compounds may be used alone or in combination of two or more. Of these cyclic unsaturated compounds, preferably cycloalkadiene,
Cycloalkenes.

The chain unsaturated compound (d) having a functional group at both terminals is represented by the general formula (VIII):

Embedded image

(VIII) wherein m and n are independently an integer of 0 to 5, X ₁ and X ₂ are independently a hydroxyl group or OCOR (R is a hydrogen atom or a carbon atom
Represents 10 to 10 hydrocarbon groups. ). And a compound for introducing a functional group into both terminals as well as a molecular weight regulator of the polyol (b) according to claim 7.

Specific examples of the functional groups X ₁ and X ₂ include an acyloxy group such as acetoxy and propionyloxy; an aroyloxy group such as benzoyloxy and toluoyloxy; and a hydroxyl group.

The unsaturated chain compound (d) represented by the general formula (VIII) includes 1,4-dihydroxy-2-butene, 1,6-dihydroxy-3-hexene, 1,8-
Di-terminal diol compounds such as dihydroxy-4-octene, 1,4-diacetoxy-2-butene, 1,6-diacetoxy-3-hexene, 1,8-diacetoxy-4-
Examples thereof include carboxylic acid ester compounds of diols at both ends such as octene. Preferably, 1,4-dihydroxy-2-butene and 1,4-diacetoxy-2-butene are used.

The ring-opening polymerization of a cyclic unsaturated compound (c) containing a compound represented by the general formula (VII) and a chain unsaturated compound (d) having a hydroxyl group, an acyloxy group or the like at both ends is carried out by a metathesis catalyst. This is implemented by using As a specific production method, a part or all of the cyclic unsaturated compound (c) is added little by little to a mixture of the chain unsaturated compound (d) and the ring-opening polymerization catalyst (metathesis catalyst) and polymerized. There is a method. More specifically, the reaction is started by adding a catalyst to a mixture containing the chain unsaturated compound (d) and a solvent, or optionally also a part of the cyclic unsaturated compound, and then the cyclic unsaturated compound ( c)
Is added to the mixture to cause a reaction. When the functional groups at both ends are acyloxy groups, after completion of the reaction,
A diol compound can be obtained by converting to a hydroxyl group by a method such as hydrolysis, saponification or transesterification.

The above-mentioned ring-opening polymerization catalyst is a catalyst capable of causing a so-called metathesis reaction to proceed, and includes titanium, zirconium, hafnium, vanadium, niobium, and the like.
Metal catalysts such as tantalum, chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium and iridium. A catalyst supported on a carrier or a complex catalyst can be used, but a complex catalyst is preferred.

Specific examples will be described below. (C_FiveH_Five) T
i (CH_Three)_TwoOr (C_FiveH_FiveN)_TwoTiCl_FourTo C_TwoH_FiveA
lCl_TwoAnd CH_ThreeAlCl_Two, A titanium catalyst mixed with
l_ThreeTa = CHSi (CH_Three)_ThreeTantalum-based catalysts such as
(N-C_FourH₉)_FourSn or (C_TwoH_Five)_ThreeTan mixed with Al
Gusten-based catalyst, ((CH_Three)_ThreeCCH_TwoO)_Two(O, P-
(Iso-C_ThreeH₇)_TwoC₆H_Three) -N = Mo = CH (te
r-C_FourH₉), MoCl5 with C_TwoH_FiveAlCl_TwoMix
Molybdenum based catalyst, ReCl5 with n-C_FourH₉)
_FourSn or (C_TwoH_Five)_ThreeRhenium-based catalyst mixed with Al
Ruthenium and osmium catalysts include RuC
l_Three, OsCl_ThreeSystem with alcohol added to
Ben complex, wherein Me is a ruthenium atom or a male
Represents a mimium atom. ), Cl_Two[P (iso-C
_ThreeH₇)_Three]_TwoMe = CH-C₆H_Five, BrCl [P (iso
-C_ThreeH₇)_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (is
o-C_ThreeH₇)_Three] _TwoMe = CH- [C₆H_Four(CH_Three)],
Cl_Two[P (iso-C_ThreeH₇)_Three]_TwoMe = CH- [C₆H
_Four(Ter-C_FourH₉)], BrCl [P (iso-C_ThreeH
₇)_Three]_TwoMe = CH-CH_TwoC₆H_Five, Cl_Two[P (sec
-C_FourH₉)_Three]_TwoMe = CH-C₆H_FiveTo phosphorus atoms such as
A carbene complex having a ligand to which a kill group is bonded, Cl_Two
[P (C_FiveH₉)_Three]_TwoMe = CH_Two, Cl_Two[P (C_FiveH₉)
_Three]_TwoMe = CH-CH_Three, Br_Two[P (C_FiveH₉)_Three]_TwoMe
= CH-iso-C_ThreeH₇, Cl_Two[P (C_FiveH₉)_Three]_TwoM
e = CH-n-C_FourH₉, Cl_Two[P (C_FiveH₉)_Three]_TwoMe
= CH-C_FiveH₉, Cl_Two[P (C_FiveH₉)_Three]_TwoMe = CH
-C₆H₁₁, F_Two[P (C_FiveH₉)_Three]_TwoMe = CH-C
₆H_Five, Cl_Two[P (C_FiveH₉)_Three]_TwoMe = CH-C₆H_Five,
Br_Two[P (C_FiveH₉)_Three]_TwoMe = CH-C₆H_Five, Br
_Two[P (C_FiveH₉)_Three]_TwoMe = CH- (C₆H_Four-OC
_TwoH_Five), Cl_Two[P (C_FiveH₉)_Three]_TwoMe = CH- (C₆H
_Four-Br), Cl_Two[P (C_FiveH₉)_Three]_TwoMe = CH- [C
₆H_Three− (CH_Three)_Two], F_Two[P (C_FiveH₉)_Three]_TwoMe = C
H- [C₆H_Three− (CH_Three)_Two], Br_Two[P (C_FiveH₉)_Three]
_TwoMe = CH-CH_TwoC₆H_FiveCyclopentic to phosphorus atom
Carbene complex having a ligand to which
_Two[P (C₆H₁₁)_Two-CH_TwoCH_Two−P (C₆H₁₁)_Two] M
e = CH-C₆H_Five, Cl_Two[P (C₆H₁₁)_Three]_TwoMe = C
H_Two, Cl_Two[P (C₆H₁₁)_Three]_TwoMe = CH-CH_Three, C
l_Two[P (C₆H₁₁)_Three]_TwoMe = CH-n-C_FourH₉, Cl
_Two[P (C₆H₁₁)_Three]_TwoMe = CH-ter-C_FourH₉, C
l_Two[P (C₆H₁₁)_Three]_TwoMe = CH-C_TenH₉, F_Two[P
(C₆H₁₁)_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆
H₁₁)_Three]_TwoMe = CH-C₆H_Five, Br_Two[P (C₆H₁₁)
_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆H₁₁)_Three]_TwoM
e = CH (C₆H_Four-CH_Three), Cl_Two[P (C₆H_{1 1})_Three]
_TwoMe = CH-C₆H_Four-CH (CH_Three)_Two, Cl_Two[P (C
₆H₁₁)_Three]_TwoMe = CH- [C₆H_Four(Ter-C
_FourH₉)], Br_Two[P (C₆H₁₁)_Three]_TwoMe = CH-C₆
H_Two− (CH_Three)_Three, Cl_Two[P (C₆H₁₁)_Three]_TwoMe = C
HC₆H_Four-OCH _Three, Br_Two[P (C₆H₁₁)_Three]_TwoMe
= CH- (C₆H_Four-NO_Two), Cl_Two[P (C₆H₁₁)_Three]
_TwoMe = CH- (C₆H_Four-Cl), BrCl [P (C₆H
₁₁)_Three]_TwoMe = CH-CH_TwoC₆H_Five, BrCl [P (C₆
H₁₁)_Three]_TwoMe = CH-CH_TwoC₆H_Five, Cl_Two[P (C₆
H₁₁)_Two(C (CH_TwoCH_Two)_TwoN (CH_Three)_TwoCl)]_TwoM
e = CH-C₆H_Five, Cl_Two[P (C₆H₁₁)_Two(CH_TwoCH
_TwoSO_ThreeNa)]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆
H₁₁)_Two(CH_TwoCH_TwoN (CH_Three)_ThreeCl)]_TwoMe = CH
-C₆H_FiveWith a cyclohexyl group bonded to a phosphorus atom such as
Carbene complex with ligand, Cl_Two[P (C₆H_Five)_Three]_Two
Me = CH-C₆H_Five, Cl_Two[P (C₆H_Four-CH_Three)_Three]_Two
Me = CH-C₆H_Five, Br_Two[P (C₆H_Three− (C
H_Three)_Two)_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆H_Two
− (CH_Three)_Three)_Three]_TwoMe = CH-C₆H_FiveSuch as phosphorus atom
Carbene complexes having a ligand to which an aromatic group is bonded, WO
  98/21214 of ruthenium and osmium
Carbene complexes, Thomas Weskamp et al., Angew. Chem. Int.
Ed., Vol. 37, 2490 (1998)
-Dialkyl-imidazoline-2-ylidene coordinated
Carbene complex or Cl_Two[P (C₆H ₁₁)_Three]_TwoRu = C =
CH (ter-C_FourH₉) And other vinylidene complexes
You.

These catalysts can be used alone or in combination of two or more. Of these, a tungsten atom, a molybdenum atom, a ruthenium atom, a complex having an osmium atom, more preferably a complex having a ruthenium atom, a carbene complex having a ligand of a phosphorus-based or nitrogen-based compound is Used.

The polyol (a) according to claim 1, which has the general formula (II) as a repeating unit, has the general formula (IV)
Can be obtained by hydrogenating the polyol (b) according to claim 7, which has a repeating unit in the main chain. In addition, in the ring-opening polymerization to the polyol (b) according to claim 7, the raw material is a chain unsaturated compound (d) (general formula (VI)
When the functional groups at both terminals of II)) are an acyloxy group or an aroyloxy group, the ring-opened polymer is hydrogenated and then hydrolyzed, saponified or transesterified to obtain a polyol (b).
Can also be obtained as

Examples of the method for hydrogenating the polyol (b) include basically all methods capable of hydrogenating a carbon-carbon double bond. For example, a stoichiometric method using a reagent such as a metal hydride, a metal hydride complex compound, borane or hydrazine, or a catalytic method using hydrogen is used. Among these methods, a hydrogenation reaction using hydrogen and a catalyst is desirable from the viewpoint of economy and mass productivity. However, when it is necessary to leave a substituent such as an aldehyde or a nitrile group without hydrogenation, a method of selectively hydrogenating only a carbon-carbon double bond is used instead of a hydrogenation method using hydrogen. There is a need.

Hydrogenation of polyol (b) with hydrogen gas
Catalysts include palladium, platinum, ruthenium, rhodium
With activated carbon, alumina, silica, etc.
Medium, Raney metal catalyst such as nickel, ruthenium, oxidation
Metal oxide catalysts such as palladium and platinum oxide and Ni (C
H_ThreeCOCHCOCH_Three)_Two/ (C_TwoH_Five)_ThreeAl, (C
_FiveH_Five)_TwoTiCl_Two/ (C_TwoH_Five)_TwoAlCl, [(C
₆H_Five)_ThreeP]_ThreeRhCl, [(C₆H _Five)_ThreeP]_ThreeRuC
l_Two, [(C₆H_Five)_ThreeP]_ThreeRuH_Two, [(C₆H_Five)_ThreeP]_Three
(CO) RuCl_Two, [(C₆H_Five)_ThreeP]_Three(CO) Ru
Nor for producing polyol (b) such as HCl
Ruthenium and Osumi used once in ring-opening polymerization of ornes
The use of homogeneous catalysts such as chromium metathesis catalysts
Can be.

The polyol residue in the polyurethane according to the present invention is a residue derived from the polyol (a) and / or the polyol (b) having a specific ring structure as a repeating unit according to claims 1 to 12. In addition to the group, it may contain a diol residue derived from another diol compound. For example, it is an alkylene group, a cycloalkylene group, an arylene group, or an arylalkylene group, and is not particularly limited as long as it is a polyol residue based on a polyol compound that can react with a polyisocyanate compound used in general polyurethane production. Specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-
Linear aliphatic diols such as butanediol, 1,6-hexanediol, and neopentyl glycol; and repeating units having an alicyclic structure such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and tricyclodecanedimethanol. Aromatic diols such as diol, bisphenol A and xylylene diol, (poly) ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol and polytetramethylene glycol, polyethylene adipate, polytetramethylene adipate, polyhexamethylene adipate and polyneo Examples include polyester polyols such as pentylene adipate and polycaprolactam, and diol residues such as polycarbonate diol, but the present invention is not limited to these. Although the ratio of the polyol residue having the specific cyclic structure repeating unit of the present invention and the other diol residue can be arbitrarily adjusted, in order to exert the effect of the present invention, the specific cyclic structure repeating unit is required. The residue of the polyol (a) and / or the residue of the polyol (b) having the general formula (I) is usually 5 to 5% based on the total amount of the polyol residue having the specific cyclic structure repeating unit of the present invention and other diol residues.
It is desirable to contain 100 mol%, preferably 10 to 100 mol%, more preferably 20 to 100 mol%. If the proportion is less than 1 mol%, the heat resistance tends to be insufficient.

The polyisocyanate compound used for the polyurethane compound shown in the present invention is not particularly limited as long as it can be used for ordinary polyurethane synthesis. Specifically, 4,4-diphenylmethane diisocyanate (MDI), polymeric MDI, tolylene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HD
I), xylylene diisocyanate (XDI), 4,
4'-Dicyclohexylmethane diisocyanate (HM
DI), isophorone diisocyanate (IPDI), tetramethylxylylene diisocyanate (TMXDI)
And diisocyanates such as triphenylmethane triisocyanate and isocyanate condensates such as isocyanurate. Further, a blocked isocyanate compound having a protecting group in the isocyanate group can also be used.

The polyurethane compound shown in the present invention is
It is obtained by a polyaddition reaction between a polyol compound having a repeating unit having a specific ring structure described in claim 1 and a polyisocyanate compound. Polyurethane containing another diol compound, the above polyol compound,
It is obtained by a polyaddition reaction of a polyisocyanate compound and another diol compound.

As an embodiment of the polyurethane synthesis reaction in the present invention, a general polyurethane production method can be applied as it is. That is, the polyisocyanate compound and the polyol compound are reacted in the presence or absence of a catalyst.

As the catalyst, those usually used in polyaddition reactions in general polyurethane synthesis can be used, and organic amine compounds, organic tin compounds and the like can be used.

In some cases, it is also possible to change the degree of polymerization of the polymer by adding a chain extender, a polyol compound as a crosslinking agent, a polyamine compound or the like.
In this case, the polyurethane is synthesized by simultaneously reacting the chain extender, the crosslinking agent, the polyol compound having the repeating unit having the specific ring structure described in Claims 1 to 12, and the polyisocyanate compound, and forming the polyurethane in one step. It is also possible to synthesize, or a polyol compound having the above specific ring structure and a polyisocyanate compound are first reacted to prepare a terminal polyisocyanate oligomer, and thereafter, the oligomer and a chain extender, a crosslinking agent Can be reacted in two stages to synthesize polyurethane.

The polyol compound and polyamine compound which can be used as a chain extender and a crosslinking agent in the synthesis of the polyurethane of the present invention are not particularly limited as long as they can be generally used for polyurethane. Examples of such polyol compounds include ethylene glycol, propylene glycol,
Trimethylene glycol, 1,4-butanediol,
Linear aliphatic diols such as 1,6-hexanediol and neopentyl glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A and tricyclodecanedimethanol, bisphenol A, xylylene diol, Aromatic diols such as hydroquinone diethylol ether, (poly) ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, trimethylolpropane, trimethylolethane, glycerin, hexanetriol, and pentaerythritol , Polyols such as sorbitol, polyethylene polyols such as polyethylene adipate and polytetramethylene adipate, polycaprolactone polyols, poly Turbo sulfonate polyol polybutadiene polyols polyols and the like. Further, specific examples of the polyamine compound include 3,3′-dichloro-
Examples thereof include aliphatic polyamine compounds such as 4,4'-diaminodiphenylmethane (MOCA), and hydroxyl-containing amines such as monoethanolamine and diethanolamine.

The polyaddition reaction can be carried out in a solvent or without solvent. The solvent is not particularly limited as long as it dissolves the polyol compound and the polyisocyanate compound in the present invention and does not inhibit the polyaddition reaction, and examples thereof include aromatic hydrocarbons such as toluene and xylene. However, since the water reacts with the isocyanate group and inhibits the polyaddition reaction with the polyol compound, it is preferable to use the solvent after dehydration (drying).

The ratio of the polyol compound (the polyol compound of the present invention containing a repeating unit having a specific ring structure and other polyols) to the polyisocyanate compound is not particularly limited. The ratio of the number of functional groups (hydroxyl group, amino group) to be reacted therewith is adjusted so that the ratio finally becomes close to 1. That is, the ratio NCO / (OH + NH) of the total molar equivalents of the NCO groups of the polyisocyanate compound to the hydroxyl groups of the polyol compound, and the total molar equivalents of the hydroxyl groups of the chain extender, the crosslinking agent, or the amino groups is preferably 0.7 to 0.7.
The mixing ratio of each raw material is determined so as to be in the range of 1.5, more preferably 0.9 to 1.2. If the content of either the isocyanate group or the hydroxyl group is extremely large, the compound having the excess functional group remains unreacted. In addition, the molecular weight of the produced polyurethane is often not sufficiently large, resulting in poor mechanical strength in many cases.

The polyurethane-based shock absorbing material of the present invention may contain other elastomers for the purpose of improving the mechanical strength. Examples of such materials include polyurethane elastomers obtained from polyisocyanate compounds such as polyether polyols, polyester polyols, polycarbonate polyols, and polyolefin polyols, and ethylene-tetrafluoroethylene copolymers and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene. Thermoplastic fluoroelastomer composed of a copolymer, thermoplastic fluoroelastomer composed of polyvinylidene fluoride and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, and the like can be given.

The polyurethane-based shock absorbing material of the present invention has a hardness of 85 A or more according to JIS K6301;
The peak temperature of the loss tangent (tan δ) at 110 Hz is 1
It is desirable that the temperature be 0 ° C. or higher. Therefore, when adding other elastomers and the like, care must be taken not to impair these properties.

Various additives such as an antioxidant, a light stabilizer and an ultraviolet absorber can be added to the polyurethane-based shock absorber of the present invention, if necessary.

[0048]

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

The reagents and solvents used in the Synthesis Examples and Examples were used as purchased without purification such as dehydration, unless otherwise specified. However, in the synthesis examples, degassing by inert gas substitution was performed before use. “Room temperature” in the examples indicates a temperature range of 10 to 25 ° C. unless otherwise specified. The obtained compound was analyzed under the following conditions.

-Vapor pressure osmotic pressure measurement (VPO) The number average molecular weight (Mn) was measured in chloroform.

Gel Permeation Chromatography (GPC) Using tetrahydrofuran or xylene as an eluent, the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) in terms of polystyrene were measured. Proton nuclear magnetic resonance spectrum ⁽¹ H-NMR) Proton NMR in Synthesis Example 1, deuterochloroform
The structure and functional groups at both terminals were confirmed and quantified.

・ Hardness It was measured according to JIS K6301A method.

Loss tangent (tan δ) Measured at a measuring frequency of 110 Hz and a temperature range of −150 to 100 ° C. using a Leo vibron apparatus (manufactured by Toyo Seiki Co., Ltd.)
The loss tangent (tan δ) was determined based on the following equation. Loss tangent (tan δ) = [Loss elastic modulus (E ″) / storage elastic modulus (E ′)] From the measurement results, a graph was created in which tan δ was plotted against temperature, and the value (maximum value) at which tan δ showed a peak and the value at that time Temperature and ta at 25 ° C.
The nδ value was determined.

(Synthesis Example 1) Synthesis of Polyol A 50 ml three-necked flask equipped with a cooling tube and a dropping funnel was purged with nitrogen, and 5.16 1,4-diacetoxy-2-butene was obtained.
g (30 mmol) and 10 ml of toluene were added. The catalyst (Cl ₂ [P (C ₆ H ₁₁ ) ₃ ] ₂ Ru = CH—C ₆
H ₅₎ was stirred with a mechanical stirrer was dissolved 0.06 g (0.07 mmol). The flask was placed in an oil bath, the bath temperature was raised to 40 ° C., and 9.0 g (75 mmol) of ethylidene norbornene adjusted separately was added to toluene 1
A solution dissolved in 0 ml was dropped from the dropping funnel over 1 hour. After completion of the dropwise addition, the reaction was carried out at 40 ° C. for 2 hours. The solution after the reaction was cooled to room temperature. The reaction solution and the catalyst (H
0.03 g of ClRu (CO) [P (C ₆ H ₅ ) ₃ ] ₃ )
The mixture was placed in a 00 ml stainless steel autoclave and subjected to a hydrogenation reaction at a hydrogen pressure of 6 MPa and a temperature of 155 ° C. for 4 hours while stirring. After the completion of the reaction, the mixture was cooled, and the reaction solution was dropped into 200 ml of methanol to precipitate a solid. This solid content was dissolved in 20 ml of toluene, and dropped into 200 ml of methanol to precipitate the solid content, and purification was repeated three times. The purified solid was dried under vacuum. It was a slightly viscous transparent viscous solid.

When the GPC of this solid was measured, Mn in terms of polystyrene was 4,800 and Mw / Mn was 2.3.

The hydrogenation rate was 99% based on the integral ratio of each peak in the proton NMR measurement. The molecular weight Mn calculated from the result of proton NMR was 3,800.

The molecular weight Mn measured by VPO is 36.
00, which was in good agreement with the molecular weight measured by proton NMR. From these results, it was found that the compound produced by the method of the present invention had an acetoxyl group introduced into both terminals without fail. Next, the ester portions at both ends were converted into diols by transesterification. The viscous solid (total amount except for the analysis) was dissolved in 30 ml of toluene,
1 g of a 28% sodium methoxide / methanol solution and 10 ml of methanol were added, and the mixture was refluxed for 5 hours. The solution after the reaction was poured into 100 ml of methanol and decanted. Further, the operation of dissolving in cyclohexane and adding methanol to precipitate was repeated three times for purification.
The solid was vacuum dried at 75 ° C. for 2 days. A soft solid was obtained.

From the result of proton NMR, it was confirmed that the acetoxyl group was transesterified and 100% hydroxylated. The molecular weight calculated from proton NMR was 3,700. Compound (A)
And

[0059]

Embedded image

(Synthesis Example 2) Synthesis of polyurethane using compound (A) Compound (A) was vacuum-dried in a beaker at 100 ° C for 2 hours, and then diphenylmethane diisocyanate (M
DI) was added in an amount of 1.1 times the molar amount of the OH group of the diol, followed by rapid stirring and mixing. This was cured by a one-shot method (130 ° C., 30 minutes).

(Synthesis Example 3) Polyurethane was synthesized in the same manner as in Synthesis Example 2 except that a polybutadiene polyol hydride (Polytail H manufactured by Mitsubishi Chemical Corporation) was used as a polyol compound. (Example 1 and Comparative Examples 1 to 3) The hardness (JIS A) and the loss tangent (tan δ) (peak value,
(Peak temperature) was measured and summarized in Table 1.

[0062]

[Table 1] Example 1: Synthesis Example 2 (Compound A / MDI) Comparative Example 1: Synthesis Example 3 (Polytail H / MDI) Comparative Example 2: Elastollan 1154 (Polyurethane manufactured by Takeda Bird Urethane Co., Ltd.) Comparative Example 3: Daiel Thermoplastic T-550 (Fluorine resin manufactured by Daikin Industries, Ltd.)

In the first embodiment, the hardness is 90 A and the hardness is high.
The loss tangent (tan δ) at room temperature is as high as 0.26.
Further, the peak temperature of the loss tangent is 39 ° C. and 10 ° C. or higher. From this, it can be seen that it has high hardness and excellent damping properties. Comparative Example 1 is a polyurethane using a hydrocarbon-based polybutadiene polyol hydride.
Both the loss tangent (tan δ) at room temperature are low. In Comparative Example 2, the polyurethane using the polyester polyol had a high hardness but a loss tangent (tan) at room temperature.
δ) is low. Comparative Example 3 is a fluorine-based elastomer, but has a low loss tangent (tan δ) at room temperature but a low hardness. From these facts, it can be seen that the shock absorber containing the polyol having a specific alicyclic structure of the present invention as a component has high hardness and excellent damping properties.

[0064]

The polyurethane-based shock absorber of the present invention is manufactured from a polyol having a specific ring structure as a repeating unit and a polyisocyanate. Useful as a shock absorber for magnetic disks.

   ────────────────────────────────────────────────── ─── Continuation of front page    F term (reference) 3J066 AA22 AA26 AA29 BA04 BD05                 4J034 BA02 BA05 CA01 CA03 CA04                       CB02 CB03 CC23 CC28 CC37                       CC52 CC61 CC62 DB03 DB04                       DC08 DC15 DC25 DC34 DC42                       DC43 DE01 DP01 DP02 DP20                       HA01 HC11 HC12 HC17 HC22                       HC35 HC52 HC61 HC63 HC64                       HC71 JA01 KA01 KB04 SA02                       SB03 SB04 SB05 SC01 SC03                       SD01 SD03

Claims (17)

[Claims] 1. A on both ends independently general formula _{(I) -CH 2 - (CH} 2) m -OH, -CH 2 - (CH 2) n -OH (I) [m, n is independently 0 Wherein at least one type of repeating unit constituting the structure is represented by the general formula (II): (II) [wherein, R _{1 to} R ₈ each independently represent a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (two of R _{1 to} R ₈ The above may be linked to form a ring.), A cyano group, a hydroxyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a formyl group, a carboxyl group (an acid anhydride may be formed from two carboxyl groups) .) Or a silyl group. An impact-absorbing material comprising, as a component, a polyurethane obtained by a polyaddition reaction of a polyol compound containing at least one polyol (a) having a ring structure represented by the following formula: 2. At least one of the polyols (a) has a structure represented by the general formula (I) at both terminals independently, and a repeating unit having a ring structure represented by the general formula (II) and carbon The shock absorbing material according to claim 1, wherein the shock absorbing material is a compound comprising a repeating unit of an alkylene group represented by Formulas 4 to 12. 3. R _{1 to} R _{8 of the} repeating unit represented by the general formula (II) each independently represent a hydrogen atom or a carbon atom having 1 to 2 carbon atoms.
The shock absorber according to claim 1 or 2, which is 0 hydrocarbon groups (two or more of R _{1 to} R ₈ may be linked to form a ring). 4. The shock absorber according to claim 1, wherein R _{1 to} R _{8 of the} repeating unit represented by the general formula (II) are hydrogen atoms. 5. The impact absorption according to claim 1, wherein R _{1 to} R ₄ and R _{6 to} R _{8 of the} repeating unit represented by the general formula (II) are a hydrogen atom, and R ₅ is an ethyl group. Wood. 6. The impact-absorbing material according to claim 1, wherein the proportion of the polyol (a) in the polyol compound constituting the polyurethane is 5 to 100 mol%. 7. on both ends independently general formula _{(III) = CH- (CH 2} ) m -OH, = CH- (CH 2) n -OH (III) [m, n are independently 0-5 Wherein at least one of the repeating units constituting the structure is represented by the general formula (IV): (IV) wherein R _{9 to} R ₁₆ are independently a halogen atom, a hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (R ₁₁ and R ₁₂ , and R ₁₃ and R ₁₄ may be each independently an alkylidene group, and R _{9 to} R ₁₆ Two or more of which may be linked to form a ring), a cyano group, a hydroxyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a formyl group, a carboxyl group (form an acid anhydride from two carboxyl groups) Or a silyl group. An impact-absorbing material comprising, as a component, a polyurethane obtained by a polyaddition reaction between a polyol compound containing at least one polyol (b) having a ring structure represented by the formula (I) and a polyisocyanate compound. 8. At least one of the polyols (b) has a structure represented by the general formula (III) at both terminals independently of each other, and a repeating unit having a ring structure represented by the general formula (IV) and carbon The shock absorbing material according to claim 7, wherein the shock absorbing material is a compound comprising a repeating unit of a hydrocarbon of Formulas 4 to 12. 9. Each of R _{9 to} R _{16 of the} repeating unit represented by the general formula (IV) is independently a hydrogen atom or a carbon atom having 1 to ₁₆ carbon atoms.
A hydrocarbon group (R ₁₁ and R ₁₂ of 20, R ₁₃ and R ₁₄ are independently each set may be an alkylidene group together, R ₉
Two or more of R ₁₆ to R ₁₆ may be linked to form a ring. )
The shock absorbing material according to claim 7 or 8, wherein 10. The shock absorbing material according to claim 7, wherein R _{9 to} R _{16 of the} repeating unit represented by the general formula (IV) are a hydrogen atom. 11. of the repeating unit represented by the general formula _{(IV) R 9 ~R 12,} R 15 ~R 1 6 is a hydrogen atom, R ₁₃ and R
_{14. A} compound according to claim 7, wherein ₁₄ is an ethylidene group.
2. The shock absorbing material according to 1. 12. The polyurethane impact absorber according to claim 7, wherein the proportion of the polyol (b) in the polyol compound constituting the polyurethane is 5 to 100 mol%. 13. A composition for producing an impact absorbing material, comprising, as a component, a polyurethane comprising the polyol (a) according to claim 1 and a polyisocyanate compound as essential components. 14. A composition for producing an impact absorbing material, comprising a polyol (b) according to claim 7 and a polyurethane having a polyisocyanate compound as an essential component. 15. A composition for producing an impact absorbing material comprising, as components, a polyol (a) according to claim 1, a polyol (b) according to claim 7, and a polyurethane having a polyisocyanate compound as an essential component. 16. An impact absorbing material obtained by subjecting the composition for producing an impact absorbing material according to claim 13 to a polyaddition reaction. 17. The shock absorber according to claim 1, wherein a peak temperature of a loss tangent at 110 Hz at a hardness of 85 A or more is 10 ° C. or more.