JP2022076284A - Laminate and method for producing the same, and soundproof member - Google Patents

Abstract

To provide a laminate that keeps rigidity, is light in weight and is particularly soundproofed against high frequency noise and a soundproof member, and a method for producing the laminate.SOLUTION: A laminate has a urethane foamed layer including continuous and opened cells and having a flow resistance of 350,000 N s/m4 or less and a density of 10 kg/m3 or more, and a resin layer containing a thermosetting resin. The laminate has a density of 50 kg/m3 or more and 200 kg/m3 or less, and a modulus of 0.01 N m2 or more as measured at 10 mm width.SELECTED DRAWING: None

Description

The present invention relates to a laminate, a method for producing the same, and a soundproof member.

It is being studied to use a composite of resin and urethane for the purpose of sound absorption and sound insulation.
For example, in Patent Document 1, as a sound absorbing / cushioning material mainly used for wall materials as a sound absorbing / cushioning material for building interior materials, etc., it adheres to one surface of a synthetic resin foam sheet having sound absorbing / cushioning performance. A sound absorbing / cushioning material in which a material layer is formed and a straight concave pressure strain line is formed on the sheet is disclosed.
Further, in Patent Document 2, in order to obtain a sound absorbing member having excellent sound absorbing property in a low frequency range, the back surface of the porous sound absorbing material with a coating film is partially attached to a substrate with a pasting area ratio of 5 to 70%. And it is disclosed that they are integrated.

Japanese Unexamined Patent Publication No. 11-210108 Japanese Unexamined Patent Publication No. 10-8591

However, the urethane foam layer of the conventional member has a skin layer and is not open because the bubbles of the urethane foam are closed cells, so that sound insulation cannot be sufficiently obtained. Further, since the surface of the member was a fiber sheet, a thin film, or the like, the rigidity was insufficient. If the rigidity of the member is insufficient, it is difficult to maintain the shape of the member, and the member cannot be fixed to the housing of the noise source by utilizing the shape of the member.

An object of the present invention is to provide a laminated body and a soundproof member which maintain rigidity, are lightweight, and have excellent soundproofing property particularly against high frequency sound, and a method for manufacturing the laminated body, and it is an object of the present invention to solve the object. And.

<1> A urethane foam layer having continuous and open bubbles, a flow resistance of 350,000 N · s / m ⁴ or less, and a density of 10 kg / m ³ or more, and a resin layer containing a thermosetting resin. A laminate having a density of 50 kg / m ³ or more and 200 kg / m ³ or less, and a modulus of 0.01 Nm ² or more measured with a width of 10 mm.

<2> The laminate according to <1>, wherein the urethane foam layer has a thickness of 16 to 50 mm.
<3> The laminate according to <1> or <2>, which has a thickness of 20 to 55 mm.
<4> The laminate according to any one of <1> to <3>, wherein the surface density of the resin layer is 0.15 to 0.50 g / cm ² .
<5> The laminate according to <4>, wherein the thermosetting resin contains at least one of an unsaturated polyester resin, a vinyl ester resin, and a urethane resin.
<6> The laminate according to any one of <1> to <5>, wherein the urethane foam layer is adjacent to the resin layer.

<7> A soundproofing member using the laminate according to any one of <1> to <6>.

<8> A urethane slab is installed in a mold, a plate-shaped composition containing a thermosetting resin raw material and a curing agent is charged on the urethane slab, and a resin layer containing a thermosetting resin is formed at the same time as shaping by a press. A method for manufacturing a laminate to be joined with a urethane foam layer.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a laminate and a soundproof member that maintain rigidity, are lightweight, and are particularly excellent in soundproofing against high-frequency sound, and a method for manufacturing the laminate.

<Laminated body>
The laminate of the present invention contains a urethane foam layer having continuous and open bubbles, a flow resistance of 350,000 N · s / m ⁴ or less, and a density of 10 kg / m ³ or more, and a thermosetting resin. It is provided with a resin layer, has a density of 50 kg / m ³ or more and 200 kg / m ³ or less, and has a modulus of 0.01 N · m ² or more measured with a width of 10 mm.
The laminate of the present invention may include a layer other than the urethane foam layer and the resin layer having the above-mentioned structure, but the urethane foam layer may be provided from the viewpoint of suppressing peeling between the layers in a high temperature environment and a high humidity environment. , It is preferable to be adjacent to the resin layer.
Since the laminated body of the present invention has continuous and open bubbles, sound waves can enter into the pores and vibrate the partition walls of the pores to convert them into heat energy, thereby absorbing sound. Further, by providing a urethane foam layer having a flow resistance of 350,000 N · s / m ⁴ or less and a density of 10 kg / m ³ or more, sound waves easily enter the inside of the retan foam layer and have soundproofing against high-frequency sound. Excellent for. Further, by providing the resin layer containing the thermosetting resin, the rigidity can be maintained while being lightweight, and the modulus of the laminated body having a width of 10 mm is 0.01 Nm ² or more.

(Modulus)
As for the modulus of the laminated body, the modulus measured with a width of 10 mm is 0.01 Nm ² or more.
From the viewpoint of further improving the rigidity of the laminated body, the modulus of the 10 mm wide laminated body is preferably 0.02 N · m ² or more, and more preferably 0.03 N · m ² or more.
The upper limit of the modulus of the laminated body is not particularly limited, but is usually preferably 0.07 N · m ² or less, and more preferably 0.06 N · m ² or less.
The modulus of the laminate can be measured by the following method.

The laminate is cut into test pieces having a length of 100 mm and a width of 10 mm. The resin layer may be cut out by grinding and then the urethane may be cut with a cutting tool, or may be cut out at once with a water jet or the like. The end of the resin layer of the test piece is sandwiched and fixed with metal fittings such as clips, and the resin layer is placed on a three-point bending jig (JIS K7171 (2010) compliant) set at a distance between fulcrums at intervals of L = 105 mm. Is placed face up, and a force is applied to the surface of the resin layer of the test piece with an indenter to perform a three-point bending test. Rigidity can be calculated from the test force and the slope of the displacement. From the load (W) [N] applied by the indenter, the deflection (δ) [mm] of the test piece, and the distance between the fulcrums (L) [mm], the modulus (EI) [N ・ mm ² of the laminate is calculated by the following formula. ] Can be calculated.
EI = [(ΔW / Δδ) × L ³ ] / (48)
It should be noted that ΔW / Δδ is calculated from the initial inclination of the 3-point bending test.

(density)
The density of the laminated body is 50 kg / m ³ or more and 200 kg / m ³ or less.
If the density (ρL) of the laminated body is less than 50 kg / m ³ , the rigidity of the laminated body cannot be obtained. Further, if the density (ρL) of the laminated body exceeds 200 kg / m ³ , a sufficient soundproofing effect against high frequency cannot be obtained.
The density of the laminate is preferably 80 kg / m ³ or more, more preferably 110 kg / m ³ or more, further preferably 120 kg / m ³ or more, and 190 kg / m ³ or less. Is more preferable, 180 kg / m ³ or less is more preferable, and 160 kg / m ³ or less is further preferable.
The density of the laminate can be measured by a method according to JIS K 7112 (1999).

(thickness)
Further, the thickness (TL) of the laminated body is preferably 20 to 55 mm.
When the thickness of the laminated body is 20 mm or more, the rigidity of the laminated body can be further improved, and when it is 55 mm or less, the laminated body can be made lighter.
It is more preferable that the thickness of the laminate is 25 mm or more. Further, the thickness of the laminated body is more preferably 50 mm or less, further preferably 40 mm or less, and particularly preferably 30 mm or less.

(Area density)
The surface density (ρAL) of the laminated body is preferably 0.17 to 0.70 g / cm ² .
When the surface density of the laminate is 0.17 g / cm ² or more, the transmission loss over the entire frequency range can be increased by mass, and when it is 0.70 g / cm ² or less, the present laminate is applied. The weight of the member can be reduced.
The surface density of the laminated body is more preferably 0.20 g / cm ² or more, and further preferably 0.22 g / cm ² or more. Further, the surface density of the laminated body is more preferably 0.60 g / cm ² or less, and further preferably 0.55 g / cm ² or less.
The surface density of the laminated body can be measured with a scale after being processed into a predetermined shape by processing such as a punching blade.

[Urethane foam layer]
The urethane foam layer has continuous and open bubbles, a flow resistance of 350,000 N · s / m ⁴ or less, and a density of 10 kg / m ³ or more.
Since the bubbles included in the urethane foam layer are continuous and open bubbles, the urethane foam layer easily absorbs high-frequency sound. For example, in the case of an ellipsoid, the bubbles may be released at one place of the ellipsoid, may be released at a plurality of places, or may be released at all, from the viewpoint of enhancing the soundproofing effect. , It is preferable that everything is open. However, when the urethane foam layer is adjacent to the resin layer, for example, the bubbles on the resin layer side of the urethane foam layer are usually non-open.

(Flow resistance)
The flow resistance is an index showing the difficulty of air flow in the urethane foam layer, and if it exceeds 350,000 N · s / m ⁴ , the soundproofing effect against high frequency sound cannot be exhibited.
From the viewpoint of further enhancing the soundproofing effect of the laminated body against high-frequency sound, the flow resistance of the urethane foam layer is preferably 300,000 N · s / m ⁴ or less, and preferably 200,000 N · s / m ⁴ or less. It is more preferably 100,000 N · s / m ⁴ or less.
The lower limit of the flow resistance of the urethane foam layer is not particularly limited, but is preferably 500 N · s / m ⁴ or more, more preferably 800 N · s / m ⁴ or more, and 1,000 N · s / m ⁴ or more. Is more preferable.
The flow resistance can be measured by, for example, a flow resistance measuring device manufactured by Nippon Acoustic Engineering Co., Ltd.
In the production of the laminated body, the flow resistance of the urethane slab used as the raw material of the urethane foam layer and the flow resistance of the urethane foam layer of the manufactured laminated body are usually unchanged and equivalent.

(thickness)
The thickness of the urethane foam layer is preferably 16 to 50 mm.
When the thickness of the urethane foam layer is 16 mm or more, the soundproofing effect against high-frequency sound can be further improved, and when it is 50 mm or less, the laminated body can be made lighter.
The thickness of the urethane foam layer is more preferably 17 mm or more, and further preferably 20 mm or more. Further, the thickness of the urethane foam layer is more preferably 45 mm or less, and further preferably 40 mm or less.

(density)
The density (ρu) of the urethane foam layer is 10 kg / m ³ or more.
If the density (ρu) of the urethane foam layer is less than 10 kg / m ³ , the soundproofing effect against high frequency sound cannot be improved. The upper limit of the density is not particularly limited, but is preferably 90 kg / m ³ or less from the viewpoint of suppressing an increase in the mass of the laminated body.
The density of the urethane foam layer is more preferably 17 kg / m ³ or more, and further preferably 20 kg / m ³ or more. Further, the density of the urethane foam layer is more preferably 85 kg / m ³ or less, and further preferably 80 kg / m ³ or less.
The density of the urethane foam layer can be measured by a method based on the method for measuring the apparent density of JIS K7222 (2005).

(Shear modulus)
The shear modulus (E) of the urethane foam layer is preferably 300,000 N / m ² or less.
When the shear modulus of the urethane foam layer is 300,000 N / m ² or less, the soundproofing effect against high-frequency sound can be further improved. The lower limit of the shear modulus is not particularly limited, but is usually 50 N / m ² or more.
The shear modulus of the urethane foam layer is more preferably 60,000 N / m ² or more, and further preferably 70,000 N / m ² or more. Further, the shear modulus of the urethane foam layer is more preferably 250,000 N / m ² or less, and further preferably 200,000 N / m ² or less.
The shear modulus of the urethane foam layer can be measured using an elastic modulus measurement system manufactured by Nippon Acoustic Engineering Co., Ltd., and the elastic modulus is determined from the vibration transmission characteristics by vibrating the sample with shearing force applied. taking measurement.
In the production of the laminated body, the shear elastic modulus of the urethane slab used as the raw material of the urethane foam layer and the shear elastic modulus of the urethane foam layer of the manufactured laminated body are usually unchanged and equivalent.

(Number of cells)
The urethane foam layer preferably has 20 to 80 cells / 25 mm.
When the number of cells is 20/25 mm or more, the soundproofing effect for high-frequency sound can be further improved, and when the number of cells is 80/25 mm or less, the decrease in rigidity can be suppressed.
The number of cells in the urethane foam layer is more preferably 25 cells / 25 mm or more, and further preferably 30 cells / 25 mm or more. Further, the number of cells in the urethane foam layer is more preferably 65 cells / 25 mm or less, and further preferably 60 cells / 25 mm or less.
The number of cells in the urethane foam layer can be measured by the method described in Annex 1 of JIS K640-1 (2004).

(Porosity)
The porosity of the urethane foam layer is preferably 0.90 or more.
When the porosity of the urethane foam layer is 0.90 or more, the soundproofing effect against high frequency sound can be further improved. Porosity is usually less than 1.00.
The porosity of the urethane foam layer is more preferably 0.92 or more, and even more preferably 0.95 or more.
The porosity of the urethane foam layer is porosity Φ = V _V / _VT , where V _V is the volume of the voids and VT is the volume of the bulk, but here it is easily calculated from the true density and bulk density of the input material. Can be done.
In the production of the laminated body, the porosity of the urethane slab used as the raw material of the urethane foam layer and the porosity of the urethane foam layer of the manufactured laminated body are usually unchanged and equivalent.

(Area density)
The surface density (ρAu) of the urethane foam layer is preferably 0.01 to 0.30 g / cm ² .
When the surface density of the urethane foam layer is within the above range, the sound absorption performance can be improved.
The surface density of the urethane foam layer is more preferably 0.02 g / cm ² or more, and further preferably 0.03 g / cm ² or more. Further, the surface density of the urethane foam layer is more preferably 0.27 g / cm ² or less, and further preferably 0.25 g / cm ² or less.
The surface density of the urethane foam layer can be calculated by measuring with a scale or the like after cutting with a standard length.

The urethane foam may be an ether-based urethane foam or an ester-based urethane foam.
The ether-based urethane refers to urethane in which the main component of the polyol constituting the urethane (80 mol% or more of the total polyol) is a polyether polyol. The ester-based urethane refers to urethane in which the main component of the polyol constituting the urethane (80 mol% or more of the total polyol) is a polyester polyol.
From the viewpoint of water resistance and moisture resistance, the urethane foam is preferably an ether urethane foam. In the ether urethane, the polyol may contain an ester group, but the concentration of the ester group in the total polyol is preferably 20 mol% or less. As the polyol, one kind of polyether polyol may be used alone, or one kind or a mixture of two or more kinds of polyols other than the polyether polyol may be used.

As a method for obtaining urethane foam in the present invention, for example, in a urethane synthesis reaction, a method of using water as a foaming agent and reacting with polyisocyanate to generate carbon dioxide is used.
Here, in order to obtain continuous and open bubbles, the foam foam that has been sufficiently foamed in the urethane foam may be cut in the thickness direction.
^In order to reduce the flow resistance to 350,000 N · s / m4 or less, the urethane may be made thicker or the number of cells may be made smaller.
In order to make the density of urethane foam 10 kg / m ³ or more, the amount of water added in the urethane synthesis reaction may be appropriately adjusted.
Further, as a urethane foam having continuous and open bubbles, a flow resistance of 350,000 N · s / m ⁴ or less, and a density of 10 kg / m ³ or more, a commercially available product may be used.

[Resin layer]
The resin layer contains a thermosetting resin.
Since the laminate of the present invention includes a resin layer, it is excellent in rigidity. The resin layer is preferably made of a thermosetting resin.
The resin layer may be a foamed resin layer from the viewpoint of further improving the soundproofing effect against high-frequency sound.

(density)
The density (ρr) of the resin layer is preferably 300 to 2000 kg / m ³ . When the density is 300 kg / m ³ or more, the rigidity of the laminated body can be further improved. If the density is 2000 kg / m ³ or less, it is unlikely to affect the sound absorbing effect. From the above viewpoint, the density of the thermosetting resin is more preferably 700 to 1950 kg / m ³ , and further preferably 1000 to 1900 kg / m ³ .

(Thermosetting resin)
Examples of the thermosetting resin include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenol resins, polyamide resins, urea resins, melamine resins, polyimide resins, diallyl phthalate resins, and urethane resins. Etc. are exemplified.
Only one type of thermosetting resin may be used, or two or more types may be used.
Among these, unsaturated polyester resin, vinyl ester resin and urethane resin are preferable, and unsaturated polyester resin is more preferable from the viewpoint of productivity.
The thermosetting resin is obtained by curing a composition containing a thermosetting resin raw material and a curing agent.

Examples of the unsaturated polyester resin raw material include known unsaturated polyester resin raw materials obtained by dissolving a condensation product obtained from an unsaturated polyvalent carboxylic acid and a polyvalent alcohol in a vinyl monomer.
Examples of the unsaturated polyvalent carboxylic acid include maleic anhydride, fumaric acid, adipic acid, phthalic anhydride, and isophthalic acid. Examples of the polyvalent alcohol include ethylene glycol, 1,3-butylene glycol, diethylene glycol, and propylene glycol. Examples of the vinyl monomer include styrene-based monomers.

A peroxide can be used as a curing agent (polymerization initiator) for the unsaturated polyester resin raw material.
Examples of the peroxide include organic peroxides such as benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, peroxyperbenzoate, peroxyketal, and dicumyl peroxide. As the peroxide, one kind may be used alone, or two or more kinds may be used. Further, a chain transfer agent may be used.
The addition ratio of the curing agent is preferably 0.1 to 10 parts by mass, and more preferably 0.3 to 5.0 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin raw material.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; Alicyclic epoxy resin; glycidyl ether type epoxy resin; glycidylated amine type epoxy resin; halogenated epoxy resin; or epoxy group-containing monomer or oligomer such as glycidylated polyester, glycidylated polyurethane, glycidylated acrylic Examples thereof include the addition polymer of.
The epoxy resin may be used alone or in combination of two or more.

As a curing agent for epoxy resin, acid anhydride such as methylhexahydrophthalic anhydride, novolak type phenol resin, phenol resin such as cresol novolac type epoxy resin, anhydrous phthalic acid derivative, dicyandiamide, imidazole compound, aluminum chelate, BF ₃ Examples thereof include an amine complex of Lewis acid such as. These curing agents may be used alone or in combination of two or more.

Compositions containing thermosetting resin raw materials and curing agents include foaming agents, bulking agents, colorants, ultraviolet absorbers, antioxidants, refractory agents, antifungal agents, plasticizers, coupling agents, and electrical conductivity. A modifier such as a filler, a magnetic filler, a heat conductive filler, an antistatic agent, and elastic fine particles can be contained as needed.

(Area density)
The surface density (ρAr) of the resin layer is preferably 0.07 to 0.60 g / cm ² .
When the surface density of the resin layer is 0.07 g / cm ² or more, rigidity can be ensured, and when it is 0.50 g / cm ² or less, a lightweight laminate can be obtained.
The surface density of the resin layer is more preferably 0.16 g / cm ² or more, and further preferably 0.17 g / cm ² or more. Further, the surface density of the resin layer is more preferably 0.46 g / cm ² or less, and further preferably 0.41 g / cm ² or less.
The surface density of the resin layer can be calculated by subtracting the surface density of the urethane to be charged from the surface density of the laminated body. The surface density of the laminated body may be calculated by cutting the laminated body into a standard size, weighing it, and then weighing it.

(thickness)
The thickness (Tr) of the resin layer is preferably 0.50 to 5.00 mm.
When the thickness of the resin layer is 0.50 mm or more, the rigidity of the laminated body can be further improved, and when the thickness is 5.00 mm or less, the laminated body can be made lighter.
The thickness of the resin layer is more preferably 0.85 mm or more, and further preferably 1.10 mm or more. Further, the thickness of the resin layer is more preferably 3.20 mm or less, and further preferably 2.80 mm or less.

<Manufacturing method of laminated body>
The method for producing the laminated body of the present invention is not particularly limited as long as it is a method capable of laminating the urethane foam layer and the resin layer described above. However, it is preferable that the urethane foam layer and the resin layer are not laminated via an adhesive or an adhesive, and the urethane foam layer is laminated so as to be adjacent to the resin layer. Since the urethane foam layer is laminated so as to be adjacent to the resin layer, the urethane foam layer and the resin layer are less likely to peel off even when the laminated body is placed in a high temperature environment, a high humidity environment, or the like.
Examples of the method for manufacturing a laminated body in which the urethane foam layer is laminated so as to be adjacent to the resin layer include the following methods.

In the manufacturing method, a urethane slab is installed in a mold, a plate-shaped composition containing a thermosetting resin raw material and a curing agent is charged on the urethane slab, and the thermosetting resin is contained at the same time as shaping by a press. This is a method of joining a resin layer and a urethane foam layer.

As the mold, a container-shaped mold that fits each other is used, and usually has a convex upper mold (core) and a concave lower mold (cavity). In order to control the thickness of the urethane slab and the plate-like composition, a spacer may be provided in the pressure receiving portion between the upper mold and the lower mold. Further, the upper mold or the lower mold may be provided with an ejector so that the manufactured laminate can be easily taken out from the mold.

It is preferable to heat the upper mold and the lower mold in advance before putting the urethane slab and the plate-like composition into the mold. When the temperature of the mold on the urethane side is Tu and the temperature of the mold on the plate-like composition side, that is, the side on which the resin layer is formed is Tr, Tu and Tr may be the same, but the temperature of the urethane slab is set. If it is raised too much, the urethane will be irreversibly crushed, so Tr> Tu is preferable.
Tr and Tu vary depending on the mass of the urethane slab and the mass of the plate-like composition. For example, when the curing temperature of the resin is 120 ° C., Tr may be 120 ° C. and Tu may be 115 ° C.

Normally, a urethane slab is installed in the lower mold (cavity), the plate-like composition is charged on the urethane slab, and the upper mold (core) is stacked.

As the urethane slab, a urethane foam having continuous and open bubbles and a flow resistance of 350,000 N · s / m ⁴ or less may be processed into a slab (block) having a desired shape. The shape of the urethane slab is usually the same as the shape of the bottom surface of the lower mold (cavity), but the shape may be such that a part of the bottom surface shape of the cavity is covered. The thickness of the urethane slab may be the same as the range of the thickness of the urethane foam layer of the laminated body.

The plate-shaped composition containing a thermosetting resin raw material and a curing agent refers to a so-called SMC (Sheet Molding Compound), and is a thermosetting resin uncured obtained by molding a composition containing a thermosetting resin raw material and a curing agent into a plate shape. It is a thing. The thermosetting resin raw material and the curing agent may use the above-mentioned components, and the plate-shaped composition may contain a modifier such as a foaming agent.
The shape of the plate-shaped composition (SMC) may be the same as that of the urethane slab, or may be a shape that covers a part of the urethane slab. The input amount (W) of the plate-shaped composition (SMC) is calculated and determined so that the thickness after curing is within the range of the thickness of the resin layer of the laminated body.

Then, it is shaped by a press. That is, the upper mold is lowered or the lower mold is raised to perform mold clamping. At this time, while applying pressure (press pressure; P) to the urethane slab and the plate-shaped composition, the plate-shaped composition is crushed to a predetermined cavity interval (L0), and at this position, a predetermined time (pressurization holding). Time; Tp) It is preferable to hold.

The cavity spacing (L0) may be adjusted by controlling the position of the press or by controlling the size of the spacer.
The press pressure (P), cavity spacing (L0) and pressure holding time (Tp) vary depending on the mass of the urethane slab and the mass and composition of the plate-like composition, but for example, P may be 3 to 15 MPa. , L0 may be 2 to 10 mm, and Tp may be 2 to 15 minutes.

Then, the upper mold is slowly raised or the lower mold is slowly lowered to remove the molded product (laminated body) from the mold. The molded product may be taken out using an ejector, or may be taken out using an end portion, a convex portion, or the like of the molded product.

<Soundproof material>
The soundproofing member of the present invention is made by using the laminated body of the present invention.
Therefore, the soundproofing member of the present invention maintains rigidity and is excellent in soundproofing against high-frequency sound.
The soundproofing member of the present invention is suitable for parts, products, etc. that are required to have rigidity and soundproofing against high-frequency sound. Examples of such parts include vehicle parts, building parts, and the like. As a vehicle part, it can be used for an engine cover.

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

<Material>
1. 1. Urethane slab As a material for forming a urethane foam layer, a urethane slab having the characteristics shown in Table 1 was prepared. Urethane 1 to 3 in Table 1 are the following products. The characteristics of urethane 1 to urethane 3 shown in Table 1 are the values described in the manufacturer's specifications.

Urethane 1:
Ether-based urethane foam, Bridgestone polyurethane foam "TP"
Urethane 2:
Ether-based urethane foam, Bridgestone polyurethane foam "VO"
Urethane 3:
Ether-based urethane foam, Bridgestone polyurethane foam "DO"

Urethanes 4 to 5 in Table 1 are virtual urethane slabs simulated. The characteristics of urethane 4 to urethane 5 shown in Table 1 are set values used in the simulation.
The simulation was performed using the laminated structure acoustic characteristic prediction software manufactured by Nippon Acoustic Engineering Co., Ltd., and the product name "STRATI-ARTZ".

2. 2. Plate-shaped composition Matrix resin (unsaturated polyester resin, number average molecular weight: 3000) 70 parts by mass, low shrinkage agent (35% styrene monomer solution of polystyrene) 25 parts by mass, viscosity modifier (styrene monomer) 30 parts by mass, curing 1 part by mass of agent (t-butyl peroxybenzoate), 0.05 part by mass of polymerization inhibitor (parabenzoquinone), 10 parts by mass of internal release agent (zinc stearate), 4 parts by mass of modifier (powdered polyethylene) and A compound paste was prepared by kneading 200 parts by mass of a filler (heavy calcium carbonate). Next, as a thickener paste, a mixture of 1 part by mass of a thickener (magnesium oxide) and 4 parts by mass of a resin (unsaturated polyester resin having an acid value of 0) was added to prepare a molding material.
The above-mentioned unsaturated polyester resin (matrix resin) is obtained by subjecting it to an esterification reaction using a combination of terephthalic acid and maleic acid as a dicarboxylic acid component and a combination of propylene glycol and neopentyl glycol as a glycol component. It was done. Next, after adding the thickener paste, glass fibers having a length of about 25 mm, which is obtained by chopping glass roving with a cutter, are added at a ratio of 20% by mass based on the total amount of the foamable preformed body, and plate-shaped according to a conventional method. A composition (SMC) was made.

<Manufacturing of laminated body>
[Example 1]
(1) Setting of mold temperature A container-shaped mold that fits each other, and has a convex upper mold (core), a concave lower mold (cavity), and a spacer.

(2) Installation of urethane slab and plate-shaped composition The urethane slab (urethane 1) is cut into a length of 200 mm, a width of 200 mm, and a thickness of 30 mm, and the plate-shaped composition A is cut to reduce the amount to be charged into the mold. The thickness was adjusted to 110.6 g.
A urethane slab was placed in the lower mold (cavity), and the plate-like composition A was charged on the urethane slab.

(3) Mold clamping Next, the upper mold was lowered and the mold was compacted so that the thickness of the urethane layer in the laminated body after pressing became the numerical value shown in Table 2. After that, the upper mold was slowly raised and the molded product was taken out from the mold. In this way, the laminated body 1 of Example 1 was manufactured.
The laminated body 1 is a two-layered body composed of a resin layer of an unsaturated polyester resin (UP) and a urethane foam layer of urethane 1.

[Examples 2 to 4]
In addition to changing the type of plate-shaped composition (SMC), the type of urethane slab, and the input amount of plate-shaped composition (SMC) to the contents shown in Table 2, the thickness of the urethane layer in the laminated body after pressing is shown in the table. The laminated bodies 2 to 4 of Examples 2 to 4 were manufactured in the same manner as in Example 1 so as to have the numerical values shown in 2.
The laminated body 2 is a two-layered body composed of a resin layer of an unsaturated polyester resin (UP) and a urethane foam layer of urethane 2.
The laminated body 3 is a two-layered body composed of a resin layer of an unsaturated polyester resin (UP) and a urethane foam layer of urethane 3.
The laminate 4 is a two-layered body composed of a resin layer of a foamed resin of an unsaturated polyester resin (UP) and a urethane foam layer of urethane 2.

[Example 5, Comparative Examples 3 to 6]
In addition to changing the type of plate-shaped composition (SMC), the type of urethane slab, and the input amount of plate-shaped composition (SMC) to the contents shown in Table 2, the thickness of the urethane layer in the laminated body after pressing is shown in the table. The laminated body 5 of Example 5 and the laminated bodies 103 to 106 of Comparative Examples 3 to 6 are manufactured in the same manner as in Example 1 so as to have the numerical values shown in 2.
Like the laminated body 1, the laminated body 5 is a two-layered body composed of a resin layer of an unsaturated polyester resin (UP) and a urethane foam layer of urethane 1, but is laminated because the thickness of the resin layer is large. Different from body 1.
The laminated body 103 is a two-layered body composed of a resin layer of an unsaturated polyester resin (UP) and a urethane foam layer of urethane 5.
The laminated body 104 is a two-layered body composed of a resin layer of unsaturated polyester resin (UP) and a urethane foam layer of urethane 4.
The laminate 105 is a two-layered body composed of a resin layer of a foamed resin of an unsaturated polyester resin (UP) and a urethane foam layer of urethane 1.
Like the laminated body 1, the laminated body 106 is a two-layered body composed of a resin layer of an unsaturated polyester resin (UP) and a urethane foam layer of urethane 1, but is laminated in that the thickness of the urethane layer is small. Different from body 1.

[Comparative Example 1]
In Comparative Example 1, a molded product 101 having only a resin layer without a urethane foam layer was manufactured.
The molded product 101 was manufactured under the same press conditions as in Example 3 except that the urethane slab was not used and the spacer for maintaining the cavity spacing was not used.
The molded product 101 is a single layer body made of a resin layer of an unsaturated polyester resin (UP).

[Comparative Example 2]
As the molded product 102 of Comparative Example 2, a single layer body made of a urethane foam layer of urethane 1 was prepared.

Table 2 shows the thickness, areal density and density of the laminates or molded products of Examples and Comparative Examples.
The surface densities of the laminates of Examples 1 to 4 and the molded product of Comparative Example 1 were measured by cutting the laminate or the molded product into a standard size and then weighing the laminate. The surface densities of the laminated bodies of the other examples and comparative examples are estimated from the resin type, the urethane type, and the thickness of the resin layer and the urethane layer after pressing.

<Evaluation>
The soundproofing and rigidity of the laminated bodies or molded products of Examples and Comparative Examples were confirmed by the following methods, and the results are shown in Tables 3 and 4.
In addition, Examples 1 to 4 and Comparative Examples 1 and 2 are actual measurement values, and Examples 5 and Comparative Examples 3 to 6 are virtual values based on simulation.

1. 1. Evaluation of soundproofing (1) Measurement using a sound absorbing box The laminated bodies or molded products of Examples 1 to 3 and 5 and Comparative Examples 1 to 6 were used as test bodies.
A sound absorbing box having a size of 500 mm × 800 mm × height of 700 mm and having an open side was placed so that the opening was on the upper side, and the speaker was put in the sound absorbing box. Next, the opening of the sound absorbing box was closed with a plate having an opening of 200 mm × 200 mm in the center. At this time, the position was adjusted so that the opening of the board was directly above the speaker. Further, the opening of the plate was closed with a test body, and the gap was closed with tape. The laminated body and the molded product having the urethane foam layer had the urethane foam layer side facing the speaker, and the molded product 101 having no urethane foam layer had the resin layer facing the speaker.

A microphone was installed at a location 20 cm away from the test piece on the outside of the sound absorbing box, sound (4 kHz) was emitted from the speaker, and the intensity of the sound sensed by the microphone was measured.
The transmission loss (sound absorbing box, 200 mm) was calculated from the following _formula , where I ₀ was the sound intensity when there was no test piece and IS was the sound intensity when there was a test piece.
Transmission loss (sound absorbing box, 200 mm) = 10 Log ( _IS / I ₀ )

The larger the value of transmission loss, the better the soundproofing.
Table 3 shows a result of the transmission loss (sound absorbing box, 200 mm) of 44.0 dB or more as ◯ (good) and a result of less than 44.0 dB as × (defective).

(2) Measurement using an acoustic tube Using the laminated body 1 of Example 1, the laminated body 4 of Example 4, and the molded product 101 of Comparative Example 1 as test pieces, vertical incident sound transmission is performed in accordance with ASTM E2611. The loss was measured.
An acoustic tube (JIS A1405-1 (2007)) having a length of 495 mm and a diameter of 40 mm was used, a speaker was installed at one end of the acoustic tube, and the other end was closed with a test body. Furthermore, to prevent sound leakage, the gap was closed with tape and clay. The laminate and the molded product having the urethane foam layer had the urethane foam layer side facing the speaker, and the molded product 101 having no urethane foam layer had the resin layer facing the speaker.

A microphone was installed at a location 10 cm away from the test piece on the outside of the acoustic tube, sound (5 kHz) was emitted from the speaker, and the intensity of the sound sensed by the microphone was measured.
The transmission loss (acoustic tube, _φ40 mm) was calculated from the following formula, where the sound intensity without the test piece was I ₀ and the sound intensity with the test piece was IS.
Transmission loss (acoustic tube, _φ40 mm) = 10 Log (IS / I ₀ )

The larger the value of transmission loss, the better the soundproofing. Table 4 shows a result of the transmission loss (acoustic tube, φ40 mm) of 40.0 dB or more as ◯ (good) and a result of less than 40.0 dB as × (defective).

2. 2. Mass The laminated bodies or molded products of Examples and Comparative Examples were processed into a circle having a diameter of 40 mm, and the mass was measured. The results are shown in Tables 3 and 4.
Tables 3 and 4 indicate that the mass is 7.0 g or less as ○ (good), that the mass is more than 7.0 g and 8.0 g or less is Δ (allowable range), and that the mass is more than 8.0 g is × (defective). It was shown to.
The masses of the laminates of Examples 5 and Comparative Examples 3 to 6 were calculated based on the set values of the simulation.

3. 3. Modularity of Laminated Body or Molded Product The laminated body or molded product of Examples and Comparative Examples was cut into a width of 10 mm, and the modulus was measured by the following method.
The laminate is cut into test pieces having a length of 100 mm and a width of 10 mm. The cutout was cut out with a water jet. The end of the resin layer of the test piece is sandwiched and fixed with metal fittings such as clips, and the resin layer is placed on a three-point bending jig (JIS K7171 (2010) compliant) set at a distance between fulcrums at intervals of L = 105 mm. Was placed face up, and a force was applied to the surface of the resin layer of the test piece with an indenter to perform a three-point bending test. Rigidity was calculated from the test force and the slope of the displacement. From the load (W) [N] applied by the indenter, the deflection (δ) [mm] of the test piece, and the distance between the fulcrums (L) [mm], the modulus (EI) [N ・ mm ² of the laminate is calculated by the following formula. ] Was calculated.
EI = [(ΔW / Δδ) × L ³ ] / (48)
It should be noted that ΔW / Δδ is calculated from the initial inclination of the 3-point bending test.
The modulus of the laminated body of Example 5 and Comparative Examples 3 to 6 was calculated by the set value of the simulation.

4. Rigidity evaluation Rigidity evaluation was performed on laminated bodies and molded products having a resin layer.
Tables 3 and 4 show the evaluations of whether the shapes of the laminates 1 to 4 and the molded products 101 to 102 were made uneven to fix the shape and the shape was maintained in the receiving part. The evaluations of the other laminated bodies are shown in Tables 3 and 4 by analogy with the test results of the laminated bodies 1 to 4 and the molded products 101 to 102.
◯: Sufficient shape retention and good rigidity ×: Sufficient shape retention and poor rigidity

Modulus (EI) [N ・ mm ² ] is calculated by the following formula from the load (W) [N] applied by the indenter, the deflection (δ) [mm] of the test piece, and the distance (L) [mm] between the fulcrums. bottom.
EI = [(ΔW / Δδ) × L ³ ] / (48)
It should be noted that ΔW / Δδ is calculated from the inclination of the three-point bending test.

5. Comprehensive judgment In the results of transmission loss, mass, 10 mm width modulus, and rigidity evaluation, if there is a × evaluation, it is evaluated as × (poor), and if it does not include the × evaluation, it is evaluated as ○ (good). ). The results are shown in Tables 3 and 4.

As can be seen from Tables 3 and 4, a urethane foam layer and a thermosetting resin having continuous and open bubbles, a flow resistance of 350,000 N · s / m ⁴ or less, and a density of 10 kg / m ³ or more. The laminate of the example including the resin layer containing the resin has a density of 50 kg / m ³ or more and 200 kg / m ³ or less, a modulus of 0.01 Nm ² or more measured with a width of 10 mm, and a transmission loss of comparison. It is larger than the molded product in the example, has excellent soundproofing properties, maintains light weight, and has excellent rigidity.

The laminate of the present invention is suitable as a vehicle part and a building part because it maintains rigidity, is lightweight, and is particularly excellent in soundproofing against high-frequency sound, and is particularly suitable as a soundproofing cover and an engine cover.

Claims (8)

A urethane foam layer having continuous and open bubbles, a flow resistance of 350,000 N · s / m ⁴ or less, and a density of 10 kg / m ³ or more.
With a resin layer containing a thermosetting resin,
A laminate having a density of 50 kg / m ³ or more and 200 kg / m ³ or less, and a modulus of 0.01 Nm ² or more measured with a width of 10 mm. The laminate according to claim 1, wherein the urethane foam layer has a thickness of 16 to 50 mm. The laminate according to claim 1 or 2, wherein the thickness is 20 to 55 mm. The laminate according to any one of claims 1 to 3, wherein the surface density of the resin layer is 0.15 to 0.50 g / cm ² . The laminate according to any one of claims 1 to 4, wherein the thermosetting resin contains at least one of an unsaturated polyester resin, a vinyl ester resin, and a urethane resin. The laminate according to any one of claims 1 to 5, wherein the urethane foam layer is adjacent to the resin layer. A soundproofing member using the laminate according to any one of claims 1 to 6. A urethane slab is installed in the mold, a plate-like composition containing a thermosetting resin raw material and a curing agent is charged on the urethane slab, and the resin layer containing the thermosetting resin and urethane foam are simultaneously shaped by pressing. A method for manufacturing a laminate to be joined to a layer.