JP2023088930A - Soundproof material and production method thereof - Google Patents

Abstract

To provide a soundproof material having high soundproof property, and being suitable for a floor silencer for a vehicle, and a dash silencer, and a production method thereof.SOLUTION: There is provided a soundproof material 10 in which a skin material 30 is integrally molded to one surface of a polyurethane foam 20, the polyurethane foam 20 is a foam being obtained from a polyurethane foam raw material and is configured so that, an opposite surface of the skin material 30 is an open cell. The skin material 30 has an impregnation layer 34 which is acquired by impregnation of the polyurethane foam raw material and curing, on the integration side with the polyurethane foam. An airflow quantity of the skin material 30 including the impregnation layer 34 on the basis of JIS K 6400-7B method:2012 is 5-80 cc/cm2/sec.SELECTED DRAWING: Figure 1

Description

The present invention relates to a soundproofing material and its manufacturing method.

2. Description of the Related Art Conventionally, as a soundproofing material used as, for example, a floor silencer placed on a floor of a vehicle, there is a polyurethane foam laminated with a skin material on one side thereof.

Patent Document 1 below describes an automotive floor carpet in which an impact material made of a skinless urethane resin foam is integrally formed on the back surface of the carpet to improve sound absorption and vibration damping.

Further, Patent Document 2 below describes a skin-integrated polyurethane foam molded product having a foam layer with an air permeability of 3.0 ft ³ /min or more and a hardness of the foam layer of 8 kg/314 cm ² or less (25% ILD). Are listed.

JP-A-10-71884 JP-A-11-5499

In Patent Document 1, an anti-ventilation film or a thin non-woven fabric film is applied to the back surface of the carpet to prevent ventilation, and an impact material made of a skinless urethane resin foam is integrally formed to improve soundproofing. .

The skin-integrated polyurethane foam molded product of Patent Document 2 is intended for good soundproofing in the low and medium frequency regions, and while improving the ventilation of the foam layer, the hardness is 8 kg / 314 cm ² or less (25 % ILD), and when it is installed in a vehicle and a load is applied to the skin material, it sinks due to its softness.

In addition, both Patent Document 1 and Patent Document 2 study the soundproofing properties of polyurethane foam on the sound source side (for example, the floor side of a vehicle) that is the incident side of noise, and the non-sound source side that is the noise emitting side ( For example, no consideration has been given to the noise permeability of the main body of the carpet and the covering material, which are the interior side of the vehicle. Furthermore, it has been difficult to achieve both hardness and shape retention when a load is applied.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a soundproofing material having a high soundproofing (sound absorption) effect, which is placed between double walls having soundproofing materials on both sides, and a method for manufacturing the same. .

The invention of claim 1 is a soundproof material in which a skin material is integrally formed on one side of a polyurethane foam, wherein the polyurethane foam is a foam obtained from a polyurethane foam raw material, and the surface opposite to the skin material is provided. is an open cell, and the skin material has an impregnated layer impregnated and cured with the polyurethane foam raw material on the side integrated with the polyurethane foam, and the skin material containing the impregnated layer JIS K6400-7B method: It is characterized by a ventilation rate of 5 to 80 cc/cm ² /sec based on 2012.

The invention of claim 2 is characterized in that, in claim 1, the skin material is made of a fiber assembly.

The invention of claim 3 is the soundproof material according to claim 1 or 2, wherein the soundproof material is 50% when a 200 mm square x 20 mm thick sample is compressed to 80% of the thickness with a φ80 mm compression jig at a test speed of 50 mm / min. It is characterized by having a compression hardness of 500 N or more, which is a measured value of a load during compression.

The invention of claim 4 is characterized in that, in any one of claims 1 to 3, the soundproof material has a reverberation room sound absorption coefficient of 40% or more measured based on JIS A1409.

The invention of claim 5 is the soundproof material according to any one of claims 1 to 4, wherein the transmission loss at 1600 Hz measured based on JIS A1441-1:2007 is 42.2 dB or more. do.

The invention of claim 6 is characterized in that, in any one of claims 1 to 5, the soundproof material is between double walls having soundproof materials on both sides.

According to a seventh aspect of the invention, a skin material is attached to the mold surface of either the upper mold or the lower mold of the foam molding mold, and the polyurethane foam raw material containing at least a polyol component, a catalyst, a blowing agent, and an isocyanate is subjected to the foam molding. In a method for producing a soundproof material in which the skin material is integrally formed on one side of a polyurethane foam by injecting the raw material into a mold and foaming the raw material of the polyurethane foam, the skin material is made of a fiber assembly, and the polyurethane foam is The foam raw material contains a polymer polyol, and the EO ratio of the polyurethane foam raw material is defined as the value obtained by dividing the weight of ethylene oxide contained in the polyurethane foam raw material by the weight of the polyurethane foam raw material. The ratio is 7 to 15%, the surface of the polyurethane foam opposite to the skin material is open cells, and the skin material integrally molded with the polyurethane foam is on the side integral with the polyurethane foam. Having an impregnated layer impregnated and cured with the polyurethane foam raw material, the skin material containing the impregnated layer has an air permeability of 5 to 80 cc/cm ² /sec based on JIS K6400-7B method: 2012, The soundproof material has a compression hardness of 500 N, which is the load at 50% compression when a sample of 200 mm square × 20 mm thickness is compressed to 80% of the thickness with a compression jig of φ80 mm at a test speed of 50 mm / min. It is characterized by the above.

In the soundproofing material of the present invention, the skin material side is the non-sound source side, and the polyurethane foam side opposite to the skin material is the sound source side. In the soundproofing material of the present invention, the surface of the polyurethane foam, which is on the sound source side, is made up of open cells, so that the sound from the sound source easily enters the polyurethane foam. The skin material has an impregnated layer, and the air permeability of the skin material including the impregnated layer is 5 cc/cm ² /sec or more based on JIS K6400-7B method: 2012, so good sound insulation (sound absorption) is obtained. In addition, by applying slit processing of 100 mm square or less only to the urethane foam, the adhesion with the sound insulating material is improved, and the damping property is further improved.

The method for producing the soundproofing material of the present invention has good soundproofing (sound absorbing) properties and sufficient hardness. In such a case, it is possible to manufacture a soundproof material that is less likely to sink under pressure.

It is a cross-sectional view of the soundproof material of the embodiment. It is sectional drawing which shows the process to the middle in the manufacturing method of soundproof material. FIG. 5 is a cross-sectional view showing the remaining steps in the method of manufacturing the soundproof material; It is a table|surface which shows the structure of an Example, and the measurement result of a physical property and soundproofing (sound absorption). It is a table|surface which shows the structure of a comparative example, and the measurement result of a physical property and soundproofing (sound absorption).

Embodiments of the present invention will be described below. The soundproof material 10 of the embodiment shown in FIG. 1 is composed of a laminate in which a skin material 30 is integrally formed on one side of a polyurethane foam 20 . The soundproofing material 10 is suitable, for example, as a floor silencer or the like placed on the floor of a vehicle as a soundproofing (sound absorbing) material between double walls having soundproofing materials on both sides. The surface on the side opposite to is the sound source side, and is placed on a sound source side member such as a vehicle floor. On the other hand, the surface material 30 side of the soundproof material 10 is the non-sound source side.

The polyurethane foam 20 is a foam obtained from a polyurethane foam raw material, and the surface 21 opposite to the skin material 30 (surface on the sound source side) is open cells.
The surface 21 (surface on the sound source side) of the polyurethane foam 20 opposite to the surface material 30 may be slit and brought into close contact with the sound insulating material to improve vibration damping. The shape of the slit is not limited, and examples thereof include those in which a plurality of cut lines are formed in a grid pattern or in parallel.

Further, the polyurethane foam 20 preferably has a density (JIS K7222:2005) of 30 to 95 kg/m ³ and a thickness of 1 to 40 mm. If the density of the polyurethane foam 20 is too low, the hardness will be low. Conversely, if the density is too high, the weight will be heavy. On the other hand, if the polyurethane foam 20 is too thin, it cannot be filled with the raw material and cannot be molded.

The polyurethane foam raw material contains at least a polyol component, a catalyst, a blowing agent and an isocyanate, and the polyol component contains a polymer polyol.

The polyol component consists of polyether polyol and polymer polyol.
Polyether polyols are polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, and sucrose, or polyhydric alcohols containing ethylene. Polyether polyols to which alkylene oxides such as oxides and propylene oxides are added can be mentioned.

As the polyether polyol, a polyether polyol having a functional group number of 2 to 8, a hydroxyl value of 20 to 168 mgKOH/g, and a number average molecular weight of 168 to 20,000 is preferable. The ethylene oxide content (EO rate) of the polyether polyol is preferably 5 to 90%. The ethylene oxide content (EO ratio) of polyether polyol is the content of ethylene oxide units when the total amount of one raw material composition unit is 100% by weight.

Polymer polyols are obtained by polymerizing ethylenically inert compounds in polyether polyols. By including the polymer polyol in the polyol component, the effect of improving air permeability and improving hardness can be obtained.
The polymer polyol preferably has a functional group number of 3 to 8, a hydroxyl value of 20 to 60 mgKOH/g, and a number average molecular weight of 2,000 to 8,000. The ethylene oxide content (EO rate) of the polymer polyol is preferably 3 to 50%. The ethylene oxide content (EO rate) of the polymer polyol is the content of ethylene oxide units when the total amount of one raw material composition unit is 100% by weight.
The weight ratio of the polymer polyol in the polyol component is preferably 20 to 100%, more preferably 50 to 100%, and the rest is polyether polyol.

A catalyst known for polyurethane foam can be used. For example, triethylamine, triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholine, tetramethylguanidine, amine catalysts such as imidazole compounds, tin catalysts such as stannus octoate and dibutyltin dilaurate, and phenylmercuric propionate. Alternatively, metal catalysts such as lead octenoate (also referred to as organometallic catalysts) can be used. A plurality of catalysts may be used in combination. A general amount of the catalyst is about 0.2 to 4 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the polyol component.

The foaming agent is not particularly limited, but water is suitable. The amount of water as a foaming agent is preferably about 2 to 10 parts by weight with respect to 100 parts by weight of the polyol component. 3 to 7 parts by weight is more preferred.

The isocyanate may be aromatic, alicyclic, or aliphatic, and may be a bifunctional isocyanate having two isocyanate groups in one molecule, or three or more isocyanates in one molecule. Tri- or more functional isocyanates having an isocyanate group may be used, and these may be used singly or in combination.

For example, bifunctional isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'- Fragrances such as diphenylmethanedianate, 2,2'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate and other cycloaliphatic ones, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropyl Aliphatic compounds such as diisocyanate, methylene diisocyanate and lysine isocyanate can be mentioned.

Further, tri- or higher functional isocyanates include 1-methylbenzol-2,4,6-triisocyanate, 1,3,5-trimethylbenzol-2,4,6-triisocyanate, biphenyl-2,4,4′. -triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'tetraisocyanate, tri Phenylmethane-4,4′,4″-triisocyanate, polymeric MDI and the like can be mentioned. In addition, urethane prepolymers can also be used. The isocyanate is not limited to one type, but one or more types. For example, one type of aliphatic isocyanate and two types of aromatic isocyanate may be used, two types of aromatic isocyanate and urethane prepolymer may be used, or three or more types of isocyanate may be used. The isocyanate index is preferably from 90 to 130, more preferably from 95 to 120. The isocyanate index is an index used in the field of polyurethanes, and is an index used in raw materials for active hydrogen groups (for example, hydroxyl groups in polyols). and the equivalent ratio of the isocyanate group of the isocyanate to the active hydrogen group contained in the active hydrogen group of water as a blowing agent, etc.) is expressed as a percentage.

The polyol component includes a foam stabilizer and an additive as components appropriately included.
The foam stabilizer may be one used for polyurethane foams, and examples thereof include silicone foam stabilizers, fluorine-containing compound foam stabilizers, and known surfactants. The content of the foam stabilizer is preferably 0 to 2 parts by weight per 100 parts by weight of the polyol component.

Additives include communicating agents, cross-linking agents, pigments, fillers, flame retardants, antioxidants, ultraviolet absorbers, and the like.
Examples of the communication agent include polyether polyol having a high EO addition ratio, polyethylene glycol, and a silicone foam stabilizer that increases air permeability (has foam breakability). When a communicating agent is blended, the amount of the communicating agent is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the polyol. The communication agent is not limited to one type, and two or more types may be used.
Examples of cross-linking agents include glycerin, trimethylolpropane, 1,2,4-butanetriol, 2-methyl-2,3,4-butanetriol, triethanolamine, pentaerythritol, and the like, either alone or in combination. You may Preferred cross-linking agents have a functional group number of 2 to 4, a molecular weight of 92 to 136, and a hydroxyl value of 1066 to 1826 mgKOH/g. Glycerin, pentaerythritol, diethanolamine, etc., may be used singly or in combination.
The amount of the cross-linking agent is preferably 1 to 6 parts by weight per 100 parts by weight of the polyol component. The cross-linking agent may have an ethylene oxide content (EO percentage) greater than 0%. For example, ethylenediamine (number of functional groups: 4, molecular weight: 280, hydroxyl value 800 mgKOH / g, EO rate 40%), trimethylolpropane system (functional group: 3, molecular weight: 183, hydroxyl value 920mgKOH / g, EO rate 50% ), etc.

Examples of pigments include carbon black and titanium oxide.
Examples of fillers include graphite, alumina, and melamine.

Specific examples of flame retardants include halogenated diphenyl ethers such as degabromodiphenyl ether and octabromodiphenyl ether, halogen compounds such as halogenated polycarbonates, antimony trioxide, antimony tetroxide, antimony pentoxide, Sodium pyroantimonate, inorganic compounds such as aluminum hydroxide, triazine ring-containing compounds, metal hydroxides, phosphate ester flame retardants, condensed phosphate ester flame retardants, phosphate flame retardants, inorganic phosphorus flame retardants, dialkyl Phosphinates, silicone flame retardants, metal oxides, boric acid compounds, expandable graphite and the like can be mentioned.

Antioxidants include naphthylamine, diphenylamine, p-phenyldiamine, quinoline, hydroquinone derivatives, monophenol, thiobisphenol, hindered phenol and phosphite.

UV absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone) 2-hydroxybenzophenones such as; 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-ditert-butylphenyl)-5-chlorobenzo triazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octyl Phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol ), 2-(2′-hydroxyphenyl)benzotriazoles such as 2-(2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl)benzotriazole; phenyl salicylate, resorcinol monobenzoate, 2,4 -di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5 - benzoates such as di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanylide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano- Cyanoacrylates such as β,β-diphenyl acrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; 2-(2-hydroxy-4-octoxyphenyl)-4,6- Bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy -5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine and other triaryltriazines.

The polyurethane foam preferably has an EO rate of 7 to 15%, more preferably 8 to 13%. If the EO ratio of the polyurethane foam is too low or too high, the soundproofing (sound absorbing) properties of the soundproofing material will be lowered.

Here, the method for measuring the EO ratio of a polyurethane foam is to put only the polyurethane foam into a Soxhlet extractor [the weight of the put-in polyurethane foam is A (g)] and wash it with a solvent (acetone) at 68 to 72°C for 8 hours. , after drying, decompose with alkali. Thereafter, only the polyol component is extracted [extracted weight is B (g)], and a part thereof is evaluated by matrix-assisted laser time-of-flight mass spectrometry <manufactured by JEOL Ltd.>. The EO rate at each molecular weight [EO rate at each molecular weight (=N number of EO (: theoretical value) x number of each molecular weight/total number)] is calculated, and C is the sum total. A method for calculating the EO ratio of the polyurethane foam is as follows.
EO rate of polyurethane foam = [B × C] / [A] × 100
However, a molecular weight of 800 or more is calculated.

The skin material 30 may be a fiber assembly such as non-woven fabric or felt, and felt is particularly preferable from the viewpoint of lightness and soundproofing (sound absorbing) properties. The skin material of the embodiment is composed of a two-layer nonwoven fabric sheet composed of a first layer 31 and a second layer 33 . The first layer 31 is the side facing away from the polyurethane foam 20 , while the second layer 33 is the side facing the polyurethane foam 20 .

Either one of the first layer 31 and the second layer 33 has a basis weight of 90 g/m 2 or ^more , preferably 90 g/m 2 or ^more and 500 g/m ^{2 or} less, consisting of a fiber diameter of 2 to 4 d, The other layer has a basis weight of 100 g/m ² or more, preferably 100 g/m ² or more and 500 g/m ² or less. When the skin material 30 is configured in this way, one layer is densely packed with thin fibers, so that the viscous polyurethane foam raw material is less likely to seep out of the skin material 30 . Either one of the two layers is impregnated with an acrylic ester resin of 35 g/m ² or more, preferably 35 g/m ² or more and 100 g/m ² or less. In the layer impregnated with the acrylic ester resin, the spaces between the fibers are filled with the acrylic ester resin, making it difficult for the polyurethane foam raw material to pass through the skin material 30 and making it even more difficult for the polyurethane foam raw material to seep out. The surface material 30 is impregnated with the acrylic acid ester resin by applying an emulsion of the acrylic acid ester resin to the surface of the surface material 30 or spraying powder of the acrylic acid ester resin on the surface of the surface material 30. This can be done by applying a hot roller or hot air to the surface.

By adjusting the basis weight of the first layer 31 and the second layer 33 and the impregnation of the acrylic acid ester resin, the permeation amount based on JIS K6400-7B method: 2012 of the skin material 30 including the impregnated layer 34 is reduced to 5. ˜80 cc/cm ² /sec. By setting the ventilation rate of the skin material 30 including the impregnated layer 34 based on JIS K6400-7B method: 2012 to 5 to 80 cc/cm ² /sec, the soundproof (sound absorption) property of the soundproof material 10 can be improved. .

A more preferred embodiment of the skin material 30 is that the second layer 33 on the side of the polyurethane foam 20 has a basis weight of 90 g/m ² or more with a fiber diameter of 2 to 4 d, and an acrylic ester resin of 35 g/m ^{2 .} It is the mode impregnated above. When the skin material 30 is configured in this manner, the second layer 33, which comes into contact with the polyurethane foam raw material during the production of the soundproof material 10, is dense with fine fibers, and is impregnated with 35 g/m ² or more of acrylic acid ester resin. Therefore, the amount of the polyurethane foam raw material that impregnates (permeates) the second layer 33 is limited. Therefore, the impregnated layer 34 formed by the impregnation and curing of the polyurethane foam raw material, which is formed in the portion of the second layer 33 in contact with the polyurethane foam 20, becomes thin or coarse, and the air permeability of the second layer 33 can be ensured. .

By setting the basis weight of the first layer 31 on the opposite side of the polyurethane foam 20 to 100 g/m ² or more, the impregnation of the urethane foam raw material into the first layer 31 is effectively prevented, and the surface material 30 is ventilated. can ensure the integrity of the
Furthermore, the first layer 31 preferably has a fiber diameter of 5 d or more to improve surface abrasion resistance. The first layer 31 and the second layer 33 are integrated by adhesion or needle punching.

For the soundproof material 10, a sample of 200 mm square and 20 mm in thickness is compressed to 80% of the thickness at a test speed of 50 mm/min with a compression jig of φ80 mm. It is preferably 500N or more, more preferably 650-1200N. If the compression hardness of the soundproofing material 10 is too low, for example, when the upper surface of the soundproofing material 10 is pressed by the passenger's foot, the pressed portion sinks, making it difficult to walk or making the posture unstable. .

A method of manufacturing the soundproof material 10 will be described with reference to FIG. The soundproof material 10 is manufactured by molding using a mold 40 . The mold 40 consists of a lower mold 41 and an upper mold 43 , and the skin material 30 is attached to either the lower mold 41 or the upper mold 43 . The skin material 30 is attached with the first layer 31 facing the mold surface of one mold and the second layer 33 facing into the mold. When the skin material 30 is attached to the upper mold 43 , the mold surface of the upper mold 43 is provided with a locking means such as a locking pin for detachably holding the skin material 30 .
In the illustrated example, the surface material 30 is attached to the mold surface of the upper mold 43 as shown in FIG. 2(2-1).

A release agent 38 is applied to the mold surface of the mold 40 before the skin material 30 is attached to the mold surface of the mold 40 . The release agent 38 preferably contains linear hydrocarbon wax in order to make the surface of the polyurethane foam 20 on the sound source side more open-celled. Examples of linear hydrocarbon waxes include paraffin wax, Fischer-Tropsch wax, and Sasol wax. Solvent-based release agents dispersed in organic solvents, water-based release agents dispersed in water using emulsifiers, and the like. can be used.

After the release agent 38 is applied to the mold surface of the mold 40 and the skin material 30 is attached, the polyurethane foam raw material 20a is mixed and injected into the mold 40 as shown in (2-2) of FIG. After molding, the polyurethane foam raw material 20 a is foamed in the molding space between the second layer 33 of the skin material 30 and the mold surface of the lower mold 41 of the mold 40 .

The polyurethane foam raw material 20a injected into the mold 40 fills the molding space between the second layer 33 of the skin material 30 and the mold surface of the lower mold of the mold 40 by foaming, and (2-3 in FIG. 2) ), the polyurethane foam 20 is formed integrally with the skin material 30 . At that time, part of the polyurethane foam raw material 20 a is impregnated into the second layer 33 of the skin material 30 and cured to form an impregnated layer 34 on the boundary side with the polyurethane foam 20 .

After that, as shown in FIG. 3, the upper mold 43 is separated from the lower mold 41 to open the mold 40, and a soundproof laminate composed of the polyurethane foam 20 shown in FIG. Material 10 is taken out.

A soundproofing material of 500 mm square and 20 mm thick was manufactured by the mold foaming method using the mold 40 shown in FIGS. The numerical value of each component in the formulations of FIGS. 4 and 5 indicates parts by weight. The mold was heated with warm water, and the lower mold 41 and the upper mold 43 were heated to 70°C. As the release agent, linear hydrocarbon wax (product name: URH-520, manufactured by Konishi Co., Ltd.) was applied to the mold surface by spray coating at 10 to 30 g/m ² .

In Examples 1 to 5 and Comparative Examples 1 to 3, the soundproofing materials were manufactured by attaching the skin material to the mold surface of the upper mold 43 as shown in FIGS. Comparative Example 4 is an example in which felt having a weight per unit area of 1200 g/m ² is used instead of polyurethane foam by molding synthetic fiber, cotton, etc., from thermoplastic resin.

The components that make up the formulation of FIG. 4 are as follows.
· Polyol-1: polyether polyol, number of functional groups 3.6, number average molecular weight 5500, hydroxyl value 31.5 mgKOH / g, EO rate 8%
· Polyol-2: polymer polyol, number of functional groups 3, number average molecular weight 5000, hydroxyl value 25 mgKOH / g, EO rate 13%, solid content concentration 30%
- Blowing agent: water - Amine catalyst 1: diethanolamine - Amine catalyst 2: Aliphatic tertiary amine composition [bis (2-dimethylaminoethyl) ether / dipropylene glycol]
・Foam stabilizer: organic modified siloxane, product name: B8715LF2, EVONIC ・Additive: polyether polyol, molecular weight 5000, functional group number 3, hydroxyl value 34 mgKOH, EO ratio 70%
・Isocyanate 1 (ISO-1): polymeric MDI, NCO% 31.5%
・Isocyanate 2 (ISO-2): 4,4'-MDI/urethane prepolymer = 75-85/15-25, NCO% 26.5%, EO rate 10%

For each example and each comparative example, the thickness of the impregnated layer in the second layer, the appearance of the polyurethane foam, the hardness of the soundproof material, the density of the polyurethane foam, the air permeability of the surface material including the impregnated layer, the reverberation room sound absorption coefficient, The absorption coefficient of the reverberation room of the polyurethane foam and the transmission loss of the soundproof material were calculated or measured.

The thickness of the impregnated layer in the skin material 30 is measured from a 500 mm square × 20 mm thick soundproof material with a scanning electron microscope (SEM: manufactured by JEOL Ltd.) at a magnification of 35 times, 5 points (including maximum and minimum ) was calculated from the average.
For the appearance of the polyurethane foam, visually observe the cross-section of a 500 mm square × 20 mm thick soundproof polyurethane foam. The presence of voids having a diameter of 5 mm or more and 18 mm or less was evaluated as "O", and the presence of voids having a maximum average diameter of 18 mm or more was evaluated as "X". The maximum average diameter refers to the average value of the major axis and the minor axis. If large voids are present, the hardness of the part is greatly reduced, and the subsidence at the part becomes large when the pressure is applied.

The hardness of the soundproofing material was measured by cutting a 500mm square × 20mm thick soundproofing material into 200mm square × 20mm thick samples. At min, compress until the displacement amount reaches 80% of the thickness (sample displacement amount 16 mm, sample remaining thickness 4 mm), and measure the load at 25% compression, 50% compression, and 75% compression at that time. read as a value.
The hardness of the soundproofing material is evaluated as follows: "◎" if the compression hardness is 1000N or more, "○" if it is 500N or more and less than 1000N, and less than 500N It was set as "x".

The density of the polyurethane foam is measured by cutting a 500 mm square × 20 mm thick soundproofing material into 100 mm square × 20 mm thick cut pieces, and the skin material portion (when an impregnated layer is present, the skin material portion including the impregnated layer). ) was removed, and the remaining polyurethane foam sample was tested according to JIS K7222:2005.

The permeability of the skin material including the impregnated layer is measured by cutting a 500 mm square x 20 mm thick soundproof material into a 100 mm square x 20 mm thick cut product, and the skin material portion (if the impregnated layer exists, the impregnated layer JIS K6400-7B with the impregnated layer placed on the lower side of the sample consisting of the cut skin material part (the skin material part including the impregnated layer when the impregnated layer is present) Measured according to the Law: 2012.

The sound absorption coefficient of the reverberation room was measured by laying a 500mm square x 20mm thick soundproofing material 10 on the floor of the reverberation room (approximately 30m ³ ) and measuring the surface of the skin material (non-sound source side surface) based on JIS A 1409. gone. All gaps between the samples and between the sample and the jig were sealed with aluminum tape. The reverberation room sound absorption coefficient is the average sound absorption coefficient obtained by averaging the measurement values of the sound absorption coefficient at each frequency (500, 630, 800, 1000, 1250, 1600, 2000, 2500, 3150, 4000, 5000, and 6300 Hz). It was taken as the sound absorption coefficient of the reverberation room. The reverberation room sound absorption coefficient of the soundproof material 10 is the average sound absorption coefficient for the surface of the skin material including the impregnated layer.
The sound absorption coefficient of the reverberation room was evaluated as "⊚" when it was 65% or more, "∘" when it was 40% or more and less than 65%, and "x" when it was less than 40%.

Transmission loss was measured according to JIS A1441-1:2007. The sound source reverberation chamber is 36 m ³ , the sound receiving anechoic chamber is 20 m ³ , and the measurement area is 400×400 mm (0.16 m ² ). A 0.8 mm thick iron plate (sound insulating material) on the surface of the polyurethane foam on the sound source side of the 500 mm square x 20 mm thick soundproofing material and a 1 mm thick rubber sheet (sound insulating material) on the skin material on the non-sound source side (1700 g/m ^{2 )} ), the soundproofing material is fixed with a 50mm wide frame, and the gap is further sealed with clay. Numerical values at 1600 Hz were measured at four locations (100 mm pitch). "Configuration A" for the transmission loss in FIGS. 4 and 5 is a configuration in which the urethane foam is adhered to the iron plate, that is, the skin material is adhered to the rubber sheet, and "configuration B" is the skin material to the iron plate, that is, the urethane foam is a rubber sheet. It is a configuration that closely adheres to.
The transmission loss was evaluated as "⊚" when it was 44.2 dB or more, "∘" when it was 42.2 or more and less than 44.2 dB, and "X" when it was less than 42.2 dB.

Comprehensive evaluation was performed for each example and each comparative example. The overall evaluation is the lowest evaluation among the evaluations. For example, if all evaluations are "◎", the overall evaluation is "◎", if at least one evaluation is "〇" and the rest are "◎", the overall evaluation is "〇", and at least one evaluation is "△". If the rest are "○" or "◎", the overall evaluation will be "△", and if at least one evaluation is "×" and the rest are "△", "〇" or "◎", the overall evaluation will be "×" .

Example 1 contains 30 parts by weight of polyol-1, 70 parts by weight of polyol 2, 5.10 parts by weight of blowing agent, 2.71 parts by weight of amine catalyst-1, and 0.39 parts by weight of amine catalyst-2. , foam stabilizer 0 parts by weight, additive 0 parts by weight, isocyanate ISO-1:ISO-2=22:78, isocyanate index 105, polyurethane foam EO ratio 9.20%. The first layer is a 6d PET fiber with a basis weight of 150 g/m ² as a skin material, and the second layer is a 3d PET fiber with a basis weight of 100 g/m ² and is impregnated with an acrylic acid ester resin of 50 g/m ² . A skin material having a total basis weight of 300 g/m ² was used.

The results of Example 1 were as follows: the thickness of the impregnated layer was 0.5 mm; the appearance of the polyurethane foam was "A"; m ³ , air permeability of skin material including impregnated layer is 20.8 cc/cm ² /sec, reverberation room sound absorption coefficient of sound insulation material is 71%, evaluation is "⊚", transmission loss of sound insulation material is "configuration A" 49. 2 dB, the evaluation was "⊚", and the overall evaluation was "⊚", indicating that the soundproofing (sound absorbing) property was good.

Example 2 contains 30 parts by weight of polyol-1, 70 parts by weight of polyol 2, 5.76 parts by weight of blowing agent, 3.06 parts by weight of amine catalyst-1, and 0.45 parts by weight of amine catalyst-2. , 0.31 parts by weight of foam stabilizer, 2.27 parts by weight of additive, isocyanate ISO-1:ISO-2 = 22:78, isocyanate index 105, EO rate of polyurethane foam was 9.65% This is an example in which a polyurethane foam raw material is used and a skin material having the same structure as in Example 1 is used as the skin material.

The results of Example 2 were as follows: the thickness of the impregnated layer was 0.5 mm; the appearance of the polyurethane foam was "A"; 47.m ³ , air permeability of skin material including impregnated layer is 11.7 cc/cm ² /sec, reverberation room sound absorption coefficient of soundproof material is 65%, evaluation is "⊚", transmission loss of soundproof material is "Configuration A" 47. 2 dB, the evaluation was "⊚", and the overall evaluation was "⊚", indicating that the soundproofing (sound absorbing) property was good.

Example 3 contains 30 parts by weight of polyol-1, 70 parts by weight of polyol 2, 5.88 parts by weight of blowing agent, 3.13 parts by weight of amine catalyst-1, and 0.45 parts by weight of amine catalyst-2. , foam stabilizer 0 parts by weight, additive 9.84 parts by weight, isocyanate ISO-1: ISO-2 = 0: 100, isocyanate index 105, polyurethane foam with EO rate of 12.56% This is an example in which a skin material having the same structure as in Example 1 is used as the skin material using raw materials.

The results of Example 3 were as follows: the thickness of the impregnated layer was 0.5 mm, the appearance of the polyurethane foam was "◯", the hardness of the soundproof material when compressed by 50% was 650 N, the evaluation was "◯", and the density of the polyurethane foam was 55 kg/ m ³ , air permeability of skin material including impregnated layer is 72 cc/cm ² /sec, reverberation room sound absorption coefficient of sound insulating material is 73%, evaluation is “⊚”, transmission loss of sound insulating material is “configuration A” 50.2 dB, The evaluation was "⊚" and the overall evaluation was "◯". The appearance of the polyurethane foam was inferior to that of the other examples, but the soundproofing (sound absorbing) property was good.

Example 4 contains 0 parts by weight of polyol-1, 100 parts by weight of polyol 2, 6.41 parts by weight of blowing agent, 3.33 parts by weight of amine catalyst-1, and 0.37 parts by weight of amine catalyst-2. , 0 parts by weight of foam stabilizer, 2.47 parts by weight of additive, isocyanate ISO-1:ISO-2 = 0:100, isocyanate index 120, polyurethane foam with EO rate of 11.26% This is an example in which a skin material having the same structure as in Example 1 is used as the skin material using raw materials.

The results of Example 4 were as follows: the thickness of the impregnated layer was 0.5 mm; the appearance of the polyurethane foam was "A"; m ³ , air permeability of skin material including impregnated layer is 8.23 cc/cm ² /sec, reverberation room sound absorption coefficient of sound insulation material is 59%, evaluation is "◯", transmission loss of sound insulation material is "configuration A" 44. 2 dB, the evaluation was “⊚”, and the overall evaluation was “◯”, indicating that the soundproofing (sound absorbing) property was good.

Example 5 contains 30 parts by weight of polyol-1, 70 parts by weight of polyol 2, 5.10 parts by weight of blowing agent, 2.71 parts by weight of amine catalyst-1, and 0.39 parts by weight of amine catalyst-2. , 0 parts by weight of foam stabilizer, 0 parts by weight of additive, isocyanate ISO-1: ISO-2 = 22: 78, isocyanate index 105, polyurethane foam EO rate of 9.20%. This is an example in which a skin material having the same structure as in Example 1 is used as the skin material.

The results of Example 5 were as follows: the thickness of the impregnated layer was 0.5 mm; the appearance of the polyurethane foam was "A"; m ³ , ventilation rate of skin material including impregnated layer is 20.8 cc/cm ² /sec, reverberation room sound absorption coefficient of sound insulation material is 71%, evaluation is "◎", sound source side and non-sound source side of sound insulation material transmission loss was set in the opposite direction and the sound source was placed on the skin material side.

In Comparative Example 1, a resin film made of polyethylene terephthalate resin with a thickness of 0.03 mm was adhered to the surface of the second layer of the skin materials of Examples 1 to 3 on the polyurethane foam side with an acrylic urethane adhesive. Other than that, the configuration is the same as that of the first embodiment.

The results of Comparative Example 1 were as follows: no impregnated layer (thickness: 0 mm), appearance of polyurethane foam: "A", hardness of soundproofing material when compressed 50%: 1230 N, evaluation: "A", density of polyurethane foam: 55 kg. /m ³ , air permeability of the skin material is 0 cc/cm ² /sec, sound absorption coefficient of the soundproof material in the reverberation room is 30%, evaluation is “×”, transmission loss of the soundproof material is “configuration A” 41.2 dB, evaluation is “×” ”, and the overall evaluation was “x”. In Comparative Example 1, since the resin film is laminated on the second layer of the skin material, the skin material has no impregnated layer and air permeability, the sound absorption coefficient of the reverberation room of the skin material is low, and the sound insulation (sound absorption) of the sound insulation material is low. The properties were inferior to those of Examples 1-3.

Comparative Example 2 contains 30 parts by weight of polyol-1, 70 parts by weight of polyol 2, 4.35 parts by weight of blowing agent, 2.50 parts by weight of amine catalyst-1, and 0.37 parts by weight of amine catalyst-2. , foam stabilizer 0.50 parts by weight, additive 1.85 parts by weight, isocyanate ISO-1:ISO-2=100:0, isocyanate index 105, EO rate of polyurethane foam 6.58% This is an example in which a polyurethane foam raw material is used and a skin material having the same structure as in Example 1 is used as the skin material.

The results of Comparative Example 2 were as follows: the thickness of the impregnated layer was 0.5 mm, the appearance of the polyurethane foam was "A", the hardness of the soundproof material when compressed by 50% was 1280 N, the evaluation was "A", and the density of the polyurethane foam was 55 kg/. 39.m ³ , air permeability of skin material including impregnated layer is 2.61 cc/cm ² /sec, reverberation room sound absorption coefficient of soundproof material is 34%, evaluation is "x", transmission loss of soundproof material is "Configuration A" 39. It was 2 dB, the evaluation was "x", and the overall evaluation was "x". In Comparative Example 2, the EO ratio of the polyurethane foam was as low as 6.58% due to the isocyanate being 100% of ISO1, and the air permeability of the skin material including the impregnated layer was extremely high at 2.61 cc/cm ² /sec. The sound absorption coefficient of the reverberation room sound absorption of the surface material including the impregnated layer and the polyurethane foam and the transmission loss of the sound insulation material were small, and the sound insulation (sound absorption) property of the sound insulation material was inferior to those of Examples 1 to 3.

Comparative Example 3 contains 30 parts by weight of polyol-1, 70 parts by weight of polyol 2, 6.73 parts by weight of blowing agent, 3.13 parts by weight of amine catalyst-1, and 0.51 parts by weight of amine catalyst-2. , foam stabilizer 0 parts by weight, additive 25.46 parts by weight, isocyanate ISO-1:ISO-2=0:100, isocyanate index 105, polyurethane foam with EO rate of 15.5% This is an example in which a skin material having the same structure as in Example 1 is used as the skin material using raw materials.

The results of Comparative Example 3 were as follows: the thickness of the impregnated layer was 0.5 mm, the appearance of the polyurethane foam was "x", the hardness of the soundproof material when compressed by 50% was 600 N, the evaluation was "Δ", and the density of the polyurethane foam was 55 kg/. m ³ , the air permeability of the skin material including the impregnated layer is 93 cc/cm ² /sec, the reverberation room sound absorption coefficient of the soundproof material is 40%, the evaluation is “◯”, the transmission loss of the soundproof material is “Configuration A” 42.2 dB, The evaluation was “◯” and the overall evaluation was “×”. In Comparative Example 3, the isocyanate was 100% of ISO2, so that the hardness of the soundproof material was low, while the EO rate of the polyurethane foam was as high as 15.5%, and the surface material including the impregnated layer was improved. The ventilation rate is as large as 93 cc/cm ² /sec, the reverberation room sound absorption coefficient of the skin material including the impregnated layer and the polyurethane foam, and the transmission loss of the soundproof material are small, and the soundproof (sound absorption) property of the soundproof material is lower than that of Examples 1 to 3. was inferior to

Comparative Example 4 is an example in which felt is used in place of polyurethane foam and laminated on the second layer of the skin material similar to that of Example 1.
The results of Comparative Example 4 were that there was no impregnated layer of the surface material, the soundproof material had a hardness of 62 N when compressed by 50%, the evaluation was "x", the felt density was 55 kg/m ³ , and the air permeability of the surface material was 106 cc/m 3 . cm ² /sec, the reverberation room sound absorption coefficient of the soundproof material was 84%, the evaluation was "⊚", the transmission loss of the soundproof material was 48.2 dB in "Configuration A", the evaluation was "⊚", and the overall evaluation was "X". In Comparative Example 4, felt was used instead of polyurethane foam, so that the hardness of the soundproofing material was extremely small at 62N, and the sinking due to pressure was large, and when used as a floor silencer, the feet of the occupants were not easily disturbed. Buried in the soundproofing material, it is difficult to move, and the posture becomes unstable.

Thus, the soundproofing material of the present invention has high soundproofing (sound absorbing) properties, and is suitable not only for soundproofing materials for vehicles such as floor silencers of vehicles, but also for soundproofing materials for buildings, industrial machines, home appliances, and the like.

10 soundproofing material 20 polyurethane foam (sound absorbing material)
20a Polyurethane foam raw material 30 Skin material (sound absorbing material)
31 first layer 33 second layer 34 impregnation layer 40 mold 41 lower mold 43 upper mold 38 release agent

Claims (6)

In the soundproofing material in which the skin material is integrally molded on one side of the polyurethane foam,
The polyurethane foam is a foam obtained from a polyurethane foam raw material, and the surface opposite to the skin material has open cells,
The skin material has an impregnated layer impregnated and cured with the polyurethane foam raw material on the side integrated with the polyurethane foam,
A soundproof material characterized by having an air permeation rate of 5 to 80 cc/cm ² /sec based on JIS K6400-7B method: 2012 for the skin material including the impregnated layer. 2. The soundproofing material according to claim 1, wherein the skin material is made of a fiber assembly. The soundproof material has a compression hardness of 500 N, which is the load at 50% compression when a sample of 200 mm square × 20 mm thickness is compressed to 80% of the thickness with a compression jig of φ80 mm at a test speed of 50 mm / min. The soundproof material according to claim 1 or 2, characterized by the above. The soundproofing material according to any one of claims 1 to 3, wherein the soundproofing material has a reverberation room sound absorption coefficient of 40% or more measured based on JIS A1409. The soundproof material according to any one of claims 1 to 4, wherein the soundproof material has a transmission loss of 42.2 dB or more at 1600 Hz measured based on JIS A1441-1:2007. 6. Soundproofing material according to any one of claims 1 to 5, characterized in that the soundproofing material is between double walls with soundproofing material on both sides.

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