JP2013124677A - Heat insulating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat insulating material with superior heat resistance and having superior low thermal conductivity.SOLUTION: The heat insulating material includes a foam having an open-cell structure having through holes between adjacent spherical bubbles. An average hole diameter of the spherical bubbles is smaller than 20 μm, and an average hole diameter of the through holes is 5 μm or smaller. In the heat insulating material, a coefficient of thermal conductivity measured according to ASTM-D5470 is 0.1 W/m*k or smaller when a compression rate is lower than 5%.

Description

  The present invention relates to a heat insulating material.

  Thermal insulation materials are widely used in various applications. The heat insulating material is required to have low thermal conductivity (high heat insulating property). As a heat insulating material having low thermal conductivity, a heat insulating material made of a polypropylene resin extruded plate-like foam that can be suitably used for a heat insulating material such as a wall of a building or a floor partition has been reported (Patent Document 1).

  However, the heat insulating material reported in Patent Document 1 achieves a low thermal conductivity, but a polypropylene resin composed of specific fine bubbles and bubbles having a specific bubble diameter larger than that of the fine bubbles. Due to the special structure of the extruded plate-like foam, there is a problem that it is difficult to use for applications requiring a thickness of less than 1 mm, for example.

JP 2001-179795 A

  The present invention has been made to solve the above-described conventional problems. The object of the present invention is to have excellent heat resistance and excellent low thermal conductivity, and can be used well even in a very small space. It is to provide insulation.

The heat insulating material of the present invention includes a foam having an open cell structure having through holes between adjacent spherical bubbles, the average pore diameter of the spherical bubbles is less than 20 μm, and the average pore diameter of the through holes is 5 μm or less. The thermal conductivity measured according to ASTM-D5470 is 0.1 W / m · K or less at a compression rate of less than 5%.
In a preferred embodiment, the heat insulating material has a dimensional change rate of less than ± 5% when stored at 125 ° C. for 22 hours.
In a preferred embodiment, the heat insulating material has a 50% compression load change rate of ± 10% or less when stored at 125 ° C. for 22 hours.
In a preferred embodiment, the foam includes a hydrophilic polyurethane-based polymer.
In a preferred embodiment, the density of the foam is 0.5 g / cm ³ or less.
In a preferred embodiment, the heat insulating material has a 50% compression load of 50 N / cm ² or less.

  According to the present invention, it is possible to provide a heat insulating material having excellent heat resistance and excellent low thermal conductivity.

It is a schematic sectional drawing explaining the heat insulating material by preferable embodiment of this invention. It is a schematic sectional drawing explaining the heat insulating material by another preferable embodiment of this invention. It is an image of the scanning electron microscope (SEM) photograph of the cross section in an example of the heat insulating material of this invention. It is an image of the SEM photograph from the diagonal direction in an example of the heat insulating material of this invention. It is a schematic diagram explaining the measuring method of thermal conductivity. It is a schematic diagram explaining the cross section of the test piece in the measuring method of thermal conductivity.

A. Thermal insulation The thermal insulation of the present invention includes a foam having an open cell structure having a through hole between adjacent spherical bubbles. As a typical structure of the heat insulating material, for example, a heat insulating material 100 (FIG. 1) made of the foam 10 and a heat insulating material 100 (FIG. 2) including a base material 20 (described later) between the foam 10a and the foam 10b. ). In FIGS. 1 and 2, the member represented by reference numeral 30 may be a base material or a release film. When the code | symbol 30 represents a base material, the said base material is the same as that of the base material 20. FIG. When the code | symbol 30 represents a peeling film, although the said peeling film is provided for protection of the surface of a heat insulating material, the said peeling film does not need to be provided.

  In the present specification, the “spherical bubble” does not have to be a strictly true spherical bubble, and may be, for example, a substantially spherical bubble having a partial strain or a bubble having a large strain. .

  In the present specification, the “open cell structure” may be an open cell structure having through holes between most or all adjacent spherical bubbles, and is a semi-independent semi-open cell structure having a relatively small number of through holes. There may be.

  The average pore diameter of the spherical bubbles is less than 20 μm, preferably 15 μm or less, more preferably 10 μm or less. The lower limit value of the average pore diameter of the spherical bubbles is not particularly limited, and is preferably 0.01 μm, more preferably 0.1 μm, and further preferably 1 μm, for example.

  By keeping the average pore diameter of the spherical bubbles within the above range, the average pore diameter of the spherical bubbles can be precisely controlled to be small, and as a result, it is possible to provide a heat insulating material having excellent heat resistance and excellent low thermal conductivity. it can.

  The through-hole formed between adjacent spherical bubbles in the foam contained in the heat insulating material of the present invention affects the physical properties of the heat insulating material. For example, the strength of the heat insulating material tends to increase as the average hole diameter of the through holes decreases. In FIG. 3, the image of the scanning electron microscope (SEM) photograph of the cross section in an example of the heat insulating material of this invention is shown. FIG. 3 clearly shows an open cell structure with through holes between adjacent spherical cells.

  The average hole diameter of the through holes is 5 μm or less, preferably 4 μm or less, more preferably 3 μm or less. The lower limit of the average pore diameter of the through holes is not particularly limited, and is preferably 0.001 μm, and more preferably 0.01 μm, for example. When the average hole diameter of the through holes is within the above range, a heat insulating material having excellent heat resistance and excellent low thermal conductivity can be provided.

  The average pore diameter of the above spherical bubbles and through-holes is obtained, for example, by photographing a cut surface in the thickness direction of the foam of the obtained heat insulating material with a scanning electron microscope at a predetermined magnification (for example, 800 to 5000 times). It can be calculated from the hole diameter measured from the photographed image.

  The heat insulating material of the present invention has a thermal conductivity measured in accordance with ASTM-D5470 of 0.1 W / m · K or less, preferably 0.08 W / m · K or less when the compression rate is less than 5%. More preferably, it is 0.06 W / m · K or less. The lower limit of the thermal conductivity is preferably 0.024 W / m · K when the compressibility is less than 5%. That the heat conductivity of the heat insulating material of the present invention falls within the above range at a compressibility of less than 5% means that the heat insulating material of the present invention has a very excellent low heat conductivity.

  In the heat insulating material of the present invention, the 50% compression load change rate when stored at 125 ° C. for 22 hours is preferably ± 10% or less, more preferably ± 9% or less, and further preferably ± 8% or less. It is. In the heat insulating material of the present invention, when the 50% compression load change rate when stored at 125 ° C. for 22 hours is within the above range, the heat insulating material of the present invention can have excellent heat resistance. In addition, according to the objective, you may employ | adopt the 50% compression load change rate in different temperature (for example, 100 degreeC, 150 degreeC).

  The thermal insulation material of the present invention has a dimensional change rate of preferably less than ± 5%, more preferably ± 3% or less, still more preferably ± 1% or less when stored at 125 ° C. for 22 hours. In the heat insulating material of the present invention, when the dimensional change rate when stored at 125 ° C. for 22 hours is within the above range, the heat insulating material of the present invention can have excellent heat resistance. In addition, a dimensional change rate is measured based on the dimensional stability evaluation at the time of high temperature of JIS-K-6767.

The density of the foam contained in the heat insulating material of the present invention is preferably 0.5 g / cm ³ or less, more preferably 0.1 g / cm ^{3 to} 0.5 g / cm ³ , and still more preferably 0.00. it is ^{15g / cm 3 ~0.45g / cm 3} . By keeping the density of the foam within the above range, it is possible to provide a heat insulating material having excellent heat resistance and excellent low thermal conductivity while widely controlling the density range of the foam.

The foam contained in the heat insulating material of the present invention has a cell ratio of preferably 30% or more, more preferably 40% or more, and further preferably 50% or more. In the heat insulating material of the present invention, when the foam ratio of the foam is within the above range, a heat insulating material having excellent heat resistance and excellent low thermal conductivity can be provided. The cell ratio can be measured, for example, as follows: only the oil phase component when producing an emulsion (described later) for forming a foam is polymerized, and the resulting polymer sheet is 100 mm × 100 mm in size. Then, 5 pieces are cut out to make a test piece, and the apparent density is obtained by dividing the weight by the volume. The average value of the apparent density obtained is defined as the density of the resin component constituting the foam, and the density obtained by dividing the density of the foam by the density of the resin component is defined as the relative density. The foam ratio of the foam is calculated using the following formula.
Bubble ratio = (1−relative density) × 100

The heat insulating material of the present invention has a 50% compressive load of preferably 50 N / cm ² or less, more preferably 45 N / cm ² or less, still more preferably 40 N / cm ² or less, particularly preferably 35 N / cm. cm ² or less. The lower limit of the 50% compression load is preferably 10 N / cm ² . When the 50% compressive load of the heat insulating material of the present invention falls within the above range, the heat insulating material of the present invention can exhibit excellent flexibility and cushioning properties.

  The foam contained in the heat insulating material of the present invention preferably contains a hydrophilic polyurethane polymer. Since the foam contained in the heat insulating material of the present invention contains a hydrophilic polyurethane polymer, the cell structure is precisely controlled, the cell rate is high, and a large number of finely controlled surface openings are precisely controlled. Thus, it is possible to provide a heat insulating material having excellent heat resistance and excellent low thermal conductivity.

  The details of the foam contained in the heat insulating material of the present invention and the details of the hydrophilic polyurethane polymer contained in the foam will be mentioned in the description of the production method described later.

  The heat insulating material of the present invention preferably has a surface opening on the surface. The average pore diameter of the surface opening is preferably 20 μm or less, more preferably less than 20 μm, still more preferably 15 μm or less, particularly preferably 10 μm or less, even more preferably 5 μm or less, especially Preferably it is 4 micrometers or less, Most preferably, it is 3 micrometers or less. The lower limit of the average pore diameter of the surface opening is not particularly limited, and is preferably 0.001 μm, and more preferably 0.01 μm, for example. The heat insulating material of the present invention has a surface opening, and the average pore diameter of the surface opening is within the above range, thereby providing a heat insulating material having excellent heat resistance and excellent low thermal conductivity. be able to. In FIG. 4, the image of the SEM photograph which looked at the surface and the cross section simultaneously from the diagonal direction in an example of the heat insulating material of this invention is shown. FIG. 4 clearly shows the surface opening.

  The heat insulating material of the present invention can take any appropriate shape. In the heat insulating material of the present invention, the length, such as the thickness, the long side, and the short side, can take any appropriate value.

  The heat insulating material of the present invention may contain any appropriate base material as long as the effects of the present invention are not impaired. Examples of the form in which the base material is contained in the heat insulating material of the present invention include a form in which a base material layer is provided inside the heat insulating material. Examples of such a substrate include fiber woven fabric, fiber nonwoven fabric, fiber laminated fabric, fiber knitted fabric, resin sheet, metal foil film sheet, and inorganic fiber.

  As the fiber woven fabric, a woven fabric formed of any appropriate fiber can be adopted. Examples of such fibers include natural fibers such as plant fibers, animal fibers, and mineral fibers; artificial fibers such as regenerated fibers, synthetic fibers, semi-synthetic fibers, and artificial inorganic fibers. Examples of synthetic fibers include fibers obtained by melt spinning thermoplastic fibers. In addition, the fiber woven fabric may be metallic processed by plating, sputtering, or the like.

  As a fiber nonwoven fabric, the nonwoven fabric formed from arbitrary appropriate fibers can be employ | adopted. Examples of such fibers include natural fibers such as plant fibers, animal fibers, and mineral fibers; artificial fibers such as regenerated fibers, synthetic fibers, semi-synthetic fibers, and artificial inorganic fibers. Examples of synthetic fibers include fibers obtained by melt spinning thermoplastic fibers. Moreover, the fiber nonwoven fabric may be metallic-processed by plating, sputtering, etc. More specifically, for example, a spunbond nonwoven fabric can be mentioned.

  As the fiber laminated fabric, a laminated fabric formed of any appropriate fiber can be adopted. Examples of such fibers include natural fibers such as plant fibers, animal fibers, and mineral fibers; artificial fibers such as regenerated fibers, synthetic fibers, semi-synthetic fibers, and artificial inorganic fibers. Examples of synthetic fibers include fibers obtained by melt spinning thermoplastic fibers. In addition, the fiber laminated fabric may be metallic processed by plating, sputtering, or the like. More specifically, for example, a polyester fiber laminated fabric can be mentioned.

  As a fiber knitted fabric, the knitted fabric formed from arbitrary appropriate fibers can be employ | adopted, for example. Examples of such fibers include natural fibers such as plant fibers, animal fibers, and mineral fibers; artificial fibers such as regenerated fibers, synthetic fibers, semi-synthetic fibers, and artificial inorganic fibers. Examples of synthetic fibers include fibers obtained by melt spinning thermoplastic fibers. Moreover, the fiber knitted fabric may be metallic-processed by plating, sputtering, etc.

  As the resin sheet, a sheet formed of any appropriate resin can be adopted. An example of such a resin is a thermoplastic resin. The resin sheet may be metallically processed by plating or sputtering.

  As the metal foil film sheet, a sheet formed from any appropriate metal foil film can be adopted.

  Any appropriate inorganic fiber can be adopted as the inorganic fiber. Specific examples of such inorganic fibers include glass fibers, metal fibers, and carbon fibers.

  In the heat insulating material of the present invention, when voids are present in the substrate, the same material as the heat insulating material may be present in a part or all of the voids.

  Only 1 type may be used for a base material and it may use 2 or more types together.

B. Manufacturing method of heat insulating material The heat insulating material of this invention can be manufactured by arbitrary appropriate methods. The heat insulating material of the present invention can be preferably produced by shaping and polymerizing a W / O emulsion.

  As a manufacturing method of the heat insulating material of the present invention, for example, a continuous oil phase component and an aqueous phase component are continuously supplied to an emulsifier to obtain the heat insulating material (substantially a foam) of the present invention. The “continuous method” is to prepare a W / O type emulsion to be obtained, subsequently polymerize the obtained W / O type emulsion to produce a hydrous polymer, and subsequently dehydrate the obtained hydrous polymer. Can be mentioned. As a method for producing the heat insulating material of the present invention, for example, an appropriate amount of an aqueous phase component with respect to a continuous oil phase component is charged into an emulsifier, and the aqueous phase component is continuously supplied while stirring. A W / O type emulsion that can be used for obtaining the heat insulating material of the present invention is prepared, and the obtained W / O type emulsion is polymerized to produce a hydrous polymer. Subsequently, the obtained hydrous polymer is dehydrated. And “batch method”. For simplicity, the W / O emulsion that can be used to obtain the heat insulating material of the present invention may be simply referred to as a W / O emulsion below.

  The continuous polymerization method in which the W / O emulsion is continuously polymerized is a preferable method because the production efficiency is high and the effect of shortening the polymerization time and the shortening of the polymerization apparatus can be most effectively utilized.

More specifically, the heat insulating material of the present invention is preferably
A step (I) of preparing a W / O type emulsion;
Step (II) of shaping the obtained W / O emulsion,
Polymerizing the shaped W / O emulsion (III);
Step (IV) of dehydrating the obtained hydrous polymer;
It can manufacture with the manufacturing method containing. Here, at least a part of the step (II) for shaping the obtained W / O emulsion and the step (III) for polymerizing the shaped W / O emulsion may be performed simultaneously.

B-1. Step of preparing W / O type emulsion (I)
The W / O type emulsion is a W / O type emulsion containing a continuous oil phase component and an aqueous phase component immiscible with the continuous oil phase component. More specifically, the W / O type emulsion is obtained by dispersing a water phase component in a continuous oil phase component.

  The ratio of the water phase component and the continuous oil phase component in the W / O type emulsion may be any appropriate ratio as long as the W / O type emulsion can be formed. The ratio of the water phase component to the continuous oil phase component in the W / O emulsion is important in determining the structural, mechanical, and performance characteristics of the foam obtained by polymerization of the W / O emulsion. Can be a factor. Specifically, the ratio of the water phase component to the continuous oil phase component in the W / O type emulsion is determined by the density, cell size, cell structure, and porous structure of the foam obtained by polymerization of the W / O type emulsion. It can be an important factor in determining the dimension of the wall to be formed.

  The ratio of the water phase component in the W / O type emulsion is preferably 30% by weight, more preferably 40% by weight, still more preferably 50% by weight, and particularly preferably 55% by weight as the lower limit. The upper limit is preferably 95% by weight, more preferably 90% by weight, still more preferably 85% by weight, and particularly preferably 80% by weight. If the ratio of the aqueous phase component in the W / O emulsion is within the above range, the effects of the present invention can be sufficiently exhibited.

  The W / O emulsion can contain any appropriate additive as long as the effects of the present invention are not impaired. Examples of such additives include tackifying resins; talc; calcium carbonate, magnesium carbonate, silicic acid and salts thereof, clay, mica powder, aluminum hydroxide, magnesium hydroxide, zinc white, bentonine, carbon black, Examples thereof include fillers such as silica, alumina, aluminum silicate, acetylene black, and aluminum powder; pigments; dyes; Only one kind of such an additive may be contained, or two or more kinds thereof may be contained.

  Any appropriate method can be adopted as a method for producing a W / O emulsion that can be used for obtaining the heat insulating material of the present invention. As a method for producing a W / O type emulsion, for example, a “continuous method” in which a W / O type emulsion is formed by continuously supplying a continuous oil phase component and an aqueous phase component to an emulsifier, or a continuous oil phase. Examples thereof include a “batch method” in which an appropriate amount of an aqueous phase component is charged into an emulsifier and the aqueous phase component is continuously supplied with stirring to form a W / O type emulsion.

  Examples of the shearing means for obtaining the emulsion state when producing the W / O type emulsion include application of high shear conditions using a rotor-stator mixer, a homogenizer, a microfluidizer, and the like. In addition, as another shearing means for obtaining an emulsion state, for example, gentle mixing of continuous and dispersed phases by application of low shear conditions using a moving blade mixer or a pin mixer, low stirring conditions using a magnetic stir bar, etc. Can be mentioned. Specifically, “TK Aji homomixer” and “TK combimix” manufactured by Primix Co., Ltd. can produce a desired W / O emulsion under reduced pressure. In the W / O type emulsion, the mixing of bubbles is greatly reduced.

  Examples of the apparatus for preparing the W / O emulsion by the “continuous method” include a static mixer, a rotor stator mixer, and a pin mixer. More intense agitation may be achieved by increasing the agitation speed or by using an apparatus designed to finely disperse the aqueous phase component in the W / O emulsion by a mixing method.

  Examples of the apparatus for preparing the W / O type emulsion by the “batch method” include manual mixing and shaking, a driven blade mixer, and three propeller mixing blades.

  Arbitrary appropriate methods can be employ | adopted as a method of preparing a continuous oil phase component. As a method for preparing the continuous oil phase component, typically, for example, a mixed syrup containing a hydrophilic polyurethane-based polymer and an ethylenically unsaturated monomer is prepared, and subsequently, a polymerization initiator, It is preferable to prepare a continuous oil phase component by blending a crosslinking agent and any other appropriate components.

  Any appropriate method can be adopted as a method of preparing the hydrophilic polyurethane-based polymer. A typical method for preparing a hydrophilic polyurethane-based polymer is, for example, by reacting polyoxyethylene polyoxypropylene glycol and a diisocyanate compound in the presence of a urethane reaction catalyst.

B-1-1. Aqueous Phase Component As the aqueous phase component, any aqueous fluid that is substantially immiscible with the continuous oil phase component may be employed. From the viewpoint of ease of handling and low cost, water such as ion-exchanged water is preferable.

  Any appropriate additive may be contained in the aqueous phase component as long as the effects of the present invention are not impaired. Examples of such additives include polymerization initiators and water-soluble salts. The water-soluble salt can be an effective additive for further stabilizing the W / O emulsion. Examples of such water-soluble salts include sodium carbonate, calcium carbonate, potassium carbonate, sodium phosphate, calcium phosphate, potassium phosphate, sodium chloride, potassium chloride and the like. Only one kind of such an additive may be contained, or two or more kinds thereof may be contained. The additive that can be contained in the aqueous phase component may be only one type or two or more types.

B-1-2. Continuous oil phase component The continuous oil phase component preferably comprises a hydrophilic polyurethane polymer and an ethylenically unsaturated monomer. The content ratio of the hydrophilic polyurethane polymer and the ethylenically unsaturated monomer in the continuous oil phase component can take any appropriate content ratio as long as the effects of the present invention are not impaired.

  The hydrophilic polyurethane-based polymer depends on the polyoxyethylene ratio in the polyoxyethylene polyoxypropylene glycol unit constituting the hydrophilic polyurethane-based polymer or the amount of the aqueous phase component to be blended. The hydrophilic polyurethane polymer is in the range of 10 to 30 parts by weight with respect to 70 to 90 parts by weight of the ethylenically unsaturated monomer, and more preferably hydrophilic to 75 to 90 parts by weight of the ethylenically unsaturated monomer. The polyurethane polymer is in the range of 10 to 25 parts by weight. Further, for example, the hydrophilic polyurethane polymer is preferably in the range of 1 to 30 parts by weight, more preferably 1 to 25 parts by weight of the hydrophilic polyurethane polymer with respect to 100 parts by weight of the aqueous phase component. It is a range. If the content ratio of the hydrophilic polyurethane polymer is within the above range, the effects of the present invention can be sufficiently exhibited.

B-2-1-1. Hydrophilic polyurethane-based polymer The hydrophilic polyurethane-based polymer preferably contains a polyoxyethylene polyoxypropylene unit derived from polyoxyethylene polyoxypropylene glycol, and the polyoxyethylene polyoxypropylene unit contains 5% by weight to 25% by weight is polyoxyethylene.

  The content ratio of polyoxyethylene in the polyoxyethylene polyoxypropylene unit is preferably 5% by weight to 25% by weight as described above, and is more preferably 10% by weight as the lower limit, and the upper limit. More preferably, it is 25% by weight, and more preferably 20% by weight. The polyoxyethylene in the polyoxyethylene polyoxypropylene unit exhibits an effect of stably dispersing the aqueous phase component in the continuous oil phase component. When the content of polyoxyethylene in the polyoxyethylene polyoxypropylene unit is less than 5% by weight, it may be difficult to stably disperse the water phase component in the continuous oil phase component. If the polyoxyethylene content in the polyoxyethylene polyoxypropylene unit exceeds 25% by weight, there is a risk of phase inversion from a W / O type emulsion to an O / W type (oil-in-water type) emulsion as it approaches the HIPE condition. There is.

  A conventional hydrophilic polyurethane polymer can be obtained by reacting a diisocyanate compound with a hydrophobic long-chain diol, polyoxyethylene glycol and derivatives thereof, and a low molecular active hydrogen compound (chain extender). Since the number of polyoxyethylene groups contained in the hydrophilic polyurethane polymer obtained in 1) is uneven, the emulsion stability of such a W / O emulsion containing such a hydrophilic polyurethane polymer may be reduced. There is. On the other hand, the hydrophilic polyurethane-based polymer contained in the continuous oil phase component of the W / O type emulsion that can be used to obtain the heat insulating material of the present invention has a characteristic structure as described above. When it is included in the continuous oil phase component of the type emulsion, excellent emulsifiability and excellent stationary storage stability can be expressed without positively adding an emulsifier or the like.

  The hydrophilic polyurethane-based polymer is preferably obtained by reacting polyoxyethylene polyoxypropylene glycol and a diisocyanate compound. In this case, the ratio between the polyoxyethylene polyoxypropylene glycol and the diisocyanate compound is NCO / OH (equivalent ratio), and the lower limit is preferably 1, more preferably 1.2, and still more preferably 1. .4, particularly preferably 1.6, and the upper limit is preferably 3, more preferably 2.5, and even more preferably 2. When NCO / OH (equivalent ratio) is less than 1, a gelled product may be easily formed when a hydrophilic polyurethane polymer is produced. When NCO / OH (equivalent ratio) exceeds 3, the amount of residual diisocyanate compound increases, and the W / O emulsion that can be used to obtain the heat insulating material of the present invention may become unstable.

  As polyoxyethylene polyoxypropylene glycol, for example, polyether polyol (ADEKA (registered trademark) Pluronic L-31, L-61, L-71, L-101, L-121, L-42 manufactured by ADEKA Corporation) , L-62, L-72, L-122, 25R-1, 25R-2, 17R-2) and polyoxyethylene polyoxypropylene glycol (Pronon (registered trademark) 052, 102, manufactured by NOF Corporation. 202). As for polyoxyethylene polyoxypropylene glycol, only 1 type may be used and 2 or more types may be used together.

  Examples of the diisocyanate compound include aromatic, aliphatic, and alicyclic diisocyanates, dimers and trimers of these diisocyanates, polyphenylmethane polyisocyanate, and the like. Aromatic, aliphatic, and alicyclic diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate. 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4 -Diisocyanate, dicyclohexylmethane-4,4-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methyl Cyclohexane diisocyanate, m- tetramethylxylylene diisocyanate. Examples of the diisocyanate trimer include isocyanurate type, burette type, and allophanate type. Only 1 type may be used for a diisocyanate compound and it may use 2 or more types together.

  The diisocyanate compound may be selected as appropriate from the viewpoint of urethane reactivity with the polyol, and the like. From the viewpoint of rapid urethane reactivity with polyol and suppression of reaction with water, it is preferable to use alicyclic diisocyanate.

  The weight average molecular weight of the hydrophilic polyurethane polymer is preferably 5000 as a lower limit, more preferably 7000, still more preferably 8000, particularly preferably 10,000, and preferably 50,000 as an upper limit. More preferably, it is 40000, more preferably 30000, and particularly preferably 20000. The weight average molecular weight can be measured, for example, by polystyrene standard gel permeation chromatography (GPC).

  The hydrophilic polyurethane-based polymer may have an unsaturated double bond capable of radical polymerization at the terminal. By having an unsaturated double bond capable of radical polymerization at the terminal of the hydrophilic polyurethane-based polymer, the effects of the present invention can be further exhibited.

B-1-2-2. Ethylenically Unsaturated Monomer As the ethylenically unsaturated monomer, any appropriate monomer can be adopted as long as it is a monomer having an ethylenically unsaturated double bond. Only one type of ethylenically unsaturated monomer may be used, or two or more types may be used.

  The ethylenically unsaturated monomer preferably comprises a (meth) acrylic ester. The content ratio of the (meth) acrylic acid ester in the ethylenically unsaturated monomer is preferably 80% by weight, more preferably 85% by weight as the lower limit, and preferably 100% by weight as the upper limit. More preferably, it is 98% by weight. Only one (meth) acrylic acid ester may be used, or two or more may be used.

  The (meth) acrylic acid ester is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms (a concept including a cycloalkyl group, an alkyl (cycloalkyl) group, and a (cycloalkyl) alkyl group). It is. Preferably the carbon number of the said alkyl group is 4-18. In addition, (meth) acryl means acryl and / or methacryl, and (meth) acrylate means acrylate and / or methacrylate.

  Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and s-butyl. (Meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isoamyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isode Ru (meth) acrylate, n-dodecyl (meth) acrylate, isomyristyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, pentadecyl (Meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, etc. It is done. Among these, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isobornyl (meth) acrylate are preferable. Only 1 type may be sufficient as the alkyl (meth) acrylate which has a C1-C20 alkyl group, and 2 or more types may be sufficient as it.

  The ethylenically unsaturated monomer preferably further comprises a polar monomer copolymerizable with the (meth) acrylic acid ester. The content of the polar monomer in the ethylenically unsaturated monomer is preferably 0% by weight, more preferably 2% by weight as the lower limit, and preferably 20% by weight, more preferably as the upper limit. 15% by weight. Only one type of polar monomer may be used, or two or more types may be used.

  Examples of polar monomers include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, itaconic acid, maleic acid, fumaric acid Carboxyl group-containing monomers such as acid and crotonic acid; acid anhydride monomers such as maleic anhydride and itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 4-hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethyl Shi Hydroxyl group-containing monomers such as cyclohexyl) methyl (meth) acrylate; amide group-containing monomers such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and hydroxyethyl (meth) acrylamide; It is done.

B-1-2-3. Polymerization initiator The continuous oil phase component preferably contains a polymerization initiator.

  Examples of the polymerization initiator include radical polymerization initiators and redox polymerization initiators. Examples of the radical polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.

  Examples of the thermal polymerization initiator include azo compounds, peroxides, peroxycarbonic acid, peroxycarboxylic acid, potassium persulfate, t-butylperoxyisobutyrate, and 2,2′-azobisisobutyronitrile. .

  Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (for example, Ciba Japan, trade name: Darocur-2959), α-hydroxy- α, α'-dimethylacetophenone (for example, Ciba Japan, trade name: Darocur-1173), methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone (for example, Ciba Japan, trade name) Acetophenone photopolymerization initiators such as Irgacure-651) and 2-hydroxy-2-cyclohexylacetophenone (for example, Ciba Japan, trade name; Irgacure-184); Ketal photopolymerization initiator such as benzyldimethyl ketal Agents; Other halogenated ketones; Acylphosphine oxides (As an example, Ciba Japan Co., Ltd., trade name: Irgacure -819); and the like.

  The polymerization initiator may contain only 1 type and may contain 2 or more types.

  The content of the polymerization initiator is preferably 0.05% by weight, more preferably 0.1% by weight, more preferably 0.1%, and preferably 5.0% as a lower limit with respect to the entire continuous oil phase component. % By weight, more preferably 1.0% by weight. When the content of the polymerization initiator is less than 0.05% by weight based on the entire continuous oil phase component, the amount of unreacted monomer components increases, and the amount of residual monomers in the resulting heat insulating material may increase. . When the content ratio of the polymerization initiator exceeds 5.0% by weight with respect to the entire continuous oil phase component, the mechanical properties of the obtained heat insulating material may be lowered.

  Note that the amount of radicals generated by the photopolymerization initiator varies depending on the type and intensity of light to be irradiated, the irradiation time, the amount of dissolved oxygen in the monomer and solvent mixture, and the like. And when there is much dissolved oxygen, the radical generation amount by a photoinitiator is suppressed, superposition | polymerization does not fully advance and an unreacted substance may increase. Therefore, before the light irradiation, it is preferable that an inert gas such as nitrogen is blown into the reaction system and oxygen is replaced with an inert gas or deaerated by a reduced pressure treatment.

B-1-2-4. Crosslinking agent The continuous oil phase component preferably includes a crosslinking agent.

  Crosslinking agents are typically used to link polymer chains together to build a more three-dimensional molecular structure. The choice of the type and content of the cross-linking agent depends on the structural, mechanical and fluid treatment properties desired for the resulting insulation. The selection of the specific type and content of the cross-linking agent is important in achieving a desirable combination of structural properties, mechanical properties, and fluid treatment properties of the insulation.

  In producing the heat insulating material of the present invention, preferably, at least two kinds of crosslinking agents having different weight average molecular weights are used as the crosslinking agent.

  In producing the heat insulating material of the present invention, the cross-linking agent is more preferably selected from “a polyfunctional (meth) acrylate having a weight average molecular weight of 800 or more, a polyfunctional (meth) acrylamide”, and a polymerization reactive oligomer. “One or more” and “one or more selected from polyfunctional (meth) acrylate and polyfunctional (meth) acrylamide having a weight average molecular weight of 500 or less” are used in combination. Here, the polyfunctional (meth) acrylate is specifically a polyfunctional (meth) acrylate having at least two ethylenically unsaturated groups in one molecule, and the polyfunctional (meth) acrylamide is Specifically, it is polyfunctional (meth) acrylamide having at least two ethylenically unsaturated groups in one molecule.

  Examples of the polyfunctional (meth) acrylate include diacrylates, triacrylates, tetraacrylates, dimethacrylates, trimethacrylates, and tetramethacrylates.

  Examples of the polyfunctional (meth) acrylamide include diacrylamides, triacrylamides, tetraacrylamides, dimethacrylamides, trimethacrylamides, tetramethacrylamides and the like.

  The polyfunctional (meth) acrylate can be derived from, for example, diols, triols, tetraols, bisphenol A and the like. Specifically, for example, 1,10-decanediol, 1,8-octanediol, 1,6 hexanediol, 1,4-butanediol, 1,3-butanediol, 1,4 butane-2-enediol , Ethylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, hydroquinone, catechol, resorcinol, triethylene glycol, polyethylene glycol, sorbitol, polypropylene glycol, polytetramethylene glycol, modified bisphenol A propylene oxide, and the like.

  The polyfunctional (meth) acrylamide can be derived from, for example, corresponding diamines, triamines, tetraamines and the like.

  Examples of the polymerization reactive oligomer include urethane (meth) acrylate, epoxy (meth) acrylate, copolyester (meth) acrylate, oligomer di (meth) acrylate and the like. Preferably, it is hydrophobic urethane (meth) acrylate.

  The weight average molecular weight of the polymerization reactive oligomer is preferably 1500 or more, more preferably 2000 or more. Although the upper limit of the weight average molecular weight of a polymerization reactive oligomer is not specifically limited, For example, Preferably it is 10,000 or less.

  As the cross-linking agent, “one or more selected from polyfunctional (meth) acrylates having a weight average molecular weight of 800 or more, polyfunctional (meth) acrylamides, and polymerization reactive oligomers” and “a weight average molecular weight of 500 or less. When using together with “one or more selected from functional (meth) acrylate and polyfunctional (meth) acrylamide” ”,“ polyfunctional (meth) acrylate having a weight average molecular weight of 800 or more, polyfunctional (meth) acrylamide, and polymerization ” The amount of “one or more selected from reactive oligomers” is preferably 40% by weight as a lower limit with respect to the total amount of the hydrophilic polyurethane polymer and the ethylenically unsaturated monomer in the continuous oil phase component. The upper limit is preferably 100% by weight, and more preferably 80% by weight. The amount of use of “one or more selected from a polyfunctional (meth) acrylate having a weight average molecular weight of 800 or more, a polyfunctional (meth) acrylamide, and a polymerization reactive oligomer” is a hydrophilic polyurethane-based heavy in the continuous oil phase component When the amount is less than 40% by weight based on the total amount of the coalesced and ethylenically unsaturated monomer, the cohesive strength of the resulting heat insulating material may be reduced, and it may be difficult to achieve both toughness and flexibility. . The amount of use of “one or more selected from a polyfunctional (meth) acrylate having a weight average molecular weight of 800 or more, a polyfunctional (meth) acrylamide, and a polymerization reactive oligomer” is a hydrophilic polyurethane-based heavy in the continuous oil phase component When it exceeds 100 weight% with respect to the total amount of a coalescence and an ethylenically unsaturated monomer, the emulsion stability of a W / O type emulsion will fall and there exists a possibility that a desired heat insulating material may not be obtained.

  As the cross-linking agent, “one or more selected from polyfunctional (meth) acrylates having a weight average molecular weight of 800 or more, polyfunctional (meth) acrylamides, and polymerization reactive oligomers” and “a weight average molecular weight of 500 or less. When using together with “one or more selected from functional (meth) acrylate and polyfunctional (meth) acrylamide” ”,“ selected from polyfunctional (meth) acrylate and polyfunctional (meth) acrylamide having a weight average molecular weight of 500 or less ” The amount of “one or more” used is preferably 1% by weight, more preferably 5% as a lower limit with respect to the total amount of the hydrophilic polyurethane polymer and the ethylenically unsaturated monomer in the continuous oil phase component. The upper limit is preferably 30% by weight, and more preferably 20% by weight. Use amount of “one or more selected from polyfunctional (meth) acrylate having a weight average molecular weight of 500 or less and polyfunctional (meth) acrylamide” is a hydrophilic polyurethane polymer and ethylenic unsaturated in a continuous oil phase component When the amount is less than 1% by weight based on the total amount of monomers, the heat resistance is lowered, and the cell structure may be crushed by contraction in the step (IV) of dehydrating the water-containing polymer. Use amount of “one or more selected from polyfunctional (meth) acrylate having a weight average molecular weight of 500 or less and polyfunctional (meth) acrylamide” is a hydrophilic polyurethane polymer and ethylenic unsaturated in a continuous oil phase component When it exceeds 30 weight% with respect to the total amount of a monomer, the toughness of the heat insulating material obtained may fall, and there exists a possibility of showing brittleness.

  The crosslinking agent may contain only 1 type and may contain 2 or more types.

B-1-2-5. Other components in the continuous oil phase component The continuous oil phase component may contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components typically include a catalyst, an antioxidant, a light stabilizer, and an organic solvent. Such other components may be only one kind or two or more kinds.

  Examples of the catalyst include a urethane reaction catalyst. Any appropriate catalyst can be adopted as the urethane reaction catalyst. Specific examples include dibutyltin dilaurate.

  Arbitrary appropriate content rates can be employ | adopted for the content rate of a catalyst according to the target catalytic reaction.

  The catalyst may contain only 1 type and may contain 2 or more types.

  Examples of the antioxidant include a phenol-based antioxidant, a thioether-based antioxidant, and a phosphorus-based antioxidant.

  Arbitrary appropriate content rates can be employ | adopted for the content rate of antioxidant in the range which does not impair the effect of this invention.

  The antioxidant may contain only 1 type and may contain 2 or more types.

  Any appropriate organic solvent can be adopted as the organic solvent as long as the effects of the present invention are not impaired.

  Arbitrary appropriate content rates can be employ | adopted for the content rate of an organic solvent in the range which does not impair the effect of this invention.

  The organic solvent may contain only 1 type and may contain 2 or more types.

  Any appropriate light stabilizer can be adopted as the light stabilizer as long as the effects of the present invention are not impaired.

  Arbitrary appropriate content rates can be employ | adopted for the content rate of a light stabilizer in the range which does not impair the effect of this invention.

  The light stabilizer may contain only 1 type and may contain 2 or more types.

B-2. Step of shaping W / O type emulsion (II)
In the step (II), any appropriate shaping method can be adopted as a method for shaping the W / O type emulsion. For example, there is a method in which a W / O emulsion is continuously supplied onto a traveling belt and shaped into a smooth sheet on the belt. Moreover, the method of apply | coating to one surface of a thermoplastic resin film, and shaping is mentioned.

  In the step (II), as a method of shaping the W / O type emulsion, when adopting a method of coating and shaping on one surface of a thermoplastic resin film, as a method of coating, for example, a roll coater, Examples include a method using a die coater, a knife coater, or the like.

B-3. Polymerizing the shaped W / O emulsion (III)
In the step (III), any appropriate polymerization method can be adopted as a method for polymerizing the shaped W / O emulsion. For example, the belt surface of a belt conveyor is heated by a heating device, and a W / O type emulsion is continuously supplied onto a traveling belt and shaped into a smooth sheet on the belt by heating. A W / O emulsion is continuously supplied onto the running belt, with a method of polymerization and a structure in which the belt surface of the belt conveyor is heated by irradiation of active energy rays, and a smooth sheet is formed on the belt. The method of superposing | polymerizing by irradiation of an active energy ray is mentioned, shaping.

  In the case of polymerization by heating, the polymerization temperature (heating temperature) is preferably 23 ° C., more preferably 50 ° C., still more preferably 70 ° C., particularly preferably 80 ° C. as the lower limit. The upper limit is preferably 90 ° C, and is preferably 150 ° C, more preferably 130 ° C, and even more preferably 110 ° C. When the polymerization temperature is less than 23 ° C., the polymerization takes a long time, and industrial productivity may be reduced. When the polymerization temperature exceeds 150 ° C., the pore diameter of the foam in the heat insulating material to be obtained may be nonuniform, and the strength of the heat insulating material may be reduced. The polymerization temperature need not be constant. For example, the polymerization temperature may be varied in two stages or multiple stages during the polymerization.

  In the case of polymerization by irradiation with active energy rays, examples of the active energy rays include ultraviolet rays, visible rays, and electron beams. The active energy ray is preferably ultraviolet light or visible light, and more preferably visible to ultraviolet light having a wavelength of 200 nm to 800 nm. Since the W / O type emulsion has a strong tendency to scatter light, it is possible to penetrate the W / O type emulsion by using visible to ultraviolet light having a wavelength of 200 nm to 800 nm. Moreover, the photoinitiator which can be activated with a wavelength of 200 nm-800 nm is easy to obtain, and a light source is easy to obtain.

  The wavelength of the active energy ray is preferably 200 nm, more preferably 300 nm as the lower limit value, and preferably 800 nm, more preferably 450 nm as the upper limit value.

  As a typical apparatus used for irradiation of active energy rays, for example, an ultraviolet lamp capable of performing ultraviolet irradiation includes an apparatus having a spectral distribution in a wavelength region of 300 to 400 nm. , Black light (trade name manufactured by Toshiba Lighting & Technology Co., Ltd.), metal halide lamp and the like.

  The illuminance at the time of irradiation with active energy rays can be set to any appropriate illuminance by adjusting the distance from the irradiation device to the irradiation object and the voltage. For example, by the method disclosed in Japanese Patent Application Laid-Open No. 2003-13015, the ultraviolet irradiation in each step is performed in a plurality of stages, thereby making it possible to precisely adjust the adhesive performance.

  In order to prevent the adverse effect of oxygen having an inhibitory action on the ultraviolet rays, for example, a W / O emulsion is applied to one surface of a substrate such as a thermoplastic resin film and then shaped under an inert gas atmosphere. UV rays such as polyethylene terephthalate coated with a release agent such as silicone after passing through a W / O emulsion on one surface of a substrate such as a thermoplastic resin film and shaping, but blocking oxygen It is preferable to carry out by covering the film.

  As the thermoplastic resin film, any appropriate thermoplastic resin film can be adopted as long as it can be formed by coating a W / O emulsion on one surface. Examples of the thermoplastic resin film include plastic films and sheets such as polyester, olefin resin, and polyvinyl chloride. One or both surfaces of the film may be subjected to a peeling treatment.

  The inert gas atmosphere refers to an atmosphere in which oxygen in the light irradiation zone is replaced with an inert gas. Therefore, in the inert gas atmosphere, it is necessary that oxygen is not present as much as possible, and the oxygen concentration is preferably 5000 ppm or less.

B-4. Step of dehydrating the obtained water-containing polymer (IV)
In step (IV), the obtained water-containing polymer is dehydrated. In the water-containing polymer obtained in step (III), the aqueous phase component is present in a dispersed state. By removing the aqueous phase component by dehydration and drying, a foam contained in the heat insulating material of the present invention is obtained. The obtained foam can be used as the heat insulating material of the present invention as it is. Moreover, it can become a heat insulating material of this invention by combining with a base material so that it may mention later.

  Arbitrary appropriate drying methods can be employ | adopted as a dehydration method in process (IV). Examples of such a drying method include vacuum drying, freeze drying, press drying, microwave drying, drying in a heat oven, drying with infrared rays, or a combination of these techniques.

B-5. When the heat insulating material of the present invention contains a base material When the heat insulating material of the present invention contains a base material, as one of the preferred embodiments of the method for producing the heat insulating material of the present invention, a W / O emulsion is used as the base material. By applying heat or irradiation with active energy rays in an inert gas atmosphere or with a UV transparent film coated with a release agent such as silicone, the oxygen is blocked. A form of a heat insulating material having a substrate / foamed layer (foamed) laminated structure is obtained by polymerizing the / O type emulsion to obtain a water-containing polymer and dehydrating the obtained water-containing polymer.

  As another preferred embodiment of the method for producing a heat insulating material of the present invention, two W / O emulsions prepared by applying one surface of an ultraviolet transmissive film coated with a release agent such as silicone are prepared. A base material is laminated on the coating surface of one of the two W / O emulsion coating sheets, and another W / O emulsion coating sheet is coated on the other surface of the laminated base material. In a state where the surfaces are laminated to each other, the W / O emulsion is polymerized by heating or irradiation with active energy rays to form a water-containing polymer, and the resulting water-containing polymer is dehydrated to obtain a foam layer ( The form made into the heat insulating material which has a laminated structure of a foam) / base material / foamed layer (foam) is mentioned.

  Examples of the method of coating the W / O type emulsion on one side of the base material or one surface of the ultraviolet ray transmissive film coated with a release agent such as silicone include a roll coater, a die coater, and a knife coater.

C. Use of heat insulating material The heat insulating material of the present invention can be used for any application that requires heat insulating properties (low thermal conductivity). Such applications include, for example, household or commercial heat generation, heat insulation, and cold insulation equipment; housing equipment, housing systems and housing building materials; household goods; various tanks; electronic equipment and electronic equipment manufacturing equipment; office equipment; Examples include conveying equipment; industrial furnaces; plant piping; and poultry houses and livestock houses. Specific examples of heating, heat insulation, and cold insulation equipment for home or business use include refrigerators, electric pots, rice cookers and rice cookers, vending machines, washing machines, coffee and tea servers, rice cookers, and electric lawn mowers. Can be mentioned. Specific examples of housing equipment, housing systems, and housing building materials include air conditioning equipment, water heaters, bathtubs, unit baths, toilet seats, floor heating, natural refrigerant heat pump water heaters, low-temperature radiation plates, building floors, walls, ceilings and roofs Examples include a heat insulating material for a base, a window frame, a floor mat, a heat insulating panel for an outer wall, a heat insulating box, and a sound insulating heat insulating plate. Specific examples of daily necessities include a cooler box, a warm case for warm plastic bottles and cans, and a water bottle. Specific examples of the various tanks include water heater tanks, hot water toilet tanks, vending machine tanks, fuel cell tanks, automobile tanks, and hydrogen fuel tanks. Specific examples of applications for electronic devices and electronic device manufacturing equipment include various types of batteries such as fuel cells and lithium ion batteries, plasma displays, digital cameras, mobile phones, laptop computers, personal computer monitors, watches, personal digital assistants (PDAs), and mobile phones. Insulates the inside and outside of the chamber of game machines, video cameras, televisions, microwave ovens, back monitors, car navigation system monitors, car audio equipment, home audio equipment, commercial store information monitors, digital information displays, and exposure equipment Chamber material for this purpose. Specific examples of office equipment include copiers, telephones, facsimiles, and printers. Specific examples of applications for transportation and transportation equipment include interior and exterior materials (for example, automotive floor spacers, door pads, tool boxes, dashboards), transportation containers, cold storage vehicles (refrigeration / Refrigerator, body). Specific examples of industrial furnace applications include furnace walls, furnace lids, covers, ceilings, skids of refractory furnaces such as steelmaking, steelmaking, rolling furnaces, etc. A fireproof and heat insulating lining constructed on the post surface and the like can be mentioned. Specific examples of poultry houses and livestock houses include poultry houses, pig houses, cowsheds, stables, and sheepsheds. By using the heat insulating material of the present invention, a very excellent heat insulating effect can be obtained in various applications. Moreover, by using the heat insulating material of the present invention, the amount of heat leakage can be reduced, and as a result, the amount of power consumption can be reduced. Further, for example, in electronic equipment or office equipment use, heat generated from an electronic component can be prevented from being transmitted to an undesired location by being stacked on the electronic component in the equipment. In particular, since the heat insulating material of the present invention has excellent low thermal conductivity even in a very small space, it can be suitably used for applications that require such characteristics.

  Hereinafter, although the present invention is explained based on an example, the present invention is not limited to these. In the examples, normal temperature means 23 ° C., and “parts” and “%” are based on weight unless otherwise specified. In addition, the evaluation items in the examples are as follows.

(1) Molecular weight measurement The weight average molecular weight was determined by GPC (gel permeation chromatography).
Equipment: “HLC-8020” manufactured by Tosoh Corporation
Column: “TSKgel GMH _HR- H (20)” manufactured by Tosoh Corporation
Solvent: Tetrahydrofuran Standard: Polystyrene

(2) Measurement of average pore diameter The obtained heat insulating material (substantially foamed material) was cut in the thickness direction with a microtome cutter and used as a measurement sample. The cut surface of the sample for measurement was photographed with a scanning electron microscope (Hitachi, S-3400N) at 800 to 5000 times. Using the photographed image, measure the pore diameter of an arbitrary range of spherical bubbles, the diameter of a through-hole penetrating between the spherical bubbles of an arbitrary range, and the pore diameter of the surface opening of an arbitrary range. The average hole diameter, the average hole diameter of the through holes, and the average hole diameter of the surface openings were calculated.

(3) Measurement of density Five pieces of the obtained heat insulating material (substantially foam) were cut into a size of 100 mm × 100 mm to form test pieces, and the apparent density was determined by dividing the weight by the volume. The average value of the apparent density obtained was taken as the density of the foam.

(4) Measurement of thermal conductivity It measured according to ASTM-D5470 using the apparatus and test piece as shown in FIG.5 and FIG.6. Specifically, it is as follows.
A test piece (20 mm × 20 mm) was sandwiched between a pair of rods L made of aluminum (A5052, thermal conductivity: 140 W / m · K) formed so as to be a cube having one side of 20 mm. Subsequently, it arrange | positioned between the heat generating body (heater block) H and the heat radiating body (cooling base board comprised so that a cooling water circulates) C so that a pair of rod might become up-down. More specifically, the heating element H is disposed on the upper rod L, and the radiator C is disposed below the rod L on the lower side. Here, the pair of rods L is located between a pair of pressure adjusting screws T that penetrates the heat generator and the heat radiator. Note that a load cell R is disposed between the pressure adjusting screw T and the heating element H, and is configured to measure the pressure when the pressure adjusting screw T is tightened. The pressure applied to the test piece was used. Further, three probes P (diameter 1 mm) of a contact displacement meter were installed so as to penetrate the lower rod L and the test piece from the radiator C side. At this time, the upper end portion of the probe P is in contact with the lower surface of the upper rod L, and the distance between the upper and lower rods L (the thickness of the test piece) can be measured. A temperature sensor D was attached to the heating element H and the upper and lower rods L. Specifically, the temperature sensor D was attached at one place on the heating element H and five places at intervals of 5 mm in the vertical direction of each rod L.
In the measurement, first, the pressure adjusting screw T was tightened, pressure was applied to the test piece, the temperature of the heating element H was set to 80 ° C., and cooling water of 20 ° C. was circulated through the radiator C. Next, after the temperature of the heating element H and the upper and lower rods L is stabilized, the temperature of the upper and lower rods L is measured by each temperature sensor D, and the heat flow passing through the test piece from the thermal conductivity and temperature gradient of the upper and lower rods L While calculating a bundle | flux, the temperature of the interface with the test piece of the upper and lower rod L was calculated. Using these, the thermal conductivity (W / m · K) at the compression rate was calculated.

(5) Measurement of 50% compressive load The obtained heat insulating material (substantially foamed material) was punched out to 25 mm × 25 mm, and then 5 layers were laminated to obtain a measurement sample. Tensilon was used for measurement, and at room temperature, the sample for measurement was compressed in the thickness direction to 50% of the initial thickness at a speed of 10 mm / min, and the maximum value when the thickness was compressed by 50% was measured. . Samples were measured at n = 2, and the average value was 50% compression load.

(6) Measurement of 50% compression load change rate After storing a sample for measurement of 50% compression load in an oven at 100 ° C. for 22 hours or in an oven at 150 ° C. for 22 hours, measure the 50% compression load, The change rate of 50% compression load before and after the heat storage treatment was determined.

(7) Measurement of heating dimensional change rate The obtained heat insulating material (substantially foam) was cut into a size of 100 mm × 100 mm to form a test piece, which was stored in an oven at 125 ° C. for 22 hours, and then JIS- Based on the dimensional stability evaluation at high temperature of K-6767, the dimensional change rate before and after the heat storage treatment was determined.

[Production Example 1]: Preparation of mixed syrup 1 In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 2-ethylhexyl acrylate (manufactured by Toagosei Co., Ltd., hereinafter "2EHA") as an ethylenically unsaturated monomer A monomer solution consisting of 173.2 parts by weight, and 100 parts by weight of Adeka (registered trademark) Pluronic L-62 (molecular weight 2500, manufactured by ADEKA Corporation, polyether polyol) as polyoxyethylene polyoxypropylene glycol, Dibutyltin dilaurate (manufactured by Kishida Chemical Co., Ltd., hereinafter abbreviated as “DBTL”) as a urethane reaction catalyst was added in an amount of 0.014 part by weight, and while stirring, hydrogenated xylylene diisocyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Takenate). 600, hereinafter abbreviated as “HXDI”) 12.4 parts by weight were added dropwise and reacted at 65 ° C. for 4 hours. Let In addition, the usage-amount of the polyisocyanate component and the polyol component was NCO / OH (equivalent ratio) = 1.6. Thereafter, 5.6 parts by weight of 2-hydroxyethyl acrylate (manufactured by Kishida Chemical Co., Ltd., hereinafter abbreviated as “HEA”) was added dropwise and reacted at 65 ° C. for 2 hours to obtain a hydrophilic polyurethane polymer / ethylenically unsaturated monomer. A mixed syrup was obtained. The weight average molecular weight of the obtained hydrophilic polyurethane polymer was 15,000. 27.3 parts by weight of 2EHA, n-butyl acrylate (manufactured by Toagosei Co., Ltd., hereinafter abbreviated as “BA”) with respect to 100 parts by weight of the obtained hydrophilic polyurethane polymer / ethylenically unsaturated monomer mixed syrup 51. 8 parts by weight, 17.4 parts by weight of isobornyl acrylate (for example, Osaka Organic Chemical Industries, Ltd., hereinafter abbreviated as “IBXA”), acrylic acid (for example, manufactured by Toa Gosei Co., Ltd.) as a polar monomer, 10.5 parts by weight of "AA") was added to obtain a hydrophilic polyurethane polymer / ethylenically unsaturated monomer mixed syrup 1.

[Production Example 2]: Preparation of mixed syrup 2 In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 173.2 parts by weight of a monomer solution composed of IBXA as an ethylenically unsaturated monomer, and polyoxyethylene polyoxy While adding 100 parts by weight of Adeka (registered trademark) Pluronic L-62 (molecular weight 2500, manufactured by ADEKA, polyether polyol) as propylene glycol and 0.014 parts by weight of DBTL as a urethane reaction catalyst, while stirring. 12.4 parts by weight of HXDI was added dropwise and reacted at 65 ° C. for 4 hours. In addition, the usage-amount of the polyisocyanate component and the polyol component was NCO / OH (equivalent ratio) = 1.6. Then, 5.6 parts by weight of HEA was added dropwise and reacted at 65 ° C. for 2 hours to obtain a hydrophilic polyurethane polymer / ethylenically unsaturated monomer mixed syrup. The weight average molecular weight of the obtained hydrophilic polyurethane polymer was 15,000. 24.7 parts by weight of 2EHA, 69.3 parts by weight of IBXA, and 10.5 parts by weight of AA as a polar monomer are added to 100 parts by weight of the obtained hydrophilic polyurethane polymer / ethylenically unsaturated monomer mixed syrup. A hydrophilic polyurethane-based polymer / ethylenically unsaturated monomer mixed syrup 2 was obtained.

[Production Example 3]: Preparation of mixed syrup 3 In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 173.2 parts by weight of a monomer solution composed of 2EHA as an ethylenically unsaturated monomer, and polyoxyethylene polyoxy While adding 100 parts by weight of Adeka (registered trademark) Pluronic L-62 (molecular weight 2500, manufactured by ADEKA, polyether polyol) as propylene glycol and 0.014 parts by weight of DBTL as a urethane reaction catalyst, while stirring. 12.4 parts by weight of HXDI was added dropwise and reacted at 65 ° C. for 4 hours. In addition, the usage-amount of the polyisocyanate component and the polyol component was NCO / OH (equivalent ratio) = 1.6. Then, 5.6 parts by weight of HEA was added dropwise and reacted at 65 ° C. for 2 hours to obtain a hydrophilic polyurethane polymer / ethylenically unsaturated monomer mixed syrup. The weight average molecular weight of the obtained hydrophilic polyurethane polymer was 15,000. As a polar monomer, 2EHA is 20.9 parts by weight, IBXA is 3.9 parts by weight, BA is 36.9 parts by weight with respect to 100 parts by weight of the obtained hydrophilic polyurethane polymer / ethylenically unsaturated monomer mixed syrup. 13.5 parts by weight of HEA was added to obtain a hydrophilic polyurethane polymer / ethylenically unsaturated monomer mixed syrup 3.

[Example 1]
To 100 parts by weight of the hydrophilic polyurethane polymer / ethylenically unsaturated monomer mixed syrup 1 obtained in Production Example 1, 1,6-hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester A” -HD-N ") (molecular weight 226) 11.9 parts by weight, synthesized as a reactive oligomer from polytetramethylene glycol (hereinafter abbreviated as" PTMG ") and isophorone diisocyanate (hereinafter abbreviated as" IPDI "). A polyurethane acrylate having both ends of polyurethane treated with HEA and having an ethylenically unsaturated group at both ends (hereinafter abbreviated as “UA”) (molecular weight 3720), 47.7 parts by weight, diphenyl (2,4,6- Trimethylbenzoyl) phosphine oxide (BASF, trade name “Lucirin TPO”) 0.48 parts by weight, hinder 0.95 parts by weight of a phenolic antioxidant (Ciba Japan, trade name “Irganox 1010”) and 2 parts by weight of a light stabilizer (trade name: TINUVIN 123, manufactured by BASF) are mixed uniformly to obtain a continuous oil. A phase component (hereinafter referred to as “oil phase”) was used. On the other hand, 300 parts by weight of ion-exchanged water as an aqueous phase component (hereinafter referred to as “aqueous phase”) with respect to 100 parts by weight of the oil phase is continuously introduced into a stirring mixer that is an emulsifier charged with the oil phase at room temperature. Were added dropwise to prepare a stable W / O emulsion. The weight ratio of the water phase to the oil phase was 75/25.
The obtained W / O emulsion was stored at room temperature for 1 hour, and then applied onto a substrate that had been subjected to a release treatment so that the thickness after light irradiation was 0.5 mm, and was continuously molded. Further, a polyethylene terephthalate film having a thickness of 38 μm and subjected to a release treatment was placed thereon. This sheet was irradiated with ultraviolet light with a light intensity of 5 mW / cm ² (measured with Topcon UVR-T1 having a peak sensitivity maximum wave of 350 nm) using black light (15 W / cm), and a highly hydrous crosslinked polymer having a thickness of 0.5 mm was obtained. Obtained. Next, the top film was peeled off, and the high water content crosslinked polymer was heated at 130 ° C. for 20 minutes to obtain a heat insulating material (1) containing a foam having a thickness of 0.5 mm.
Moreover, the photograph figure of the surface / cross-section SEM photograph which image | photographed the obtained heat insulating material (1) from diagonally was shown in FIG.
The obtained heat insulating material (1) was subjected to the evaluations (2) to (7) above. The results are shown in Table 1.
Moreover, when the heat insulating material obtained was bonded to the outer periphery of the paper cup, hot water of about 90 ° C. was poured, and the paper cup was held by hand through the heat insulating material, it could be held without feeling the heat.

[Example 2]
To 100 parts by weight of the hydrophilic polyurethane polymer / ethylenically unsaturated monomer mixed syrup 1 obtained in Production Example 2, 15.9 parts by weight of 1,6-hexanediol diacrylate as a reactive oligomer, PTMG and 47.7 parts by weight of UA (molecular weight 3720) having ethylenically unsaturated groups at both ends, diphenyl (2,4,6-trimethylbenzoyl) phosphine treated with HEA at both ends of polyurethane synthesized from IPDI Finoxide (BASF, trade name “Lucirin TPO”) 0.48 parts by weight, hindered phenolic antioxidant (Ciba Japan, trade name “Irganox 1010”) 0.95 parts by weight, light stable 2 parts by weight of an agent (manufactured by BASF, trade name: TINUVIN 123) is uniformly mixed to obtain a continuous oil phase component (hereinafter referred to as “oil phase”). To) and the. On the other hand, 300 parts by weight of ion-exchanged water as an aqueous phase component (hereinafter referred to as “aqueous phase”) with respect to 100 parts by weight of the oil phase is continuously introduced into a stirring mixer that is an emulsifier charged with the oil phase at room temperature. Were added dropwise to prepare a stable W / O emulsion. The weight ratio of the water phase to the oil phase was 75/25.
The obtained W / O emulsion was stored at room temperature for 1 hour, and then applied onto a substrate that had been subjected to a release treatment so that the thickness after light irradiation was 0.5 mm, and was continuously molded. Further, a polyethylene terephthalate film having a thickness of 38 μm and subjected to a release treatment was placed thereon. This sheet was irradiated with ultraviolet light with a light intensity of 5 mW / cm ² (measured with Topcon UVR-T1 having a peak sensitivity maximum wave of 350 nm) using black light (15 W / cm), and a highly hydrous crosslinked polymer having a thickness of 0.5 mm was obtained. Obtained. Next, the top film was peeled off, and the high water content crosslinked polymer was heated at 130 ° C. for 20 minutes to obtain a heat insulating material (2) containing a foam having a thickness of 0.5 mm.
The obtained heat insulating material (2) was subjected to the evaluations (2) to (7) above. The results are shown in Table 1.
Further, when the obtained heat insulating material was bonded to the toilet seat, the coldness of the toilet seat was not felt even when sitting on the waist.

Example 3
From PTMG and IPDI, 100 parts by weight of the hydrophilic polyurethane polymer / ethylenically unsaturated monomer mixed syrup 1 obtained in Production Example 3 and 20 parts by weight of 1,6-hexanediol diacrylate as a reactive oligomer 47.7 parts by weight of UA (molecular weight 3720) having ethylenically unsaturated groups at both ends, both ends of the polyurethane to be synthesized treated with HEA, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (BASF, trade name “Lucirin TPO”) 0.49 parts by weight, hindered phenol-based antioxidant (Ciba Japan, trade name “Irganox 1010”) 0.99 parts by weight, light stabilizer ( BASF Co., Ltd., trade name: TINUVIN123) 2.05 parts by weight are uniformly mixed to form a continuous oil phase component (hereinafter “oil phase”). It was referred to as). On the other hand, in an agitation mixer which is an emulsifier in which 566.7 parts by weight of ion-exchanged water as an aqueous phase component (hereinafter referred to as “aqueous phase”) is charged at room temperature with respect to 100 parts by weight of the oil phase. Were continuously added dropwise to prepare a stable W / O emulsion. The weight ratio of the water phase to the oil phase was 85/15.
The obtained W / O emulsion was stored at room temperature for 1 hour, and then applied onto a substrate that had been subjected to a release treatment so that the thickness after light irradiation was 0.5 mm, and was continuously molded. Further, a polyethylene terephthalate film having a thickness of 38 μm and subjected to a release treatment was placed thereon. This sheet was irradiated with ultraviolet light with a light intensity of 5 mW / cm ² (measured with Topcon UVR-T1 having a peak sensitivity maximum wave of 350 nm) using black light (15 W / cm), and a highly hydrous crosslinked polymer having a thickness of 0.5 mm was obtained. Obtained. Next, the top film was peeled off, and the high water content crosslinked polymer was heated at 130 ° C. for 20 minutes to obtain a heat insulating material (3) containing a foam having a thickness of 0.5 mm.
The obtained heat insulating material (3) was subjected to the evaluations (2) to (7) above. The results are shown in Table 1.
Moreover, when the obtained heat insulating material was affixed to the indoor window frame, even if the window frame was touched, the coldness of the window frame was not felt.

  The heat insulating material of the present invention can be suitably used for any application that requires heat insulating properties (low thermal conductivity) in a very small space.

DESCRIPTION OF SYMBOLS 100 Thermal insulation material 10 Foam 10a Foam 10b Foam 20 Base material 30 Base material or peeling film

Claims (6)

Comprising a foam having an open cell structure with through-holes between adjacent spherical cells;
The average pore diameter of the spherical bubbles is less than 20 μm, the average pore diameter of the through-holes is 5 μm or less,
The thermal conductivity measured according to ASTM-D5470 is 0.1 W / m · K or less at a compression rate of less than 5%.
Insulation.   The heat insulating material according to claim 1, wherein a dimensional change rate when stored at 125 ° C for 22 hours is less than ± 5%.   The heat insulating material according to claim 1 or 2, wherein a 50% compression load change rate when stored at 125 ° C for 22 hours is ± 10% or less.   The heat insulating material according to any one of claims 1 to 3, wherein the foam includes a hydrophilic polyurethane-based polymer. The heat insulating material in any one of Claim 1 to 4 whose density of the said foam is 0.5 g / cm < ³ > or less. The heat insulating material according to any one of claims 1 to 5, wherein the 50% compressive load is 50 N / cm ² or less.