JP2012166399A - Heat insulating and retaining material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat insulating and retaining material having excellent heat insulating performance and heat retaining performance.SOLUTION: The heat insulating and retaining material is constituted by laminating a first cloth, a high foamed layer and a second cloth in this order and bonding them to one another. Alternatively, the heat insulating and retaining material is constituted by laminating the first cloth, a first high foamed layer, a synthetic resin film layer, a second foamed layer and the second cloth in this order and bonding them to one another. The high foamed layer includes an adhesive, thermally expanded microcapsules and hydrophilic and microporous silica fine powder. While holding the microcapsules and silica fine powder, the adhesive bonds the high foamed layer to the first cloth and the high foamed layer to the second cloth. As the first cloth, a cloth having a synthetic layer arranged on an inner face thereof may be used. Instead of the second cloth, a synthetic resin film layer may be used. The high foamed layer may be arranged on the entire surface or arranged to form a design pattern. As the adhesive, it is appropriate to use a cross-linked adhesive.

Description

  The present invention relates to a heat insulating material or a heat insulating material provided with a fabric and a thermally expanded microcapsule.

  Conventionally, as a heat insulating material or a heat insulating material, a synthetic resin foam such as a urethane foam has been used in a sheet form. And what strengthened the fabric on both surfaces of the sheet-like synthetic resin foam for reinforcement is also known (patent document 1).

  By the way, the present inventors have invented the following fabrics. That is, a highly foamed layer is laminated and bonded to one side of the fabric. The highly foamed layer includes a thermally expanded microcapsule, a synthetic resin for holding the microcapsule on one side of the fabric, and the microcapsule. A fabric comprising a highly foamed layer formed of a hydrophilic and microporous silica fine powder present on the surface or in a synthetic resin was invented (Patent Document 2). A fabric provided with such a highly foamed layer has a three-dimensional effect and is excellent in design.

JP-T 2009-540159 (Claims) WO2007 / 83641 pamphlet (Claims)

  The present inventors have found that a fabric provided with such a highly foamed layer is excellent in heat insulation performance or heat retention performance. Therefore, the present invention has come to the idea that fabrics and the like can be bonded to both sides of such a highly foamed layer and can be used as a heat insulating material or a heat insulating material. That is, the present invention corresponds to an application invention for the article described in Patent Document 2.

  The present invention comprises a first fabric, a highly foamed layer, and a second fabric in this order, and the highly foamed layer contains an adhesive, thermally expanded microcapsules, and hydrophilic and microporous silica fine powder. And the adhesive holds the microcapsules and the silica fine powder while the highly foamed layer and the first fabric and the highly foamed layer and the second fabric are bonded together. It relates to materials.

  As the fabric used as the first fabric and the second fabric, woven fabric, knitted fabric, nonwoven fabric, synthetic leather, or the like is generally used. The fiber constituting the fabric is optional, but, for example, polyamide synthetic fiber represented by nylon 6 or nylon 66, polyester synthetic fiber represented by polyethylene terephthalate, polyacrylonitrile synthetic fiber, polyvinyl alcohol synthetic Fibers, semi-synthetic fibers such as triacetate, and natural fibers such as silk and cotton are used alone or in combination. The same thing may be employ | adopted for a 1st fabric and a 2nd fabric, and a different thing may be employ | adopted.

  The fabric may be subjected to water repellent treatment. It is preferable to perform a water repellent treatment because water hardly enters the interior when used as a heat insulating material or a heat insulating material. As the water repellent used for the water repellent treatment, known ones such as a paraffin water repellent, a polysiloxane water repellent, a fluorine water repellent can be used. The water repellent treatment may be performed by a known method such as a spray method, a padding method, or a coating method. When particularly good water repellency is required, for example, NUVA N2114 LIQ (manufactured by Clariant Japan Co., Ltd., fluorine-based water repellent emulsion) is padded with a 5% aqueous dispersion (pickup rate 40%) A method of performing heat treatment at 150 to 180 ° C. for 20 seconds to 2 minutes may be adopted.

  Since the heat insulating material or heat insulating material according to the present invention may be used by being bonded to a base material with an aqueous adhesive or the like, in order to further prevent the aqueous adhesive or the like from entering the fabric, A crushing process may be performed. The method of crushing is not particularly limited, but generally, the cloth may be run between a mirror roll having a temperature control function and a cotton roll or a plastic roll to crush the mirror roll side.

  The highly foamed layer present between the first fabric and the second fabric contains an adhesive, thermally expanded microcapsules, and hydrophilic and microporous silica fine powder. The highly foamed layer may be present on the entire surface between the first fabric and the second fabric, or may be partially present in a pattern. As the adhesive, conventionally known ones may be used. For example, natural rubber, nitrile rubber, synthetic rubber such as chloroprene rubber, vinyl acetate resin, acrylic resin, polyamide resin, polyester resin, ethylene- Examples thereof include vinyl acetate copolymer resins, polyurethane resins, phenol resins, epoxy resins, and the like, and these can be used as an emulsion system, a solvent type, or a hot melt type as appropriate. From the viewpoint of durability and from the viewpoint of adhesion between the fabric and the highly foamed layer, it is preferable to use a curable adhesive, that is, a cross-linked adhesive. Specifically, it is more preferable to use a material mainly composed of a crosslinked polyurethane resin adhesive.

  The thermally expanded microcapsule is obtained by heating and expanding a thermally expandable microcapsule. Any thermally expandable microcapsule can be used as long as it is conventionally known. Specifically, the particle diameter is about 5 to 50 μm, and the outer shell is formed of a thermoplastic resin made of a polymer such as vinylidene chloride or acrylonitrile. In this outer shell, isobutane, isopentane, n- Thermally expandable microcapsules in which low boiling point hydrocarbons such as pentane are encapsulated can be used. Such a heat-expandable microcapsule expands in volume 20 to 70 times under heating at about 80 to 200 ° C. to become a thermally expanded microcapsule.

  As the hydrophilic and microporous silica fine powder, any conventionally known fine powder can be used. For example, it is manufactured by a wet method (precipitation method, gel method) or a dry method, and a hydrophilic and microporous silica fine powder having a large number of pores and having OH groups as hydrophilic groups on the surface is used. be able to. The particle diameter of the silica fine powder is about 0.01 to 200 μm, preferably about 1 to 150 μm, and is close to or larger than the particle diameter of the thermally expandable microcapsule. Is particularly preferred.

  The content of the thermally expanded microcapsule and silica fine powder with respect to the adhesive is preferably 1 to 25% by mass, particularly preferably 3 to 15% by mass, in terms of solid content. Moreover, as total content of both, 2-40 mass% is preferable at solid content ratio, and 4-30 mass% is especially preferable. The highly foamed layer used in the present invention is obtained by forming a layer containing an adhesive, thermally expandable microcapsules and silica fine powder, and then heating and expanding the thermally expandable microcapsules. When the content of the powder is small, the degree of volume expansion of the thermally expandable microcapsules becomes small, which is not preferable. Further, if the content of the thermally expanded microcapsules is small, the heat insulating performance or the heat retaining performance is lowered, which is not preferable. In addition, when there is too much content of the thermally expanded microcapsule or silica fine powder, the content of the adhesive is relatively reduced, and the adhesiveness between the highly foamed layer and each fabric is deteriorated.

  The ratio of the thermally expanded microcapsule and the silica fine powder is preferably the same or more silica fine powder. Specifically, the thermally expanded microcapsule: silica fine powder = 1: 0.8-3. It may be about 0. When the proportion of silica fine powder used is relatively large, the volume expansion of the thermally expandable microcapsules increases under heating, and the thermally expanded microcapsules increase.

  Moreover, in this invention, you may use what has a synthetic resin layer provided in the inner surface as a 1st fabric. That is, a laminate of a fabric and a synthetic resin layer may be used as the first fabric, the synthetic resin layer may be bonded to the highly foamed layer, and the fabric may be exposed on the outer surface. As the synthetic resin, any resin can be used. For example, polyamide resins such as nylon 6, nylon 46, nylon 66, nylon 6,10, nylon 11 and nylon 12, aromatics such as polyethylene terephthalate and polybutylene terephthalate. Known synthetic resins such as polyester resins, aliphatic polyester resins mainly composed of L-lactic acid and D-lactic acid, polyolefin resins such as polyethylene and polypropylene, polyurethane resins, and ethylene-vinyl acetate resins alone. Or it mixes and is used. In the present invention, a polyurethane-based resin is particularly preferably used from the viewpoint of flexibility and high elongation. Examples of such polyurethane resins include polymers obtained by the reaction of an isocyanate component and a polyol component. As the isocyanate component, aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates and the like can be used. As such, polyether polyol, polyester polyol, polycarbonate polyol and the like can be used.

  The synthetic resin may contain a filler such as titanium dioxide and calcium carbonate, an inorganic or organic pigment, a zeolite deodorant, a titanium oxide antibacterial agent having a photocatalytic function, and the like. As a method of obtaining a laminate of a fabric and a synthetic resin layer, a method of laminating a synthetic resin film and a fabric via an adhesive, or a resin solution in which a synthetic resin is dissolved or dispersed is applied, Examples include a dry film forming method or a wet film forming method. In addition, as thickness of a synthetic resin layer, 2-100 micrometers may be sufficient, and it is preferable that it is 5-50 micrometers.

  In the present invention, a synthetic resin film layer may be employed as the second fabric. What is necessary is just to employ | adopt the thing similar to an above described synthetic resin layer as a synthetic resin film layer.

  Moreover, in this invention, the heat insulation heat insulating material comprised in order of a 1st fabric, a 1st highly foamed layer, a synthetic resin film layer, a 2nd highly foamed layer, and a 2nd fabric may be sufficient. What was mentioned above should just be adopted as the 1st cloth and the 2nd cloth. The first highly foamed layer and the second highly foamed layer may be the above-described highly foamed layer, and the synthetic resin film layer may be the same as the above-described synthetic resin layer. And between each layer is bonded by the adhesive agent in a 1st highly foamed layer and a 2nd highly foamed layer.

  The heat insulation heat insulating material which concerns on this invention can be obtained with the following method, for example. First, an adhesive solution containing a thermally expandable microcapsule and a hydrophilic and microporous silica fine powder is prepared. Then, this adhesive solution is applied to one surface of the first fabric by a known method such as a comma coating method or a roll-on knife coating method. After application, the second fabric is laminated on the adhesive layer before or after drying and solidifying the adhesive solution. After the adhesive solution is solidified, heat treatment is performed to expand the thermally expandable microcapsules, thereby increasing the thickness of the adhesive layer and obtaining a highly foamed resin layer. At this time, if a pin tenter or the like is used, foaming can be performed while serving as a set process for the first fabric and the second fabric. However, it is preferable that the optimum expansion temperature range of the thermally expandable microcapsules at this time is set higher than the set temperature of the first fabric and the second fabric. This is because, as a characteristic of the thermally expandable microcapsule, as the thermal history is stepped, the expansion temperature range tends to decrease.

  Even when a first fabric having a synthetic resin layer on its inner surface is used, a heat insulating and heat insulating material can be obtained by the same method as described above. For example, a laminate of a fabric and a synthetic resin layer is prepared, an adhesive solution is applied to the surface of the synthetic resin layer, and the same method as described above may be adopted.

  In the case of employing a synthetic resin film layer instead of the second fabric, the second fabric of the above method may be changed to a synthetic resin film layer.

  In the case of the heat insulating heat insulating material composed of the first fabric, the first highly foamed layer, the synthetic resin film layer, the second highly foamed layer and the second fabric in this order, first, the first fabric, the first highly foamed layer And after obtaining the three-layer laminate of the synthetic resin film layer by the method described above, the method of applying the adhesive solution to the synthetic resin film layer and laminating the second fabric is employed.

  The heat insulating and heat insulating material according to the present invention is excellent in heat insulating performance or heat retaining performance because the thermally expanded microcapsules in the highly foamed layer are present in a gas-containing state. And since the hydrophilic and microporous silica fine powder exists in a highly foamed layer, the volume of the microcapsule thermally expanded is large. Therefore, there is an effect that the heat insulating performance or the heat retaining performance can be further improved. Moreover, since the cloth or the synthetic resin film exists on both surfaces of the highly foamed layer, the physical properties such as strength are excellent.

Example 1
[Preparation of the first fabric]
Weaving taffeta with a warp density of 120 / 2.5cm and a weft density of 95 / 2.5cm using nylon filament 78 dtex 68 filaments for both warp and weft, and scouring and dyeing by ordinary methods (Nippon Kayaku) After making Kayanol Blue NR 1% omf), padded with an emulsion type fluorine-based water repellent NUVA N2114 LIQ (manufactured by Clariant Japan) 6% aqueous dispersion (pickup rate 40%) After drying, heat treatment was performed at 170 ° C. for 45 seconds. Subsequently, using a calendar processing machine having a mirror surface roll, crushing was performed under the conditions of a temperature of 170 ° C., a pressure of 300 kPa, and a speed of 20 m / min to prepare a first fabric.

[Preparation of second fabric]
Using a nylon filament 44 decitex 48 filament, a taffeta having a warp density of 150 yarns / 2.5 cm and a weft density of 110 yarns / 2.5 cm was woven and scoured by a usual method to prepare a second fabric.

[Preparation of adhesive solution]
A polyurethane adhesive solution (resin solid content 57 mass%, viscosity 8000 mPa · s / 25 ° C.) of the following <Prescription 1> was prepared.
<Prescription 1>
Crisbon TA175 100 parts by mass (manufactured by DIC Corporation, moisture-permeable polyurethane adhesive having a solid content of 60% by mass)
Resamine NE crosslinking agent 8 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., 70% solid content isocyanate crosslinking agent)
Crisbon Axel T-81 1 part by mass (manufactured by DIC Corporation, crosslinking accelerator)
Matsumoto Microsphere FN-100D 2 parts by mass (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., thermally expandable microcapsules with an average particle size of about 30 μm, a foaming start temperature of about 130 ° C., and a maximum expansion temperature of about 185 ° C.)
4 parts by mass of silica powder RA70 (manufactured by Fuji Silysia Chemical Ltd., hydrophilic microporous silica powder having an average particle size of about 70 μm)
Methyl ethyl ketone 8 parts by mass N, N-dimethylformamide 4 parts by mass

[Manufacture of heat insulation materials]
The polyurethane-based adhesive solution of <Prescription 1> is applied to the water-repellent crushed surface of the first fabric with a comma coater at an application amount of 100 g / m ² and dried at 120 ° C. for 3 minutes to obtain 2 thermally expandable microcapsules. After forming an adhesive layer having a thickness of about 60 μm and containing 5.6% by mass of silica powder and 5.6% by mass, a second fabric is laminated on the surface of the adhesive layer, and the pressure is 200 kPa and the temperature is 100 ° C. Thus, a three-layer laminate was obtained in which the first fabric, the adhesive layer, and the second fabric were laminated in this order. Then, after aging at 40 ° C for 3 days, heat treatment was performed at 170 ° C for 2 minutes with a pin tenter to foam the thermally expandable microcapsules, and the first fabric, the highly foamed layer, and the second fabric were laminated and laminated in this order. A heat insulating heat insulating material was obtained. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 100 to 140 μm. Moreover, the thickness of the heat insulation heat insulating material was about 340 micrometers.

Example 2
[Preparation of the first fabric]
On the water-repellent crushing surface of the first fabric used in Example 1, a resin solution of the following <Prescription 2> (resin solid content 20 mass%, viscosity: 10000 mPa · s / 25 ° C.) was applied with a comma coater at an application amount of 80 g / m. after coating with ^2, after solidification of the resin component by immersing for 2 minutes in a coagulation bath at a concentration of 10% one N, N-dimethylformamide solution (20 ° C.), carried out with hot water for 5 minutes at 50 ° C., squeezed with a mangle, Subsequently, drying was performed at 130 ° C. for 2 minutes to form a microporous film having a thickness of about 30 μm on the water-repellent crushing surface of the first fabric used in Example 1 to prepare a first fabric. The first fabric used in Example 2 is one in which a synthetic resin layer made of a polyurethane-based microporous film is provided on the inner surface of the first fabric used in Example 1.
<Prescription 2>
Rezamin CU4555 100 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., polyurethane resin for forming a microporous film having a solid content of 27% by mass)
Rezamin X cross-linking agent 2 parts by mass (produced by Daiichi Seika Kogyo Co., Ltd., isocyanate compound)
N, N-dimethylformamide 40 parts by mass

[Preparation of second fabric]
The second fabric used in Example 1 was used as the second fabric used in Example 2 as it was.

[Preparation of adhesive solution]
A polyurethane adhesive solution (resin solid content 46 mass%, viscosity 2000 mPa · s / 25 ° C.) of the following <Prescription 3> was prepared.
<Prescription 3>
Crisbon TA175 100 parts by weight Resamine NE cross-linking agent 8 parts by weight Crisbon Axel T-81 1 part by weight Matsumoto Microsphere FN-100D 2 parts by weight Silica powder RA70 4 parts by weight Methyl ethyl ketone 20 parts by weight N, N-dimethylformamide 20 parts by weight

[Manufacture of heat insulation materials]
A polyurethane adhesive solution of <Prescription 3> is applied to the surface of the microporous membrane of the first fabric with a comma coater at a coating amount of 130 g / m ² , and dried at 120 ° C. for 3 minutes to form thermally expandable microcapsules. After forming an adhesive layer having a thickness of about 60 μm containing 2.8% by mass and 5.6% by mass of silica fine powder, a second fabric was laminated on the surface of the adhesive layer, and the pressure was 200 kPa and the temperature was 100 ° C. Thus, a laminate was obtained in which the first fabric (attached with a microporous membrane), the adhesive layer, and the second fabric were laminated in this order. Then, after aging at 40 ° C. for 3 days, heat treatment was performed at 170 ° C. for 2 minutes with a pin tenter to foam the thermally expandable microcapsules, and the first fabric (with a microporous membrane), the high foam layer and the second A heat insulating heat insulating material laminated and bonded in the order of the fabric was obtained. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 100 to 140 μm. Moreover, the thickness of the heat insulation heat insulating material was about 370 micrometers.

Example 3
[Preparation of the first fabric]
Using a release paper EV130TPD manufactured by Lintec Co., Ltd. as a release material, and using a comma coater on the release surface, a polyurethane resin solution of the following <Prescription 4> (resin solid content 19 mass%, viscosity 2000 mPa · s / 25 ° C. ) Was applied at a coating amount of 50 g / m ² and dried at 100 ° C. for 2 minutes to form a synthetic resin layer having a thickness of about 10 μm.
<Prescription 4>
Heimlen Y-274FM 100 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., moisture-permeable polyurethane resin having a solid content of 21% by mass)
Seika Seven DUT4093 White 8 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., white pigment with a solid content of 60% by mass)
Methyl ethyl ketone 15 parts by mass N, N-dimethylformamide 15 parts by mass And, on the surface of the synthetic resin layer, a polyurethane-based adhesive solution (resin solid content 43 mass%, viscosity 1500 mPa · s / 25 ° C.) shown below is applied in an amount of 100 g. / m ^{2 and} drying at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of about 40 μm, and then crushing the first fabric used in Example 1 under the conditions of pressure 200 kPa and temperature 120 ° C. The surface was pasted and aged at 40 ° C. for 3 days. And the mold release material was peeled and it was set as the 1st fabric used in Example 3. The first fabric used in Example 3 is obtained by providing a polyurethane-based synthetic resin layer on the inner surface of the first fabric used in Example 1.
<Prescription 5>
Crisbon TA175 100 parts by weight Rezamin NE cross-linking agent 8 parts by weight Crisbon Axel T-81 1 part by weight Methyl ethyl ketone 30 parts by weight N, N-dimethylformamide 15 parts by weight

[Preparation of second fabric]
The second fabric used in Example 1 was directly used as the second fabric used in Example 3.

[Preparation of adhesive solution]
A polyurethane adhesive solution (resin solid content: 47% by mass, viscosity: 2000 mPa · s / 25 ° C.) of <Prescription 6> below was prepared.
<Prescription 6>
Crisbon TA175 100 parts by weight Rezamin NE cross-linking agent 8 parts by weight Crisbon Axel T-81 1 part by weight Matsumoto Microsphere FN-100D 4 parts by weight Silica powder RA70 4 parts by weight Methyl ethyl ketone 20 parts by weight N, N-dimethylformamide 20 parts by weight

[Manufacture of heat insulation materials]
The polyurethane-based adhesive solution of <Prescription 6> is applied to the surface of the polyurethane-based synthetic resin layer of the first fabric with a comma coater at a coating amount of 130 g / m ² and dried at 120 ° C. for 3 minutes to form thermally expandable microcapsules. After forming an adhesive layer containing 5.4% by mass and 5.4% by mass of silica fine powder and having a thickness of about 50 μm, a second fabric is laminated on the surface of the adhesive layer, pressure 200 kPa, temperature 100 ° C. Thus, a laminate was obtained in which the first fabric (with a synthetic resin layer), the adhesive layer, and the second fabric were laminated in this order. Then, after aging at 40 ° C. for 3 days, heat treatment was performed at 170 ° C. for 2 minutes in a pin tenter to foam the thermally expandable microcapsules, and the first fabric (with a synthetic resin layer), the high foam layer and the second fabric The heat insulation heat insulating material laminated and bonded in this order was obtained. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 100 to 140 μm. Moreover, the thickness of the heat insulation heat insulating material was about 380 micrometers.

Example 4
[Preparation of the first fabric]
The first fabric used in Example 1 was directly used as the first fabric used in Example 4.
[Preparation of second fabric]
The second fabric used in Example 1 was used as the second fabric used in Example 4 as it was.

[Preparation of synthetic resin film layer]
Using a release paper EV130TPD manufactured by Lintec Corporation as a release material, and using a comma coater on its release surface, the polyurethane resin solution of <Prescription 4> (resin solid content 19 mass%, viscosity 2000 mPa · s / 25 ° C. ) Was applied at a coating amount of 50 g / m ^{2, and} a polyurethane synthetic resin film layer having a thickness of about 10 μm was obtained by drying at 100 ° C. for 2 minutes.

[Preparation of first adhesive solution and second adhesive solution]
The adhesive solution of <Prescription 6> used in Example 3 was directly used as the first and second adhesive solutions used in Example 4.

[Manufacture of heat insulation materials]
The first adhesive solution was applied to the surface of the polyurethane synthetic resin film layer with a release agent at a coating amount of 130 g / m ² with a comma coater, and dried at 120 ° C. for 3 minutes to obtain 5.4 mass of thermally expandable microcapsules. %, 5.4% by mass of silica fine powder, and an adhesive layer having a thickness of about 50 μm was formed, and then bonded to the crushing surface of the first fabric under the conditions of a pressure of 200 kPa and a temperature of 100 ° C. Subsequently, the second adhesive solution was applied to the surface of the polyurethane-based synthetic resin film layer from which the release material had been peeled off at a coating amount of 130 g / m ² with a comma coater, and dried at 120 ° C. for 3 minutes to thermally expand microcapsules. 5.4% by mass and silica fine powder 5.4% by mass, and after forming an adhesive layer having a thickness of about 50 μm, a second fabric is laminated on the adhesive layer surface, and the pressure is 200 kPa and the temperature is 100 ° C. Under the conditions, a laminate was obtained in which the first fabric, the first adhesive layer, the polyurethane synthetic resin film layer, the second adhesive layer, and the second fabric were laminated in this order. Then, after aging at 40 ° C. for 3 days, heat treatment was performed at 170 ° C. for 2 minutes in a pin tenter to foam the thermally expandable microcapsules, and the first fabric, the first highly foamed layer, the synthetic resin film layer, The heat insulation heat insulating material laminated and bonded in the order of the two highly foamed layers and the second fabric was obtained. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 100 to 140 μm. Moreover, the thickness of the heat insulation heat insulating material was about 470 micrometers.

Example 5
[Preparation of the first fabric]
Weaving taffeta with a warp density of 110 / 2.5 cm and a weft density of 90 / 2.5 cm using nylon filament 78 dtex 68 filaments for both warp and weft, and scouring and dyeing by ordinary methods (Nippon Kayaku) After making Kayanol Blue NR 1% omf), padding with an emulsion type fluorine-based water repellent NUVA N2114 LIQ (manufactured by Clariant Japan) 6% aqueous dispersion (pickup rate 35%) After drying, heat treatment was performed at 170 ° C. for 45 seconds. Subsequently, using a calendar processing machine having a mirror surface roll, crushing was performed under conditions of a temperature of 150 ° C., a pressure of 300 kPa, and a speed of 30 m / min to prepare a first fabric.

[Preparation of a synthetic resin film layer to replace the second fabric]
Using a release paper EV130TPD manufactured by Lintec Co., Ltd. as a release material, and using a comma coater on its release surface, a polyurethane resin solution (resin solid content 23 mass%, viscosity 3000 mPa · s / 25) shown below. At a coating amount of 20 g / m ^2, a polyurethane synthetic resin film layer having a thickness of about 5 μm was formed by drying at 100 ° C. for 2 minutes, and a synthetic resin film layer with a release material was prepared. .
<Prescription 7>
100 parts by weight of Rezamin NE-302HV (manufactured by Dainichi Seika Kogyo Co., Ltd., polyurethane resin for skin having a solid content of 35% by mass)
25 parts by mass of toluene 25 parts by mass of isopropyl alcohol

[Preparation of adhesive solution]
A polyurethane adhesive solution (resin solid content: 47% by mass, viscosity: 2000 mPa · s / 25 ° C.) of the following <Prescription 8> was prepared.
<Prescription 8>
Crisbon 4365T 100 parts by mass (manufactured by DIC Corporation, moisture-impermeable type polyurethane adhesive with a solid content of 65%)
Resamine NE cross-linking agent 8 parts by mass Crisbon Axel T-81 1 part by mass Matsumoto Microsphere FN-100D 2 parts by mass Silica powder RA70 4 parts by mass Methyl ethyl ketone 30 parts by mass N, N-dimethylformamide 20 parts by mass

[Manufacture of heat insulation materials]
The adhesive solution is applied at a coating amount of 130 g / m ² with a comma coater on the film layer surface of the synthetic resin film layer with a release material that replaces the second fabric, and the thermally expandable microcapsules are dried at 100 ° C. for 2 minutes. After forming an adhesive layer containing 2.8% by mass and 5.6% by mass of silica fine powder and having a thickness of about 60 μm, it is bonded to the crushing surface of the first fabric under the conditions of a pressure of 200 kPa and a temperature of 100 ° C. did. Thereafter, the release material added to the synthetic resin film layer is peeled off, and after aging at 40 ° C. for 3 days, heat treatment is performed at 170 ° C. for 1 minute in a pin tenter to foam the thermally expandable microcapsules, The heat insulation heat insulating material laminated and bonded in the order of the first fabric, the highly foamed layer, and the synthetic resin film layer was obtained. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 100 to 140 μm. Moreover, the thickness of the heat insulation heat insulating material was about 280 micrometers.

Example 6
[Preparation of the first fabric]
The first fabric used in Example 5 was directly used as the first fabric used in Example 6.
[Preparation of a synthetic resin film layer to replace the second fabric]
The synthetic resin film layer used in Example 4 was directly used as the synthetic resin film layer used in Example 6. This synthetic resin film layer is a synthetic resin film layer with a release material.
[Preparation of adhesive solution]
The adhesive solution used in Example 2 was directly used as the adhesive solution used in Example 6.

[Manufacture of heat insulation materials]
The adhesive solution is applied at a coating amount of 130 g / m ² with a comma coater on the film layer surface of the synthetic resin film layer with a release material that replaces the second fabric, and the thermally expandable microcapsules are dried at 100 ° C. for 2 minutes. After forming an adhesive layer containing 2.8% by mass and 5.6% by mass of silica fine powder and having a thickness of about 60 μm, it is bonded to the crushing surface of the first fabric under the conditions of a pressure of 200 kPa and a temperature of 100 ° C. did. Thereafter, the release material added to the synthetic resin film layer is peeled off, and after aging at 40 ° C. for 3 days, heat treatment is performed at 170 ° C. for 1 minute in a pin tenter to foam the thermally expandable microcapsules, The heat insulation heat insulating material laminated and bonded in the order of the first fabric, the highly foamed layer, and the synthetic resin film layer was obtained. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 100 to 140 μm. Moreover, the thickness of the heat insulation heat insulating material was about 290 micrometers.

Example 7
[Preparation of the first fabric]
The first fabric used in Example 5 was directly used as the first fabric used in Example 7.
[Preparation of a synthetic resin film layer to replace the second fabric]
The synthetic resin film layer used in Example 4 was directly used as the synthetic resin film layer used in Example 7. This synthetic resin film layer is a synthetic resin film layer with a release material.
[Preparation of adhesive solution]
The adhesive solution used in Example 3 was directly used as the adhesive solution used in Example 7.

[Manufacture of heat insulation materials]
The adhesive solution is applied at a coating amount of 130 g / m ² with a comma coater on the film layer surface of the synthetic resin film layer with a release material that replaces the second fabric, and the thermally expandable microcapsules are dried at 100 ° C. for 2 minutes. After forming an adhesive layer containing 5.4% by mass and 5.4% by mass of silica fine powder and having a thickness of about 60 μm, it is bonded to the crushed surface of the first fabric under the conditions of a pressure of 200 kPa and a temperature of 100 ° C. did. Thereafter, the release material added to the synthetic resin film layer is peeled off, and after aging at 40 ° C. for 3 days, heat treatment is performed at 170 ° C. for 1 minute in a pin tenter to foam the thermally expandable microcapsules, The heat insulation heat insulating material laminated and bonded in the order of the first fabric, the highly foamed layer, and the synthetic resin film layer was obtained. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 100 to 150 μm. Moreover, the thickness of the heat insulation heat insulating material was about 385 micrometers.

Example 8
In the [Production of heat insulation material] process of Example 7, before the heat treatment composition by the pin tenter, a polyurethane resin solution (resin solid content 24 mass%, viscosity 3500 mPa · s / 25 ° C.) of the following prescription <prescription 9> The same as Example 7, except that a knife coater was applied to the surface of the synthetic resin film layer at a coating amount of 20 g / m ² and dried at 100 ° C. for 1 minute to form a 5 μm thick slippery moisture permeable waterproof membrane. By the method, the heat insulation heat insulating material laminated | stacked in order of the 1st fabric, the highly foamed layer, the synthetic resin film layer, and the moisture-permeable waterproof membrane was obtained. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 100 to 150 μm. Moreover, the thickness of the heat insulation heat insulating material was about 390 micrometers.
<Prescription 9>
Heimlen C-61 100 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., polyurethane resin having moisture permeability of 25% by mass)
NP fiber W10-MG2 5 parts by mass (manufactured by Nippon Paper Chemicals Co., Ltd., cellulose-based lubricity improver)
Methyl ethyl ketone 15 parts by mass N, N-dimethylformamide 5 parts by mass

Example 9
[Preparation of the first fabric]
The first fabric used in Example 5 was directly used as the first fabric used in Example 9.
[Preparation of a synthetic resin film layer to replace the second fabric]
The synthetic resin film layer used in Example 4 was directly used as the synthetic resin film layer used in Example 9. This synthetic resin film layer is a synthetic resin film layer with a release material.
[Preparation of adhesive solution]
The adhesive solution used in Example 3 was directly used as the adhesive solution used in Example 9.

[Manufacture of heat insulation materials]
The adhesive solution was applied in the form of dots at a coating amount of 80 g / m ² with a 12-mesh gravure roll on the film layer surface of the synthetic resin film layer with a release material instead of the second fabric. A gravure roll having a dot diameter of 1.85 mmφ, a depth of 200 μm, and a coating area ratio of about 60% was used. After coating, by drying at 100 ° C. for 2 minutes, after forming an adhesive layer containing 5.4% by mass of thermally expandable microcapsules and 5.4% by mass of silica fine powder and having a thickness of about 60 μm, a pressure of 200 kPa The first cloth was bonded to the crushed surface at a temperature of 100 ° C. Thereafter, the release material added to the synthetic resin film layer was peeled off, and after aging at 40 ° C. for 3 days, the polyurethane resin solution of the above prescription <Prescription 9> (resin solid content 24 mass%, viscosity 3500 mPa · s / 25 ° C.) was applied to the surface of the synthetic resin film layer with a knife coater at a coating amount of 20 g / m ² , and dried at 100 ° C. for 1 minute to form a 5 μm thick slippery moisture permeable waterproof membrane. Subsequently, heat treatment is performed at 170 ° C. for 1 minute with a pin tenter to foam the thermally expandable microcapsules, and the first fabric, the dot-like highly foamed layer, the synthetic resin film layer, and the moisture-permeable waterproof membrane are laminated in this order. A bonded heat insulating material was obtained. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 100 to 150 μm. Moreover, the thickness of the heat insulation heat insulating material was about 380 micrometers in the location where a dot-like highly foamed layer exists, and it was about 200-250 micrometers in the location where a highly foamed layer does not exist.

Comparative Example 1
A heat insulating and heat insulating material was obtained from the adhesive solution used in Example 1 by exactly the same method as in Example 1 except that both Matsumoto Microsphere FN-100D and silica powder RA70 were omitted. The thickness of the obtained heat insulating heat insulating material was about 240 μm.

Comparative Example 2
A heat insulating and heat insulating material was obtained from the adhesive solution used in Example 1 by exactly the same method as in Example 1 except that the silica powder RA70 was omitted. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 70 to 100 μm. Moreover, the thickness of the heat insulation heat insulating material was about 280 micrometers.

Comparative Example 3
A heat insulating and heat insulating material was obtained from the adhesive solution used in Example 2 by exactly the same method as in Example 2 except that both Matsumoto Microsphere FN-100D and silica powder RA70 were omitted. The thickness of the heat insulation heat insulating material obtained was about 270 μm.

Comparative Example 4
A heat insulating and heat insulating material was obtained from the adhesive solution used in Example 2 by exactly the same method as in Example 2 except that the silica powder RA70 was omitted. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 70 to 100 μm. Moreover, the thickness of the heat insulation heat insulating material was about 310 micrometers.

Comparative Example 5
A heat insulating and heat insulating material was obtained from the adhesive solution used in Example 3 by exactly the same method as in Example 3 except that both Matsumoto Microsphere FN-100D and silica powder RA70 were omitted. The thickness of the heat insulation heat insulating material obtained was about 280 μm.

Comparative Example 6
A heat insulating and heat insulating material was obtained from the adhesive solution used in Example 3 by exactly the same method as in Example 3 except that silica powder RA70 was omitted. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 70 to 100 μm. Moreover, the thickness of the heat insulation heat insulating material was about 330 micrometers.

Comparative Example 7
A heat insulating and heat insulating material was obtained from the adhesive solution used in Example 5 by exactly the same method as in Example 5 except that both Matsumoto Microsphere FN-100D and silica powder RA70 were omitted. The thickness of the heat insulation heat insulating material obtained was about 170 μm.

Comparative Example 8
A heat insulating and heat insulating material was obtained from the adhesive solution used in Example 6 by exactly the same method as in Example 6, except that both Matsumoto Microsphere FN-100D and silica powder RA70 were omitted. The thickness of the heat insulating heat insulating material obtained was about 175 μm.

Comparative Example 9
A heat insulating and heat insulating material was obtained from the adhesive solution used in Example 6 by exactly the same method as in Example 6 except that the silica powder RA70 was omitted. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 70 to 100 μm. Moreover, the thickness of the heat insulation heat insulating material was about 250 micrometers.

Comparative Example 10
A heat insulating and heat insulating material was obtained from the adhesive solution used in Example 8 by exactly the same method as in Example 8 except that the silica powder RA70 was omitted. In addition, when the cross-sectional form was examined with an optical photograph, the thermally expanded microcapsules in the highly foamed layer had a diameter of 70 to 100 μm. Moreover, the thickness of the heat insulation heat insulating material was about 270 micrometers.

The heat insulation and heat insulation of the heat insulation materials obtained in Examples 1-9 and Comparative Examples 1-10 were measured by the following methods. The results are shown in Table 1.
[Thermal insulation properties]
A sample of size 5 cm × 5 cm is placed on a cooling plate (surface area 5 cm × 5 cm, water is circulated and the ambient temperature is kept at 20 ° C.), and a hot plate (surface area 5 cm is controlled at 30 ° C. (ambient temperature + 10 ° C.)). The heat consumption (W / m ² · ° C.) when the sample was overlaid on the sample surface was measured, and the numerical value when the heat consumption was stabilized was used as a measure of heat insulation. The one with less heat consumption (W / m ² · ° C) has better heat insulation.
[Heat retention]
The temperature of the hot plate with a surface area of 10 cm × 10 cm is set to 30 ° C. (environmental temperature + 10 ° C.), the heat consumption at the equilibrium state is blank, and the heat consumption at the equilibrium state when covered with the sample with the surface area of 10 cm × 10 cm The heat retention rate (%) was calculated from the difference between {[(blank consumed heat amount−sample consumed heat amount) / blank consumed heat amount] × 100}, and used as a measure of heat retention. The larger the value of the heat retention rate (%), the better the heat retention.

[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Heat consumption (W / m ² · ° C) Thermal insulation rate (%)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 117 7.3
Example 2 110 8.2
Example 3 104 9.5
Example 4 72 14.8
Example 5 178 4.8
Example 6 177 5.0
Example 7 132 7.5
Example 8 128 7.8
Example 9 146 6.6
Comparative Example 1 305 1.2
Comparative Example 2 192 4.4
Comparative Example 3 291 1.4
Comparative Example 4 188 4.9
Comparative Example 5 285 1.7
Comparative Example 6 164 4.8
Comparative Example 7 462 0.5
Comparative Example 8 431 0.7
Comparative Example 9 225 3.3
Comparative Example 10 205 5.0
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

  As is clear from the results in Table 1, the heat insulating and heat insulating materials according to Examples 1 to 9 have relatively less heat consumption and the heat insulating rate than the heat insulating and heat insulating materials according to Comparative Examples 1 to 10. It was generally large. Therefore, what was obtained by the method concerning Examples 1-9 could be used as a heat insulation heat insulating material.

Claims (6)

  A first fabric, a highly foamed layer, and a second fabric are configured in this order, and the highly foamed layer contains an adhesive, a thermally expanded microcapsule, and a hydrophilic and microporous silica fine powder. Is a heat insulating heat-retaining material in which the highly foamed layer and the first fabric, and the highly foamed layer and the second fabric are bonded while holding the microcapsules and the silica fine powder.   The heat removal and heat insulation material according to claim 1, wherein the first fabric is provided with a synthetic resin layer on its inner surface.   The heat insulation heat insulating material according to claim 1, wherein a synthetic resin film layer is used instead of the second fabric.   The first fabric, the first highly foamed layer, the synthetic resin film layer, the second highly foamed layer, and the second fabric are configured in this order. One microcapsule and a hydrophilic and microporous first silica fine powder, and the second highly foamed layer comprises a second adhesive, a thermally expanded second microcapsule and a hydrophilic and microporous second Silica fine powder is contained, and the first adhesive holds the first microcapsule and the first silica fine powder, and the first high foam layer, the first fabric, the first high foam layer, and the A synthetic resin film layer is bonded, and the second adhesive holds the second microcapsule and the second silica fine powder while the second highly foamed layer, the synthetic resin film layer, and the A heat insulating and heat insulating material, wherein the second highly foamed layer and the second fabric are bonded together.   The heat insulating heat insulating material according to any one of claims 1 to 4, wherein the adhesive is a cross-linked adhesive.   The heat insulation heat insulating material according to any one of claims 1 to 5, wherein the highly foamed layer is present in a pattern.