JP6955722B2 - Sound absorbing material containing a crosslinked body formed with polyrotaxane - Google Patents

Description

The present invention relates to a material having (A) a material having voids; and (B) a crosslinked body provided in at least a part of the material (A). In particular, the present invention relates to a material having a crosslinked body in which the (B) crosslinked body is formed with polyrotaxane. More particularly, the present invention relates to a material for which the material is used as a sound absorbing material.

Various materials are used as sound absorbing materials, but in particular, materials having voids are widely used as sound absorbing materials because they can reduce the weight in addition to high performance.
Patent Documents 1 and 2 disclose a fibrous material having voids and a resin material having voids, respectively, and disclose that each material is produced by a special process.
More specifically, Patent Document 1 discloses a non-woven fabric web having a non-woven fabric having the melt-blown fiber and a binder fiber fused to the melt-blown fiber at an entanglement point between the melt-blown fiber and the melt-blown fiber, and the non-woven fabric web is used as a sound absorbing material. Disclose that it will be.

Patent Document 2 discloses a polyethylene-based resin foam molded product obtained by molding polyethylene-based resin pre-foamed particles, and discloses that the molded product is used as a sound absorbing material.
Further, Patent Document 3 discloses that a sound absorbing material useful in a particularly low frequency region can be produced by combining an organic material and an inorganic material.

As described above, various sound absorbing materials have been proposed, but sound absorbing materials used in automobiles, building materials, home appliances, etc. are required to be further lightened and highly functional. Especially in automobiles, as noise countermeasures for engine noise, road noise, wind noise, motor electromagnetic vibration, squealing electronic noise, brake noise, etc., in addition to weight reduction and high functionality, sound absorbing materials with different frequency characteristics must be used. It doesn't become.

Therefore, there is a demand for a material that can meet the needs for further weight reduction and / or higher functionality, particularly a sound absorbing material. Further, in addition to weight reduction and / or high functionality, there is a demand for a material capable of easily providing a sound absorbing material having different frequency characteristics and a method for manufacturing the same.

Japanese Patent Application Laid-Open No. 2015-212442. JP-A-2007-44877. Japanese Patent Application Laid-Open No. 8-30275.

Therefore, an object of the present invention is to provide a material that can meet the needs for further weight reduction and / or high functionality, particularly a sound absorbing material.
Further, an object of the present invention is to provide a material and a method for producing the same, which can easily provide a sound absorbing material having different frequency characteristics in addition to the above-mentioned object or in addition to the above-mentioned object, in addition to weight reduction and / or high functionality. To provide.

The present inventors have found the following inventions.
<1> (A) a material having voids; and (B) a crosslinked body provided in at least a part of the (A) material;
Is a material that has
The crosslinked body (B) is
(B) -1) A polyrotaxane in which a blocking group is arranged at both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached; B) -2) The above-mentioned material, which is a crosslinked product formed by having a polymer capable of binding to polyrotaxane.

<2> In the above <1>, it is preferable that the (B) crosslinked body is provided on at least a part of the surface layer of the (A) material.
<3> In the above <1> or <2>, the cyclic molecule of (B) -1) polyrotaxane preferably has a hydroxyl group.
<4> In any of the above <1> to <3>, the (B) -2) polymer preferably has a polyol.

<5> In the above <4>, the polyol is preferably at least one selected from a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polysiloxane polyol.
<6> In any of the above <1> to <5>, the crosslinked body (B) is preferably formed with a further crosslinking agent.
<7> In the above <6>, the cross-linking agent preferably has a polyisocyanate cross-linking agent.

<8> In any of the above <1> to <7>, the material (A) is selected from the fibrous material group consisting of rock wool, glass wool, non-woven fabric, and felt, and / or urethane foam, rubber. It is preferably selected from the foam material group consisting of foam and cellulose foam, preferably selected from the fibrous material group, and more preferably glass wool or non-woven fabric.
<9> In any of the above <1> to <8>, the material (A) is preferably selected from the fibrous material group consisting of rock wool, glass wool, non-woven fabric, and felt, preferably glass wool or. It is preferably a non-woven fabric, and the weight of the material per unit area is 50 to 2000 g / m ² , preferably 80 to 1500 g / m ² , more preferably 100 to 1000 g / ^{m 2, still more preferably 100 to 800 g / m 2.} It should be ^{m 2.}

<10> It is preferable that any of the above materials <1> to <9> is a sound absorbing material.
<11> In the above <10>, the ratio of the vertically incident sound absorption coefficient X1 of the sound absorbing material at a sound absorbing frequency of 1000 Hz to the vertically incident sound absorbing coefficient X2 of the material consisting of only the material (A) of the sound absorbing materials at a sound absorbing frequency of 1000 Hz. , X1 / X2 is preferably 1.1 or more, preferably 1.3 or more, and more preferably 1.5 or more.
<12> In the above <10> or <11>, the vertically incident sound absorption coefficient X11 of the sound absorbing material at a sound absorbing frequency of 3000 Hz and the vertically incident sound absorbing coefficient of the material consisting of only the material (A) of the sound absorbing materials at a sound absorbing frequency of 3000 Hz. The ratio of X11 / X12 to X12 is preferably 1.1 or more, preferably 1.3 or more, and more preferably 1.5 or more.

<13> A sound absorbing material for a vehicle using the material described in any of the above <1> to <9>; or the sound absorbing material described in any of the above <10> to <12>.
<14> A vehicle using the material described in any of the above <1> to <9>; or the sound absorbing material described in any of the above <10> to <12>.

<15> (A) Material having voids; and (B) (A) Crosslinked body provided in at least a part of the material:
It is a manufacturing method of a material having
(I) (A) Step of preparing materials;
(II-1) (B) -1) Closing groups are arranged at both ends of the pseudopolyrotaxane in which the openings of the cyclic molecule are skewered by the linear molecule so that the cyclic molecule is not detached. The process of preparing polyrotaxane
(II-2) (B) -2) Step of preparing a polymer capable of binding to the polyrotaxane;
(II-3) A step of preparing a composition having the (B) -1) polyrotaxane; and the (B) -2) polymer;
(III) The step of applying the composition to at least a part of the (A) material; and (IV) After the (III) coating step, the (B) -1) polyrotaxane; and the (B) -2. ) Polymer; step of forming a crosslinked body formed with;
The above method, wherein a layer of the crosslinked body is formed on at least a part of the material (A).

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a material that can meet the needs for further weight reduction and / or high functionality, particularly a sound absorbing material.
Further, the present invention provides a material and a method for producing the same, which can easily provide a sound absorbing material having different frequency characteristics in addition to the above effects or in addition to the above effects, in addition to weight reduction and / or high functionality. be able to.

The vertical incident sound absorption coefficient by frequency of the sound absorbing material K1 to K6 (Examples 1 to 6) of the present invention and the sound absorbing material H1 (Comparative Example 1) containing only the base material 1 is shown. The vertical incident sound absorption coefficient by frequency of the sound absorbing materials K7 to K12 (Examples 7 to 12) of the present invention and the sound absorbing material H2 (Comparative Example 2) which is only the base material 2 is shown. The vertical incident sound absorption coefficient by frequency of the sound absorbing materials K13 to K17 (Examples 13 to 17) of the present invention and the sound absorbing material H3 (Comparative Example 3) which is only the base material 3 is shown. The vertical incident sound absorption coefficient by frequency of the sound absorbing materials K18 to K19 (Examples 18 to 19) of the present invention and the sound absorbing material H4 (Comparative Example 4) which is only the base material 4 is shown. The vertical incident sound absorption coefficient by frequency of the sound absorbing materials K20 to K21 (Examples 20 to 21) of the present invention and the sound absorbing material H5 (Comparative Example 5) containing only the base material 5 is shown.

Hereinafter, the invention described in the present application will be described in detail.
The present application provides a material having (A) a material having voids; and (B) a crosslinked body provided in at least a part of the material: a material that can be used as a sound absorbing material in particular.
Hereinafter, the materials provided by the present application will be described.

<(A) Material with voids>
The material of the present application has (A) a material having voids.
(A) A material having voids means a material in which voids are one of the constituent components of the material. Here, as the voids, when the constituent components other than the voids of the material are fibrous materials, the voids are generated by the entanglement of the fibers, or the voids are generated by the dispersion of air bubbles in the constituent components of the material. Things, etc. are included, but not limited to these.
The "components other than the voids" are preferably fibrous materials, and particularly preferably fibrous materials when the material of the present application is used as the sound absorbing material.

(A) Examples of the material having voids include, but are not limited to, a fibrous material group; and a foam material group.
Specific examples of the fibrous material included in the fibrous material group include, but are not limited to, rock wool, glass wool, non-woven fabric, and felt.
Further, examples of the foam material included in the foam material group include a material in which air bubbles are dispersed and / or a foam material, and specific examples thereof include urethane foam, rubber foam, and cellulose foam, but are limited thereto. Not done.
When these materials are used as a sound absorbing material, rock wool, glass wool, non-woven fabric, and felt are preferable, glass wool and non-woven fabric are more preferable, and non-woven fabric is particularly preferable.
The shape of the above-mentioned material can be appropriately determined depending on the intended use, and may be, for example, a sheet shape, a plate shape, a spherical shape, or an amorphous shape.

The material provided by the present application may have a material other than the "(A) material having voids" as long as it has (A) a material having voids. When it has a material other than the "material having (A) voids", it may be a composite material of the "material having (A) voids" and the material other than the "material having (A) voids". If the composite material is "a material in which voids are one of the constituent components of the material", the composite material corresponds to the material having voids (A) of the present application.

(A) The material having voids is preferably selected from the above-mentioned fibrous material group, and its texture, that is, the weight per unit area is 50 to 2000 g / m ² , preferably 80 to 1500 g / m ² , and more. preferably 100 to 1000 g / ^{m 2,} may further preferably 100 to 800 g / ^{m 2.}
In particular, when the material is used as a sound absorbing material, (A) the material having voids is preferably rock wool, glass wool, non-woven fabric, or felt, more preferably glass wool or non-woven fabric, and particularly preferably non-woven fabric, and the texture. , i.e. weight per unit area, 50 to 2000 g / ^{m 2,} preferably 80~1500g / ^{m 2,} more preferably 100 to 1000 g / ^{m 2,} more preferably may be between 100 to 800 g / ^{m 2.}

<(B) Crosslinked body>
The material of the present application has (B) a crosslinked product. The (B) crosslinked body is provided on at least a part of the above (A) material. The crosslinked body (B) is preferably provided so as to be provided on the surface layer of at least a part of the material (A).
(B) The crosslinked body is
(B) -1) A polyrotaxane in which a blocking group is arranged at both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached; and ( B) -2) Polymer that can bind to polyrotaxane;
It is a crosslinked body formed by having.
The details of the polymer (B) -2) capable of binding to polyrotaxane will be described later. The "polymer" of the "(B) -2) polymer capable of binding to polyrotaxane" includes the above "(B) -1) polyrotaxane. Is not included.
The "polymer" of "(B) -2) polymer capable of binding to polyrotaxane, which is a component contained in" (B) crosslinked product "included in the material of the present invention, includes the above "(B) -1". ) Polyrotaxane ”is not included, but the material of the present invention may contain a crosslinked product of the above“ (B) -1) polyrotaxane ”.

^{The crosslinked body is 50 g / m 2 to} 400 g / m ² , preferably 70 g / m ² to the above-mentioned material having voids (A), for example, a fibrous material such as a non-woven fabric. 350 g / ^{m 2,} and more preferably may have an amount of ^{80g / m 2 ~300g / m 2} .

<< (B) -1) Polyrotaxane >>
The (B) crosslinked product is formed with (B) -1) polyrotaxane;
(B) -1) Polyrotaxane is formed with a cyclic molecule, a linear molecule, and a blocking group, and both ends of the pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by the linear molecule. Is formed by arranging a blocking group so that the cyclic molecule does not escape. Hereinafter, the components contained in polyrotaxane will be described.

<Cyclic molecule>
(B) -1) The cyclic molecule of polyrotaxane is not particularly limited as long as it is cyclic, has an opening, and is skewered by a linear molecule.
The cyclic molecule depends on a desired material, a material other than "(B) -1) polyrotaxane" used for forming the material, and the like, but preferably has a hydroxyl group (-OH group).
The hydroxyl group (-OH group) may be directly bonded to the cyclic skeleton of the cyclic molecule or may be bonded to the cyclic skeleton via the first spacer, although it depends on the properties of the desired material and the like. ..

Further, the cyclic molecule is selected from the group consisting of other groups, for example, 1) hydrophobic modifying group; 2) -NH _{2, -COOH, and -SH; depending on the properties of the desired material and the like.} Group, 3) A group selected from the group consisting of an acrylic group, a methacryl group, a styryl group, a vinyl group, a vinylidene group, a polymerizable group of a maleic anhydride-containing functional group; and the like.

1) As hydrophobic modifying groups, acetyl group, butyl ester group, hexyl ester group, octadecyl ester group, polycaprolactone group, poly (δ-valerolactone) group, polylactic acid group, polyalkylene carbonate group, polypropylene glycol group, poly Groups having a hydrophobic group such as a tetramethylene glycol group, a methyl polyacrylate group and an ethylhexyl polyacrylate group can be mentioned, but are not limited thereto. Of these, a polycaprolactone group, a polypropylene glycol group, and a polyalkylene carbonate group are preferable.

The groups described in 2) and 3) above may be directly attached to the cyclic molecule or may be attached via a second spacer. The second spacer may be the same as or different from the first spacer, and may be the same type or different types.
The first or second spacer is not particularly limited, but may be an alkylene group, an alkylene oxide group, a hydroxyalkylene group, a carbamoyl group, an acrylic acid ester chain, a polyalkylene ether chain, or a polyalkylene carbonate chain.
The cyclic molecule may be selected, for example, from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

<Linear molecule>
(B) -1) The linear molecule of polyrotaxane is not particularly limited as long as it can be skewered into the opening of the cyclic molecule to be used.
For example, as linear molecules, polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylic acid, cellulose-based resin (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl. Acetal resins, polyvinyl methyl ethers, polyamines, polyethyleneimines, caseins, gelatins, starches and / or copolymers thereof, copolymers of polyethylene, polypropylene, and other olefin monomers, and other polyolefin resins. Polyester resin, polyvinyl chloride resin, polystyrene resin such as polystyrene and acrylonitrile-styrene copolymer resin, polymethylmethacrylate and (meth) acrylic acid ester copolymer, acrylic resin such as acrylonitrile-methylacrylate copolymer resin, polycarbonate Resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, etc .; and derivatives or modified products thereof, polyisobutylene, poly tetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), nylon, etc. Polyamides, polyimides, polyisoprenes, polydiene such as polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyanacetic acetic acids, polyureas, polysulfides, polyphosphazenes, polyketones. , Polyphenylenes, polyhaloolefins, and derivatives thereof. For example, it is preferably selected from the group consisting of polyethylene glycol, polyisobutylene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether. Especially polyethylene glycol is preferable.

The weight average molecular weight of the linear molecule is preferably 1,000 or more, preferably 3,000 to 100,000, and more preferably 6,000 to 50,000.
In polyrotaxane, the combination of (cyclic molecule, linear molecule) is preferably (derived from α-cyclodextrin, derived from polyethylene glycol).

<Closing group>
(B) -1) The blocking group of polyrotaxane is not particularly limited as long as it is a group that is arranged at both ends of the pseudopolyrotaxane and acts to prevent the cyclic molecule used from being detached.
For example, as a blocking group, dinitrophenyl groups, cyclodextrins, adamantan groups, trityl groups, fluoresceins, silsesquioxanes, pyrenes, substituted benzenes (as substituents, alkyl, alkyloxy, hydroxy, Halogen, cyano, sulfonyl, carboxyl, amino, phenyl and the like can be mentioned, but not limited to these. One or more substituents may be present), and optionally substituted polynuclear aromatics (substitution). As the group, the same group as above can be mentioned, but the group is not limited thereto. One or more substituents may be present), and it is preferable to be selected from the group consisting of steroids. It is preferable to select from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes, and more preferably adamantane groups or cyclodextrins. It should be kind.

<< (B) -2) Polymer that can bind to polyrotaxane >>
The (B) crosslinked product is formed with (B) -2) a polymer capable of binding to polyrotaxane;
Here, it is intended that the "polymer" of the "(B) -2) polymer capable of binding to polyrotaxane" does not include the above-mentioned "(B) -1) polyrotaxane" as described above.
The "(B) -2) polymer capable of binding to polyrotaxane" refers to a polymer capable of directly and / or indirectly binding to the above "(B) -1) polyrotaxane".
The “polymer that can be directly bonded” refers to a polymer that can be bonded to (B) -1) polyrotaxane in the presence of heat, a catalyst, or the like, and is not limited thereto, which will be described later.
The “indirectly bondable polymer” refers to a polymer that can bind to (B) -1) polyrotaxane using a cross-linking agent or the like, and is not limited thereto, although it will be described specifically later.

When the "(B) -2) polymer capable of binding to polyrotaxane" is "(B) -1) polyrotaxane" and "polymer capable of directly binding", the following combination is preferable.
That is, it is preferable to impart the first functional group to the cyclic molecule of (B) -1) polyrotaxane, while imparting the second functional group to the polymer capable of binding to (B) -2) polyrotaxane. It is preferable to form the (B) crosslinked product by reacting the functional group with the second functional group.

Here, as a combination of the first functional group and the second functional group, for example, an epoxy group and a carboxylic acid group, an epoxy group and an amine residue, an epoxy group and a phenol group, an isocyanate group and a hydroxyl group, and an isocyanate group and a thiol group. , An isocyanate group and an amino group, a carbodiimide group and a carboxylic acid group, an acid anhydride residue and a hydroxyl group, an acid anhydride residue and an amino group, and the like, but are not limited thereto. Since the above is intended to describe a "combination", for example, when the combination of the first functional group and the second functional group is an epoxy group and a carboxylic acid group, the first functional group is an epoxy. It is intended to include when the group is a carboxylic acid group and the second functional group is a carboxylic acid group, and when the first functional group is a carboxylic acid group and the second functional group is an epoxy group.

In this case, as "(B) -2) polymer capable of binding to polyrotaxane", poly (meth) acrylic acid ester, polyamide, polyester, polyether, polyolefin, polydiene, polysiloxane, polystyrene, polyurethane, polyurea, polycarbonate, and these. Examples of the polymer obtained by imparting the first or second functional group to the copolymer of the above are not limited thereto.

When the reaction is carried out in the above combination, heating or a catalyst may be used.
The catalyst depends on the (B) -2) polymer used, the (B) -1) polyrotaxane used, and the like, and examples thereof include a tin catalyst, a bismuth catalyst, a zinc catalyst, a base catalyst, and an acid catalyst. , Not limited to these.
When heating, the temperature is 25 to 200 ° C., depending on (A) the material having voids, (B) -2) polymer, (B) -1) polyrotaxane, and the like. It is preferably carried out at 50 to 170 ° C., more preferably 70 to 150 ° C.

Further, both the first and second functional groups are radically polymerizable groups (first and second radically polymerizable groups, respectively), and depending on the radical initiator, the first and second functional groups (radical polymerizable groups). It is preferable that the radicals are bonded to each other to form a crosslinked product by "directly bonding" with "(B) -2) a polymer capable of binding to polyrotaxane" and "(B) -1) polyrotaxane".

Examples of the first and second radically polymerizable groups include, but are not limited to, an acrylic group, a methacryl group, a styryl group, a vinyl group, a vinylidene group, and a maleic acid anhydride / maleinimide-containing functional group.
In this case, as "(B) -2) a polymer capable of binding to polyrotaxane, that is, a polymer having a second radically polymerizable group, poly (meth) acrylic acid ester, polyamide, polyester, polyether, polyolefin, polydiene, poly Examples thereof include, but are not limited to, siloxane, polystyrene, polyurethane, polyurea, polycarbonate, and a polymer obtained by imparting a radically polymerizable group to a copolymer thereof.

Radical Polymerization Initiator (B) -2) When the polymer capable of binding to polyrotaxane has a polymer having a radically polymerizable group, it is preferable to use a radical polymerization initiator.
Examples of the radical polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. These are not particularly limited, and known polymerization initiators can be used.
The amount of the polymerization initiator added is preferably in the range of 0.05 to 5% by mass with respect to the mixture.

Examples of thermal polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-. Organic peroxide-based polymerization initiators such as xylperoxypivalate, diisopropylperoxydicarbonate, and bis (4-t-butylcyclohexyl) peroxydicarbonate; 2,2'-azobisisobutyronitrile, 2, Azo-based polymerization initiators such as 2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); potassium persulfate, ammonium persulfate, persulfate Examples thereof include persulfates such as sodium. These may be used alone or in combination of two or more.

Examples of the photopolymerization initiator include 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methylphenylglioxylate, acetophenone, benzophenone, diethoxyacetophenone, 2,2. -Dimethoxy-2-phenylacetophenone, 1-phenyl-1,2-propane-dione-2- (o-ethoxycarbonyl) oxime, 2-methyl [4- (methylthio) phenyl] -2 morpholino-1-propanone, benzyl , Bensoine isobutyl ether, 2-chlorothioxanthone, isopropylthioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, benzoyldimethoxyphosphine oxide, etc. Can be mentioned. These may be used alone or in combination of two or more.

The material of the present application may contain "other components" for forming the crosslinked body.
Other components include, but are not limited to, inorganic fillers, antioxidants, flame retardants, UV absorbers, dyes, pigments, antistatic agents and the like.

When the "(B) -2) polymer capable of binding to polyrotaxane" is "(B) -1) polyrotaxane" and "polymer capable of indirectly binding", a cross-linking agent is added as described above, and the cross-linking agent is added. It is preferable to bond "(B) -1) polyrotaxane" and "a polymer that can be indirectly bonded" to form a crosslinked product.
In this case, (B) -1) polyrotaxane has an eleventh functional group that reacts with the cross-linking agent used, and the "indirectly bondable polymer" has a twelfth functional group that reacts with the cross-linking agent used. However, it is preferable to form a crosslinked product by reacting with the cross-linking agent used, the eleventh functional group, and the twelfth functional group.
The eleventh and twelfth functional groups are preferably hydroxyl groups, amino groups, thiol groups and the like, and as the cross-linking agent in that case, a polyisocyanate cross-linking agent having two or more isocyanate groups and two or more epoxy groups. Examples include, but are not limited to, epoxy compounds, compounds having two or more acid anhydride residues, carbodiimide crosslinkers, and the like.

The polymer capable of binding to (B) -2) polyrotaxane is preferably a polyol, and (B) -1) polyrotaxane is preferably a cyclic molecule having a hydroxyl group.
Polyol In the present application, the polyol means a substance having two or more OH groups.
As the polyol, a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, a polysiloxane polyol, a block copolymer or graft of a plurality of types of polyols (for example, a polyol obtained by block-polymerizing polyester on a polyether polyol), a side chain. Examples thereof include, but are not limited to, polymers having two or more hydroxyl groups.
The polyol is preferably at least one selected from a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polysiloxane polyol, preferably at least one selected from a polyether polyol, a polyester polyol, and a polycarbonate polyol. It is preferably at least one selected from the species, more preferably the polyether polyol and the polyester polyol.

Examples of polymers having two or more hydroxyl groups in the side chain include side chain hydroxyl group-imparted products such as poly (meth) acrylic acid ester, polyvinyl chloride, and polyvinyl acetate.

The OH group of the polyol may be 2 or 3 or more. (B) -2) When the polymer capable of binding to polyrotaxane has a polyol, the polyol may be only one type or a plurality of types may be used in combination.
The polyol preferably has a weight average molecular weight of 50 to 30,000, preferably 250 to 10,000, and more preferably 250 to 8000.

Further, when the polymer capable of binding to (B) -2) polyrotaxane has a polyol, as described above, it is convenient for (B) -1) polyrotaxane to have a hydroxyl group in cross-linking. In this case, it is preferable to use polyisocyanate as the cross-linking agent. The polyisocyanate refers to a compound having two or more isocyanate groups.
As the polyisocyanate, known aliphatic, alicyclic and aromatic isocyanates may be used, or newly synthesized ones may be used.

Examples of polyisocyanates are hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl). Fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexyl Sirenized isocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene 1,3- and / or 1,4-phenylenediocyanate, 2,4- and / or 2, 6-Toluene diisocyanate (TDI), crude TDI, 2,4'-and / or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4 '-Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, m- and / or p-xylylene diisocyanate (XDI), α , Α, α', α'-tetramethylxylylene diisocyanate (TMXDI), etc., as well as derivatives or multimers of these, and polyisocyanates thereof, and having a polymer moiety in which a plurality of isocyanate groups are added to an existing polymer. Polyisocyanates, etc. can be mentioned, but are not limited thereto.

When polyisocyanate is used, the amount of the polyisocyanate is preferably in the following range.
The ratio of the number of moles of isocyanate groups of polyisocyanate to the number of moles of active hydrogen of polyol and polyrotaxane, that is, (number of moles of isocyanate groups of polyisocyanate) / (number of moles of active hydrogen of polyol and polyrotaxan) is 0. It is preferable to adjust the amount of the polyisocyanate compound so that it is 30 to 2.00, preferably 0.50 to 1.50, and more preferably 0.60 to 1.20.
The ratio (number of moles of isocyanate group of polyisocyanate) / (number of moles of active hydrogen of polyol and polyrotaxane) may be expressed as "NCO index".

Specific examples of the active hydrogen include hydrogen having an OH group present in a polyol and hydrogen having an OH group present in a polyrotaxane. Further, not only hydrogen derived from OH group but also hydrogen such as thiol group, primary amino group, secondary amino group and carboxylic acid group existing in polyol and polyrotaxane also acts as active hydrogen, so the total number of moles thereof is ". The number of moles of active hydrogen of polyol and polyrotaxane ".
When the active hydrogen is derived only from the OH group, the amount of the active hydrogen can be expressed by the hydroxyl value OHV.

As the catalyst used for accelerating the reaction between the polyol and / or (B) -1) polyrotaxane and polyisocyanate, various known urethanization catalysts can be used. For example, triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethylbenzylamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N, N', N'. , N ″ -pentamethyldiethylenetriamine, bis- (2-dimethylaminoethyl) ether, N, N-dimethylethanolamine, N, N-diethylethanolamine, 1,8-diazabicyclo [5.4.0] undecene-7 , 1,5-diazabicyclo [4.3.0] nonen-5, 1,5-diazabicyclo [4.4.0] decene-5 and other tertiary amines; metal carboxylates such as potassium acetate and potassium octylate. Examples thereof include salts, stanas octoate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dilaurate, zinc naphthenate, bismastriooctate (2-ethylhexanoic acid), and organic metal compounds such as aluminum octylate.
It is preferable to add at least one of these catalysts to the formation of the crosslinked product.
The amount added is preferably 0.001 to 5.0% by mass with respect to the polyol.

Moreover, you may use a solvent in forming a crosslinked body. It is preferable to remove the solvent after the crosslinked product manufacturing step. The solvent makes it easier to mix the crosslinked components, enhances the compatibility between the crosslinked components, and adjusts the viscosity when applied to the material having voids. It can be used for purposes such as adjusting.
Examples of the solvent include, but are not limited to, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene and the like.

<"Other components" in the material of the present application>
The material of the present application may contain "other components" in addition to (A) a material having voids; and (B) a crosslinked body: if desired.
Examples of other components include antioxidants, flame retardants, ultraviolet absorbers, dyes, pigments, antistatic agents, etc. described in radical polymerization, as well as various fillers. Not limited.

The material of the present application can be used in various applications in which a material having voids is used. For example, sound absorbing materials, heat insulating materials, filters, buffers, packaging materials, interior members and the like can be mentioned, but are not particularly limited. In particular, as a sound absorbing material, it can be used in various fields where sound insulation or muffling is required, such as buildings such as houses and buildings; vehicles; home appliances; soundproof walls of transportation infrastructure of highways, railways, airports, and ports; and air conditioning equipment. can.

<Sound absorbing material>
When the material of the present application is used as the sound absorbing material, the material of the present application can meet the needs for weight reduction and / or high functionality required for the sound absorbing material. Further, in addition to weight reduction and / or high functionality, sound absorbing materials having different frequency characteristics can be easily provided.
Specifically, the material (sound absorbing material) of the present application can have the following characteristics, particularly preferable vertically incident sound absorbing coefficient.

That is, the sound absorbing material C1 made of the material of the present application and the sound absorbing material C2 made of only the material (A) among the materials of the present application are prepared, and the vertically incident sound absorption coefficient of each is compared to form the material of the present application. It can be seen that the sound absorbing material C1 exhibits desired sound absorbing characteristics.

The sound absorbing material made of the material of the present application has a specific frequency in the frequency range of 500 Hz to 4500 Hz, which is higher than the sound absorbing rate of the sound absorbing material made of only the material having (A) voids. The sound absorbing material made of the material of the present application preferably has a high sound absorbing coefficient particularly at a low frequency of 500 Hz to 1500 Hz, and in that case, among the above-mentioned applications, vehicle engine noise, gear differential noise, motor electromagnetic noise, etc. It is effective as a sound absorbing material to absorb. Further, the sound absorbing material made of the material of the present application preferably has a high sound absorbing coefficient at 2000 Hz to 4500 Hz in addition to the sound absorbing characteristic at the low frequency or in addition to the sound absorbing characteristic at the low frequency. It is effective as a sound absorbing material that absorbs brake noise, electronic noise, wind noise, etc.

The vertical incident sound absorption coefficient of the sound absorbing material C1 made of the material of the present application at a sound absorbing frequency of 1000 Hz is X1, while the ratio of the sound absorbing material C2 made of only the material (A) to the vertically incident sound absorbing coefficient X2 at a sound absorbing frequency of 1000 Hz is taken. The ratio X1 / X2 is 1.1 or more, preferably 1.3 or more, and more preferably 1.5 or more.

Further, the vertically incident sound absorption coefficient of the sound absorbing material C1 made of the material of the present application at a sound absorbing frequency of 3000 Hz is X11, while the ratio of the sound absorbing material C2 made of only the material (A) to the vertically incident sound absorbing coefficient X12 at a sound absorbing frequency of 3000 Hz. The ratio X11 / X12 is 1.1 or more, preferably 1.3 or more, and more preferably 1.5 or more.

It is preferable that only one type of sound absorbing material of the present application has a high vertical incident sound absorption coefficient in the above frequency region, specifically, in a specific region of the frequency region of 500 Hz to 4500 Hz. Specifically, it is preferable that the vertically incident sound absorption coefficient at the sound absorption frequencies of 1000 Hz and 3000 Hz exhibits the above values with only one type of sound absorbing material of the present application.
The sound absorbing material C11 of the present application has a vertically incident sound absorption coefficient at a sound absorbing frequency of 1000 Hz having the above value, and the other sound absorbing material C12 has a vertically incident sound absorbing coefficient at a sound absorbing frequency of 3000 Hz having the above value. Depending on the combination of C11 and C12, the vertically incident sound absorption coefficient at the sound absorption frequencies of 1000 Hz and 3000 Hz may exhibit the above values.

The material or sound absorbing material of the present application can be used as a sound absorbing material for vehicles. Specifically, it can be used as a sound absorbing material for engine head covers, pillars, fender liners, head liners, trunk liners, door panels, dashboards, and bonnets.
Further, the material or sound absorbing material of the present application can be used for a vehicle.

<Manufacturing method of the material of the present application>
The above-mentioned material can be produced by the following method.
That is, (I) the step of preparing the above-mentioned (A) material;
(II-1) Step of preparing the above-mentioned (B) -1) polyrotaxane;
(II-2) Step of preparing the above-mentioned (B) -2) polymer;
Step of preparing a composition having (II-3) (B) -1) polyrotaxane; and (B) -2) polymer;
(III) The step of applying the composition to at least a part of the (A) material; and (IV) (III) after the coating step, (B) -1) polyrotaxane; and (B) -2) polymer; Step of forming a crosslinked body formed by
The above-mentioned layer of the crosslinked product (B) is formed on at least a part of the material (A), whereby the material of the present application can be produced.

<Step (I)>
Step (I) is a step of preparing the above-mentioned material (A).
In this step, the existing material (A) may be purchased commercially or newly prepared.
<Step (II-1)>
Step (II-1) is a step of preparing the above-mentioned (B) -1) polyrotaxane.
In this step, a commercially available polyrotaxane may be used, or a newly synthesized one may be used.

<Step (II-2)>
Step (II-2) is a step of preparing the above-mentioned (B) -2) polymer.
In this step, the above-mentioned (B) -2) polymer may be purchased commercially or newly prepared. <Step (II-3)>
Step (II-3) is a step of preparing a composition having (B) -1) polyrotaxane; and (B) -2) polymer.
If desired, a solvent may be used in preparing the composition. As the solvent, the above-mentioned solvent can be used.

<Step (III)>
Step (III) is a step of applying the composition to at least a part of the material (A).
For coating, a conventionally known method can be used, depending on the characteristics of the composition used. Examples of the coating method include, but are not limited to, spray coating, dip coating, roll coating, and knife coating.

<Process (IV)>
The step (IV) is a step of forming a crosslinked product formed having (B) -1) polyrotaxane; and (B) -2) polymer; after the step (III), that is, after the coating step.
In step (IV), a reaction for forming a crosslinked product can be adopted depending on the (B) -1) polyrotaxane used and the (B) -2) polymer used.
For example, when (B) -1) polyrotaxane and (B) -2) polymer have the above-mentioned first and second radically polymerizable groups, respectively, the polymerization conditions depending on the radically polymerizable groups should be adopted. Can be done.
Further, for example, when (B) -1) polyrotaxane and (B) -2) polymer have the above-mentioned eleventh and twelfth functional groups, respectively, and they are bonded and crosslinked via a cross-linking agent, the said. Conditions can be adopted according to the bonding / cross-linking conditions.

<Other processes>
In the method of the present invention, other steps may be provided, if necessary, in addition to the above steps (I) to (IV).
Examples of the “other step” include, but are not limited to, the step of adding the above-mentioned “other component”.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the present Examples.
<(A) Material preparation>
As the material (A), the following base materials 1 to 3 were used.
Base material 1 (made of polypropylene (PP) and polyethylene terephthalate (PET), non-woven fabric grain: 442 g / m ² , thickness 26 mm);
Base material 2 (made of PET, non-woven fabric, grain: 600 g / m ² , thickness 15 mm);
Base material 3 (made of PET, non-woven fabric, grain: 300 g / m ² , thickness 10 mm);
Base material 4 (made of PET, non-woven fabric grain: 200 g / m ² , thickness 10 mm); and base material 5 (made of PET, non-woven fabric grain: 650 g / m ² , thickness 25 mm).

<(B) -1) Preparation of polyrotaxane>
The following commercially available products were used as polyrotaxane.
Commercially available Selm Superpolymer SH2400P (manufactured by Advanced Soft Materials, weight average molecular weight 400000, OHV = 76 mgKOH / g, linear molecule: polyethylene glycol (weight average molecular weight: 20000); cyclic molecule: modified α-cyclodextrin ( After substituting a part of the hydroxyl group with a hydroxypropyl group, a caprolactone group was added); Closing group: Adamantane group); 72 mgKOH / g, linear molecule: polyethylene glycol (weight average molecular weight: 35000); cyclic molecule: modified α-cyclodextrin (part of the hydroxyl group was replaced with a hydroxypropyl group, and then a caprolactone group was added); : Adamantan group).

<(B) -2) Polymer preparation>
(B) -2) The following polymers were used as the polymers.
Polycarbonate diol, Duranol (registered trademark) T-5650J (manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 800);
Polycarbonate diol, Duranol (registered trademark) T-5650E (manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 500)

<Preparation of cross-linking agent>
The following polyisocyanate X and polyisocyanate Y were prepared as cross-linking agents.
<< Preparation of polyisocyanate X >>
280 g of 1,3-bis (isocyanatomethyl) cyclohexane (Takenate 600 manufactured by Mitsui Chemicals, Inc.) was placed in a reaction vessel, and the temperature was raised to 80 ° C. with stirring under a nitrogen stream.
498 g of polycarbonate diol, Duranol (registered trademark) T-5650J (manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 800) was warmed to 70 ° C., slowly added dropwise to the above reaction vessel, and then stirred for another 3 hours to reach both ends. Polyisocyanate X (778 g) having an isocyanate group-modified polycarbonate and 1,3-bis (isocyanatomethyl) cyclohexane was obtained. The isocyanate concentration was 8.9 wt%.

<< Polyisocyanate Y >>
300 g of 1,3-bis (isocyanatomethyl) cyclohexane (Takenate 600 manufactured by Mitsui Chemicals, Inc.) was placed in a reaction vessel, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream.
332 g of polycarbonate diol, Duranol (registered trademark) T-5650E (manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 500) was warmed to 70 ° C., slowly added dropwise to the above reaction vessel, and then stirred for another 3 hours to reach both ends. Polyisocyanate Y (632 g) having isocyanate group-modified polycarbonate and 1,3-bis (isocyanatomethyl) cyclohexane was obtained. The isocyanate concentration was 11.7 wt%.

<Preparation of composition C1 for forming crosslinked CL1>
The above-mentioned polyrotaxane SH2400P (manufactured by Advanced Soft Materials Co., Ltd.) 100 g, the above-mentioned polycarbonate diol, toluene (registered trademark) T-5650J (manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 800) 49.6 g, dibutyl tin dilaurate (Tokyo) 0.034 g (manufactured by Kasei Kogyo Co., Ltd.) and 6.55 g of Irganox 1726 (manufactured by BASF) were dissolved in 156.2 g of toluene to obtain a mixture.
133.1 g of an isocyanate cross-linking agent X, which was previously dissolved in 90 g of toluene, was mixed with the above mixture and stirred uniformly to obtain a crosslinked CL1 forming composition C1 having a non-volatile concentration of 53 wt%.

<Preparation of composition C2 for forming crosslinked CL2>
In the preparation of the above composition C1, the same operation was carried out except that the above-mentioned polyrotaxane SH3400P (manufactured by Advanced Soft Materials Co., Ltd.) was used instead of the polyrotaxane SH2400P, and the composition for forming a crosslinked CL2 having a non-volatile concentration of 53 wt% was performed. I got the thing C2.

<Preparation of composition C3 for forming crosslinked CL3>
The above-mentioned polyrotaxane SH2400P 100 g, the above-mentioned polycarbonate diol, toluene (registered trademark) T-5650J 109.5 g, dibutyl tin dilaurate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.034 g, and Irganox 1726 (manufactured by BASF) 6.55 g. Was dissolved in 144 g of toluene to obtain a mixture.
119.4 g of an isocyanate cross-linking agent X previously dissolved in 80 g of toluene was mixed with the above mixture and stirred uniformly to obtain a crosslinked CL3 forming composition C1 having a non-volatile concentration of 60 wt%.

<Preparation of composition C4 for forming crosslinked CL4>
In the preparation of the above composition C3, the same operation was carried out except that the above-mentioned polyrotaxane SH3400P was used instead of the polyrotaxane SH2400P to obtain a crosslinked CL4 forming composition C4 having a non-volatile concentration of 60 wt%.

<Preparation of composition C5 for forming crosslinked CL5>
The above-mentioned polyrotaxane SH2400P 100 g, the above-mentioned polycarbonate diol, toluene (registered trademark) T-5650E (Asahi Kasei Chemicals Co., Ltd., Mn: 500) 223 g, dibutyltin dilaurate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.172 g, and Irga 6.07 g of Knox 1726 (manufactured by BASF) was dissolved in 219 g of toluene to obtain a mixture.
206.7 g of an isocyanate cross-linking agent Y previously dissolved in 138 g of toluene was mixed with the above mixture and stirred uniformly to obtain a crosslinked CL5 forming composition C5 having a non-volatile concentration of 60 wt%.

(Example 1)
An appropriate amount of the composition C1 is applied to the surface of the coating roll, and the roll is rolled on one side of the above-mentioned base material 1 (size: 13 cm × 13 cm) so that the composition C1 is uniformly spread on one side of the above-mentioned base material 1. Applied.
The obtained base material was placed in a drying oven at 100 ° C., the solvent was removed (dried) for 30 minutes, and at the same time, the composition C1 was cured to obtain the material D1.
Prior to drying, the applied composition C1 was weighed (155 g / m ² ). Moreover, the weight of the crosslinked body CL1 after drying was measured (96 g / m ² ).
From the difference between the weight of the material D1 obtained after drying and the weight of only the base material 1 before coating, the amount (g / m ² ) of the crosslinked body CL1 provided on the material D1 was converted, and the values are shown in Table 1. do.
The material D1 obtained in this example was used as the sound absorbing material K1, and its characteristics and vertical incident sound absorption coefficient were measured.
Further, using the base material 1 as the sound absorbing material H1, its characteristics and the vertically incident sound absorbing coefficient were measured (Comparative Example 1).
The results are also shown in Table 1 and FIG.
The vertical incident sound absorption coefficient was measured under the following conditions.

<Measurement of vertical incident sound absorption coefficient>
The vertical incident sound absorption coefficient was measured by the transfer function method (JIS A 1405-2). In this method, the transfer function between the sound pressures at two positions in the acoustic tube (simultaneous measurement with two microphones or sequential measurement with one microphone) was obtained, and the vertical incident sound absorption coefficient was calculated.

(Examples 2 to 6)
The composition C1 used in Example 1 and the amount thereof were changed as shown in Table 1 to obtain materials D2 to D6 in the same manner as in Example 1. The materials D2 to D6 obtained in this example were used as sound absorbing materials K2 to K6, and their characteristics and vertical incident sound absorption coefficient were measured in the same manner as in Example 1. In addition, the characteristics of the base material 1 and the vertical incident sound absorption coefficient were measured. The results are also shown in Table 1 and FIG.
From Table 1 and FIG. 1, the sound absorbing materials K1 to K6 of the present invention have a high sound absorbing coefficient at a frequency of 500 to 4500 Hz, and particularly at 1000 Hz, they show a higher sound absorbing coefficient than the sound absorbing material H1 which is only a base material. It can be seen that it has a high sound absorption coefficient of up to 66%.

(Examples 7 to 12)
In Example 1, a base material 2 was used instead of the base material 1.
Further, the composition C1 used in Example 1 and the amount thereof were changed as shown in Table 2 to obtain materials D7 to D12 in the same manner as in Example 1. The materials D7 to D12 obtained in this example were used as sound absorbing materials K7 to K12, and their characteristics and vertical incident sound absorption coefficient were measured in the same manner as in Example 1.
Further, the base material 2 was used as the sound absorbing material H2, and its characteristics and the vertically incident sound absorbing coefficient were measured (Comparative Example 2).
The results are also shown in Table 2 and FIG. The vertical incident sound absorption coefficient was measured under the same conditions as described above.
From Table 2 and FIG. 2, it was found that the sound absorbing materials K7 to K12 of the present invention exhibited excellent sound absorbing characteristics in a wide frequency range of 500 to 4500 Hz. In particular, it can be seen that the sound absorbing materials K7 to K12 of the present invention have a sound absorbing coefficient up to 44% higher at 3000 Hz than the sound absorbing material H2 which is only a base material.

(Examples 13 to 17)
In Example 1, a base material 3 was used instead of the base material 1.
Further, the composition C1 used in Example 1 and the amount thereof were changed as shown in Table 3 to obtain materials D13 to D17 in the same manner as in Example 1. The materials D13 to D17 obtained in this example were used as sound absorbing materials K13 to K17, and their characteristics and vertical incident sound absorption coefficient were measured in the same manner as in Example 1.
Further, the base material 3 was used as the sound absorbing material H3, and its characteristics and the vertical incident sound absorption coefficient were measured (Comparative Example 3).
The results are also shown in Table 3 and FIG. The vertical incident sound absorption coefficient was measured under the same conditions as described above.
From Table 3 and FIG. 3, it was found that the sound absorbing materials K13 to K17 of the present invention exhibited excellent sound absorbing characteristics in a wide frequency range of 500 to 4500 Hz. In particular, it can be seen that the sound absorbing materials K13 to K17 of the present invention have a sound absorbing coefficient up to 35% higher at 3000 Hz than the sound absorbing material H3 which is only a base material. Further, at a frequency of 3000 Hz or higher, the sound absorption coefficient tends to be higher than that of the sound absorbing material H3 which is only a base material.

(Example 18 and Example 19)
In Example 1, a base material 4 was used instead of the base material 1.
Moreover, the composition C1 used in Example 1 and the amount thereof were changed as shown in Table 4, and the materials D18 to D19 were obtained in the same manner as in Example 1. The materials D18 to D19 obtained in this example were used as sound absorbing materials K18 to K19, and their characteristics and vertical incident sound absorption coefficient were measured in the same manner as in Example 1.
Further, the base material 4 was used as the sound absorbing material H4, and its characteristics and the vertical incident sound absorption coefficient were measured (Comparative Example 4).
The results are also shown in Table 4 and FIG. The vertical incident sound absorption coefficient was measured under the same conditions as described above.
From Table 4 and FIG. 4, it was found that the sound absorbing materials K18 to K19 of the present invention exhibited excellent sound absorbing characteristics in a wide frequency range of 500 to 4500 Hz. In particular, it can be seen that the sound absorbing materials K18 to K19 of the present invention have a higher sound absorbing coefficient at both 1000 Hz and 3000 Hz than the sound absorbing material H4 which is only a base material.

(Example 20 and Example 21)
In Example 1, a base material 4 was used instead of the base material 1.
Moreover, the composition C1 used in Example 1 and the amount thereof were changed as shown in Table 5, and the materials D20 to D21 were obtained in the same manner as in Example 1. The materials D20 to D21 obtained in this example were used as sound absorbing materials K20 to K21, and their characteristics and vertical incident sound absorption coefficient were measured in the same manner as in Example 1.
Further, the base material 5 was used as the sound absorbing material H5, and its characteristics and the vertical incident sound absorption coefficient were measured (Comparative Example 5).
The results are also shown in Table 5 and FIG. The vertical incident sound absorption coefficient was measured under the same conditions as described above.
From Table 5 and FIG. 5, it was found that the sound absorbing materials K20 to K21 of the present invention exhibited excellent sound absorbing characteristics in a wide frequency range of 500 to 4500 Hz. In particular, it can be seen that the sound absorbing materials K20 to K21 of the present invention have a higher sound absorbing coefficient at both 1000 Hz and 3000 Hz than the sound absorbing material H5 which is only a base material.

Claims (13)

(A) a material having voids; and (B) a crosslinked body provided in at least a part of the (A) material;
It is a sound absorbing material that has
The crosslinked body (B) is
(B) -1) A polyrotaxane in which a blocking group is arranged at both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached; B) -2) a polyrotaxane and binding can polymer; Ri crosslinked der which is formed with a,
The ratio of the vertically incident sound absorption coefficient X11 of the sound absorbing material at a sound absorbing frequency of 3000 Hz to the vertically incident sound absorbing coefficient X12 of the material made of only the material (A) at a sound absorbing frequency of 3000 Hz, X11 / X12 is 1.1 or more. , The above sound absorbing material . The sound absorbing material according to claim 1, wherein the crosslinked body (B) is provided on the surface layer of at least a part of the material (A). (B) -1) The sound absorbing material according to claim 1 or 2, wherein the cyclic molecule of polyrotaxane has a hydroxyl group. The sound absorbing material according to any one of claims 1 to 3, wherein the polymer (B) -2) has a polyol. The sound absorbing material according to claim 4, wherein the polyol is at least one selected from a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polysiloxane polyol. The sound absorbing material according to any one of claims 1 to 5, wherein the crosslinked body (B) is further provided with a crosslinking agent. The sound absorbing material according to claim 6, wherein the cross-linking agent is a polyisocyanate cross-linking agent. Claim that the material (A) is selected from the fibrous material group consisting of rock wool, glass wool, non-woven fabric, and felt, and / or from the foam material group consisting of urethane foam, rubber foam, and cellulose foam. The sound absorbing material according to any one of 1 to 7. Any of claims 1 to 8, wherein the material (A) is selected from the fibrous material group consisting of rock wool, glass wool, non-woven fabric, and felt, and the weight per unit area thereof is 50 to 2000 g / m ^2. The sound absorbing material according to item 1. The ratio of the vertically incident sound absorption coefficient X1 of the sound absorbing material at a sound absorbing frequency of 1000 Hz to the vertically incident sound absorbing coefficient X2 of the material made of only the material (A) at a sound absorbing frequency of 1000 Hz, X1 / X2 is 1.1 or more. The sound absorbing material according to any one of claims 1 to 9. A sound absorbing material for a vehicle using the sound absorbing material according to any one of claims 1 to 10. A vehicle using the sound absorbing material according to any one of claims 1 to 11. (A) a material having voids; and (B) a crosslinked body provided in at least a part of the (A) material:
It is a manufacturing method of a sound absorbing material having
(I) Step of preparing the material (A);
(II-1) (B) -1) Closing groups are arranged at both ends of the pseudopolyrotaxane in which the openings of the cyclic molecule are skewered by the linear molecule so that the cyclic molecule is not detached. The process of preparing polyrotaxane
(II-2) (B) -2) Step of preparing a polymer capable of binding to the polyrotaxane;
(II-3) A step of preparing a composition having the (B) -1) polyrotaxane; and the (B) -2) polymer;
(III) The step of applying the composition to at least a part of the (A) material; and (IV) After the (III) coating step, the (B) -1) polyrotaxane; and the (B) -2. ) Polymer; step of forming a crosslinked body formed with;
A layer of the crosslinked body is formed on at least a part of the material (A) .
The ratio of the vertically incident sound absorption coefficient X11 of the sound absorbing material at a sound absorbing frequency of 3000 Hz to the vertically incident sound absorbing coefficient X12 of the material made of only the material (A) at a sound absorbing frequency of 3000 Hz, X11 / X12 is 1.1 or more. , The above method.

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