JP2005289043A - Damping laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a damping laminate having damping performance excellent enough to reduce a vibration energy such as air propagating noise, solid propagating noise or the like, and capable of keeping the excellent damping performance. <P>SOLUTION: The damping laminate comprises a damping layer (A) and a heat storage layer (X) both being laminated. The damping layer (A) contains a damping resin and has the maximum value of a loss factor (tanδ) of not less than 0.5 measured by dynamic viscoelasticity measurement. The heat storage layer (X) contains a heat storage material, and the phase change temperature of the heat storage material exists in the temperature range of the temperature where the damping layer (A) shows the maximum value of the loss factor (tanδ)±10°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a vibration-damping laminate having excellent vibration-damping performance capable of reducing vibration energy such as air-borne sound and solid-borne sound, and capable of maintaining the excellent vibration-damping performance.

  In recent years, interest in comfortable living spaces has increased, and low vibration and low noise properties are required. Under such circumstances, resin-based vibration damping materials such as rubber and elastomer are those that convert vibration energy into heat energy to attenuate vibrations, such as buildings such as rooftops, floors, partition walls, household appliances, Used for vibration and noise suppression of vehicles, OA equipment, precision equipment, etc.

  In general, a loss factor (tan δ) is given as one means of showing the damping performance of the resin damping material, and it is known that the damping performance is excellent around a temperature at which tan δ shows a maximum value. This tan δ has a correlation with the glass transition temperature (Tg) of the resin, and in order to exhibit the damping performance in a specific temperature range, the Tg of the resin is set so that tan δ becomes the maximum value in the specific temperature range. Setting is important.

  Such a resin-based damping material is a viscoelastic body that receives vibrational energy such as airborne sound and solid-borne sound and converts it into thermal energy by the resin's molecular motion to attenuate vibrations. For example, butyl rubber, polynorbornene rubber, urethane rubber, vinyl chloride rubber and the like are widely used.

  For example, in Patent Document 1, Tg is adjusted by blending resin compositions having different Tg or adding a plasticizer to improve the vibration damping performance in a specific temperature range.

JP-A-7-138439

  However, the resin-based damping material of Patent Document 1 or the like largely depends on the Tg of the resin, and in a temperature region other than the set Tg, the value of tan δ tends to be small and the damping performance is poor. There was a problem.

  The present invention has been made in view of the above points, and has excellent vibration damping performance in a target temperature range, and can maintain excellent vibration damping performance even if the ambient temperature changes. The present invention provides a vibration-damping laminate.

  As a result of intensive studies to solve the above problems, a damping layer (A) made of a damping resin having a maximum loss coefficient (tan δ) of 0.5 or more determined by dynamic viscoelasticity measurement, and The heat storage layer (X) containing the heat storage material (x-1) having the phase change temperature is laminated in the temperature range of plus or minus 10 ° C. of the temperature indicating the maximum value of the loss coefficient (tan δ) in the damping layer (A). As a result, it was found that excellent vibration damping performance and excellent vibration damping performance can be maintained, and the present invention has been completed.

（Ｒ^１は水素（−Ｈ）またはメチル基（−ＣＨ_３）、Ｘはエステル結合（−ＣＯＯ−）、エーテル結合（−Ｏ−）またはアミド結合（−ＣＯＮＨ−）、Ｒ^２は炭素数１２から３６の直鎖アルキル基）
６．蓄熱層（Ｘ）が、蓄熱材（ｘ−１）を多孔体に充填したものであることを特徴とする１．から３．のいずれかに記載の制振性積層体。
７．蓄熱層（Ｘ）が、蓄熱材（ｘ−１）と、粘性調整剤及び／または熱伝導性物質を多孔体に充填したものであることを特徴とする６．に記載の制振性積層体。
８．多孔体が、反応性官能基を含有する化合物（ｘ−２）と該反応性官能基と反応可能な反応性官能基を含有する化合物（ｘ−３）との反応により形成されたものであることを特徴とする６．または７．に記載の制振性積層体。
９．蓄熱層（Ｘ）が、蓄熱材（ｘ−１）、反応性官能基を含有する化合物（ｘ−２）と該反応性官能基と反応可能な反応性官能基を含有する化合物（ｘ−３）を均一に混合し、（ｘ−２）成分と（ｘ−３）成分を反応させて得られるものであることを特徴とする１．から３．のいずれかに記載の制振性積層体。
１０．蓄熱層（Ｘ）が、蓄熱材（ｘ−１）と、粘性調整剤及び／または熱伝導性物質、反応性官能基を含有する化合物（ｘ−２）と該反応性官能基と反応可能な反応性官能基を含有する化合物（ｘ−３）を均一に混合し、（ｘ−２）成分と（ｘ−３）成分を反応させて得られるものであることを特徴とする１．から３．のいずれかに記載の制振性積層体。
１１．蓄熱層が、蓄熱材（ｘ−１）、親水親油バランス（ＨＬＢ値）が１０以上の非イオン性界面活性剤、反応性官能基を含有する化合物（ｘ−２）と該反応性官能基と反応可能な反応性官能基を含有する化合物（ｘ−３）を混合し、蓄熱材をコロイド状に分散させ、（ｘ−２）成分と（ｘ−３）成分を反応させて得られるものであることを特徴とする１．から３．のいずれかに記載の制振性積層体。
１２．蓄熱層が、蓄熱材（ｘ−１）と、粘性調整剤及び／または熱伝導性物質、親水親油バランス（ＨＬＢ値）が１０以上の非イオン性界面活性剤、反応性官能基を含有する化合物（ｘ−２）と該反応性官能基と反応可能な反応性官能基を含有する化合物（ｘ−３）を混合し、蓄熱材をコロイド状に分散させ、（ｘ−２）成分と（ｘ−３）成分を反応させて得られるものであることを特徴とする１．から３．のいずれかに記載の制振性積層体。
１３．蓄熱材（ｘ−１）が有機潜熱蓄熱材であることを特徴とする１．から１２．のいずれかに記載の制振性積層体。 That is, the present invention has the following characteristics.
1. The damping layer (A) and the heat storage layer (X) are laminated,
The damping layer (A) contains a damping resin, and the maximum value of the loss coefficient (tan δ) determined by dynamic viscoelasticity measurement is 0.5 or more,
The heat storage layer (X) contains the heat storage material (x-1), and the phase change temperature of the heat storage material (x-1) is a temperature at which the loss coefficient (tan δ) in the damping layer (A) is the maximum value. A vibration-damping laminate having a temperature range of plus or minus 10 ° C.
2. Damping resin
(A) Hydroxyl group having a hydroxyl value of 50 to 150 mgKOH / g, polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.0 or less, and number average molecular weight (Mn) of 1000 to 15000 Compound,
(B) a polyisocyanate compound,
It is characterized by containing 1. The vibration-damping laminate described in 1.
3. Damping resin
(A) (a-1) Copolymer obtained by polymerizing a mixture of a (meth) acrylic monomer containing a hydroxyl group and (a-2) a polymerizable unsaturated monomer other than (a-1) It has a hydroxyl value of 50 to 150 mgKOH / g, a polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.0 or less, and a number average molecular weight (Mn) of 1000 to 15000. Copolymer,
(B) a polyisocyanate compound,
It is characterized by containing 1. Or 2. The vibration-damping laminate described in 1.
4). The heat storage layer (X) contains a heat storage capsule in which the heat storage material (x-1) is encapsulated. To 3. A vibration-damping laminate according to any one of the above.
5). In the heat storage capsule encapsulating the heat storage material (x-1), the capsule wall of the capsule is formed from a polymer obtained by polymerizing a monomer mainly composed of a crystalline vinyl monomer represented by the following chemical formula 1. 3. It is characterized by the above. The vibration-damping laminate described in 1.
(Chemical formula 1)

(R ¹ is hydrogen (—H) or a methyl group (—CH ₃ ), X is an ester bond (—COO—), an ether bond (—O—) or an amide bond (—CONH—), and R ² is 12 carbon atoms. To 36 linear alkyl groups)
6). The heat storage layer (X) is a porous material filled with a heat storage material (x-1). To 3. A vibration-damping laminate according to any one of the above.
7). 5. The heat storage layer (X) is a porous material filled with a heat storage material (x-1), a viscosity modifier and / or a heat conductive material. The vibration-damping laminate described in 1.
8). The porous body is formed by a reaction between a compound (x-2) containing a reactive functional group and a compound (x-3) containing a reactive functional group capable of reacting with the reactive functional group. 5. It is characterized by this. Or 7. The vibration-damping laminate described in 1.
9. The heat storage layer (X) is a heat storage material (x-1), a compound (x-2) containing a reactive functional group and a compound (x-3) containing a reactive functional group capable of reacting with the reactive functional group. ) Are mixed uniformly, and (x-2) component and (x-3) component are made to react. To 3. A vibration-damping laminate according to any one of the above.
10. The heat storage layer (X) can react with the heat storage material (x-1), the viscosity modifier and / or the heat conductive material, the compound (x-2) containing a reactive functional group, and the reactive functional group. 1. It is obtained by uniformly mixing the compound (x-3) containing a reactive functional group and reacting the component (x-2) and the component (x-3). To 3. A vibration-damping laminate according to any one of the above.
11. The heat storage layer is a heat storage material (x-1), a hydrophilic / lipophilic balance (HLB value) of 10 or more, a nonionic surfactant, a compound (x-2) containing a reactive functional group, and the reactive functional group Obtained by mixing the compound (x-3) containing a reactive functional group capable of reacting with the component, dispersing the heat storage material in a colloidal form, and reacting the component (x-2) and the component (x-3) It is characterized by the following. To 3. A vibration-damping laminate according to any one of the above.
12 The heat storage layer contains a heat storage material (x-1), a viscosity modifier and / or a heat conductive substance, a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, and a reactive functional group. The compound (x-2) and the compound (x-3) containing a reactive functional group capable of reacting with the reactive functional group are mixed, the heat storage material is dispersed in a colloidal form, and the component (x-2) and ( x-3) It is obtained by reacting the components. To 3. A vibration-damping laminate according to any one of the above.
13. 1. The heat storage material (x-1) is an organic latent heat storage material. To 12. A vibration-damping laminate according to any one of the above.

  The vibration-damping laminate of the present invention has excellent vibration-damping performance in a target temperature range, and can maintain excellent vibration-damping performance even when the ambient temperature changes.

  Hereinafter, it explains in detail with the best form for carrying out the present invention.

  The vibration damping laminate of the present invention is a laminate of a damping layer (hereinafter also referred to as “(A) layer”) and a heat storage layer (hereinafter also referred to as “(X) layer”).

  The layer (A) contains a vibration-damping resin, and the maximum value of the loss coefficient (tan δ) determined by dynamic viscoelasticity measurement is 0.5 or more (preferably 0.8 or more, preferably 1.0 That is the above. When the maximum value of the loss coefficient (tan δ) is 0.5 or more, excellent vibration damping performance can be exhibited.

  Further, the (X) layer contains a heat storage material, and the phase change temperature (melting point) of the heat storage material has a temperature that shows the maximum value of the loss coefficient (tan δ) in the layer (A) plus or minus 10 ° C. (preferably plus or minus) 5 ° C., more preferably plus or minus 3 ° C.). Even if the ambient temperature changes due to the presence of the phase change temperature (melting point) of the heat storage material in such a temperature range, the temperature control layer of the present invention has a temperature range that exhibits excellent damping performance for a long time. Can be maintained, and excellent vibration control performance can be maintained over a long period of time.

  The loss factor (tan δ) is measured in a compression mode using a forced vibration type viscoelastic device (Rheogel E-4000 manufactured by UBM Co., Ltd.). The temperature rises at 2.0 ° C./min and the frequency is 10 Hz. The measurement is performed under the condition of a strain of 0.1 mm.

-Damping layer ((A) layer)-
In the layer (A) in the present invention, the damping value having a maximum loss coefficient (tan δ) determined by dynamic viscoelasticity measurement is 0.5 or more (preferably 0.8 or more, more preferably 1.0 or more). The resin is not particularly limited as long as it is formed from a functional resin.

  The vibration damping resin of the present invention is not particularly limited. For example, polyvinyl chloride, polyethylene, chlorinated polyethylene, polypropylene, ethylene / vinyl acetate copolymer, polymethyl methacrylate, polyvinylidene fluoride, polyisoprene, polystyrene, Examples thereof include styrene / butadiene / acrylonitrile copolymers, styrene / acrylonitrile copolymers, polyurethanes, polyesters, polyolefins, and the like. Among these, one or two or more can be used in combination. Further, rubbers such as acrylonitrile / butadiene copolymer rubber (NBR), styrene / butadiene copolymer rubber (SBR), butadiene rubber (BR), natural rubber (NR), and isoprene rubber (IR) may be contained.

In the present invention, in consideration of mechanical properties, it is preferable to use a polyurethane-based vibration-damping resin as the vibration-damping resin.
As the polyurethane-based vibration-damping resin, for example, a compound containing a hydroxyl group (hereinafter also referred to as “(a) component”) and a polyisocyanate compound (hereinafter also referred to as “(b) component”) are reacted. Is obtained. Such a reaction-curable polyurethane-based vibration-damping resin of component (a) and component (b) is advantageous in that tan δ can be easily set and excellent mechanical properties can be obtained.

When the component (a) and the component (b) are used as the vibration-damping resin, the component (a) has a hydroxyl value of 50 to 150 mgKOH / g, polydispersity (weight average molecular weight (Mw) / number average molecular weight ( It is preferable to use a hydroxyl group-containing compound having a Mn)) of 2.0 or less and a number average molecular weight (Mn) of 1000 to 15000.
The component (a) having a specific hydroxyl value, polydispersity, and number average molecular weight can exhibit excellent vibration damping performance.

  The hydroxyl value of the component (a) is preferably 50 to 150 mgKOH / g, more preferably 60 to 130 mgKOH / g. When the hydroxyl value is 50 to 150 mgKOH / g, a vibration damping material exhibiting excellent vibration damping performance and mechanical properties can be obtained. When it is smaller than 50 mgKOH / g, the curability becomes insufficient and the mechanical properties may be inferior. When it is larger than 150 mgKOH / g, the crosslinking density of the cured product becomes too high, and the vibration damping performance may be lowered.

  The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the component (a) is preferably 2.0 or less, more preferably 1.8 or less. When the polydispersity is 2.0 or less, the molecular weight distribution of the cured product becomes narrow, and excellent vibration damping performance is exhibited. When the polydispersity is greater than 2.0, there is a tendency for the vibration damping to decrease.

  (A) The number average molecular weight (Mn) of a component becomes like this. Preferably it is 1000-15000, More preferably, it is 2000-10000. If the number average molecular weight (Mn) is 1000 to 15000, the viscosity is relatively low, and the curing reaction with the component (b) proceeds uniformly, so that the vibration damping performance of the cured product is improved. When the number average molecular weight (Mn) is smaller than 1000, mechanical properties such as shear strength may be inferior. When it is larger than 15000, the viscosity becomes high, the crosslinking reaction tends to proceed non-uniformly, and the vibration damping performance of the cured product may be lowered.

  The polydispersity and the number average molecular weight are calculated in terms of polystyrene using gel permeation chromatography (GPC) (LC-6A, manufactured by Shimadzu Corporation) using tetrahydrofuran as a solvent.

  Such a component (a) is obtained, for example, by polymerizing one or more of (meth) acrylic monomers containing a hydroxyl group (hereinafter also referred to as “component (a-1)”). Can do. In addition, a polymerizable unsaturated monomer other than the component (a-1) and the component (a-1) (hereinafter also referred to as “component (a-2)”) can be copolymerized to obtain.

  Examples of the component (a-1) include 2-hydroxy (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate, glycerin mono Examples thereof include mono- or poly (meth) acrylates of polyhydric alcohols such as (meth) acrylate and pentaerythritol tri (meth) acrylate.

As the component (a-2), for example, unsaturated carboxylic acids such as (meth) acrylic acid and itaconic acid;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid 2 Unsaturated carboxylic acid esters such as ethoxyethyl, 2-isobornyl (meth) acrylate and benzyl (meth) acrylate;
Unsaturated polycarboxylic acids such as maleic anhydride;
Epoxy group-containing unsaturated compounds such as glycidyl (meth) acrylate;
Nitrile group-containing unsaturated compounds such as (meth) acrylonitrile;
Amino group-containing unsaturated compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether;
Amide group-containing unsaturated compounds such as (meth) acrylamide and N-isopropylacrylamide;
Aliphatic vinyl monomers such as ethylene, propylene and isobutylene;
Aromatic hydrocarbon vinyl monomers such as styrene and α-methylstyrene;
Dienes such as butadiene and isoprene;
Vinyl esters such as vinyl acetate and vinyl propionate;
Etc.

  The component (a) of the present invention is preferably obtained by copolymerizing the component (a-1) and the component (a-2). By copolymerizing the component (a-1) and the component (a-2), the amount of hydroxyl group per molecule can be controlled, and the crosslinking reaction with the component (b) can be controlled.

  The ratio of the component (a-1) to the component (a-2) is preferably 100 to 500 parts by weight of the component (a-2) with respect to 100 parts by weight of the component (a-1). By being in such a range, more excellent vibration suppression capability is exhibited. When the amount of the component (a-2) is less than 100 parts by weight, the number of hydroxyl groups per molecule increases, so that the crosslinking density with the component (b) increases and the vibration damping ability may be inferior. When the amount of the component (a-2) is more than 500 parts by weight, the number of hydroxyl groups per molecule decreases, so that the crosslink density with the component (b) decreases and the mechanical properties may be inferior.

  The manufacturing method of (a) component is not specifically limited, It can manufacture by a well-known method. For example, it can be produced by solution polymerization, bulk polymerization, suspension polymerization, oxidation-reduction polymerization, photopolymerization or the like, and can be produced by multistage polymerization as necessary. In particular, continuous bulk polymerization is preferably performed at a high temperature of 150 to 300 ° C., and in such a production method, a copolymer having a low molecular weight and a narrow molecular weight distribution can be obtained as compared with solution polymerization. The solvent content can be reduced, which is preferable.

  The initiator is not particularly limited, and known ones can be used. For example, azobisisobutyronitrile and its hydrochloride; organic peroxides such as cumene hydroperoxide and t-butyl hydroperoxide : Redox initiators in combination of these persulfates or peroxides with metal ions such as iron ions and reducing agents such as sodium sulfoxylate, formaldehyde, sodium pyrosulfite, and L-ascorbic acid. The amount of these used is not particularly limited, but may be about 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer mixture.

  Examples of the solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, and ethylene glycol. Ethylene glycols such as monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, propylene glycols such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, n- Methyl pyrrolidone, acetone, methyl ethyl ketone, methyl isobuty Ketones such as ketones, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as cyclohexane, isoparaffin, cyclohexanone and mineral spirits, esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, etc. A mixture thereof may be mentioned. The amount of the solvent used may be about 0 to 1000 parts by weight with respect to 100 parts by weight of the monomer mixture.

The component (b) is a polyisocyanate compound. The polyisocyanate compound may be any one that can be cured by reacting with the component (a).
Examples of such component (b) include 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XDI), tolylene diisocyanate, hexamethylene diisocyanate (HMDI), and isophorone diisocyanate (IPDI). , Derivatized isocyanate monomers such as hydrogenated XDI and hydrogenated MDI by allophanatization, biuretization, dimerization (uretidioneization), trimerization (isocyanurate), adduct formation, carbodiimidization reaction, and the like Can be used. Of these components (b), aliphatic polyisocyanate compounds that are derivatives of HMDI, IPDI, hydrogenated XDI, hydrogenated MDI, and the like are preferred.
In the present invention, it is desirable to use the component (b) having a low solvent content, and a solvent-free polyisocyanate is preferred.

The mixing ratio of the component (b) and the component (a) is not particularly limited, but is preferably 0.2 to 2.0, more preferably 0.7 to 1.3 in terms of an NCO / OH equivalent ratio.
By being in such a range, more excellent vibration damping performance and mechanical properties can be exhibited. If it is outside such a range, the crosslinking density becomes insufficient and the mechanical properties tend to be inferior.

Furthermore, the vibration-damping resin composition of the present invention comprises (A) component ((a-1) component, (a-2) component), (b) component various compositions, NCO / OH equivalent ratio, hydroxyl value, etc. Is set appropriately, the maximum value in a specific temperature region of the loss coefficient (tan δ) obtained by dynamic viscoelasticity measurement can be set.
In the present invention, when used in a normal temperature region, the maximum value of tan δ may be in a temperature region of 0 to 50 ° C.

When the component (a) and the component (b) described above are used as the vibration-damping resin, it is preferable to form the layer (A) using a curing aid. The curing aid has an effect of promoting the curing reaction of the component (a) and the component (b).
Examples of the curing aid include amines such as triethylamine, triethylenediamine, tetramethylbutanediamine, dimethylaminoethanol, dimer diamine, and dimer acid polyamidoamine;
Tin carboxylates such as butyltin dilaurate, dibutyltin diacetate, tin octate, tin octylate;
Metal carboxylates such as iron octylate, cobalt octylate, manganese octylate, zinc octylate, iron octylate, cobalt octylate, manganese octylate, zinc octylate;
Carboxylates such as dibutyltin thiocarboxylate, dioctyltin thiocarboxylate, tributylmethylammonium acetate, trioctylmethylammonium acetate;
Aluminum compounds such as aluminum trisacetylacetate can be used. Among these, it is particularly preferable to use tin carboxylates. The mixing ratio of the curing aid is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the solid content of the component (A).

  In addition to the above components, the layer (A) of the present invention preferably further contains (c) fine particles having a primary particle diameter of 100 nm or less (preferably 5 to 30 nm) (hereinafter referred to as “component (c)”). By containing the component (c), the contact interface between the vibration-damping resin and the component (c) is remarkably large, and the thermal energy divergence due to friction between the two becomes large. The loss factor (tan δ) can be maintained, and excellent vibration damping can be maintained.

Examples of the component (c) include metal oxides such as titanium oxide, zinc oxide and iron oxide, porous powders such as silica gel and zeolite, clay minerals such as mica, kaolin, perlite and montmorillonite, calcium carbonate, graphite, Inorganic powders such as talc and barium sulfate, and other organic powders can be used. Of these, metal oxides are preferably used in the present invention. The shape of the component (c) is not particularly limited, and flakes, spheres, flakes, needles, and the like can be used.
The component (c) used in the present invention can also be obtained by various pulverization methods and dispersion methods, for example. In such atomization treatment, for example, a ball mill, a bead mill, a sand mill, an attritor, a three roll, a basket mill, a disperser, a coball mill, a pearl mill, a nanomizer, and the like can be used.
The primary particle diameter in the present invention is measured by observation with a transmission electron microscope.

  The mixing ratio of the component (c) is preferably 20 to 300 parts by weight, more preferably 30 to 100 parts by weight with respect to 100 parts by weight of the solid content of the component (a). When the mixing amount is in such a range, a higher loss factor can be maintained in a temperature range higher than the glass transition temperature of the resin.

  In the layer (A) of the present invention, in addition to the above, the following additives may be added within a range that does not impair the effects of the present invention. Examples of such additives include solvents, pigments, dyes, aggregates, matting agents, fibers, thickeners, leveling agents, plasticizers, antifungal agents, dispersants, antifoaming agents, pH adjusters, An ultraviolet absorber, antioxidant, etc. are mentioned.

-Thermal storage layer ((X) layer)-
The (X) layer of the present invention contains a heat storage material (hereinafter also referred to as “(x-1) component”), and the phase change temperature (melting point) of the heat storage material is a loss coefficient (tan δ) in the damping resin. ) Is not particularly limited as long as it exists in the temperature range of plus or minus 10 ° C. (preferably plus or minus 5 ° C., more preferably plus or minus 3 ° C.).
Such an (X) layer has an effect of relaxing the temperature change of the (A) layer and maintaining excellent vibration damping performance in a target temperature range.

  In the present invention, it is preferable to use a latent heat storage material such as an inorganic latent heat storage material or an organic latent heat storage material as the heat storage material.

  Examples of the inorganic latent heat storage material include hydrates such as sodium sulfate decahydrate, sodium carbonate decahydrate, sodium hydrogen phosphate dodecahydrate, sodium thiosulfate pentahydrate, calcium chloride hexahydrate, etc. Examples include salts.

  Examples of the organic latent heat storage material include aliphatic hydrocarbons, long chain alcohols, long chain fatty acids, long chain fatty acid esters, polyether compounds, aromatic hydrocarbons, fatty acid triglycerides, and the like. Among these heat storage materials, 1 Species or two or more can be used.

  In the present invention, an organic latent heat storage material can be particularly preferably used. Organic latent heat storage materials are preferred because they have a high boiling point and are less likely to volatilize, so there is almost no volume change (thinning) during the heat storage layer molding and the heat storage performance lasts for a long time. Furthermore, when an organic latent heat storage material is used, it is easy to set the phase change temperature according to the application. For example, by mixing two or more organic latent heat storage materials having different phase change temperatures, the phase change temperature can be easily set. Can be set.

  As the aliphatic hydrocarbon, for example, an aliphatic hydrocarbon having 8 to 36 carbon atoms can be used. Specifically, n-decane (melting point −30 ° C.), n-undecane (melting point −25 ° C.), n-dodecane (melting point -8 ° C), n-tridecane (melting point -5 ° C), n-tetradecane (melting point 8 ° C), pentadecane (melting point 10 ° C), n-hexadecane (melting point 17 ° C), n-heptadecane (melting point) 22 ° C), n-octadecane (melting point 28 ° C), n-nonadecane (melting point 32 ° C), icosane (melting point 36 ° C), docosan (melting point 44 ° C), and a mixture thereof. Etc.

  As the long chain alcohol, for example, a long chain alcohol having 8 to 36 carbon atoms can be used. Specifically, capryl alcohol (melting point: 7 ° C.), lauryl alcohol (melting point: 24 ° C.), myristyl alcohol (melting point: 38 ° C.) ), Stearyl alcohol (melting point: 58 ° C.), and the like.

  As the long chain fatty acid, for example, a long chain fatty acid having 8 to 36 carbon atoms can be used. Specifically, octanoic acid (melting point: 17 ° C.), decanoic acid (melting point: 32 ° C.), dodecanoic acid (melting point: 44 ° C.). ), Fatty acids such as tetradecanoic acid (melting point 50 ° C.), octadecanoic acid (melting point 70 ° C.), hexadecanoic acid (melting point 63 ° C.), and the like.

  As the long-chain fatty acid ester, for example, a long-chain fatty acid ester having 8 to 36 carbon atoms can be used. Specifically, methyl laurate (melting point 5 ° C.), methyl myristate (melting point 19 ° C.), palmitic acid Examples include methyl (melting point: 32 ° C.), methyl stearate (melting point: 38 ° C.), butyl stearate (melting point: 25 ° C.), and methyl arachidate (melting point: 45 ° C.).

  Examples of the polyether compound include diethylene glycol, triethylene glycol, tetraethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, polypropylene glycol, polyethylene glycol, polypropylene glycol diacrylate, and ethyl ethylene glycol.

  Examples of the fatty acid triglyceride include vegetable oils such as coconut oil and palm kernel oil, and medium-chain fatty acid triglycerides and long-chain fatty acid triglycerides that are refined processed products thereof.

  In the present invention, as the component (x-1), in particular, an aliphatic hydrocarbon having 8 to 36 carbon atoms, a long chain alcohol having 8 to 36 carbon atoms, a long chain fatty acid having 8 to 36 carbon atoms, and 8 to 36 carbon atoms. It is preferable to use a long chain fatty acid ester, and it is more preferable to use an aliphatic hydrocarbon having 8 to 36 carbon atoms and a long chain fatty acid ester having 8 to 36 carbon atoms. Among these, it is preferable to use a long-chain fatty acid ester having 15 to 22 carbon atoms and an aliphatic hydrocarbon having 15 to 22 carbon atoms. Such a heat storage material has a high latent heat amount and has a phase change temperature ( Since it has a melting point), it is easy to use for various purposes.

  Such heat storage materials may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to use an organic latent heat storage material in that the melting point can be freely designed. In particular, it is preferable to use a heat storage material having a melting point of 0 ° C. or higher and lower than 50 ° C.

When mixing and using 2 or more types of (x-1) components, it is preferable to use a compatibilizing agent. By using a compatibilizing agent, the compatibility between the components (x-1) (particularly, the organic latent heat storage material) can be improved.
Examples of the compatibilizing agent include fatty acid triglycerides, nonionic surfactants having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 (preferably 1 or more and 5 or less), and one or two of these. The above can be mixed and used.

  As described above, the fatty acid triglyceride is a substance that is also used as an organic latent heat storage material. Such fatty acid triglycerides are particularly preferable because they can further improve the compatibility between the organic latent heat storage materials and have excellent heat storage properties. Examples of the fatty acid triglyceride include vegetable oils such as coconut oil and palm kernel oil, and fatty acid triglycerides such as caprylic acid triglyceride, palmitic acid triglyceride, and stearic acid triglyceride, which are refined processed products thereof. More than seeds can be used.

  Examples of the nonionic surfactant having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 (preferably 1 or more and 5 or less) include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, Sorbitan sesquioleate, sorbitan trioleate, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, glycerol monostearate, glycerol monostearate, glycerol monooleate, stearic acid Examples include glyceryl, glyceryl caprylate, sorbitan stearate, sorbitan oleate, sorbitan sesquioleate, and coconut fatty acid sorbitan.

  The mixing ratio of the compatibilizer and the component (x-1) is usually 0.1 to 20 parts by weight (preferably 0.5 to 10 parts by weight) with respect to 100 parts by weight of the component (x-1). Part by weight).

  Furthermore, a viscosity modifier, a heat conductive substance, etc. can be mixed and used for (x-1) component.

Examples of the viscosity modifier include clay minerals, and it is particularly preferable to use an organically treated layered clay mineral (hereinafter also referred to as “organically treated clay mineral”).
By mixing the component (x-1) and the organically treated clay mineral, the component (x-1) enters between the layers of the organically treated clay mineral, so that the heat storage material is easily held between the layers of the organically treated clay mineral.
Furthermore, since the organically treated clay mineral is organically treated, the component (x-1) easily enters between the layers of the organically treated clay mineral, and the component (x-1) is retained between the layers of the organically treated clay mineral. It has a structure that is easy to do.

  By mixing such an organically treated clay mineral and the component (x-1), as a result, the viscosity of the component (x-1) is increased, and the component (x-1) is supported in the heat storage layer. It is stably supported and can be held. As will be described later, even when the component (x-1) is encapsulated or filled into a porous body, the component (x-1) can be more stably supported and held in the capsule or porous body. .

  Furthermore, when the organic latent heat storage material is used as the component (x-1), the organically treated clay mineral hardly reacts with the organic latent heat storage material and affects the melting point and other various physical properties of the organic latent heat storage material. Therefore, it is preferable because the performance as a heat storage material can be efficiently exhibited and the phase change temperature (melting point) can be easily set.

  The distance between the bottom surfaces of the organically treated clay mineral is preferably about 13.0 to 30.0 mm (preferably 15.0 to 26.0 mm). By being in such a range, the component (x-1) can easily enter between layers of the organically treated clay mineral. The bottom surface interval is a value calculated from (001) reflection in the X-ray diffraction pattern.

The viscosity at the time of mixing the (x-1) component and the organically treated clay mineral may be about 0.5 to 20.0 Pa · s. The viscosity is a value measured using a B-type rotational viscometer at a temperature of 23 ° C. and a relative humidity of 50% RH.
Moreover, what is necessary is just to set the TI value at the time of (x-1) component and organic processing clay mineral mixing to about 4.0-9.0. In addition, TI value is a value calculated | required by following formula 1 using a B-type rotational viscometer.
TI value = η1 / η2 (Formula 1)
(However, η1: Viscosity at 2 rpm (Pa · s: guide value for the second rotation), η2: Viscosity at 20 rpm (Pa · s: Guide value for the fourth rotation))

  By setting such a viscosity and TI value, the (x-1) component is easily carried in the heat storage layer, and the (x-1) component carried in the heat storage layer is easily held. Even when the component (x-1) is encapsulated or filled in a porous body, the component (x-1) can be stably supported and held in the capsule or porous body. Therefore, it is possible to prevent the heat storage material from leaking to the outside of the heat storage layer, and to obtain a heat storage layer that is more excellent in heat storage property and more excellent in workability and workability.

  Examples of the organically treated clay mineral include smectite, vermiculite, kaolinite, allophane, mica, talc, halloysite, and sepiolite. In addition, swellable fluorine mica, swellable synthetic mica, and the like can be used.

Examples of the organic treatment include ion exchange (intercalation) of a cation existing between layers of a layered clay mineral with a long-chain alkylammonium ion or the like.
In the present invention, smectite and vermiculite are particularly preferably used because they are easily organically treated. Furthermore, among the smectites, montmorillonite is particularly preferably used, and in the present invention, organically treated montmorillonite can be particularly preferably used.

Specifically, as an organically treated montmorillonite,
Hojun Co., Ltd., Esben C, Esben E, Esben W, Esben P, Esben WX, Esven NX, Esven NZ, Esven N-400, Organite, Organite D, Organite T (trade name)
TIXOGEL MP, TIXOGEL VP, TIXOGEL VP, TIXOGEL MP, TIXOGEL EZ 100, MP 100, TIXOGEL UN, TIXOGEL DS, TIXOGEL VP-A, TIXOGEL VP-A, TIXOGEL VP-A, TIXOGEL VP-A )
BENTONE 34, 38, 52, 500, 1000, 128, 27, SD-1, SD-3 (trade names) manufactured by Elementis Japan
Etc.

  The mixing ratio of the organically treated layered clay mineral and the (x-1) component is usually 0.5 to 50 parts by weight (preferably 1 to 30 parts by weight, based on 100 parts by weight of the (x-1) component, More preferably, it may be about 3 to 15 parts by weight.

  Furthermore, a heat conductive substance can also be mixed with (x-1) component. By mixing the heat conductive substance, the movement of heat can be made smooth, the thermal efficiency of the heat storage material can be improved, and more excellent heat storage performance can be obtained.

  Examples of the thermally conductive material include metals such as copper, iron, zinc, beryllium, magnesium, cobalt, nickel, titanium, zirconium, molybdenum, tungsten, boron, aluminum, gallium, silicon, germanium, tin, and alloys thereof. Or metal oxides containing these metals, metal nitrides, metal carbides, metal phosphides and other metal compounds, and scaly graphite, massive graphite, earth graphite, fibrous graphite, etc. One kind or a mixture of two or more kinds can be used.

The thermal conductivity of the thermally conductive material is preferably 1 W / (m · K) or more, more preferably 3 W / (m · K) or more, and further preferably 5 W / (m · K) or more. By mixing a heat conductive material having such a heat conductivity, the heat efficiency of the heat storage material can be improved more efficiently.
Moreover, it is preferable to use a heat conductive substance as microparticles | fine-particles, and it is preferable that an average particle diameter is 1-100 micrometers, Furthermore, it is preferable that it is 5-50 micrometers.

  The mixing ratio of the thermally conductive substance and the component (x-1) is usually 5 parts by weight to 200 parts by weight (preferably 10 parts by weight to 80 parts by weight, more preferably 100 parts by weight of the component (x-1). 20 parts by weight to 60 parts by weight).

In the present invention, such a component (x-1) can be enclosed in a film as it is to form a heat storage layer, or the component (x-1) encapsulated or the component (x-1) What filled the porous body can also be used for a thermal storage layer.
In the present invention, in particular, an encapsulated component (x-1) or a material filled with a porous material (x-1) can be suitably used for a heat storage layer. , (X-1) component can be prevented from leaking or exuding.

As a method (laminating method) in which the (x-1) component is encapsulated in the film as it is, even if the (x-1) component is directly encapsulated in the laminate film, the (x-1) component is gelled with a gelling agent. You may enclose it. In the present invention, a gel-treated product can be suitably used from the viewpoint of shape stability.
In the present invention, the component (x-1) (preferably a latent heat storage material) laminated by such a lamination method can be used as a heat storage layer. Moreover, you may use the 2 or more types of thing which laminated the heat storage material from which melting | fusing point differs.

  The material and shape of the laminate film are not particularly limited. For example, organic materials such as polyethylene, polypropylene, nylon, polyester, polyethylene terephthalate, vinylidene chloride, ethylene / vinyl acetate copolymer, aluminum, gold, silver, copper, chromium , Zinc, titanium, nickel, cobalt, etc. or a metal such as an alloy thereof, silicon oxide, titanium oxide, indium oxide, metal oxides such as aluminum oxide, etc. Can be used.

  In the present invention, in particular, in terms of thermal efficiency, heat resistance, and film strength, 10.0 W / (m · K) or more (preferably 20.0 W / (m · K) or more, more preferably 100 W / (m · K). It is preferable to use a film containing a metal or metal oxide having a thermal conductivity of In the present invention, it is particularly preferable to use aluminum as a material having a thermal conductivity of 10.0 W / (m · K) or more.

As a method for encapsulating the component (x-1), a chemical production method such as an interfacial polymerization method, an in-situ polymerization method, a double orifice method, a physicochemical production method such as a coacervation method, a submerged drying method, or the like. Is available. The size and shape of the capsule of the heat storage capsule thus obtained are not particularly limited. From the viewpoint of handling and filling rate, dry spherical capsules are desirable.
In the present invention, the component (x-1) (preferably a latent heat storage material) encapsulated by such an encapsulation method can be used for the heat storage layer.

  For example, as a method of encapsulating the component (x-1) by the interfacial polymerization method, it may be encapsulated by a known method, but the emulsion polymerization method is performed by mixing the component (x-1) and the monomer shown below. Then, by polymerizing the monomer by a known polymerization method such as a suspension polymerization method, the heat storage material can be enclosed in a capsule having the polymer of the monomer as a capsule wall.

Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl (meth) acrylate. , T-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate and the like containing a lower alkyl group (Meth) acrylic monomers;
Higher alkyl group-containing (meth) acrylic monomers such as lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate;

Carboxyl group-containing (meth) acrylic monomers such as (meth) acrylic acid;
(Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxymethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid- Hydroxyl group-containing monomers such as 2-hydroxybutyl, 4-hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate;

Aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, N-tbutylamino Ethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate Amine-containing (meth) acrylic monomers such as N, N-dimethylaminopropyl (meth) acrylate and N, N-diethylaminopropyl (meth) acrylate;
(Meth) acrylamide, ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-cyclopropyl ( (Meth) acrylamide, N- (meth) acryloylpyrrolidine, N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N-methyl Amide-containing (meth) acrylic monomers such as -N-n-propyl (meth) acrylamide;

Glycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, (meth) acrylic acid-ε-caprolactone modified glycidyl, (meth) acrylic acid-β -Epoxy group-containing (meth) acrylic monomers such as methylglycidyl;
Nitrile group-containing (meth) acrylic monomers such as acrylonitrile and methacrylonitrile;
Diacetone (meth) acrylate, diacetone acrylamide, acrolein, vinyl methyl ketone, acetonyl acrylate, diacetone methacrylamide, vinyl ethyl ketone, vinyl isobutyl ketone, acryloxyalkylpropanals, methacryloxyalkylpropanals, 2-hydroxy Carbonyl group-containing monomers such as propyl acrylate acetyl acetate and butanediol acrylate acetyl acetate;

Isocyanate group-containing monomers such as methacryloyl isocyanate;
Hydrazino group-containing monomers such as propylene-1,3-dihydrazine and butylene-1,4-dihydrazine;
Oxazoline group-containing monomers such as 2-vinyl-2-oxazoline and 2-isopropenyl-2-oxazoline;
Di (meth) acrylate such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, bisphenol A type di (meth) acrylate, divinylbenzene, N, N′-methylenebisacrylamide (Meth) acrylic monomers;
Alkoxysilyl group-containing monomers such as (meth) acrylic acid trimethoxysilylpropyl and (meth) acrylic acid triethoxysilylpropyl;
Hydrolyzable silyl group-containing monomers such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ- (meth) acrylopropyltrimethoxysilane;
Methylol group-containing monomers such as N-methylol (meth) acrylamide;

Aromatic hydrocarbon monomers such as styrene, methylstyrene, chlorostyrene, vinyltoluene;
Sulfonic acid-containing monomers such as styrene sulfonic acid and vinyl sulfonic acid;
Vinyl ester vinyl monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate;
Vinylidene halide monomers such as vinylidene fluoride;
Vinyl ether vinyl monomers such as lauryl vinyl ether, myristyl vinyl ether, palmityl vinyl ether, stearyl vinyl ether;
Non-vinyl monomers such as melamine are listed.

  When an organic latent heat storage material is used as the heat storage material, it is preferable to use a monomer mainly composed of a crystalline vinyl monomer represented by the following chemical formula 1 as the monomer.

（Ｒ^１は水素（−Ｈ）またはメチル基（−ＣＨ_３）、Ｘはエステル結合（−ＣＯＯ−）、エーテル結合（−Ｏ−）またはアミド結合（−ＣＯＮＨ−）、Ｒ^２は炭素数１２から３６（好ましくは炭素数が１２から３０、さらに好ましくは炭素数が１４から２２）の直鎖アルキル基） (Chemical formula 1)

(R ¹ is hydrogen (—H) or a methyl group (—CH ₃ ), X is an ester bond (—COO—), an ether bond (—O—) or an amide bond (—CONH—), and R ² is 12 carbon atoms. To 36 (preferably a linear alkyl group having 12 to 30 carbon atoms, more preferably 14 to 22 carbon atoms)

Examples of such crystalline vinyl monomers include higher alkyl groups (meth) such as lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate. Acrylic monomers;
Vinyl ester vinyl monomers such as vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate;
Vinyl ether vinyl monomers such as lauryl vinyl ether, myristyl vinyl ether, palmityl vinyl ether, stearyl vinyl ether;
Etc.

  A heat storage capsule encapsulated with such a monomer can also prevent cracking and shape change of the heat storage layer due to volume shrinkage due to phase change of the heat storage material (particularly change from liquid to solid).

  When encapsulated using such a crystalline vinyl monomer, the capsule wall of the heat storage capsule is hardly plasticized by the organic latent heat storage material, and the capsules are not easily fused and aggregated. In addition, since a vinyl-based monomer is used, there is flexibility with respect to force, and when the capsule is kneaded and stirred, the organic latent heat storage material is less likely to leak without crushing the capsule wall, which is preferable.

  Further, as the crystalline vinyl monomer, a crystalline vinyl monomer having a linear alkyl group having 12 to 36 carbon atoms (preferably having 12 to 30 carbon atoms, more preferably 15 to 22 carbon atoms) is used. Excellent compatibility with organic latent heat storage materials. Therefore, a high content of organic latent heat storage material can be included in the capsule, and excellent heat storage properties can be exhibited.

  The content of the crystalline vinyl monomer is not particularly limited as long as the effect of the present invention is not impaired, and is 50% by weight or more, further 70% by weight or more based on the total amount of monomers constituting the capsule wall. Is preferred.

  Furthermore, the crystallization temperature of the capsule wall obtained by polymerizing the above monomer containing a crystalline vinyl monomer may be appropriately set according to the intended use, but is usually 25 to 90 ° C, more preferably 30 to 70 ° C. Preferably there is. Such a crystallization temperature is preferable because the effects of the present invention can be obtained at a practical level. If the crystallization temperature is too low, the capsule may soften at room temperature and the capsules may be fused and aggregated.

  The crystallization temperature is a value measured with a differential scanning calorimeter (DSC220CU: manufactured by Seiko Instruments Inc.) at a heating rate of 10 ° C./min.

  In the present invention, the method of encapsulating the latent heat storage material includes, for example, mixing the latent heat storage material and the above monomer, emulsion polymerization, miniemulsion polymerization, microemulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, seed polymerization, seed polymerization. By polymerizing the monomer by a method such as dispersion polymerization, feed polymerization, suspension polymerization, or the like, a heat storage capsule using a polymer of the monomer as the latent heat storage material as a capsule wall can be produced. In such an encapsulation method, in addition to the latent heat storage material and monomer, known initiators, emulsifiers, dispersants, solvents, polymerization inhibitors, polymerization inhibitors, buffering agents, cross-linking agents, pH adjusters, chain transfer agents Etc. can also be mixed.

As the emulsifier, anionic emulsifier, cationic emulsifier, nonionic emulsifier, amphoteric emulsifier, nonionic emulsifier and the like are not particularly limited and can be used.
For example, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylsulfate, fatty acid salts, rosinates, alkyl sulfates, alkylsulfosuccinates, α-olefin sulfonates, alkylnaphthalenesulfonates, polyoxyethylene Anionic emulsifiers such as alkyl (aryl) sulfate esters,
Quaternary ammonium salts such as lauryl trialkyl ammonium salts, stearyl trialkyl ammonium salts, trialkyl benzyl ammonium salts, primary to tertiary amine salts, lauryl pyridinium salts, benzalkonium salts, benzethonium salts, or Cationic surfactants such as laurylamine acetate,
C1-C20 alkanol, phenol, naphthol, bisphenols, C1-C20 alkylphenol, C1-C20 alkyl naphthol, polyoxyethylene (propylene) glycol, ethylene oxide and / or propylene such as aliphatic amine Nonionic surfactants such as oxide adducts,
Examples include amphoteric surfactants such as carboxybetaine type, sulfobetaine type, aminocarboxylic acid type, and imidazoline derivative type.
In the present invention, it is particularly preferable to use a nonionic surfactant and / or an anionic emulsifier.

  Examples of the initiator include persulfate initiators such as ammonium persulfate, potassium persulfate, and sodium persulfate, 2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis [2- (2-imidazoline) -2-yl) propane] dihydrochloride, azo initiators such as 2,2′-azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, dialkyl peroxides such as decanoyl peroxide, t-butyl Peroxyesters such as peroxybenzoate, organic peroxide initiators such as cumene hydroperoxide, paramentane hydroperoxide, hydroperoxide such as t-butyl hydroperoxide, hydrogen peroxide, redox initiator, photopolymerization An initiator, a reactive initiator, etc. can be used.

For example, when an organic latent heat storage material is used as the heat storage material, as a method of encapsulating the organic latent heat storage material, in particular,
(1) A step of mixing a monomer having a crystalline vinyl monomer represented by Chemical Formula 1 as a main component with an organic latent heat storage material or the like and performing emulsion polymerization at a temperature higher than the crystallization temperature of the polymer of the monomer. ,
(2) It is preferable to encapsulate after the polymerization by a step of cooling to a temperature lower than the crystallization temperature of the polymer.

In such a production method, a polymer obtained by polymerizing monomers forms the outermost wall of the capsule, and a heat storage capsule in which an organic latent heat storage material is included in the capsule can be easily obtained by a general emulsion polymerization method. It is characteristic that it can be manufactured. In particular, the crystalline vinyl monomer has excellent compatibility with the organic latent heat storage material, the crystalline vinyl monomer and the organic latent heat storage material can be uniformly mixed before the emulsion polymerization, and the capsule obtained after the emulsion polymerization has a high content. The organic latent heat storage material can be included, and a capsule having excellent heat storage properties can be manufactured.
In the emulsion polymerization, it is essential to carry out the emulsion polymerization at a temperature higher than the crystallization temperature of the polymer obtained by polymerizing the monomer. By emulsion polymerization at such a temperature, an amorphous polymer (capsule wall) is formed during the polymerization, and the organic latent heat storage material is easily encapsulated in the capsule. Furthermore, after the polymerization, the polymer is phase-changed by cooling to a temperature lower than the crystallization temperature of the polymer to form a capsule wall which is the outermost wall of the capsule, and the encapsulated organic latent heat A heat storage capsule can be obtained in which the heat storage material does not leak from the capsule.
With such a phase change mechanism, it is possible to obtain a heat storage capsule in which the organic latent heat storage material does not leak from the capsule even though the organic latent heat storage material with a high content is included in the capsule. Further, such a heat storage capsule is not particularly limited as long as the outermost wall is a polymer obtained by polymerizing monomers, and the capsule may be a core-shell shape in which the organic latent heat storage material is a core and the polymer is a shell. It may be a porous shape in which a large number of organic latent heat storage materials are dispersed, or a gel shape.

Specifically, in the first step, by using a crystalline vinyl monomer, the capsule wall is hardly plasticized by the organic latent heat storage material, and the capsules are not easily fused and aggregated. In addition, since a vinyl monomer is used, it is more flexible than melamine and the like, and when the capsule is kneaded and stirred, the capsule wall is not crushed and the organic latent heat storage material does not leak. Therefore, heat storage capsules are easy to handle when dispersed in a solvent such as water, and are easy to recover and easy to handle when used as a solid fine powder.
Moreover, since the crystalline vinyl monomer which has a C12-C36 linear alkyl group is used, it is excellent in compatibility with an organic latent heat storage material. Therefore, a high content of organic latent heat storage material can be included in the capsule, and excellent heat storage properties can be exhibited.

The second step (2) is characterized by cooling to a temperature lower than the crystallization temperature of the polymer. By cooling to such a temperature, the polymer that forms the capsule wall that is the outermost wall is phase-changed and crystallized, and the encapsulated organic latent heat storage material is obtained without leaking from the capsule. be able to.
The cooling method is not particularly limited, but a known cooling device or a cooling substance may be used, and depending on the crystallization temperature, if the crystallization temperature is higher than room temperature, natural cooling is performed at room temperature. You can also.

The heat storage capsule thus obtained can be used as a heat storage capsule dispersion, or the heat storage capsule can be taken out of the emulsion liquid and used as a solid fine powder.
When using a heat storage capsule as a solid fine powder, it is preferable to collect | recover at a temperature lower than the crystallization temperature of a polymer as a 3rd process. The recovery process in the present invention includes a separation process, a drying process, a classification process, and the like, and a solid fine powder capsule is obtained by such a recovery process. In the present invention, by collecting at a temperature lower than the crystallization temperature of the polymer, the polymer can be recovered while maintaining the crystallinity, the organic latent heat storage material does not leak from the capsule, and the capsule wall It is also possible to prevent the capsules from being fused and agglomerated without breaking. Therefore, it is easy to collect the capsule as a solid fine powder, and the solid fine powder can be obtained in a high yield. As the recovery step, a known method may be adopted as long as the temperature is lower than the crystallization temperature of the polymer.
Moreover, the obtained capsule solid fine powder can be used again by being dispersed in a solvent such as water.

The encapsulated heat storage capsule can contain the latent heat storage material at a high content. Specifically, it can be encapsulated in an amount of usually 30% by weight or more, further 50% by weight or more with respect to the total amount of the heat storage capsule. By being such content, the outstanding thermal storage property can also be shown. In addition, since the capsule wall of the heat storage capsule is crystalline, the capsule wall is hardly plasticized by the organic latent heat storage material included in the capsule, and fusion / aggregation of the capsules can be prevented.
Furthermore, the capsule wall itself formed from the crystalline vinyl monomer used in the present invention has a heat storage property. Therefore, more excellent heat storage property can be shown by the heat storage property of the organic latent heat storage material and the heat storage property of the capsule wall.

  When the encapsulated heat storage capsule is used as a heat storage layer, for example, the heat storage capsule can be encapsulated in the above-described film as it is, or a molded product of a slurry in which the heat storage capsule and the binder are kneaded is enclosed in the film. In addition, it can be manufactured by a method of impregnating various materials by a dipping method, a reduced pressure / pressure injection method, or a combination of these.

  For example, as a method of encapsulating the heat storage capsule as it is in the film, a film in which the heat storage capsule is dispersed in a solvent such as water or a solid fine powder of the heat storage capsule may be enclosed in the film.

Moreover, what is necessary is just to form using the well-known thing as a method of forming the slurry which knead | mixed the heat storage capsule and binder.
Examples of such binders include acrylic resin, silicon resin, polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, polycarbonate resin, fluororesin, vinyl acetate resin, acrylic / acetic acid Solvent soluble types such as vinyl resin, acrylic / urethane resin, acrylic / silicone resin, silicon-modified acrylic resin, ethylene / vinyl acetate / versaic acid vinyl ester resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS resin, AS resin Synthetic rubber such as resin, NAD type resin, water soluble resin, water dispersion type resin, solventless type resin, chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, butadiene rubber Organic binder such as
Examples include inorganic binders such as Portland cement, blast furnace cement, silica cement, fly ash cement, white cement, calcined gypsum, colloidal silica, and water-soluble alkali metal silicates. Use one or more of these. Can do.

  In the present invention, it is particularly preferable to use an organic binder. Among the organic binders, either a one-component type or a two-component type can be used, but a two-component type is more preferable. The use of the two-component type is preferable because the reaction proceeds quickly, a high-strength molded product is formed, and a molded product in which the heat storage capsules are uniformly dispersed is easily obtained.

  As the two-component type, for example, hydroxyl group and isocyanate group, hydroxyl group and carboxyl group, hydroxyl group and imide group, hydroxyl group and aldehyde group, epoxy group and amino group, epoxy group and carboxyl group, carboxyl group and carbodiimide group, Examples include those utilizing a crosslinking reaction such as a carboxyl group and an oxazoline group, a carbonyl group and a hydrazide group, and a carboxyl group and an aziridine group. In particular, it is preferable to use a crosslinking reaction between a hydroxyl group and an isocyanate group because the reaction proceeds quickly and a molded product in which the heat storage capsules are more uniformly dispersed is easily obtained.

  In addition to the binder, the slurry includes a solvent, a pigment, an aggregate, a viscosity modifier, a buffer, a dispersant, an antifoaming agent, a plasticizer, an antiseptic, an antifungal agent, an antialgae, a flame retardant, Various additives such as a leveling agent, an anti-settling agent, an anti-sagging agent, and a dehydrating agent can be kneaded.

  In the formation of such a molded product, such a slurry may be formed into a sheet by a known method, or may be formed by enclosing the slurry in the aforementioned film. In the present invention, since a heat storage capsule having a specific capsule wall is used, the capsule wall can be efficiently dispersed in the slurry without being crushed and without being fused or agglomerated between the capsules during formation. Further, a molded product having excellent heat storage properties, and further a heat storage layer can be easily produced.

Further, in the method of impregnation by the dipping method, the reduced pressure / pressure injection method or the like, the material shown below may be impregnated with the heat storage capsule.
Examples of materials include inorganic materials such as concrete, gypsum board, mortar, and slate board,
Synthetic fibers such as glass fiber, pulp fiber, polyethylene fiber, polypropylene fiber, vinylon fiber, tetron fiber, polyester fiber, cellulose fiber, nylon fiber, natural fiber such as cotton, cotton, asbestos, hemp, palm, cork, kenaf, etc. Fiber material,
Acrylic resin, silicone resin, polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, polycarbonate resin, fluororesin, vinyl acetate resin, acrylic / vinyl acetate resin, acrylic / urethane resin, acrylic / urethane resin Silicone resin, silicon-modified acrylic resin, ethylene / vinyl acetate / versaic acid vinyl ester resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS resin, AS resin, chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methacryl Organic materials such as acid-methyl-butadiene rubber, synthetic rubber such as butadiene rubber,
Wood materials such as pine, lawan, beech, hinoki and plywood, and other papers, synthetic papers, ceramic papers and the like can be mentioned, and one or more of these can be used.

  In the present invention, in particular, when encapsulated using a crystalline vinyl monomer, the capsule wall is not crushed, and the capsules are not fused or aggregated, so that they are dispersed in a solvent such as water. Even when used as a solid fine powder or as a slurry, a heat storage layer having excellent heat storage properties can be easily produced.

  The content of the heat storage capsule in the heat storage layer is preferably 10% by weight or more, more preferably 20% by weight or more and 70% by weight or less with respect to the total amount of the heat storage layer. By being in such a range, it can have the outstanding heat storage property.

  The porous material filled with the heat storage material is not particularly limited as long as the heat storage material is supported and held on the porous material. In the case where the porous body is filled with such a heat storage material, since the heat storage material is subdivided in the pores of the porous body, the heat conduction between the heat storage material and the heat storage material is delayed, and the solid-liquid of the heat storage material This is preferable because the change is suppressed and the heat storage effect is sustained.

The shape of the porous body is not particularly limited as long as the heat storage material can be supported and held, and examples thereof include those having a shape such as a particle aggregation type porous body, a sponge type porous body, and a three-dimensional stitch structure type porous body. In the present invention, in particular, a three-dimensional stitch structure type porous body is preferable because the heat storage material is more easily supported and held.
Moreover, when the thermal conductivity of the porous body component is low (specifically, 0.15 W / (m · K) or less), it is preferable because the thermal conduction is further delayed and the heat storage effect is further sustained.

  As the porous body, an inorganic porous body, an organic porous body, and the like can be used without particular limitation, but an organic porous body is preferably used from the viewpoint that the heat storage material is more easily supported and held. Furthermore, the organic porous body can also prevent cracking and shape change of the heat storage layer due to volume shrinkage due to phase change of the heat storage material (particularly, change from liquid to solid).

  Examples of the resin component that forms such an organic porous material include acrylic resin, silicon resin, polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, polycarbonate resin, fluororesin, and acetic acid. Solvents such as vinyl resin, acrylic / vinyl acetate resin, acrylic / urethane resin, acrylic / silicone resin, silicon-modified acrylic resin, ethylene / vinyl acetate / veova resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS resin, AS resin, etc. Soluble type, NAD type, water soluble type, water dispersion type, solventless type, etc., or synthetic rubber such as chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, butadiene rubber Of these, among these Or more can be used species or two or.

  Further, in the present invention, among the resin components, either one liquid type or two liquid type can be used, but the two liquid type is more preferable. For example, a compound containing a reactive functional group (hereinafter referred to as “(x-2) component”) and a compound containing a reactive functional group capable of reacting with the reactive functional group (hereinafter referred to as “(x-3) A two-component type consisting of “component”) is preferably used.

  Such reactive functional group combinations include hydroxyl group and isocyanate group, hydroxyl group and carboxyl group, hydroxyl group and imide group, hydroxyl group and aldehyde group, epoxy group and amino group, epoxy group and carboxyl group, carboxyl group. Group and carbodiimide group, carboxyl group and oxazoline group, carbonyl group and hydrazide group, carboxyl group and aziridine group, and the like.

Examples of the compound containing a hydroxyl group include:
A hydroxyl group-containing monomer;
Polyhydric alcohols;
Polyester polyol, acrylic polyol, polycarbonate polyol, polyolefin polyol, polyether polyol, polycaprolactone polyol, polytetramethylene glycol polyol, polybutadiene polyol, polyoxypropylene polyol, polyoxypropylene ethylene polyol, epoxy polyol, alkyd polyol, fluorine-containing polyol, Polyols such as silicon-containing polyols;
Cellulose and / or derivatives thereof, polysaccharides such as amylose;
Etc.

  In the present invention, it is particularly preferable to use one or more selected from polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, celluloses and derivatives thereof, and by using such a compound containing a hydroxyl group, In addition, it can be suitably used because it forms a well-crosslinked structure, has good compatibility with the heat storage material, and easily suppresses leakage of the heat storage material from the porous body.

  Specifically, examples of the hydroxyl group-containing monomer include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxymethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) ) -3-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono ( And (meth) acrylate.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,3-tetra Methylenediol, 1,4-tetramethylenediol, 1,6-hexanediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, trimethylpentanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, cyclohexanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexamethylenediol, 3-methyl-1 , 5-pentamethylenediol, 2 4-diethyl-1,5-pentamethylenediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, metaxylene glycol, paraxylene glycol, bishydroxyethoxybenzene, bishydroxyethyl terephthalate Glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, cyclohexanedimethanol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol and sorbitol) Etc.), pentaerythritol, dipentaerythritol, 2-methylolpropanediol, ethoxylated trimethylolpropane and the like.

  Examples of the polyester polyol include a condensation polymerization product of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymerization product of a cyclic ester (lactone); a reaction with three components of a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. Thing etc. are mentioned.

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, maleic anhydride, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid;
Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid;
Examples include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic anhydride, terephthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, aromatic dicarboxylic acid such as trimellitic acid, and the like.

In the ring-opening polymer of the cyclic ester, examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.
In the reaction product of the three types of components, those exemplified above can be used as the polyhydric alcohol, polycarboxylic acid, and cyclic ester.

In the present invention, the polyester polyol is particularly preferably a condensation polymerization product of a polyhydric alcohol and a polycarboxylic acid. For example, as the polyhydric alcohol, 2,4-diethyl-1,5-pentamethylenediol, 3-methyl It is preferable to use adipic acid or the like as the polyvalent carboxylic acid such as -1,5-pentamethylenediol and 2-butyl-2-ethyl-1,3-propanediol.
The manufacturing method of polyester polyol can be performed by a conventional method, and a known curing agent, curing catalyst or the like may be used as necessary.

  The acrylic polyol can be obtained, for example, by homopolymerizing or copolymerizing an acrylic monomer having one or more hydroxyl groups in one molecule, or by copolymerizing another copolymerizable monomer. it can.

As an acrylic monomer having one or more hydroxyl groups in one molecule, for example,
(Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxymethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid- (Meth) acrylic acid esters such as 2-hydroxybutyl and (meth) acrylic acid-4-hydroxybutyl (meth) acrylic acid monoesters of triols such as glycerin and trimethylolpropane;
Monoethers of the above (meth) acrylic acid esters and polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol;
Adducts of glycidyl (meth) acrylate with monobasic acids such as acetic acid, propionic acid, p-tert-butylbenzoic acid;
An adduct obtained by ring-opening polymerization of the (meth) acrylic acid ester and a lactone such as ε-caprolactam or γ-valerolactone;
Can be obtained by homopolymerization or copolymerization thereof.

As other copolymerizable monomers,
Carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, salicylic acid, cinnamic acid;

  Aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, (meth) acrylic Acid-N-methylaminoethyl, (meth) acrylic acid-Nt-butylaminoethyl, (meth) acrylic acid-N, N-dimethylaminoethyl, (meth) acrylic acid-N, N-dimethylaminopropyl, (Meth) acrylic acid-N, N-diethylaminoethyl, (meth) acrylic acid-N, N-dimethylaminopropyl, (meth) acrylic acid-N, N-diethylaminopropyl, N- [2- (meth) acryloyloxy Ethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine, N- [ -(Meth) acryloyloxyethyl] morpholine, 4- [N, N-dimethylamino] styrene, 4- [N, N-diethylamino] styrene, 2-vinylpyridine, 4-vinylpyridine and other amino group-containing monomers ;

  (Meth) acrylic acid glycidyl, diglycidyl fumarate, (meth) acrylic acid-3,4-epoxycyclohexyl, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, (meth) acrylic acid-ε-caprolactone-modified glycidyl, An epoxy group-containing monomer such as (meth) acrylic acid-β-methylglycidyl;

  (Meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N-monoalkyl (meth) acrylamide, N-isobutoxymethylacrylamide, N, N-dialkyl (meth) acrylamide, 2- (dimethylamino) ) Amide group-containing monomers such as ethyl (methacrylate), N- [3- (dimethylamino) propyl] (meth) acrylamide and vinylamide;

Alkoxysilyl group-containing monomers such as (meth) acrylic acid trimethoxysilylpropyl and (meth) acrylic acid triethoxysilylpropyl;
Hydrolyzable silyl group-containing monomers such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ- (meth) acrylopropyltrimethoxysilane;
Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Methylol group-containing monomers such as N-methylol (meth) acrylamide;
Oxazoline group-containing monomers such as vinyloxazoline and 2-propenyl 2-oxazoline;

Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-t-butyl , (Meth) acrylic acid-sec-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid Octyl, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, trifluoroethyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, (meta ) Octyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Dodecenyl acid, Otadecyl (meth) acrylate, Cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, Phenyl (meth) acrylate, Isobornyl (meth) acrylate, Benzyl (meth) acrylate (Meth) acrylate monomers such as 2-phenylethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and 4-methoxybutyl (meth) acrylate;

Vinylidene halide monomers such as vinylidene fluoride;
Aromatic vinyl monomers such as styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, vinylanisole, vinylnaphthalene, divinylbenzene;
Other monomers such as ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ether, vinyl ketone, silicone macromer;
Etc., and one or more of these can be used.

  The polymerization method is not particularly limited, and a known block polymerization, suspension polymerization, solution polymerization, dispersion polymerization, emulsion polymerization, oxidation-reduction polymerization, etc. may be used, and an initiator, a chain transfer agent, or the like, if necessary. These additives may be added. For example, the monomer component can be obtained by solution polymerization in the presence of a known radical polymerization initiator such as a peroxide or an azo compound.

  Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.

  In the ring-opening polymer of the cyclic carbonate, examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like.

  In addition, the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule | numerator, and the terminal is a hydroxyl group, and may have an ester bond with a carbonate bond.

  The polyolefin polyol is a polyol having an olefin as a component of the skeleton (or main chain) of the polymer or copolymer and having at least two hydroxyl groups in the molecule (particularly at the terminal), and having a number average molecular weight of 500 or more. Can be used. The olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, an α-olefin such as ethylene or propylene), or an olefin having a carbon-carbon double bond at a position other than the terminal. (For example, isobutene) may be used, and diene (for example, butadiene, isoprene, etc.) may be used.

  Examples of the polyether polyol include monomers such as an ethylene oxide-propylene oxide copolymer in addition to a polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol monoalkyl ether, and polypropylene glycol monoalkyl ether. Examples include (alkylene oxide-other alkylene oxide) copolymers containing a plurality of alkylene oxides as components.

  The hydroxyl value of such a polyol is not particularly limited, but may be about 20 to 150 KOHmg / g (preferably 25 to 120 KOHmg / g, more preferably 30 to 80 KOHmg / g).

  The molecular weight of the polyol is not particularly limited, but is preferably 500 to 10,000, and more preferably 1000 to 4000. If it is such molecular weight, the bridge | crosslinking structure which can suppress the leakage of a thermal storage material can be obtained by the combination with the compound containing an isocyanate group, the compound containing a carboxyl group, etc. If the molecular weight is too small, the heat storage material may easily leak. If the molecular weight is too large, the heat storage material may not be sufficiently retained.

  Cellulose and / or derivatives thereof include cellulose acetates such as cellulose, cellulose acetate, cellulose diacetate, and cellulose triacetate, and celluloses such as methyl cellulose, ethyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, and cellulose nitrate. Examples include esters, cellulose ethers such as ethyl cellulose, benzyl cellulose, cyanoethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, and the like.

Cellulose and / or derivatives thereof have a hydroxyl group, but a portion of the hydroxyl group is preferably substituted with an alkoxyl group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.). .
Specifically, the substitution degree is preferably 1.8 to 2.8, more preferably 2.2 to 2.6. The degree of substitution means a ratio in which three hydroxyl groups present in the glycolose unit constituting cellulose are substituted with alkoxyl groups and the like, and the degree of substitution is 3 when 100% substitution is performed.
By controlling the degree of substitution in such a range, the interaction with the heat storage material can be improved, and the heat storage material can be retained in the porous body for a long period of time.
When the degree of substitution is less than 1.8, the interaction with the heat storage material may be reduced, and the heat storage material may not be sufficiently retained in the porous body. On the other hand, when the ratio is larger than 2.8, the hydroxyl group in cellulose is decreased, and a three-dimensional crosslinked structure having sufficient strength may not be obtained.

  The molecular weight of cellulose and / or a derivative thereof is not particularly limited, but is preferably 1000 to 30000, and more preferably 5000 to 20000. If it is such molecular weight, the bridge | crosslinking structure which can suppress the leakage of a thermal storage material most can be obtained. If the molecular weight is too small, the heat storage material may easily leak. If the molecular weight is too large, the heat storage material may not be sufficiently retained.

  Examples of the compound containing an isocyanate group include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate. (HMDI), 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1, 5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl capro Over DOO, lysine diisocyanate - DOO, dimer acid diisocyanate, aliphatic diisocyanates such as norbornene diisocyanate;

1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl- 2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate (IPDI), norbornane diisocyanate, dicyclohexylmethane diisocyanate Alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate and hydrogenated xylylene diisocyanate;

m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4, 4′-diphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4′-diisocyanate, 2, 2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'- Diiso Aneto, dianisidine diisocyanate, aromatic diisocyanates such as tetramethylene diisocyanate;

1,3-xylylene diisocyanate (XDI), 1,4-xylylene diisocyanate (XDI), ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis (1-isocyanate-1- Araliphatic diisocyanates such as methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene;
, And these isocyanate group-containing compounds derivatized by allohanation, biuretization, dimerization (uretidione), trimerization (isocyanurate), adduct formation, carbodiimide reaction, etc., and mixtures thereof, and these isocyanates Examples thereof include a copolymer of a group-containing compound and the above-described copolymerizable monomer.

  In the present invention, it is particularly preferable to use an aliphatic diisocyanate, and HMDI and a derivative thereof are particularly preferable.

Examples of the compound containing a carboxyl group include the polyvalent carboxylic acid and the carboxyl group-containing monomer described above, a polymer obtained by homopolymerizing or copolymerizing a carboxyl group-containing monomer, and other copolymerizable monomers. And a copolymer obtained by copolymerizing these monomers.
Examples of the other copolymerizable monomers include the hydroxyl group-containing monomer, amino group-containing monomer, epoxy group-containing monomer, amide group-containing monomer, alkoxysilyl group-containing monomer, Hydrolyzable silyl group-containing monomer, nitrile group-containing monomer, methylol group-containing monomer, oxazoline group-containing monomer, acrylate ester monomer, vinylidene halide monomer, aromatic vinyl And other monomers.

  Examples of the compound containing an epoxy group include an epi-bis type bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol AD type epoxy compound, and a bisphenol S type epoxy compound obtained by a condensation reaction such as bisphenol A and epichlorohydrin. Are generally used, and hydrogenated epoxy compounds, 3,4-epoxyvinylcyclohexane, vinylcyclohexene monoepoxide alicyclic epoxy compounds, phenol novolac epoxy compounds, bisphenol A novolac epoxy compounds, cresol novolacs Type epoxy compound, diaminodiphenylmethane type epoxy compound, β-methyl epichloro type epoxy compound, n-butyl glycidyl ether, allyl glycidyl ether, 2 Glycidyl ether type epoxy compounds such as ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, diglycidyl ether type epoxy compounds such as diglycidyl ether, glycidyl (meth) acrylate, (meth) acrylic acid 3,4-epoxy Cyclohexyl, (meth) acrylic acid-ε-caprolactone-modified glycidyl, glycidyl ester type epoxy compound such as (meth) acrylic acid-β-methylglycidyl, polyglycol ether type epoxy compound, glycol ether type epoxy compound, urethane having urethane bond Rubber-modified epoxy compounds containing modified epoxy compounds, amine-modified epoxy compounds, fluorinated epoxy compounds, polybutadiene or acrylonitrile-butadiene copolymer rubber Compounds, flame retardant epoxy compounds such as glycidyl ether of tetrabromobisphenol A, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- ( And epoxy group-containing silicon compounds such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

The epoxy equivalent of the compound containing an epoxy group is not particularly limited, but is preferably 100 g / eq or more and 400 g / eq or less (preferably 150 g / eq or more and 350 g / eq or less), and one or more of these is preferable. Can be used.
Particularly in the present invention, a compound containing an epoxy group of 100 g / eq or more and less than 250 g / eq (preferably 120 g / eq or more and 230 g / eq or less, more preferably 150 g / eq or more and 200 g / eq or less), and an epoxy equivalent of 250 g. It is preferable to use together a compound containing an epoxy group of / eq or more and 400 g / eq or less (preferably 280 g / eq or more and 350 g / eq or less). By including such a compound containing two or more types of epoxy groups, both excellent curability and flexibility can be achieved. Moreover, compatibility with a heat storage material can be adjusted.
Furthermore, the epoxy resin of the present invention preferably has two or more epoxy groups in one molecule. By having two or more, the curability and the reaction rate can be improved, the crosslinking density can be increased, and the strength of the resulting porous body can be increased.

As a compound containing an amino group,
Aliphatic amino group-containing compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, oleylamine;
Mensendiamine, isophoronediamine, norbornanediamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, 1,2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl) methane, bis (4- Aminocyclohexyl) alicyclic amino group-containing compounds such as methane, polycyclohexylpolyamine, DBU;
Aromatic amino group-containing compounds such as metaphenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone;
aliphatic aromatic amino group-containing compounds such as m-xylylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol;

3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylenediamine, polyoxypropylenetriamine, An amino group-containing compound having an ether bond such as polyoxyethylenediamine;
Hydroxyl and amino group-containing compounds such as diethanolamine and triethanolamine;
Acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride;
Polyamideamines such as polyamides obtained by reacting dimer acids with polyamines such as diethylenetriamine and triethylenetetramine, and polyamides using polycarboxylic acids other than dimer acids;
Imidazoles such as 2-ethyl-4-methylimidazole;
Polyoxypropylene amines such as polyoxypropylene diamine and polyoxypropylene triamine;
Epoxy-modified amine obtained by reacting an epoxy compound with the amines, modified amines such as Mannich-modified amine, Michael addition-modified amine, ketimine and aldimine obtained by reacting the amines with formalin and phenols; 2, 4 , 6-tris (dimethylaminomethyl) phenol 2-amine hexanoate and other amine salts.

  As a combination of the component (x-2) and the component (x-3), in the present invention, a compound containing a hydroxyl group and a compound containing an isocyanate group, a compound containing an epoxy group and a compound containing an amino group, etc. A combination is preferred, and a combination of a compound containing a hydroxyl group and a compound containing an isocyanate group is particularly preferred. Such a combination is preferable because the crosslinking reaction is likely to proceed under mild conditions and the adjustment of the crosslinking density and the like is easy.

Moreover, the mixing ratio of the (x-2) component and the (x-3) component is not particularly limited, and may be set as appropriate according to the application.
For example, when using a compound containing a hydroxyl group and a compound containing an isocyanate group, the NCO / OH ratio is usually 0.1 to 1.8, preferably 0.2 to 1.5, more preferably 0.3. What is necessary is just to set in the range used as -1.3.
By being within such a range of the NCO / OH ratio, the strength of the porous body can be made strong, and a uniform and dense cross-linked structure with no leakage of the heat storage material can be obtained.

Further, in the reaction of the component (x-2) and the component (x-3), the curing reaction can be rapidly advanced using a reaction accelerator.
For example, in the reaction of a compound containing a hydroxyl group and a compound containing an isocyanate group, as a reaction accelerator, for example, triethylamine, triethylenediamine, triethylamine, tetramethylbutanediamine, dimethylaminoethanol, dimeramine amine, dimer acid polyamidoamine, etc. Amines of
Tin carboxylates such as dibutyltin dilaurate, dibutyltin diacetate, tin octate;
Metal carboxylates such as iron naphthenate, cobalt naphthenate, manganese naphthenate, zinc naphthenate, iron octylate, cobalt octylate, manganese octylate, zinc octylate;
Carboxylates such as dibutyltin thiocarboxylate, dioctyltin thiocarboxylate, tributylmethylammonium acetate, trioctylmethylammonium acetate;
Aluminum compounds such as aluminum trisacetylacetate;
1 type, or 2 or more types can be used.

  The reaction accelerator is usually mixed at a ratio of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the solid content of the compound containing a hydroxyl group. When the reaction accelerator is less than 0.01 parts by weight, the curability and strength of the porous body are insufficient, and the swelling tends to occur easily. When the amount is more than 10 parts by weight, the weather resistance, discoloration resistance and the like tend to decrease.

  In addition to the above components, as a component for forming a porous body, pigments, aggregates, plasticizers, antiseptics, antifungal agents, antialgae agents, antifoaming agents, foaming agents, leveling agents, pigment dispersants, antisettling agents Additives such as a sagging inhibitor, a dehydrating agent, a matting agent, a flame retardant, an ultraviolet absorber, and a light stabilizer may be mixed.

  What is necessary is just to manufacture a porous body by a well-known method using the said component.

  As a method of filling the porous body with the heat storage material, a method of filling the porous body with the heat storage material by an immersion method, a reduced pressure / pressure injection method, or the like, or mixing the heat storage material in advance when manufacturing the porous body And the like.

  In this invention, the method of mixing and filling a heat storage material beforehand at the time of porous body manufacture is preferable, and such a method can prevent that a heat storage material leaks from a porous body more, and is preferable.

  Specifically, first, the heat storage material and the porous body forming component are mixed, and then the porous body forming component is cured to obtain a heat storage material in which the heat storage material is filled in the porous body.

For example,
(I) (x-1) component (if necessary, a viscosity modifier, a thermally conductive substance, etc.), (x-2) component, (x-3) component are uniformly mixed, and (x-2) component And (x-3) component are reacted to fill the porous body with the heat storage material,
(Ii) component (x-1) (if necessary, a viscosity modifier, a thermally conductive substance, etc.), a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, (x-2) ) Component and (x-3) component are mixed, (x-1) component is dispersed in a colloidal form, (x-2) component and (x-3) component are reacted to make the heat storage material porous. The method of filling, etc. are mentioned.

In the method (i), the (x-1) component, the (x-2) component, and the (x-3) component are uniformly mixed to obtain a compatible state. Next, a porous body filled with the component (x-1) is obtained by reacting the component (x-2) and the component (x-3).
In this process, microphase separation occurs due to the change from the compatible state to the incompatible state, and a densely packed three-dimensional stitch structure type porous body composed of the (x-2) component and the (x-3) component is formed. It seems to be done.
This three-dimensional stitch structure type porous body is filled with the (x-1) component, and a porous body filled with the (x-1) component is formed.

In particular, when a viscosity modifier is mixed in addition to the component (x-1), the viscosity of the component (x-1) is adjusted, and the component (x-1) filled in the porous body leaks to the outside. Can be prevented. Therefore, it is preferable because a high heat storage material content can be achieved.
Furthermore, by appropriately setting the formation component of the porous body, the interaction with the porous body formation component works, and the (x-1) component can be further prevented from leaking to the outside.
Further, if the porous body is a three-dimensional stitch structure type porous body, the (x-1) component can be further prevented from leaking to the outside because of its dense structure.

In the production of such a three-dimensional stitch structure type porous body, it is preferable that the compatibilizer described above is further mixed and produced. The compatibilizer improves not only the compatibility between the components (x-1) but also the compatibility between the component (x-1) and the resin component ((x-2) component, (x-3) component, etc.). Therefore, it is possible to further prevent the (x-1) component from leaking from the porous body by forming a denser three-dimensional stitch structure type porous body.
Examples of the compatibilizer include the above-described fatty acid triglycerides and nonionic surfactants having a hydrophilic / lipophilic balance (HLB) of 1 to less than 10, and the compatibility between the component (x-1) and the resin component. In particular, a nonionic surfactant having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 is preferred.

  In the method (i), the reaction temperature is preferably equal to or higher than the melting point of the component (x-1). Although specific reaction temperature changes with kinds of (x-1) component, it is about 20 to 100 degreeC normally. (X-1) By making it react above melting | fusing point of a component, it will be in a compatible state easily. Moreover, what is necessary is just to make reaction time into about 0.2 to 10 hours normally.

In the method (i), for example, when using a compound containing a hydroxyl group and a compound containing an isocyanate group, the molecular weight of the compound containing a hydroxyl group is not particularly limited, but is 500 to 10,000. It is desirable that it is 1000-3000. With such a molecular weight, it can be easily melted and mixed with the component (x-1), and a compatible state can be easily produced. Therefore, a more excellent three-dimensional crosslinked structure can be obtained.
Furthermore, the mixing ratio of the compound containing a hydroxyl group and the compound containing an isocyanate group is not particularly limited and may be set as appropriate, but the NCO / OH ratio is 0.1 to 1.8, preferably 0.8. A more excellent three-dimensional crosslinked structure can be obtained by being 2-1.7, more preferably 0.3-1.6, more preferably 0.5-1.5.

  In the method (ii), the component (x-1), a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, the component (x-2) and the component (x-3) Mix and disperse the (x-1) component colloidally in the (x-2) component and the (x-3) component. Next, a porous body filled with the component (x-1) can be obtained by reacting the component (x-2) and the component (x-3).

  In such a method, the component (x-1) is contained in the component (x-2) and / or the component (x-3) by a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more. It is possible to create a fine colloidal dispersion. By reacting the (x-2) component and the (x-3) component in such a state, a porous body filled with the (x-1) component can be obtained.

  Specific examples of the production method of the present invention include (x-1) component, nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, (x-2) component, and (x-3). ) Component is mixed and (x-2) component and (x-3) component are reacted, or (x-1) component and non-ionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more The method of making it react by mixing an agent, (x-2) component (or (x-3) component), and adding (x-3) component (or (x-2) component) is mentioned.

In such a production method, the content of the (x-1) component can be increased, and although it has a high (x-1) component content, (x-1) ) No component leaks. Further, even when the porous body filled with the component (x-1) is cut, the (x-1) component is not leaked from the cut surface, and the workability is excellent. Since there is no leakage of components, it is excellent in installation workability.
Furthermore, since the (x-1) component is in a finely and uniformly dispersed state, the shape change of the porous body itself due to the volume change accompanying the solid-liquid change of the (x-1) component can be reduced.

  What is necessary is just to select suitably as a nonionic surfactant whose hydrophilic lipophilic balance (HLB value) is 10 or more by (x-1) component, (x-2) component, and (x-3) component. Further, the hydrophilic / lipophilic balance (HLB value) is 10 or more (preferably more than 10 and 20 or less, more preferably 11 or more and 19 or less, more preferably 12 or more and 18 or less, most preferably 13 or more and 17 or less). In particular, the component (x-1) (particularly, the organic latent heat storage material) is preferable because it is easily dispersed in a colloidal form.

Examples of the nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene. Polyoxyethylene sorbitan fatty acid esters such as sorbitan monooleate,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyldodecyl ether,
Polyoxyethylene sorbitol fatty acid esters such as tetraoleic acid polyoxyethylene sorbit,
Polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate,
Examples include polyoxyethylene hydrogenated castor oil and polyoxyethylene coconut oil fatty acid sorbitan.

  In particular, as the component (x-1), an aliphatic hydrocarbon having 8 to 36 carbon atoms, a long chain alcohol having 8 to 36 carbon atoms, a long chain fatty acid having 8 to 36 carbon atoms, and a long chain fatty acid ester having 8 to 36 carbon atoms When is used, it is preferable to have a long-chain alkyl group having 8 to 36 carbon atoms in the structure of the surfactant. In particular, the effect of the present invention can be further enhanced by selecting the component (x-1) that is similar to the carbon number of the long-chain alkyl group of the surfactant or the similar one.

The mixing ratio of the nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more and the component (x-1) is as follows: (x-1) component, (x-2) component, (x-3) component However, the amount of the surfactant is usually 0.01 to 30 parts by weight (preferably 0.1 to 20 parts by weight) with respect to 100 parts by weight of the component (x-1). That's fine.
When the surfactant is less than 0.01 parts by weight, the component (x-1) and the component (x-2) and / or the component (x-3) are easily separated or cause a creaming phenomenon. The colloidal dispersion may not be performed efficiently, and the effects of the present invention may not be obtained. When the amount is more than 30 parts by weight, physical properties such as water resistance of the obtained heat storage layer may be adversely affected.

  In the above production method, the component (x-1) has a particle size of about 10 μm to 1000 μm (preferably 50 μm to 900 μm, more preferably 100 μm to 800 μm, more preferably 200 μm to 700 μm) in the state before the reaction. It is characterized by being in a colloidally dispersed state. By reacting the (x-2) component and the (x-3) component from such a state, the (x-1) component can be finely dispersed (filled) in the porous body.

In the state before the reaction, the temperature in the system is preferably equal to or higher than the melting point of the component (x-1). Specifically, it is usually about 20 ° C. to 80 ° C., and at such a temperature, the (x-1) component is easily dispersed in a colloidal state, which is preferable.
The particle size is a value measured using an optical microscope (BHT-364M, manufactured by Olympus Optical Co., Ltd.).

  In such a production method, the specific reaction temperature varies depending on the type of the component (x-1), but is usually about 20 ° C to 80 ° C. Above the melting point of the component (x-1), the component (x-1) tends to be in a colloidal state, which is preferable. Moreover, reaction time should just be normally about 0.2 to 5 hours.

In such production, for example, when using a compound containing a hydroxyl group and a compound containing an isocyanate group, the molecular weight of the compound containing a hydroxyl group is not particularly limited, and should be selected within a wide range. In general, it is preferably 500 to 10,000, more preferably 1000 to 3000. With such a molecular weight, the (x-1) component can be dispersed in a finer colloidal form, and the (x-1) component content can be further increased. Therefore, it is excellent in heat storage property, and it is possible to further reduce the shape change of the porous body itself due to the volume change accompanying the solid-liquid change of the component (x-1).
Furthermore, the mixing ratio of the compound containing a hydroxyl group and the compound containing an isocyanate group is not particularly limited and may be set as appropriate, but the NCO / OH ratio is 0.1 to 1.8, preferably 0.8. The effect can be further enhanced by being 2 to 1.7, more preferably 0.3 to 1.6, and more preferably 0.5 to 1.5.

  In the method of mixing and filling the (x-1) component in advance during the production of the porous body, when using an isocyanate group, a carboxyl group, an imide group or an aldehyde group as the reactive functional group, a long chain as a heat storage material The use of alcohol and polyether compounds is excluded. In addition, when a hydroxyl group, an epoxy group, a carbodiimide group, an oxazoline group, or an aziridine group is used as a reactive functional group, the use of a long chain fatty acid as a heat storage material is excluded.

  In the production of the heat storage layer in the present invention, in addition to the above components, pigment, aggregate, plasticizer, preservative, antifungal agent, antialgae, antifoaming agent, foaming agent, leveling agent, pigment dispersant, anti-settling agent Additives such as an agent, an anti-sagging agent, a lubricant, a dehydrating agent, a matting agent, a flame retardant, an ultraviolet absorber, and a light stabilizer can also be contained.

-Lamination method-
The vibration damping laminate of the present invention is obtained by laminating the vibration damping layer (A) and the heat storage layer (X), and the laminating method is not particularly limited. For example, a two-layer structure in which a damping layer (A) and a heat storage layer (X) are stacked may be used, or a multilayer structure having three or more layers may be used.

Specifically, the lamination method is a method in which a heat storage layer (X) is prepared in advance by a known method and a damping layer (A) forming component such as a damping resin is applied and laminated, or a damping resin or the like is previously prepared. The damping layer (A) is formed from the damping layer (A) forming component, and can be laminated by a method of laminating with a known adhesive / adhesive or adhesive / adhesive tape, a method of laminating by heat fusion, or the like .
On the contrary, the damping layer (A) is prepared in advance by a known method, and the heat storage layer (X) forming component is applied and laminated, or the heat storage layer (X) is previously formed from the heat storage layer (X) forming component. It can form and laminate | stack by the method of laminating | stacking with a well-known adhesive agent / adhesive, an adhesion | attachment / adhesive tape, the method of laminating | stacking by heat sealing | fusion, etc.

Furthermore, the damping laminate may be laminated on a base material to be described later. In this case, the heat storage layer (X) and the damping layer (A) can be laminated in order on the substrate, and the damping layer (A) and the heat storage layer (X) are sequentially laminated on the substrate. It can also be laminated.
Also when laminating on the base material, the damping layer (A) or the heat storage layer (X) is laminated on the base material in the same manner as described above, and further the heat storage layer (X) or the damping layer (A ) Can be laminated. Moreover, it can also inject | pour and fill between base materials.

  In the method of applying the damping layer (A) forming component and the heat storage layer (X) forming component, it may be applied using a coating device such as a brush, a trowel, a spray, a roller, a roll coater or a flow coater. There is no particular limitation such as recoating, multi-coating and the like.

Examples of the base material include concrete, mortar, lightweight mortar, lightweight concrete, extruded board, slate board, ALC board, siding board, gypsum board, fiber-mixed cement board, cement calcium silicate board, slag cement pearlite board, asbestos cement Examples include a plate, a metal plate, a plywood, a steel plate, a porcelain tile, a plastic forming plate, a glass plate, and the like, and such a base material may have been subjected to some surface treatment in advance.
In the present invention, it is particularly preferable to use a gypsum board, a calcium silicate board, a slate board, etc. in consideration of utilization for buildings.

  The thicknesses of the damping layer (A) and the heat storage layer (X) can be appropriately set depending on the intended use, but are usually 0.1 to 100 mm, preferably about 0.5 to 50 mm. The greater the thickness, the better the vibration control performance and sound insulation performance. In this invention, it is preferable to shape | mold into a sheet form from the point which can adjust thickness easily and freely.

  Experimental examples are shown below to clarify the features of the present invention.

(Experimental example 1)
(Manufacture of damping structures)
Using the raw materials shown in Table 1, the resin, polyisocyanate compound, curing aid, and additive are uniformly mixed in the blending amounts shown in Table 2, poured into a mold, and cured at 50 ° C. for 3 hours. A damping layer having a thickness of 2 mm was produced.
Using the raw materials shown in Table 3, the heat storage material C, the organically treated layered clay mineral A, the hydroxyl group-containing compound A, and the isocyanate group-containing compound B were uniformly mixed at a temperature of 40 ° C. in the amounts shown in Table 4. Then, a reaction accelerator was added and stirred sufficiently to obtain a heat storage slurry.
The obtained heat storage slurry is poured into a mold having the vibration damping layer as a bottom surface and cured at 50 ° C. for 3 hours to obtain a heat storage layer having a thickness of 1 mm, demolded from the mold, and the vibration damping layer and the heat storage layer. A vibration-damping laminate having a thickness of 3 mm was obtained.

(Vibration suppression test)
Using the forced vibration type viscoelastic device (Rhegel E-4000 manufactured by UBM Co., Ltd.), the vibration-damping laminate thus produced was subjected to amplitude distortion at a temperature rising temperature of 2.0 ° C./min and a frequency of 10 Hz. Tan δ was measured under the condition of 0.1 mm.
In the vibration damping test, the value of tan δ at 20 ° C., 30 ° C., and 40 ° C. when the temperature was raised at 2.0 ° C./min in the temperature range from 0 ° C. to 60 ° C. was measured. The results are shown in Table 5.

  As a reference example, Table 5 also shows the results of a vibration damping test performed using only the vibration damping layer. In the reference example, the maximum value of tan δ was 1.95 at 30 ° C.

(Experimental example 2)
Using the raw materials shown in Table 3, the heat storage material C, the hydroxyl group-containing compound A, and the isocyanate group-containing compound B were uniformly mixed at a temperature of 40 ° C. with the blending amounts shown in Table 4, added with a reaction accelerator, and sufficiently stirred And the damping laminated body was manufactured by the method similar to Experimental example 1 except having obtained the thermal storage slurry. Further, the obtained vibration damping laminate was subjected to a vibration damping test in the same manner as in Experimental Example 1. The results are shown in Table 5.

(Experimental example 3)
Using the raw materials shown in Table 3, the heat storage material A, the heat storage material C, the compatibilizing agent, the organically treated layered clay mineral B, the hydroxyl group-containing compound B, and the isocyanate group-containing compound A in the blending amounts shown in Table 4 A vibration-damping laminate was produced in the same manner as in Experimental Example 1 except that the mixture was uniformly mixed at a temperature of 40 ° C., a reaction accelerator was added, and the mixture was sufficiently stirred to obtain a heat storage slurry. Further, the obtained vibration damping laminate was subjected to a vibration damping test in the same manner as in Experimental Example 1. The results are shown in Table 5.

(Experimental example 4)
Using the raw materials shown in Table 3, the heat storage material C, the organically treated layered clay mineral B, the hydroxyl group-containing compound B, the isocyanate group-containing compound A, and the thermally conductive material at a blending amount shown in Table 4 were heated to 40 ° C. The vibration-damping laminate was produced in the same manner as in Experimental Example 1, except that the reaction accelerator was added and stirred sufficiently to obtain a heat storage slurry. Further, the obtained vibration damping laminate was subjected to a vibration damping test in the same manner as in Experimental Example 1. The results are shown in Table 5.

(Experimental example 5)
Using the raw materials shown in Table 3, the heat storage material C, the hydroxyl group-containing compound B, the isocyanate group-containing compound A, and the heat conductive material are uniformly mixed at a temperature of 40 ° C. in the blending amounts shown in Table 4, and a reaction accelerator Was added, and the mixture was sufficiently stirred to obtain a heat storage slurry, and a vibration damping laminate was produced in the same manner as in Experimental Example 1. Further, the obtained vibration damping laminate was subjected to a vibration damping test in the same manner as in Experimental Example 1. The results are shown in Table 5.

(Experimental example 6)
Using the raw materials shown in Table 3, the heat storage material C, the surfactant, the hydroxyl group-containing compound A, and the isocyanate group-containing compound B were mixed at a temperature of 40 ° C. in the blending amounts shown in Table 4, and the heat storage material C was colloidal. A vibration-damping laminate was produced in the same manner as in Experimental Example 1 except that it was dispersed in (average particle diameter 190 nm), a reaction accelerator was added, and the mixture was sufficiently stirred to obtain a heat storage slurry. Further, the obtained vibration damping laminate was subjected to a vibration damping test in the same manner as in Experimental Example 1. The results are shown in Table 5.

(Experimental example 7)
Using the raw materials shown in Table 3, the heat storage material C, the surfactant, the organically treated layered clay mineral B, the hydroxyl group-containing compound A, and the isocyanate group-containing compound B are mixed at a temperature of 40 ° C. in the amounts shown in Table 4. Mixing and dispersing the heat storage material C in a colloidal form (average particle diameter 430 nm), adding a reaction accelerator, stirring sufficiently, and obtaining a heat storage slurry, a vibration damping laminate in the same manner as in Experimental Example 1 Manufactured. Further, the obtained vibration damping laminate was subjected to a vibration damping test in the same manner as in Experimental Example 1. The results are shown in Table 5.

(Experimental example 8)
Using the raw materials shown in Table 3, the heat storage material A, the heat storage material C, the compatibilizer, the surfactant, the organically treated layered clay mineral B, the hydroxyl group-containing compound A, and the isocyanate group in the blending amounts shown in Table 4 Except that the contained compound B was mixed at a temperature of 40 ° C., the heat storage material A and the heat storage material C were dispersed in a colloidal form (average particle diameter 600 nm), a reaction accelerator was added, and the mixture was sufficiently stirred to obtain a heat storage slurry. A vibration-damping laminate was produced in the same manner as in Example 1. Further, the obtained vibration damping laminate was subjected to a vibration damping test in the same manner as in Experimental Example 1. The results are shown in Table 5.

(Experimental example 9)
A vibration-damping laminate was produced in the same manner as in Experimental Example 1, except that the following heat storage slurry was used. Further, the obtained vibration damping laminate was subjected to a vibration damping test in the same manner as in Experimental Example 1. The results are shown in Table 5.
Thermal storage slurry: 60 parts by weight of n-nonadecane (phase change temperature 32.0 ° C), 40 parts by weight of stearyl acrylate and 3 parts by weight of polyethylene glycol dimethacrylate are uniformly mixed, and further 2 parts by weight of polyoxyethylene oleyl ether ammonium sulfate Then, 1 part by weight of polyoxyethylene stearyl ether, 1 part by weight of ammonium persulfate and 100 parts by weight of water were added and mixed in a polymerization tank to prepare a pre-emulsion solution. Next, the inside of a polymerization tank was deaerated and emulsion polymerization was performed at 80 ° C. for 3 hours in a nitrogen atmosphere. After the polymerization, the polymerization tank was cooled to room temperature (25 ° C.) to obtain a heat storage capsule (average particle size 1.7 μm). This capsule was separated from the aqueous layer, pulverized and washed with a small pulverizer, dried in a dryer at 25 ° C. for 3 hours, and classified (100 mesh) to obtain a solid powder-like heat storage capsule. At this time, separation from the aqueous layer was simple, and the heat storage material did not leak from the capsule during pulverization, and the obtained capsule could be recovered with a size of approximately 100 mesh or less.
Next, 60 parts by weight of the obtained heat storage capsule, 33 parts by weight of the hydroxyl group-containing compound A shown in Table 1, and 9 parts by weight of the isocyanate group-containing compound B shown in Table 1 were mixed at a temperature of 40 ° C., and the reaction promotion shown in Table 1 was performed. 0.1 parts by weight of the agent was added and stirred sufficiently to obtain a heat storage slurry.
At this time, the heat storage capsule could easily produce the heat storage slurry without the capsule wall being crushed.

(Experimental example 10)
A vibration-damping laminate was produced in the same manner as in Experimental Example 1, except that the following heat storage slurry was used. Further, the obtained vibration damping laminate was subjected to a vibration damping test in the same manner as in Experimental Example 1. The results are shown in Table 5.
Thermal storage slurry: 60 parts by weight of thermal storage material A, 40 parts by weight of stearyl acrylate, 3 parts by weight of polyethylene glycol dimethacrylate, 3 parts by weight of sodium dodecyl sulfate, 1 part by weight of ammonium persulfate, 100 parts by weight of water And mixed in a polymerization tank to prepare a pre-emulsion solution. Next, the inside of a polymerization tank was deaerated and emulsion polymerization was performed at 80 ° C. for 3 hours in a nitrogen atmosphere. After the polymerization, the polymerization tank was cooled to room temperature (25 ° C.) to obtain a heat storage capsule (average particle size 1.8 μm).
This capsule was separated from the aqueous layer, pulverized and washed with a small pulverizer, dried in a dryer at 25 ° C. for 3 hours, and classified (100 mesh) to obtain a solid powder-like heat storage capsule. At this time, separation from the aqueous layer was simple, and the heat storage material did not leak from the capsule during pulverization, and the obtained capsule could be recovered with a size of approximately 100 mesh or less.
Next, 60 parts by weight of the obtained heat storage capsule, 33 parts by weight of the hydroxyl group-containing compound A shown in Table 1, and 9 parts by weight of the isocyanate group-containing compound A shown in Table 1 were mixed at a temperature of 40 ° C., and the reaction promotion shown in Table 1 was performed. 0.1 parts by weight of the agent was added and stirred sufficiently to obtain a heat storage slurry.
At this time, the heat storage capsule could easily produce the heat storage slurry without the capsule wall being crushed.

(Experimental example 11)
As shown in Table 3 and Table 4, except that the heat storage material C was replaced with the heat storage material B, a vibration damping laminate was obtained in the same manner as in Experimental Example 1, and a vibration damping test was performed. The results are shown in Table 5.

Claims (6)

The damping layer (A) and the heat storage layer (X) are laminated,
The damping layer (A) contains a damping resin, and the maximum value of the loss coefficient (tan δ) determined by dynamic viscoelasticity measurement is 0.5 or more,
The heat storage layer (X) contains the heat storage material (x-1), and the phase change temperature of the heat storage material (x-1) is a temperature at which the loss coefficient (tan δ) in the damping layer (A) is the maximum value. A vibration-damping laminate having a temperature range of plus or minus 10 ° C. Damping resin
(A) Hydroxyl group having a hydroxyl value of 50 to 150 mgKOH / g, polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.0 or less, and number average molecular weight (Mn) of 1000 to 15000 Compound,
(B) a polyisocyanate compound,
The vibration-damping laminate according to claim 1, comprising: Damping resin
(A) (a-1) Copolymer obtained by polymerizing a mixture of a (meth) acrylic monomer containing a hydroxyl group and (a-2) a polymerizable unsaturated monomer other than (a-1) It has a hydroxyl value of 50 to 150 mgKOH / g, a polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.0 or less, and a number average molecular weight (Mn) of 1000 to 15000. Copolymer,
(B) a polyisocyanate compound,
The vibration-damping laminate according to claim 1 or 2, further comprising:   The heat storage layer (X) contains the heat storage capsule which encapsulated the heat storage material (x-1), The damping damping laminated body in any one of Claim 1 to 3 characterized by the above-mentioned. .   The damping layered product according to any one of claims 1 to 3, wherein the heat storage layer (X) is a porous material filled with the heat storage material (x-1). The damping structure according to any one of claims 1 to 5, wherein the heat storage material (x-1) is an organic latent heat storage material.