JP3329687B2 - Integrally molded sheet, sound insulation sheet and vibration damping sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an integrally molded sheet. More specifically, the present invention relates to an integrally molded sheet including a viscoelastic body of a predetermined liquid polymer and particles having a specific gravity different from that of the liquid polymer and having a specific gravity gradient in a vertical cross-sectional direction.

[0002]

2. Description of the Related Art Conventionally, various functions can be assigned to a plurality of layers, and many features can be assigned to one sheet. Therefore, noise and vibration prevention, waterproofing, moistureproofing, reinforcement, grass weeding, and the like can be achieved. In various fields, multi-layer sheets have been used. Such a multilayer structure sheet is manufactured by laminating separate sheets each having a limited function.

[0003] Various functional sheets are manufactured by a method based on a solid polymer. For this reason, such sheet production machines are considered based on solid polymers, and in particular, a sheet to which a compounding agent such as a filler or a plasticizer is added is uniformly dispersed and mixed in a sheet form. Molded into The plastic sheet is produced by a method of winding an extruded and stretched sheet or a method of inflation of hot-melted plastic.

[0004]

However, a multi-layered sheet to which such functional sheets are attached has a high risk of delamination. On the other hand, with respect to the prevention of sound and vibration, a wide range of sound and vibration cannot be prevented except for a laminated product of different types of sheets formed in advance. For this reason, it is desirable that the soundproof sheet or the like can exhibit a wide range of functions without laminating a plurality of sheets.

[0005] Sheets having such a wide range of functions cannot be obtained without lamination by any conventional manufacturing method. In particular, the method for producing a plastic sheet utilizes thermoplasticity, and is generally not suitable for producing a thick sheet due to problems such as distortion of the obtained sheet.

[0006] Also, the production of a multi-layer laminated sheet is costly. The biggest factor is that it is usually nearly impossible to produce all necessary layers of sheets in one company. In the multi-layer laminated sheet, sheets for forming layers are diversified for the purpose of combining various functions. For this reason, several types of purchase sheets and in-house products must be used in combination. The purchase sheet includes profits associated with distribution of goods at the purchaser, expenses for transportation, packing, and the like.

Furthermore, in addition to the high material cost itself, interlayer bonding is required at the time of production to form a multilayer. If the number of required processes increases, the number of laminations in one process or one line is limited, and several processes are required. In addition, since such a multi-layer laminated sheet has a long production lead time, production costs such as requiring a stock yard for raw materials and work-in-progress are required. For this reason, conventionally, the multilayer laminated sheet has been used only for applications that can be used even at high cost.

As described above, in recent years, single-function sheets have
We have a system that can produce according to various requests. However, such a single-function sheet cannot sufficiently satisfy a plurality of functions. In addition, a laminated sheet in which such single-function sheets are variously combined and laminated in multiple layers requires many steps to produce, and is very expensive. Therefore, it is beneficial to provide an integrally molded sheet having multiple functions with one sheet at a lower cost than before, as it satisfies many requirements.

An object of the present invention is to form a plurality of layers in an integrally molded sheet and to allow these layers to perform various functions without causing delamination.

[0010]

The present invention provides an integrally molded sheet comprising a cured product of a liquid polymer and particles having a specific gravity different from the specific gravity of the liquid polymer, wherein the liquid polymer has room temperature reactivity. Wherein the main chain skeleton of the liquid polymer is composed of polychloroprene, polyisoprene, polybutadiene, styrene butadiene copolymer, acrylonitrile butadiene copolymer, and the molecular end of the liquid polymer has at least two or more hydroxyl groups and amino groups. , A carboxyl group, an alkyl xanthate group, wherein the particles,
Settling particles having a specific gravity higher than the specific gravity of the liquid polymer;
Buoyant particles having a specific gravity lower than the specific gravity of the liquid polymer, wherein the particles mixed with the liquid polymer are moved in a layered manner due to a difference between the specific gravity of the particles and the specific gravity of the liquid polymer, The cured product is a viscoelastic body, the particles are bound by the viscoelastic body, the settling particles are distributed in a layer, the floating particles are distributed in a layer, and the integral molding is performed. Sheet, in the order of the layer containing the buoyant particles and the viscoelastic body, the layer of the viscoelastic body and the layer containing the sedimentable particles and the viscoelastic body, forming a specific gravity gradient in the thickness direction And a sound insulation sheet and a vibration damping sheet using the integrally formed sheet.

In the integrally molded sheet of the present invention, since a single-function layer formed in advance is not laminated in multiple layers, delamination does not occur. Moreover, the sheet of the present invention has a high specific gravity layer,
Since the presence / absence, properties, thickness, etc. of the viscoelastic layer, low specific gravity layer, adhesive layer, etc. can be set arbitrarily, various functions such as vibration suppression, vibration proof, sound absorption, sound insulation, dynamic vibration absorption etc. It is possible to carry it. In addition, since the sheet of the present invention can be processed and formed in one step, it can be easily manufactured with simple equipment, and is advantageous in terms of cost.

The present inventors have used a liquid reaction type polymer as a matrix, and distributed particles having a specific gravity different from the specific gravity of the liquid polymer in a predetermined position in the matrix in a layered manner. Nevertheless, it has been found that a sheet having a plurality of functions can be obtained.

Further, the present inventors can control the viscosity of the polymer and adjust the sedimentation speed or the floating speed of the particles to be blended, so that a single sheet performs multiple functions such as vibration suppression and vibration proof. It was confirmed that it was possible to do. Further, the present inventors have found that such an integrally molded sheet can be easily manufactured in one molding step, and have reached the present invention.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The particles having a specific gravity different from the specific gravity of the liquid polymer used in the present invention are sedimentable particles having a specific gravity higher than the specific gravity of the liquid polymer or floating particles having a specific gravity lower than the specific gravity of the liquid polymer. In the present invention, the settling particles and the floating particles are mixed with a liquid polymer, and the liquid polymer is cured by reaction. By the time the liquid polymer is cured, the added settling particles or floating particles respectively settle and float, and move in layers in the liquid polymer.
Such particles are finally bound by the cured product of the liquid polymer. If particles having predetermined physical properties are used, buoyant particles can be fixed on the upper surface of the sheet and sedimentable particles can be fixed on the lower surface of the sheet.

In the present invention, utilizing the difference between the specific gravity of the particles to be blended and the specific gravity of the liquid polymer, the various components are moved in layers, and are equal to or more than a multilayer sheet obtained by laminating a plurality of preformed single layers. A multifunctional integrally molded sheet can be obtained. The specific gravity of the settling particles is greater than the specific gravity of the liquid polymer,
It is preferable that the difference in specific gravity is higher by 1.0 or more. Further, the floating particles preferably have a specific gravity difference of 0.3 or more lower than the specific gravity of the liquid polymer. Further, the particle diameter of the sedimentable particles or the floating particles is preferably controlled within a range of 0.1 to 100 μm.

In the present invention, various functions can be enhanced by adjusting the amount of the particles. The cured product of the liquid polymer has a large difference in hardness, strength, and elongation between the case where the content of the sedimentable particles is large and the case where the content is small, and a property difference is generated that cannot be considered as the same component. Also, the difference in the properties of the cured product increases depending on the content of the floating particles, as in the case of the sedimentable particles.

In the present invention, an adhesive layer can be formed on the surface of the obtained integrally molded sheet. Further, in the present invention, before the liquid polymer component is cured by reaction, the liquid polymer component can be brought into contact with various base materials to adhere the base material to the particles or to impregnate the base material with the liquid polymer component. . In this way, an integrally molded sheet provided with a base material on one or both sides can be manufactured, and improvement in vibration damping properties and strength that cannot be obtained with a single sheet can be achieved. As the substrate, a film, a net, a nonwoven fabric, a woven fabric, or the like is used.

The application of the integrally molded sheet of the present invention can be applied to fields other than noise and vibration prevention. For example,
The sheet of the present invention can be widely used in fields such as waterproofing, moistureproofing, reinforcement, and grassproofing. That is, in the field of waterproofing and moistureproofing, it is possible to provide a thick sheet by giving viscosity to the installation surface side of the sheet. Such a sheet can easily follow the movement of the frame, and if used as a roof base, the sealing effect of the nail hole can be improved.

In the field of reinforcement and weed control, a sheet containing fibers can be provided. Such a sheet can easily be increased in strength and can prevent breakage by impact or grass. In addition, such a sheet can exert a remarkable stress relaxation function, and can improve the impact absorption and the weed control effect, particularly when viscosity is imparted to the installation surface side of the sheet. Thus, in the integrally molded sheet of the present invention, it is possible to selectively impart functions that meet various purposes,
There are many other fields of application other than the above.

In the present invention, the room-temperature-reactive liquid polymer has a main chain skeleton of polychloroprene, polyisoprene, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and at least two or more hydroxyl groups, amino groups, A reactive group such as a carboxyl group or an alkyl xanthate group is provided at a molecular terminal. Table 1 shows examples of combinations of the reactive groups of these liquid polymers and the reactive groups of the curing agent. In the present invention, these combinations can be used alone or in combination.

[0021]

[Table 1]

[0022] The liquid polymer is that having a room temperature reactive,
When manufacturing the integrally molded sheet of the present invention, from the viewpoint of utilizing the difference in specific gravity between the liquid polymer and the particles and increasing the efficiency of the manufacturing cycle, it is possible to heat as necessary to obtain low viscosity and high activity. preferable. When a polymer is used in combination, a plurality of polymers may be mixed and used in advance, or a method of applying a plurality of polymers in the same application step by shifting the application timing of the polymer may be used. Further, by using a foamable polymer, it is possible to reduce the weight after curing.
In addition, antioxidants, antioxidants, flame retardants and other additives commonly used in the rubber and plastics industries can be added to the liquid polymer.

Examples of the sedimentable particles having a specific gravity higher than the specific gravity of the liquid polymer include metal particles of iron, lead, copper, and aluminum, alloy particles of brass, duralumin, stainless steel, and the like, iron oxide, ferrite, and zinc. Examples thereof include powders of metal oxides such as flower, lithopone and aluminum oxide, and powders of barium sulfate, calcium carbonate, silica sand, borax, glass and the like. These powders can be used alone or in combination, but from the viewpoint of imparting multiple functions to the integrally molded sheet, it is preferable to use them together.

The particles need to move in layers due to a difference in specific gravity under certain production conditions. The movement of the particles in the liquid polymer largely depends on the specific gravity difference and the particle size. If the difference in specific gravity is large, the influence of gravity, centrifugal force and the like will be significantly different, and it will be easy to obtain a clear layered distribution of each particle. If the particle size is large, the sedimentary particles will have a large weight per se and will be susceptible to gravity and centrifugal force, so that the layered distribution will be performed quickly. Conversely, in the case of buoyant particles, if the particle size is large, the liquid polymer becomes heavier and moves below the buoyant particles,
Particles are easily distributed in layers. Such a difference in mobility depending on the particle size of the particles is greatly affected by the viscosity of the liquid polymer, and thus it is necessary to set optimum conditions according to the temperature, the particle size distribution, and the viscosity of the compound. Further, a large difference occurs in the mechanical properties of the obtained sheet due to the particle size distribution of the particles. For this reason, it is necessary to adjust the particle size and the particle size distribution of the compounded particles according to the application.

Further, in order to improve the adhesion between the particles and the cured product of the liquid polymer, to reduce the increase in viscosity of the liquid polymer after the addition of the particles, or to bond the particles with a high specific gravity filler or a low specific gravity filler. Silane coupling agent,
Titanate coupling agents, surfactants and the like can also be used.

Examples of the buoyant particles having a specific gravity lower than the specific gravity of the liquid polymer include a pulverized product of a rubber foam or a polymer foam.
Examples thereof include organic balloons, pearlite, glass balloons, hollow bodies such as hollow short fibers, porous bodies such as cork powder, synthetic or natural fibers, and ground paper.

Both the sedimentable particles and the floating particles must not be completely separated from the cured liquid polymer. In the present invention, it is preferable that such particles are bound by a cured product of the liquid polymer, and a plurality of layers mainly containing settling particles and a plurality of layers mainly containing floating particles are provided. Further, the present invention does not necessarily require a single layer made of a cured liquid polymer as the intermediate layer.

The method for producing the integrally molded sheet of the present invention includes:
There are roughly two methods. One is a method in which at least one of the settling particles and the floating particles is mixed with a curing agent in a liquid polymer, the mixture is poured into the inside of a cylinder, and the mixture is reacted and cured while rotating the cylinder to form the mixture. It is.

FIG. 11 is a side view of an example rotary molding machine partially shown in cross section. The rotary molding machine 53 includes a cylinder 5
4, including a receiving roll 55 and a motor 56. Cylinder 54
An integrally molded sheet 1 is formed on the inner surface of the sheet.

In this method, the settling particles and the like are added to the liquid polymer in a temperature-controlled environment, a curing agent is added at a set temperature, or the viscosity of these mixtures is adjusted. Can be. Also,
In such a method, the sedimentable particles and the buoyant particles are separately prepared, and these particles can be mixed when the curing agent is added. Furthermore, in such a method, while performing rotational molding,
Sedimentable particles and buoyant particles can also be separately and uniformly sprayed over the entire surface. Further, in such a method, a plurality of nozzles may be provided in a cylinder, and reactive liquids having different properties may be applied simultaneously or at different times in a layered manner.

In the case of such a method, it is most important to appropriately control the curing speed of the mixture. Preferably, the viscosity of the mixture is kept as low as possible until the particles settle or float and a layer is formed, after which the mixture is hardened rapidly. This is because if the curing speed is increased, the time until demolding can be shortened, and the cost can be reduced. Further, by adjusting the rotation speed of the cylinder used, the sedimentation and floating efficiency can be increased.

Another method is to produce an integrally molded sheet on a coating line. In such a method, a sheet forming material containing sedimentable particles or the like in a liquid polymer can be applied to a substrate, and the particles in the material can be allowed to settle or float naturally. As in the case of the rotational molding method, the liquid polymer or the mixture of the liquid polymer and the curing agent is also pre-heated, a heating section is provided in the line, and sedimentable particles and buoyant particles are sprayed and sprayed later. You can also.

FIG. 12 is a side view showing an example of a coating production line. The line 57 includes a heating furnace 58, a conveyor 59, and a winder 60. The substrate 23 is sent out to the application line, and the sheet forming material 61 is applied onto the substrate 23. Next, the sheet forming material 61 is applied to the base material 2.
3 is passed through a heating furnace 58 to be cured. If desired, a base material 27 similar to the base material 23 is placed on the surface of the sheet near the exit of the heating furnace 58, and the base material 23 is placed in one line.
And the base material 27 can be manufactured.

According to the method using such a production line, a long object, a soft integrally molded sheet, or an integrally molded sheet having increased adhesive strength can be produced relatively easily. Such a method is more advantageous than rotary molding because an integrally molded sheet including a base cloth can be manufactured in one step.

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings. Example 1 A rotary molding machine shown in FIG. 11 was used for molding the integrally molded sheet of this example. The main agent of Formulation A shown in Table 2 and the hardener were mixed at a mixing ratio of 100 / 4.3 (main agent / hardener, wt%), and the resulting mixture was charged into a cylinder and the cylinder was rotated. Thus, a sheet having a uniform thickness was formed. In the integrally molded sheet of this example, liquid polybutadiene rubber (specific gravity 0.90) as a liquid polymer, sedimentable barium sulfate (specific gravity 4.5) as sedimentable particles, and silica sand (NSP,
Specific gravity 2.6).

[0036]

[Table 2]

FIG. 1 is a cross-sectional view of the integrally molded sheet of this embodiment cut in the thickness direction. In this integrally molded sheet 1, silica sand (NSP) 3 and sedimentable barium sulfate 4 are contained in a cured product 2 of liquid polybutadiene rubber. The silica sand (NSP) 3 has a larger particle diameter than the sedimentable barium sulfate 4 and is distributed in a layered manner at the lowermost part of the integrally molded sheet 1. The sedimentable barium sulfate 4 mainly has a smaller particle size than the silica sand (NSP) 3 and is distributed in a layered manner on the upper part of the silica sand (NSP) 3. The cured product 2 of the liquid polybutadiene rubber binds the sedimentable barium sulfate 4 and the silica sand (NSP) 3 respectively, and forms a single layer on the upper part of the integrally molded sheet 1.

In such an integrally molded sheet, the ratio of the sedimentable particles having a large particle diameter and a high specific gravity becomes higher toward the lower part in the thickness direction, and a specific gravity gradient is formed in the vertical direction of the thickness.

The obtained integrally molded sheet was tested for test items 1 to 7 according to the following method. Table 7 shows the results
Shown in Test method Tensile strength, elongation at break In accordance with JIS-K-6251, four dumbbell-shaped No. 1 samples were prepared. For each of these samples, the thickness and width were measured, a marking line for determining the length before being pulled was set, and the distance between the marking lines was measured. Next, the sample was pulled in the length direction at a pulling speed of 500 mm / min, and the maximum tensile force and the distance between marked lines at the time of cutting were measured. Based on the measured values, the tensile strength and elongation at break of each sample were determined according to the following formula, and the median was calculated. T _B = F _B / A in formula, T _B: tensile strength (MPa), F _B: maximum tensile force (N), A: shows the cross-sectional area of the test piece (mm ^2). E _B = (L ₁ −L ₀ ) / L ₀ × 100 where E _B : elongation at break (%), L ₀ : distance between marked lines (m)
m), L ₁ : distance between marked lines (mm) at the time of cutting.

2. Tear strength Five angle-shaped samples having cuts were prepared according to JIS-K-6251, and the thickness of each sample was measured. Thereafter, the maximum tearing force of each sample was measured at a tensile speed of 500 mm / min, the tearing strength of each sample was determined according to the following formula, and the median value was calculated. TR = F / t In the formula, TR: tear strength (N / mm), F: maximum tear force (N), and t: thickness (mm) of the test piece.

3. FIG. 13 is a side view showing an apparatus for measuring the sound generation amount and the decay time. In this device 62, 30 cm × 20 cm,
A sample 64 is attached to one side of a 1.2 mm thick iron plate 63,
Holes are provided at two upper corners, and the suspension is made with the hanging string 65. The iron ball 66 tied with a string is pulled in the direction of 90 °, falls naturally, and makes a ４ circular motion to vibrate the center of the iron plate 63. At a distance of 1 m on the sample side, a microphone 67 was placed at a height of 1.2 m.
And the sound level and the time for 20 dB attenuation from the maximum sound level were measured using a precision sound level meter 68 and a frequency analyzer 69. Table 7 shows a difference between each measured value and a value obtained by using the iron plate 63 alone as an improvement amount.

4. Loss Factor FIG. 14 is a side view showing a loss factor measuring device.
1.2mm thickness x 15mm width x 200mm length iron plate,
The specimen was stuck, leaving a gripping area of 22 mm.
2 was created. A test sample 72 was attached to a complex elastic modulus measuring device 71 in a loss coefficient measuring device 70, a sample was vibrated by a non-contact electromagnetic transducer 73, and the response was picked up by a non-contact capacitive transducer 74. . A response signal of the vibration is input to an FFT analyzer 76 via a preamplifier 75,
On the channel FFT screen, the frequencies f ₁ and f ₂ of −3 dB were measured from the resonance frequency f ₀ and the peak thereof, and the loss coefficient was obtained from the following equation. η = (f ₁ −f ₂ ) / f _{0 In the} equation, η: loss coefficient, f ₀ : resonance frequency, f ₁ : frequency of −3 dB from resonance peak, f ₂ : frequency of −3 dB from resonance peak Show.

5. Dew condensation A waterproof sheet was stuck on a 96 mm glass wool plate having a thickness of 25 mm. 150mm rigid vinyl chloride VU tube
, And a sample was stuck on the entire outer periphery of the tube. The VU pipe was set up on a waterproof sheet, and a leak preventing treatment was performed on the inside of the circumference where the waterproof sheet and the VU pipe were in contact with a caulking agent. After the caulking agent had set, 1 liter of ice water was placed in the VU tube. The measuring device thus prepared was placed in a constant temperature bath (40 ° C., 70% RH), the VU tube was covered with a glass wool cover, and the time when dew condensation started was measured.

6. Water Permeability FIG. 15 is a side view showing an apparatus for measuring water permeability. 12
A sample 78 and a waterproof sheet 79 were pasted in this order on a plywood 77 having a thickness of mm, and the wooden sheet 80 was used to fix a sample 78 and a waterproof sheet 79 thereon. Next, the funnel 82 having a diameter of 10 cm is turned upside down and put on the waterproof sheet 79 so as to cover the caulking material 8.
At 3 the leakage around the funnel 82 was stopped. Finally, the tip of the funnel 83 was connected to the female pipette 85 with a rubber pipe 84, and the female pipette 85 was fixed to the support 86. Water was placed in the funnel 82 and the female pipette 85. After a lapse of 24 hours, the weight loss value of the water is measured on a scale 87 of the pipette 85.
Was measured.

7. Impact resistance A DuPont type impact deformation tester of JIS-K-5400 was used. A sample stuck on a 3 mm-thick plywood with a radius of 6.3
A 5 mm shooting die was attached to a pedestal, a 500 g weight was dropped, and the drop height at which a hole was formed in the sample was examined.

As shown in Table 7, the integrally molded sheet of Example 1 was obtained as a viscoelastic body having a low tensile strength and a large elongation at the time of cutting. This sheet has a specific gravity gradient in which the sedimentable particles are localized in layers in the thickness direction. The sound output of this sheet was reduced by 14 dB (A) as compared with the iron plate alone. Also, the decay time of this sheet is
0.40 seconds faster. The loss factor is 0.17,
Since it is significantly higher than 0.05, which is usually considered to have vibration damping properties, it can be seen that it is very good. The water permeability is also 0 cc, and application to a roof base or the like is possible.

Example 2 In the same manner as in Example 1, a rotary molding machine shown in FIG. 11 was used for molding the integrally molded sheet of this example. The main agent of Formulation B shown in Table 3 and the curing agent were mixed at a mixing ratio of 2/1 (main agent / curing agent, wt%), and the obtained mixture was charged into a cylinder, and the cylinder was rotated. A sheet having a uniform thickness was formed. In the integrally molded sheet of this example, a polyol (specific gravity 0.96) as a liquid polymer, a glass balloon (specific gravity 0.26) and cork powder (specific gravity 0.16) as floating particles were used.

[0048]

[Table 3]

FIG. 2 is a cross-sectional view of the integrally molded sheet of this example cut in the thickness direction. In the integrally molded sheet 5, a glass balloon 7 and a cork powder 8 are contained in a cured product 6 of a polyol. The cork powder 8 mainly has a larger particle diameter than the glass balloon 7, and is distributed in a layer at the uppermost part of the integrally molded sheet 5. On the other hand, the glass balloon 7 mainly has a smaller particle size than the cork powder 8 and is distributed in a layered manner below the cork powder 8. The cured product 6 of the polyol binds the cork powder 8 and the glass balloon 7 to each other.
A single layer is formed.

In such an integrally molded sheet, the ratio of the buoyant particles having a large particle diameter and low specific gravity becomes higher toward the upper part in the thickness direction, and a specific gravity gradient is formed in the vertical direction of the thickness.

The obtained integrally formed sheet was tested in the same manner as in Example 1. Table 7 shows the results.

The integrally molded sheet of this example is a viscoelastic body having a low tensile strength and a large elongation at the time of cutting, and its cross-sectional direction is different from a sheet having a specific gravity gradient in which buoyant particles are localized in a layer on one side. Has become. The sound volume of this sheet is reduced by 11 dB (A) compared to the iron plate alone, and the sound is reduced by 2 from the peak value.
The time for 0 dB (A) decay was also 0.29 seconds faster than the iron plate alone. Further, the loss coefficient was 0.08, and the vibration damping property was sufficient. It took 40 minutes for the dew to condense and was excellent in heat insulation.

Example 3 In the same manner as in Example 1, a rotary molding machine shown in FIG. 11 was used for molding the integrally molded sheet of this example. The mixing ratio of the main agent of the compounding formula C shown in Table 4 and the compounding agent containing the curing agent was 1 /
1 (base / hardener, weight%), but in this example, at the time of mixing, 100 parts by weight of the base and 10 parts by weight of a glass balloon (other than the one used in Example 2) with respect to 100 parts by weight of the base. The same). The obtained mixture was charged into a cylinder, and the cylinder was rotated to form a sheet having a uniform thickness.
In the integrally molded sheet of this example, epoxy resin A (specific gravity 1.17) and epoxy resin B (specific gravity 1.18) were used as liquid polymers, and the same sedimentation particles as those used in Example 1 were used as sedimentable particles. Barium sulfate and silica sand were used.
Fine silica powder (specific gravity: 1.19, particle size: 16 mμ) was used as the floating particles.

[0054]

[Table 4]

FIG. 3 is a cross-sectional view of the integrally molded sheet of this example cut in the thickness direction. In this integrally molded sheet 9, silica sand (NSP) 11, precipitated barium sulfate 12, fine powder silica 13, and glass balloon 14 are contained in a cured product 10 containing a cured product of epoxy resin A and a cured product of epoxy resin B. include. Since there is not much difference in the specific gravity between the cured product of the epoxy resin A and the cured product of the epoxy resin B, these liquid polymers form the cured product 10 which is almost uniformly mixed. As with the sheet of Example 1, silica sand (NS
P) 11 is mainly distributed in a layered manner at the bottom of the integrally molded sheet 9, and the sedimentable barium sulfate 12 is mainly distributed in a layered manner at the upper part of the silica sand (NSP) 11.

Further, in the integrally molded sheet 9 of this example, similarly to the sheet of Example 2, the glass balloon 14 mainly has a larger particle diameter than the finely divided silica 13 and is formed in a layer at the uppermost portion of the integrally molded sheet 9. Are distributed. On the other hand, the finely divided silica 13 mainly has a smaller particle diameter than the glass balloon 14 and is distributed in a layered manner below the glass balloon 14. The cured product 10 of the epoxy resin A and the epoxy resin B is
The sedimentable barium sulfate 12, silica sand (NSP) 11, finely divided silica 13, and glass balloon 14 are bound to each other, and a single layer is formed in the middle of the integrally molded sheet 9.

In such an integrally molded sheet, the ratio of the sedimentable particles having a large particle size and high specific gravity becomes higher toward the lower part in the thickness direction, and the ratio of the floating particles having a large particle size and low specific gravity is increased.
It has a structure in which the sheet of Example 1 and the sheet of Example 2 are overlapped with each other as the height increases toward the top in the thickness direction.
In such an integrally molded sheet, an extremely large specific gravity gradient is formed in the vertical direction of the thickness.

The obtained integrally molded sheet was tested in the same manner as in Example 1. Table 7 shows the results.

The integrally formed sheet of this example had a high tensile strength and a small elongation at the time of cutting. The amount of improvement in pronunciation is also 13 dB (A), which is quite quiet. The decay time was also increased by 0.34 seconds. The loss coefficient was 0.15, indicating excellent vibration damping properties.

Example 4 The rotary molding machine shown in FIG. 11 was also used for molding the integrally molded sheet of this example. The main agent of Formulation D shown in Table 5 and the curing agent were mixed at a mixing ratio of 4/1 (main agent / curing agent, wt%), and the obtained mixture was charged into a cylinder, and the cylinder was rotated. A sheet having a uniform thickness was formed. In the integrally molded sheet of this example, a liquid polybutadiene rubber as a liquid polymer (same as that used in Example 1) and a sedimentable barium sulfate (same as that used in Example 1) as sedimentable particles are used. Using. 60/80 straight asphalt (specific gravity 0.92) is uniformly dispersed in the integrally molded sheet.

[0061]

[Table 5]

FIG. 4 is a cross-sectional view of the integrally molded sheet of this example cut in the thickness direction. In the integrally molded sheet 15, the liquid polybutadiene rubber is foamed and cured, and the cured product 16 contains precipitated barium sulfate 17 and precipitated barium sulfate 18. Settling barium sulfate 17
Have a larger particle size than the sedimentable barium sulfate 18 and are distributed in a layered manner at the lowermost part of the integrally molded sheet 15. The sedimentable barium sulfate 18 has a smaller particle size than the sedimentable barium sulfate 17 and is distributed in a layered manner above the sedimentable barium sulfate 17. Liquid polybutadiene rubber foam cured product 16
Are precipitated barium sulfate 18, precipitated barium sulfate 17
And a single layer is formed on the upper part of the integrally formed sheet 15.

In such an integrally molded sheet, the ratio of the sedimentable particles having a large particle diameter and a high specific gravity becomes higher toward the lower part in the thickness direction, and a specific gravity gradient is formed in the vertical direction of the thickness.

The obtained integrally molded sheet was tested in the same manner as in Example 1. Table 7 shows the results.

The sheet of this example is of a foaming type, and has a greater specific gravity gradient in the cross-sectional direction due to the settling particles and the polymer foam layer. The pronunciation improvement amount is 9dB (A)
And the decay time improved by 0.26 seconds. The loss coefficient was also 0.13, indicating a sufficient damping property. Further, it was found that the dew condensation had a good heat insulating effect of 65 minutes.

Example 5 FIG. 5 is a sectional view of the integrally molded sheet of this example cut in the thickness direction. This integrally molded sheet 19 is obtained by reacting and curing a polymer in exactly the same manner as in Example 3, spraying an acrylic pressure-sensitive adhesive 20 while rotating and molding, and bonding a release paper 21 to the sheet surface.

The obtained integrally molded sheet was tested in the same manner as in Example 1. Table 7 shows the results.

The integrally molded sheet of this example is an example in which the sheet of Example 3 is provided with an adhesive layer. This sheet is the same as Example 4 in terms of performance, but is advantageous in that it can be attached with one touch without testing.

Example 6 In this example, the coating production line shown in FIG. 12 was used. FIG. 6 is a sectional view of the integrally molded sheet of this example cut in the thickness direction. The integrally molded sheet 22 is prepared by applying the composition of the formulation A used in Example 1 onto the polyester film 23 on the conveyor line, and leaving the heating furnace, and on the sheet surface during the reaction curing, The same polyester film 27 is laminated.

Although it is spontaneous sedimentation, as in Example 1,
Precipitable barium sulfate 26 and silica sand 25 are bound by the cured product of the liquid polybutadiene rubber. A specific gravity gradient similar to that of the first embodiment is formed. The obtained integrally molded sheet was tested in the same manner as in Example 1. Table 8 shows the results.

In the sheet of this example, the polyester film was provided on both sides of the sheet while using the same formulation A as in Example 1, so that the tensile strength was very high and the tear strength was also high. Example 1 also improves the amount of sound and the decay time
Better than ever. In addition, the impact resistance was doubled without impairing the water permeability.

Example 7 In this example, the same coating production line as in Example 6 was used. FIG. 7 is a cross-sectional view of the integrally molded sheet of this example cut in the thickness direction. The integrally molded sheet 28 is obtained by flowing a release paper 29 on a conveyor line, flowing a net 30 thereon, and further applying a mixture of the formulation B shown in Table 3 from above. The periphery of the network 30 is covered with a cured product 31 of a polyol, and the upper portion thereof is a glass balloon 32
And a cork powder 33, and have a cross-sectional configuration similar to that of the second embodiment.

The obtained integrally molded sheet was tested in the same manner as in Example 1. Table 8 shows the results.

In the sheet of this example, while using the same formulation B as in Example 2, a mesh was provided on one side of the sheet, so that the base cloth exerted a restraining effect. As a result, the reinforcing effect was superior to that of the sheet of Example 2, and the tensile strength, tear strength and impact resistance were all improved, and the vibration damping effect was also increased.

Example 8 FIG. 8 is a sectional view of the integrally molded sheet of this example cut in the thickness direction. In this integrally molded sheet 34, the nonwoven fabric 3
5, the composition used in Example 1 was applied and cured.
The nonwoven fabric 35 is partially impregnated with a cured product 36 of liquid polybutadiene rubber, and partially hardened by incorporating silica sand 37 as sedimentable particles. This integrally molded sheet 3
In the upper part of 4, the sedimentable barium sulfate 38 is distributed in layers, and has the same configuration as the sheet of the first embodiment.

The obtained integrally molded sheet was tested in the same manner as in Example 1. Table 8 shows the results.

The sheet of this example is obtained by blending formulation A of Example 1.
This is an example in which a nonwoven fabric is provided on one side using a liquid crystal, and the nonwoven fabric is impregnated with a part of liquid polymer or settling particles. The reinforcing effect was further increased as compared with the sheet of Example 7, and the impact resistance, tensile strength, and tear strength were increased. With the restraining effect of the impregnated non-woven fabric,
The results for vibration were also good. In addition, the dew condensation time was prolonged due to the heat insulating property of the nonwoven fabric layer.

Embodiment 9 FIG. 9 is a sectional view of the integrally molded sheet of this embodiment cut in the thickness direction. In this integrally molded sheet 39, the nonwoven fabric 4
The mixture of the formulation A used in Example 1 was applied and cured from above on the split cloth 41 on the line, and the liquid polymer passed through the gap of the split cloth 41 to form the nonwoven fabric 40. Is hardly impregnated with the liquid polybutadiene rubber cured material 42 over the entire surface of the substrate. Silica sand 43 is gathered on the split cloth 41, and the sedimentable barium sulfate 44 is layered on the silica sand 43, as in the first embodiment.

The obtained integrally molded sheet was tested in the same manner as in Example 1. Table 8 shows the results.

In the sheet of this example, since the nonwoven fabric was slightly impregnated with the cured product of the liquid polymer, the reinforcing and restraining effects were slightly inferior to those in Example 8, but good results were obtained. On the other hand, impregnation of the non-woven fabric with the cured product is suppressed by the split cloth.
Is, the time until you condensation was longer than that of Example 8.

Example 10 FIG. 10 is a sectional view of the integrally molded sheet of this example cut in the thickness direction. In the integrally molded sheet 45, the compounding formula D, the compounding formula E shown in Table 6, and the mixing ratio 100 / 3.3 were used.
A mixture of the two polymers (base / hardener, wt%) was cured by spin casting. At the bottom in the thickness direction,
The cured product 46 of the liquid polychloroprene of the formulation E binds the sedimentable barium sulfate 47 in the lowermost layer, and the sedimentable barium sulfate 48 and the heavy calcium carbonate (specific gravity 2.7) are formed above the sedimentable barium sulfate 47. 49 are bonded and distributed in layers. In addition, this integrally molded sheet 4
In the upper part of No. 5, the foamed cured product 50 of the liquid polybutadiene rubber of the formulation D binds the cork powder 52 (the same as that used in Example 2). Bubbles 51 are formed in the foamed cured product 50 of the liquid polybutadiene rubber.
In the middle part of the integrally molded sheet 45, two types of cured products 4
6, 50 each form a boundary.

[0082]

[Table 6]

The obtained integrally molded sheet was tested in the same manner as in Example 1. Table 8 shows the results.

The sheet of this example consists of a mixture of Formulations D and E. In the cross section in the thickness direction of the sheet, the main layer is a cured layer of liquid chloroprene and sedimentable particles, the main layer is a layer of cured liquid chloroprene, the main layer is a foamed layer, and the main layer is a foamed layer and floating particles. This is a sheet which is a continuous layer to a layer having a large specific gravity gradient. Items related to sound and vibration were all good. The time required for dew condensation was increased by the foamed layer and the floating particles.

It was found that all of the integrally molded sheets of Examples 1 to 10 were particularly excellent in loss coefficient and high in damping effect. Further, by providing the base cloth, particularly high reinforcement and restraining effects can be obtained even with the same liquid polymer formulation.
These integrally molded sheets were suitable for improving vibration damping and impact resistance. As for the water permeability, Formulation A or E was particularly excellent. The dew condensation was improved by using a foam type, and it was possible to mix materials having different blending formulations and to provide an adhesive layer within one manufacturing process.

[0086]

[Table 7]

[0087]

[Table 8]

[0088]

According to the integrally molded sheet of the present invention, predetermined particles are bound by a viscoelastic body of a predetermined liquid polymer to form a plurality of layers. Therefore, it is easy to follow the movement of the skeleton, there is no delamination due to particles, and excellent functions such as vibration suppression, vibration proof, sound absorption, sound insulation, and dynamic vibration absorption can be performed.

[Brief description of the drawings]

FIG. 1 is a sectional view of an example of an integrally molded sheet cut in a thickness direction.

FIG. 2 is a cross-sectional view of another example of an integrally molded sheet cut in a thickness direction.

FIG. 3 is a cross-sectional view of another integrally formed sheet cut in a thickness direction.

FIG. 4 is a cross-sectional view of another example of an integrally molded sheet cut in a thickness direction.

FIG. 5 is a cross-sectional view of another example of an integrally molded sheet cut in a thickness direction.

FIG. 6 is a cross-sectional view of another example of an integrally molded sheet cut in a thickness direction.

FIG. 7 is a cross-sectional view of another example of an integrally molded sheet cut in a thickness direction.

FIG. 8 is a cross-sectional view of another example of an integrally molded sheet cut in a thickness direction.

FIG. 9 is a cross-sectional view of another integrally formed sheet cut in a thickness direction.

FIG. 10 is a cross-sectional view of another example of an integrally molded sheet cut in a thickness direction.

FIG. 11 is a side view of an example rotary molding machine partially shown in section.

FIG. 12 is a side view showing an example of a coating production line.

FIG. 13 is a side view showing a sound amount and decay time measuring device.

FIG. 14 is a side view showing a loss coefficient measuring device.

FIG. 15 is a side view showing an apparatus for measuring water permeability.

[Explanation of symbols]

1, 5, 9, 15, 19, 22, 28, 34, 39, 4
5 Integrated molded sheet 2, 24, 36, 42 Cured product of liquid polybutadiene rubber 3, 11, 25, 37, 43 Silica sand NSP 4, 12, 17, 18, 26, 38, 44, 47, 48
Precipitating barium sulfate 6,31 Cured product of polyol 7,14,32 Glass balloon 8,33,52 Cork powder 10 Cured product of epoxy resin A and cured product of epoxy resin B 13 Fine silica 16,50 Foaming of liquid polybutadiene rubber Cured product 20 Acrylic adhesive 21, 29 Release paper 23, 27 Polyester film 30 Reticulated material 35, 40 Nonwoven fabric 41 Split cloth 46 Cured liquid polychloroprene 49 Heavy calcium carbonate 51 Bubbles 53 Rotary molding machine 54 Rotary molding machine Cylinder 55 Receiving roll 56 Motor 57 Coating production line 58 Heating furnace 59 Conveyor 60 Winding machine 61 Sheet molding material 62 Measuring device of sound output and decay time 63 Iron plate 64 Sample 65 Suspension thread 66 Iron ball 67 Microphone 68 Microphone 69 Microphone 69 Frequency Analyzer 70 Measurement of loss factor Device 71 Complex elastic modulus measuring device 72 Specimen 73 Non-contact type electromagnetic transducer 74 Non-contact type capacitive transducer 75 Preamplifier 76 FFT analyzer 77 Plywood 78 Sample 79 Waterproof sheet 80 Wood screw 81 Through hole 82 Roth 83 Caulking material 84 Rubber pipe 85 Female pipette 86 Supporter 87 Scale

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 B29C 41/00-41/52 C08J 5/18 C09K 3/00

Claims (4)

(57) [Claims] An integrally molded sheet comprising a cured product of a liquid polymer and particles having a specific gravity different from the specific gravity of the liquid polymer , wherein the liquid polymer has room temperature reactivity,
Polymer main chain skeleton is polychloroprene, polyisoprene
, Polybutadiene, styrene-butadiene copolymer,
The liquid is composed of acrylonitrile butadiene copolymer.
The molecular terminal of the polymer has at least two or more hydroxyl groups,
Amino, carboxyl, or alkyl xanthate groups
The particles have a specific gravity higher than the specific gravity of the liquid polymer.
And a specific gravity lower than the specific gravity of the liquid polymer.
Mixed with the liquid polymer.
The particles are the specific gravity of the particles and the liquid polymer
The cured product is moving in a layer due to the difference from the specific gravity,
An elastic body, wherein the particles are bound by the viscoelastic body, and the settling particles are distributed in a layered manner,
The particles are distributed in layers, and the integrally molded sheet
Is a layer containing the buoyant particles and the viscoelastic body,
Including an elastic layer, the settling particles, and the viscoelastic body
An integrally molded sheet , wherein a specific gravity gradient is formed in the thickness direction in the order of layers . 2. The integrated molded sheet according to claim 2, wherein said sheet has different specific gravities.
Comprising a cured product of at least one kind of the liquid polymer,
Each cured product forms a layer in the integrally molded sheet.
The integral molding according to claim 1, wherein the integral molding is performed.
Sheet. 3. A cured product of a liquid polymer, and the liquid polymer
Integrally molded sound insulation that contains particles of different specific gravity
The integrally molded sheet according to claim 1 or 2 , wherein the sound insulation sheet is a sheet.
A sound insulation sheet characterized by the following. 4. A cured product of a liquid polymer and the liquid polymer
Vibration Suppression of Integral Molding Including Particles of Different Specific Gravity
3. The integrally molded sheet according to claim 1 , wherein the vibration damping sheet is a sheet.
A vibration damping sheet, characterized in that: