JPWO2018168729A1 - Sound absorbing material containing crosslinked product formed with polyrotaxane - Google Patents

Abstract

The present invention provides a material, particularly a sound absorbing material, that meets the needs for further weight reduction and / or higher functionality. Further, the present invention provides a material capable of easily providing sound absorbing materials having different frequency characteristics, in addition to weight reduction and / or high performance, and a method of manufacturing the same. The present invention relates to a material comprising (A) a material having voids; and (B) a crosslinked product provided in at least a part of the material (A), wherein (B) the crosslinked product is (B) -1) (B) -2) a polyrotaxane in which a blocking group is arranged at both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule is skewer-enclosed by a linear molecule so that the cyclic molecule is not detached; And a polymer capable of bonding to the above material.

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 (A) material. In particular, the present invention relates to a material having a crosslinked product formed by the crosslinked product (B) having a polyrotaxane. More particularly, the present invention relates to a material in which the material is used for a sound absorbing material.

Various materials are used as a sound absorbing material. In particular, a material having a void can achieve weight reduction in addition to high performance, and is widely used as a sound absorbing material.
Patent Documents 1 and 2 each disclose a fibrous material having voids and a resin material having voids, and disclose that each material is manufactured by special processing.
More specifically, Patent Literature 1 discloses a nonwoven fabric web having a nonwoven fabric having a meltblown fiber and a binder fiber fused to the meltblown fiber at an interlacing point of the meltblown fiber, and the nonwoven fabric web is used as a sound absorbing material. It is disclosed that it can be.

Patent Document 2 discloses a polyethylene resin foam molded article formed by molding polyethylene resin pre-expanded particles, and discloses that the molded article is used as a sound absorbing material.
Patent Document 3 discloses that an organic material and an inorganic material can be combined to produce a useful sound absorbing material particularly in a low frequency region.

  As described above, various sound absorbing materials have been proposed. Sound absorbing materials used in automobiles, building materials, home appliances, and the like are required to be further reduced in weight and function. In particular, in automobiles, as a countermeasure against noise such as engine noise, road noise, wind noise, motor electromagnetic vibration, squealing electronic noise, brake noise, etc., it is necessary to use sound absorbing materials with different frequency characteristics in addition to weight reduction and high functionality. No.

  Therefore, there is a demand for a material that can meet the needs for further weight reduction and / or higher functionality, especially a sound absorbing material. In addition to weight reduction and / or high functionality, there is a need for a material that can easily provide sound absorbing materials having different frequency characteristics and a method of manufacturing the same.

JP 2015-212442. JP 2007-44877. JP-A-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 higher functionality, in particular, a sound absorbing material.
Further, an object of the present invention is to provide a material capable of easily providing a sound absorbing material having a different frequency characteristic and a method of manufacturing the same in addition to the above object or in addition to the above object, in addition to weight reduction and / or high functionality. To provide.

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

<2> In the above item <1>, the crosslinked product (B) may be provided on at least a part of the surface layer of the material (A).
<3> In the above item <1> or <2>, (B) -1) the cyclic molecule of the polyrotaxane preferably has a hydroxyl group.
<4> In any one of the above items <1> to <3>, the (B) -2) polymer may have a polyol.

<5> In the above item <4>, the polyol may be at least one selected from a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polysiloxane polyol.
<6> In any one of the above items <1> to <5>, it is preferable that the crosslinked product (B) is further formed with a crosslinking agent.
<7> In the above item <6>, the crosslinking agent may include a polyisocyanate crosslinking agent.

<8> In any one of the above items <1> to <7>, the material (A) may be selected from a group of fibrous materials including rock wool, glass wool, nonwoven fabric, and felt, and / or urethane foam and rubber. It is preferably selected from a foam material group consisting of foam and cellulose foam, preferably from a fibrous material group, and more preferably glass wool or nonwoven fabric.
<9> In any one of the above items <1> to <8>, the material (A) may be selected from a group of fibrous materials consisting of rock wool, glass wool, nonwoven fabric, and felt, and is preferably glass wool or well that a nonwoven fabric, the weight per unit area of the material is, 50 to 2000 g / ^{m 2,} preferably 80~1500g / ^{m 2,} more preferably 100 to 1000 g / ^{m 2,} more preferably 100 to 800 g / m ² is preferable.

<10> It is preferable that any one of the above <1> to <9> is a sound absorbing material.
<11> In the above item <10>, a ratio of the normal incidence sound absorption coefficient X1 at a sound absorption frequency of 1000 Hz of the sound absorbing material to the normal incidence sound absorption coefficient X2 at a sound absorption frequency of 1000 Hz of the material made of only the material (A) among the sound absorbing materials. , X1 / X2 are 1.1 or more, preferably 1.3 or more, and more preferably 1.5 or more.
<12> In the above item <10> or <11>, the normal-incidence sound absorption coefficient X11 of the sound-absorbing material at the sound absorption frequency of 3000 Hz and the normal-incidence sound absorption coefficient of the material made of only the material (A) among the sound-absorbing materials at 3000 Hz are used. It is good that the ratio to X12, X11 / X12, is 1.1 or more, preferably 1.3 or more, more preferably 1.5 or more.

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

<15> (A) a material having voids; and (B) a crosslinked body provided in at least a part of the material:
A method for producing a material having
(I) (A) a step of preparing a material;
(II-1) (B) -1) A blocking group is arranged at both ends of a pseudo-polyrotaxane in which the opening of the cyclic molecule is skewered by linear molecules so that the cyclic molecule is not detached. Preparing a polyrotaxane comprising:
(II-2) (B) -2) a step of preparing a polymer capable of binding to the polyrotaxane;
(II-3) a step of preparing a composition comprising (B) -1) a polyrotaxane; and (B) -2) a polymer;
(III) a step of applying the composition to at least a part of the (A) material; and (IV) after the (III) applying step, the (B) -1) a polyrotaxane; and the (B) -2 A) a step of forming a crosslinked product having a polymer;
The above method, wherein a layer of the crosslinked body is formed on at least a part of the material (A).

ADVANTAGE OF THE INVENTION According to this invention, the material which respond | corresponds to the need of further weight reduction and / or high functionality, especially a sound absorbing material can be provided.
Further, according to the present invention, in addition to the above-mentioned effects, or in addition to the above-mentioned effects, in addition to weight reduction and / or high functionality, a material capable of easily providing sound absorbing materials having different frequency characteristics and a method for producing the same are provided. be able to.

The vertical incidence sound absorption coefficient according to the frequency of the sound absorbing materials K1 to K6 (Examples 1 to 6) of the present invention and the sound absorbing material H1 (Comparative Example 1) which is only the substrate 1 is shown. The vertical incidence sound absorption coefficient according to the 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 substrate 2 is shown. The vertical incidence sound absorption coefficient according to the 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 incidence sound absorption coefficient according to the 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 substrate 4 is shown. The vertical incidence sound absorption coefficient according to the frequency of the sound absorbing materials K20 to K21 of the present invention (Examples 20 to 21) and the sound absorbing material H5 which is only the base material 5 (Comparative Example 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 a void; and (B) a crosslinked body provided in at least a part of the (A) material, particularly a material that can be used as a sound absorbing material.
Hereinafter, the materials provided by the present application will be described.

<(A) Material having void>
The material of the present application includes (A) a material having a void.
(A) The material having a void refers to a material in which the void is one of the constituent components of the material. Here, as the void, when a component other than the void of the material is a fibrous material, a void is generated by entanglement of the fiber, or a void is generated by dispersing bubbles in the component of the material. And the like, but are not limited to these.
The “components other than the voids” are preferably fibrous materials, and particularly when the material of the present invention is used as a sound absorbing material, the fibrous materials are particularly preferable.

(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, nonwoven fabric, and felt.
Examples of the foam material included in the foam material group include a material in which bubbles are dispersed and / or a foam material, and specific examples thereof include urethane foam, rubber foam, and cellulose foam, but are not limited thereto. Not done.
When these materials are used as a sound absorbing material, rock wool, glass wool, nonwoven fabric and felt are preferred, glass wool and nonwoven fabric are more preferred, and nonwoven fabric is particularly preferred.
The shape of the above-mentioned material can be appropriately determined according to the application, and may be, for example, a sheet, plate, sphere, or amorphous.

  Note that the material provided by the present application may include a material other than the “(A) material having a void” as long as it has a material having a void (A). When a material other than the “(A) material having a void” is used, a composite material of the material other than the “(A) material having a void” and a material other than the “(A) material having a void” may be used. If the composite material is “a material in which a void is one of the constituent components of the material”, the composite material corresponds to the material (A) having a void in the present application.

(A) The material having voids is preferably selected from the group of fibrous materials described above, and has a basis weight, that is, a weight per unit area of 50 to 2000 g / m ² , preferably 80 to 1500 g / m ² , Preferably it is 100 to 1000 g / m ² , more 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, nonwoven fabric, or felt, more preferably glass wool or nonwoven fabric, particularly preferably nonwoven fabric, and the basis weight. , 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 body. The crosslinked product (B) is provided on at least a part of the material (A). The crosslinked product (B) is preferably provided so as to be provided on at least a part of the surface layer of the material (A).
(B) The crosslinked product is
(B) -1) a polyrotaxane in which a blocking group is arranged at both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule is skewingly included by linear molecules so that the cyclic molecule is not detached; and B) -2) a polymer capable of binding to the polyrotaxane;
It is a crosslinked body formed having
(B) -2) The polymer capable of binding to the polyrotaxane will be described in detail later. The “polymer” of the “(B) -2) polymer capable of binding to the polyrotaxane” includes the above “(B) -1) polyrotaxane”. "Is not intended to be included.
The “polymer” of “(B) -2) a polymer that can be bonded to polyrotaxane”, which is a constituent element included in the “(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 include a crosslinked product of the above“ (B) -1) polyrotaxane ”.

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

<< (B) -1) polyrotaxane >>
(B) The crosslinked product is formed having (B) -1) a polyrotaxane;
(B) -1) The polyrotaxane is formed having a cyclic molecule, a linear molecule, and a blocking group, and both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is included in a skewered manner by the linear molecule. In addition, a blocking group is arranged so that a cyclic molecule is not eliminated. Hereinafter, components included in the polyrotaxane will be described.

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

The cyclic molecule is selected from the group consisting of other groups, for example, 1) a hydrophobic modifying group; 2) —NH ₂ , —COOH, and —SH; A group selected from the group consisting of an acrylic group, a methacrylic group, a styryl group, a vinyl group, a vinylidene group, and a maleic anhydride-containing functional group; and the like.

  1) As the hydrophobic modifying group, 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 Examples thereof include, but are not limited to, groups having a hydrophobic group such as a tetramethylene glycol group, a polymethyl acrylate group, and a polyethyl hexyl group. Among these, a polycaprolactone group, a polypropylene glycol group and a polyalkylene carbonate group are preferred.

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

<Linear molecule>
(B) -1) The linear molecule of the polyrotaxane is not particularly limited as long as it can be included in a skewered manner at the opening of the cyclic molecule to be used.
For example, as linear molecules, polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylic acid, cellulosic resins (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl Acetal resins, polyvinyl methyl ether, polyamines, polyethylene imine, casein, gelatin, starch and / or copolymers thereof, polyethylene, polypropylene, and polyolefin resins such as copolymer resins with other olefin monomers, Polystyrene resin such as polyester resin, polyvinyl chloride resin, polystyrene and acrylonitrile-styrene copolymer resin, polymethyl resin Acrylic resin such as acrylate or (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, etc .; and derivatives thereof or Modified products, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polydienes such as polyisoprene and polybutadiene, and polysiloxanes such as polydimethylsiloxane , Polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and It may be selected from the group consisting of these derivatives. For example, it is preferable to be selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether. Particularly, polyethylene glycol is preferred.

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

<Blocking group>
(B) -1) The blocking group of the polyrotaxane is not particularly limited as long as it is a group arranged at both ends of the pseudopolyrotaxane and acts so as not to leave the cyclic molecule used.
For example, as blocking groups, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, pyrenes, substituted benzenes (substituents such as alkyl, alkyloxy, hydroxy, Examples include, but are not limited to, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc. One or more substituents may be present.) And optionally substituted polynuclear aromatics (substituted). Examples of the group include, but are not limited to, the same as those described above. One or more substituents may be present.), And steroids. Incidentally, it is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes, more preferably adamantane groups or cyclodextrin It should be kind.

<< (B) -2) Polymer that can bind to polyrotaxane >>
(B) The crosslinked body is formed having (B) -2) a polymer capable of binding to the polyrotaxane.
Here, it is intended that the “polymer” of “(B) -2) the polymer capable of binding to the polyrotaxane” does not include the “(B) -1) polyrotaxane” as described above.
The “(B) -2) polymer capable of binding to the 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) a polyrotaxane in the presence of heat, a catalyst, or the like, and is specifically, but not limited to, described later.
The “polymer that can be indirectly bonded” refers to a polymer that can be bonded to (B) -1) a polyrotaxane using a crosslinking agent or the like, and is specifically, but not limited to, described later.

When “(B) -2) a polymer capable of binding to a polyrotaxane” is “(B) -1) polyrotaxane” and “a polymer capable of directly binding”, the following combinations are preferred.
That is, (B) -1) the first functional group is provided to the cyclic molecule of the polyrotaxane, while (B) -2) the second functional group is preferably provided to the polymer capable of binding to the polyrotaxane. It is preferable to form the crosslinked product (B) by reacting the functional group with the second functional group.

  Here, as the 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, 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, and an acid anhydride residue and an amino group. Since the above is intended to describe “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 may be an epoxy group. It is intended to include the case where the group is a group and the second functional group is a carboxylic acid group, and the case where the first functional group is a carboxylic acid group and the second functional group is an epoxy group.

  In this case, “(B) -2) a polymer capable of binding to a polyrotaxane” includes poly (meth) acrylate, polyamide, polyester, polyether, polyolefin, polydiene, polysiloxane, polystyrene, polyurethane, polyurea, polycarbonate, and these. Examples of the above-mentioned copolymer include a polymer having the first or second functional group added thereto, but are not limited thereto.

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

  Further, both the first and second functional groups are radical polymerizable groups (first and second radical polymerizable groups, respectively), and the first and second functional groups (radical polymerizable groups) It is preferable that the (groups) are bonded to each other, and that “(B) -2) a polymer capable of bonding to a polyrotaxane” and “(B) -1) a polyrotaxane” be “directly bonded” to form a crosslinked body.

Examples of the first and second radical 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 anhydride / maleimide-containing functional group.
In this case, “(B) -2) a polymer capable of binding to a polyrotaxane”, that is, a polymer having a second radically polymerizable group, includes poly (meth) acrylate, polyamide, polyester, polyether, polyolefin, polydiene, and polydiene. Examples thereof include, but are not limited to, siloxane, polystyrene, polyurethane, polyurea, polycarbonate, and a polymer obtained by adding a radical polymerizable group to a copolymer thereof.

Radical polymerization initiator (B) -2) When the polymer capable of binding to the polyrotaxane has a polymer having a radical 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 addition amount of the polymerization initiator is preferably in the range of 0.05 to 5% by mass based on the mixture.

  Examples of the thermal polymerization initiator include benzoyl peroxide, lauroyl peroxide, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t- Organic peroxide-based polymerization initiators such as xyl peroxy pivalate, diisopropyl peroxy dicarbonate, and bis (4-t-butylcyclohexyl) peroxy dicarbonate; 2,2′-azobisisobutyronitrile; Azo-based polymerization initiators such as 2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); potassium persulfate, ammonium persulfate, persulfuric acid And 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, methylphenylglyoxylate, acetophenone, benzophenone, diethoxyacetophenone, and 2,2. -Dimethoxy-2-phenylacetophenone, 1-phenyl-1,2-propane-dione-2- (o-ethoxycarbonyl) oxime, 2-methyl [4- (methylthio) phenyl] -2morpholino-1-propanone, benzyl , Bensoin isobutyl ether, 2-chlorothioxanthone, isopropylthioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphospho In'okisaido, benzoyl dimethoxy phosphine oxa-de, and the like. These may be used alone or in combination of two or more.

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

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

(B) -2) The polymer capable of binding to the polyrotaxane is preferably a polyol, and (B) -1) the polyrotaxane is preferably such that its cyclic molecule has a hydroxyl group.
Polyol In the present application, the polyol refers to a substance having two or more OH groups.
As polyols, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, polysiloxane polyols, block copolymers or grafts of a plurality of types of polyols (for example, polyols obtained by block-polymerizing polyester on polyether polyol), side chains And a polymer having two or more hydroxyl groups, but are not limited thereto.
The polyol may be at least one selected from a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polysiloxane polyol, and preferably at least one selected from a polyether polyol, a polyester polyol, and a polycarbonate polyol. Species, more preferably at least one selected from polyether polyols and polyester polyols.

  Examples of the polymer having two or more hydroxyl groups in the side chain include products having a side chain hydroxyl group such as poly (meth) acrylate, polyvinyl chloride, and polyvinyl acetate.

The case where the number of OH groups contained in the polyol is 2 or the case where the number of OH groups is 3 or more may be used. (B) -2) When the polymer capable of binding to the polyrotaxane has a polyol, the polyol may be used alone or in combination of two or more.
The polyol has a weight average molecular weight of 50 to 30,000, preferably 250 to 10,000, and more preferably 250 to 8,000.

When the polymer capable of binding to (B) -2) the polyrotaxane has a polyol, as described above, the (B) -1) polyrotaxane has a hydroxyl group, which is convenient for crosslinking. In this case, a polyisocyanate is preferably used as a crosslinking agent. Note that polyisocyanate refers to a compound having two or more isocyanate groups.
As the polyisocyanate, a known aliphatic, alicyclic and aromatic isocyanate may be used, or a newly synthesized polyisocyanate may be used.

  Examples of polyisocyanates include 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 Silylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene 1,3- and / or 1,4-phenylene diisocyanate 2,4- and / or 2,6-toluene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanato biphenyl 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, m- and / or Or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), or a derivative or multimer thereof, or an existing polymer using these polyisocyanates. And a polyisocyanate having a polymer site having a plurality of isocyanate groups added thereto. But not limited to these.

When using a polyisocyanate, the amount of the polyisocyanate is preferably in the following range.
The ratio of the number of moles of the isocyanate groups of the polyisocyanate to the number of moles of the active hydrogen of the polyol and the polyrotaxane, that is, (the number of moles of the isocyanate group of the polyisocyanate) / (the number of moles of the active hydrogen of the polyol and the polyrotaxane) is 0. The amount of the polyisocyanate compound is preferably adjusted so as to be 30 to 2.00, preferably 0.50 to 1.50, and more preferably 0.60 to 1.20.
The ratio (molar number of isocyanate groups of polyisocyanate) / (molar number of active hydrogen of polyol and polyrotaxane) may be expressed as “NCO index” in some cases.

Specific examples of the active hydrogen include hydrogen of an OH group present in a polyol and hydrogen of an OH group present in a polyrotaxane. In addition, not only hydrogen derived from OH groups, but also hydrogen such as thiol groups, primary amino groups, secondary amino groups, and carboxylic acid groups present in polyols and polyrotaxanes act as active hydrogens. And the number of moles of active hydrogen of the polyol and the polyrotaxane.
When active hydrogen is derived only from OH groups, the amount of active hydrogen can be represented by a hydroxyl value OHV.

As the catalyst used to promote the reaction between the polyol and / or (B) -1) the polyrotaxane and the 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 Tertiary amines such as 1,5-diazabicyclo [4.3.0] nonene-5 and 1,5-diazabicyclo [4.4.0] decene-5; metal carboxylate such as potassium acetate and potassium octylate Salt, Stanas octoate, dibutyltin dilaurate, dioctyltin versatate, dioctylchi Dilaurate, zinc naphthenate, bismuth trio dioctate (2-ethylhexanoate), organometallic compounds such as octyl aluminum and the like.
It is preferable to add at least one of these catalysts to the formation of the crosslinked product.
The amount added is preferably from 0.001 to 5.0% by mass based on the polyol.

Further, a solvent may be used in forming the crosslinked body. After the step of producing a crosslinked product, the solvent is preferably removed. The solvent is used to facilitate the mixing of the crosslinked component, to increase the compatibility between the crosslinked components, to adjust the viscosity when applied to the material having voids, and to increase the crosslinking reaction rate after application to the material having voids. It can be used for such purposes as adjustment.
Examples of the solvent include, but are not limited to, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, and xylene.

<"Other components" in the material of the present application>
The material of the present application may contain “other components” as required, in addition to (A) a material having voids; and (B) a crosslinked product.
As other components, in addition to the antioxidants, flame retardants, ultraviolet absorbers, dyes, pigments, antistatic agents and the like described in the radical polymerization, various fillers and the like can be mentioned. Not limited.

  The material of the present application can be used for various applications in which a material having a void is used. For example, a sound-absorbing material, a heat-insulating material, a filter, a buffer, a packaging material, an interior member, and the like can be given, but are not particularly limited. In particular, as a sound absorbing material, it can be used in various fields where sound insulation or noise reduction is required, such as buildings such as houses and buildings; vehicles; home appliances; noise barriers for transportation infrastructure of expressways, railways, airports, and ports; it can.

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

  That is, the sound absorbing material C1 made of the material of the present invention and the sound absorbing material C2 made of only the material (A) among the materials of the present invention are prepared, and their normal incidence sound absorbing coefficients are compared to obtain the sound absorbing material C1 made of the material of the present invention. 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 that shows a higher sound absorbing coefficient than the sound absorbing material made of only the material having the void (A). The sound absorbing material made of the material of the present application preferably has a high sound absorption coefficient particularly at a low frequency of 500 Hz to 1500 Hz. In this case, among the above-mentioned applications, the engine sound of a vehicle, the gear differential sound, the motor electromagnetic noise, and the like are reduced. It is effective as a sound absorbing material to absorb. In addition, 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 characteristics at the low frequency or in addition to the sound absorbing characteristics at the low frequency. Of these uses, it is effective as a sound absorbing material that absorbs brake noise, electronic noise, wind noise, and the like.

  The sound absorption material C1 made of the material of the present invention has a normal incidence sound absorption coefficient X1 at a sound absorption frequency of 1000 Hz, while the sound absorption material C2 made of only the material (A) has a ratio to the normal incidence sound absorption coefficient X2 at a sound absorption frequency of 1000 Hz. And the ratio X1 / X2 is 1.1 or more, preferably 1.3 or more, and more preferably 1.5 or more.

  In addition, while the sound absorbing material C1 made of the material of the present application has a normal incidence sound absorption coefficient X11 at a sound absorption frequency of 3000 Hz, the sound absorbing material C2 consisting of only the material (A) has a ratio to the normal incidence sound absorption coefficient X12 at a sound absorption frequency of 3000 Hz. And 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 kind of the sound absorbing material of the present application has a high normal incidence sound absorption coefficient in the above frequency range, specifically, in a specific range of the frequency range of 500 Hz to 4500 Hz. Specifically, it is preferable that only one kind of the sound absorbing material of the present application has the above-described values of the normal incidence sound absorption coefficient at the sound absorption frequencies of 1000 Hz and 3000 Hz.
The sound absorbing material C11 of the present application has the above-described value of the normal incidence sound absorption coefficient at a sound absorption frequency of 1000 Hz, and the other sound absorbing material C12 has the above-described value of the normal incidence sound absorption coefficient at a sound absorption frequency of 3000 Hz. By combining C11 and C12, the normal incidence sound absorption coefficient at the sound absorption frequencies of 1000 Hz and 3000 Hz may have the above value.

The material or the sound absorbing material of the present application can be used as a sound absorbing material for a vehicle. 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 the sound absorbing material of the present application can be used for a vehicle.

<Production method of the material of the present application>
The above-mentioned materials can be manufactured by the following method.
That is, (I) a step of preparing the above-mentioned (A) material;
(II-1) a step of preparing the above-mentioned (B) -1) polyrotaxane;
(II-2) a step of preparing the above-mentioned (B) -2) polymer;
(II-3) a step of preparing a composition having (B) -1) a polyrotaxane; and (B) -2) a polymer;
(III) (A) a step of applying the composition to at least a part of the material; and (IV) (III) after the applying step, (B) -1) a polyrotaxane; and (B) -2) a polymer. Forming a cross-linked body formed by the process;
By having (A), a layer of the above-mentioned (B) crosslinked body 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 (A) material.
In this step, the existing (A) material may be purchased commercially or may be 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 product 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 may be newly prepared. <Step (II-3)>
Step (II-3) is a step of preparing a composition having (B) -1) a polyrotaxane; and (B) -2) a polymer.
In preparing the composition, a solvent may be used, if desired. As the solvent, those described above can be used.

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

<Step (IV)>
The step (IV) is a step of forming a crosslinked body formed after the step (III), that is, after the coating step, including (B) -1) a polyrotaxane; and (B) -2) a polymer.
In the step (IV), a reaction for forming a crosslinked product can be adopted depending on the used (B) -1) polyrotaxane and the used (B) -2) polymer.
For example, when the (B) -1) polyrotaxane and the (B) -2) polymer have the above-described first and second radically polymerizable groups, respectively, the polymerization conditions depending on the radically polymerizable groups are employed. Can be.
Further, for example, when the (B) -1) polyrotaxane and the (B) -2) polymer have the above-described eleventh and twelfth functional groups, respectively, and bond and cross-link them via a cross-linking agent, Conditions according to the conditions of bonding and crosslinking can be employed.

<Other steps>
The method of the present invention may include other steps as necessary in addition to the above steps (I) to (IV).
As the “other steps”, for example, a step of adding the above-mentioned “other components” can be mentioned, but it is not limited thereto.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.
<(A) Preparation of materials>
(A) The following base materials 1 to 3 were used as materials.
Substrate 1 (made of polypropylene (PP) and polyethylene terephthalate (PET), nonwoven fabric basis weight: 442 g / m ² , thickness 26 mm);
Substrate 2 (made of PET, nonwoven fabric weight: 600 g / m ² , thickness 15 mm);
Substrate 3 (made of PET, nonwoven fabric weight: 300 g / m ² , thickness 10 mm);
Base material 4 (made of PET, nonwoven fabric weight: 200 g / m ² , thickness 10 mm); and Base material 5 (made of PET, nonwoven fabric weight: 650 g / m ² , thickness 25 mm).

<(B) -1) Preparation of polyrotaxane>
The following commercial products were used as polyrotaxanes.
Commercial product Celum superpolymer SH2400P (manufactured by Advanced Soft Materials Co., Ltd., weight average molecular weight 400000, OHV = 76 mgKOH / g, linear molecule: polyethylene glycol (weight average molecular weight: 20,000); cyclic molecule: modified α-cyclodextrin ( A caprolactone group was added after a part of the hydroxyl group was substituted with a hydroxypropyl group); a blocking group: an adamantane group); and a commercially available Celum superpolymer SH3400P (manufactured by Advanced Soft Materials, weight average molecular weight 700,000, OHV = 72 mgKOH / g, linear molecule: polyethylene glycol (weight average molecular weight: 35000); cyclic molecule: modified α-cyclodextrin (a part of the hydroxyl group was replaced with a hydroxypropyl group, and then a caprolactone group was added. ; Blocking groups: adamantane group).

<(B) -2) Preparation of polymer>
(B) -2) The following polymer was used as the polymer.
Polycarbonate diol, Duranol (registered trademark) T-5650J (manufactured by Asahi Kasei Chemicals Corporation, Mn: 800);
Polycarbonate diol, Duranol (registered trademark) T-5650E (manufactured by Asahi Kasei Chemicals Corporation, Mn: 500)

<Preparation of crosslinking agent>
The following polyisocyanate X and polyisocyanate Y were prepared as crosslinking agents.
<< Preparation of Polyisocyanate X >>
280 g of 1,3-bis (isocyanatomethyl) cyclohexane (Takenate 600 manufactured by Mitsui Chemicals, Inc.) was placed in the reaction vessel, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream.
498 g of polycarbonate diol, Duranol (registered trademark) T-5650J (manufactured by Asahi Kasei Chemicals Corporation, Mn: 800) was warmed to 70 ° C., and slowly added dropwise to the reaction tank, followed by stirring for 3 hours and stirring at both ends. Polyisocyanate X (778 g) having 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 the 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 Corporation, Mn: 500) was warmed to 70 ° C., and slowly added dropwise to the reaction tank, followed by further stirring for 3 hours, followed by stirring at 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 body CL1>
100 g of the above-mentioned polyrotaxane SH2400P (manufactured by Advanced Soft Materials Co., Ltd.), 49.6 g of the above-mentioned polycarbonate diol, Duranol (registered trademark) T-5650J (manufactured by Asahi Kasei Chemicals Corporation, Mn: 800), dibutyltin dilaurate (Tokyo) 0.034 g of Kasei Kogyo Co., Ltd. and 6.55 g of Irganox 1726 (from BASF) were dissolved in 156.2 g of toluene to obtain a mixture.
133.1 g of isocyanate crosslinking agent X previously dissolved in 90 g of toluene was mixed with the above mixture, and the mixture was stirred uniformly to obtain a crosslinked product CL1 forming composition C1 having a nonvolatile concentration of 53 wt%.

<Preparation of composition C2 for forming crosslinked body CL2>
In the preparation of the composition C1, a similar operation was performed except that the above-mentioned polyrotaxane SH3400P (manufactured by Advanced Soft Materials Co., Ltd.) was used instead of the polyrotaxane SH2400P, and a composition for forming a crosslinked body CL2 having a nonvolatile concentration of 53 wt% was used. The product C2 was obtained.

<Preparation of composition C3 for forming crosslinked body CL3>
100 g of the above-mentioned polyrotaxane SH2400P, 109.5 g of the above-mentioned polycarbonate diol, Duranol (registered trademark) T-5650J, 0.034 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 6.55 g of Irganox 1726 (manufactured by BASF). Was dissolved in 144 g of toluene to obtain a mixture.
119.4 g of isocyanate crosslinking agent X previously dissolved in 80 g of toluene was mixed with the above mixture, and the mixture was stirred uniformly to obtain a crosslinked product CL3 forming composition C1 having a nonvolatile concentration of 60 wt%.

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

<Preparation of composition C5 for forming crosslinked body CL5>
100 g of the above-mentioned polyrotaxane SH2400P, 223 g of the above-mentioned polycarbonate diol, Duranol (registered trademark) T-5650E (manufactured by Asahi Kasei Chemicals Corporation, Mn: 500), 0.172 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.), 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 the isocyanate crosslinking agent Y previously dissolved in 138 g of toluene was mixed with the above mixture, and the mixture was stirred uniformly to obtain a crosslinked product CL5 forming composition C5 having a nonvolatile concentration of 60 wt%.

(Example 1)
An appropriate amount of the composition C1 is applied to the surface of the application roll, and the roll is rolled on one surface of the above-described substrate 1 (size: 13 cm × 13 cm), so that the composition C1 is uniformly applied to one surface of the above-described substrate 1. Applied.
The obtained substrate was placed in a drying oven at 100 ° C., and the solvent was removed (dried) for 30 minutes, and at the same time, the composition C1 was cured to obtain a material D1.
Before drying, the weight of the applied composition C1 was measured (155 g / m ² ). Further, 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 substrate 1 before application, the amount (g / m ² ) of the crosslinked body CL1 provided on the material D1 was converted, and the value is shown in Table 1. I do.
Using the material D1 obtained in this example as a sound absorbing material K1, its characteristics and the normal incidence sound absorbing coefficient were measured.
Further, using the base material 1 as the sound absorbing material H1, its characteristics and the normal incidence sound absorption coefficient were measured (Comparative Example 1).
The results are also shown in Table 1 and FIG.
The measurement of the normal incidence sound absorption coefficient was performed under the following conditions.

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

(Examples 2 to 6)
Materials D2 to D6 were obtained in the same manner as in Example 1, except that the composition C1 used in Example 1 and the amount thereof were changed as shown in Table 1. Using the materials D2 to D6 obtained in this example as sound absorbing materials K2 to K6, the characteristics and the normal incidence sound absorption coefficient were measured in the same manner as in Example 1. Further, the characteristics of the base material 1 and the normal incidence 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 especially at 1000 Hz, show a higher sound absorbing coefficient as compared with the sound absorbing material H1 which is only the base material. It has a high sound absorption coefficient as high as 66%.

(Examples 7 to 12)
In Example 1, the substrate 2 was used instead of the substrate 1.
Further, the compositions C1 used in Example 1 and the amounts thereof were changed as shown in Table 2, and materials D7 to D12 were obtained in the same manner as in Example 1. Using the materials D7 to D12 obtained in this example as sound absorbing materials K7 to K12, the characteristics and the normal incidence sound absorption coefficient were measured in the same manner as in Example 1.
Further, using the base material 2 as the sound absorbing material H2, the characteristics and the normal incidence sound absorption coefficient were measured (Comparative Example 2).
The results are also shown in Table 2 and FIG. The measurement of the normal incidence sound absorption coefficient was performed 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 higher sound absorbing coefficient by up to 44% at 3000 Hz as compared with the sound absorbing material H2 which is only the base material.

(Examples 13 to 17)
In Example 1, the substrate 3 was used instead of the substrate 1.
Further, the compositions C1 and the amounts thereof used in Example 1 were changed as shown in Table 3, and materials D13 to D17 were obtained in the same manner as in Example 1. Using the materials D13 to D17 obtained in this example as sound absorbing materials K13 to K17, the characteristics and the normal incidence sound absorption coefficient were measured in the same manner as in Example 1.
Further, using the base material 3 as the sound absorbing material H3, its characteristics and the normal incidence sound absorption coefficient were measured (Comparative Example 3).
The results are also shown in Table 3 and FIG. The measurement of the normal incidence sound absorption coefficient was performed 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 maximum 35% higher sound absorbing coefficient at 3000 Hz than the sound absorbing material H3 which is only the base material. Further, at a frequency of 3000 Hz or more, the sound absorption coefficient tends to be higher than that of the sound absorbing material H3 which is only the base material.

(Examples 18 and 19)
In Example 1, the substrate 4 was used instead of the substrate 1.
Further, the composition C1 and the amount thereof used in Example 1 were changed as shown in Table 4, and materials D18 to D19 were obtained in the same manner as in Example 1. Using the materials D18 to D19 obtained in this example as sound absorbing materials K18 to K19, the characteristics and the normal incidence sound absorption coefficient were measured in the same manner as in Example 1.
Further, using the base material 4 as the sound absorbing material H4, its characteristics and the normal incidence sound absorbing coefficient were measured (Comparative Example 4).
The results are also shown in Table 4 and FIG. The measurement of the normal incidence sound absorption coefficient was performed 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 absorption coefficient at both 1000 Hz and 3000 Hz as compared with the sound absorbing material H4 which is a base material alone.

(Examples 20 and 21)
In Example 1, the substrate 4 was used instead of the substrate 1.
Further, the composition C1 and the amount thereof used in Example 1 were changed as shown in Table 5, and materials D20 to D21 were obtained in the same manner as in Example 1. Using the materials D20 to D21 obtained in this example as sound absorbing materials K20 to K21, the characteristics and the normal incidence sound absorption coefficient were measured in the same manner as in Example 1.
Further, using the base material 5 as the sound absorbing material H5, its characteristics and the normal incidence sound absorption coefficient were measured (Comparative Example 5).
The results are also shown in Table 5 and FIG. The measurement of the normal incidence sound absorption coefficient was performed 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 as compared with the sound absorbing material H5 which is only the base material.

Claims (15)

(A) a material having voids; and (B) a crosslinked body provided in at least a part of the (A) material;
A material having
The crosslinked product (B) is
(B) -1) a polyrotaxane in which a blocking group is arranged at both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule is skewingly included by linear molecules so that the cyclic molecule is not detached; and B) -2) The above-mentioned material, which is a crosslinked product formed having a polymer capable of binding to a polyrotaxane.   The material according to claim 1, wherein the (B) crosslinked body is provided on at least a part of a surface layer of the (A) material.   The material according to claim 1 or 2, wherein the cyclic molecule of the (B) -1) polyrotaxane has a hydroxyl group.   The material according to any one of claims 1 to 3, wherein the (B) -2) polymer has a polyol.   The 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 material according to any one of claims 1 to 5, wherein the crosslinked body (B) is further formed with a crosslinking agent.   7. The material of claim 6, wherein said crosslinking agent is a polyisocyanate crosslinking agent.   The said (A) material is selected from the group of fibrous materials consisting of rock wool, glass wool, nonwoven fabric and felt, and / or selected from the group of foam materials consisting of urethane foam, rubber foam, and cellulose foam. The material according to any one of claims 1 to 7. The material (A) is selected from a group of fibrous materials consisting of rock wool, glass wool, nonwoven fabric, and felt, and has a weight per unit area of 50 to 2000 g / m ^2. 2. The material according to claim 1.   A sound absorbing material, wherein the material according to any one of claims 1 to 9 is a sound absorbing material.   The ratio of the normal incidence sound absorption coefficient X1 at a sound absorption frequency of 1000 Hz of the sound absorbing material at a frequency of 1000 Hz to the normal incidence sound absorption coefficient X2 at a sound absorption frequency of 1000 Hz of the material consisting only of the material (A), X1 / X2, is 1.1 or more. The sound absorbing material according to claim 10.   The ratio of the normal incidence sound absorption coefficient X11 at 3000 Hz of the sound absorbing material at a sound absorption frequency of 3000 Hz to the normal incidence sound absorption coefficient X12 at a sound absorption frequency of 3000 Hz of the material consisting only of the material (A), X11 / X12 is 1.1 or more. The sound absorbing material according to claim 10.   A sound absorbing material for a vehicle using the material according to any one of claims 1 to 9 and / or the sound absorbing material according to any one of claims 10 to 12.   A vehicle using the material according to any one of claims 1 to 9 and / or the sound absorbing material according to any one of claims 10 to 12. (A) a material having voids; and (B) a crosslinked body provided in at least a part of the (A) material:
A method for producing a material having
(I) a step of preparing the material (A);
(II-1) (B) -1) A blocking group is arranged at both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by linear molecules so that the cyclic molecule is not detached. Preparing a polyrotaxane comprising:
(II-2) (B) -2) a step of preparing a polymer capable of binding to the polyrotaxane;
(II-3) a step of preparing a composition comprising (B) -1) a polyrotaxane; and (B) -2) a polymer;
(III) a step of applying the composition to at least a part of the (A) material; and (IV) after the (III) application step, the (B) -1) a polyrotaxane; and the (B) -2 A) a step of forming a crosslinked product having a polymer;
The above method, wherein a layer of the crosslinked body is formed on at least a part of the material (A).

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