CN101421358A - Heat-storing composition, and heat-storing fiber, sheet and film each made of the same - Google Patents
Heat-storing composition, and heat-storing fiber, sheet and film each made of the same Download PDFInfo
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- CN101421358A CN101421358A CNA2007800133497A CN200780013349A CN101421358A CN 101421358 A CN101421358 A CN 101421358A CN A2007800133497 A CNA2007800133497 A CN A2007800133497A CN 200780013349 A CN200780013349 A CN 200780013349A CN 101421358 A CN101421358 A CN 101421358A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
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- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Disclosed is a heat-storing composition containing a temperature regulating agent and a thermoplastic resin. This heat-storing composition is characterized in that the temperature regulating agent is composed of a polymer, an oligomer or a crosslinked product of an oligomer, while having a melting point of from -10 to 100 DEG C, a latent heat of not less than 30 J/g, and a weight average molecular weight of 5,000-65,000.
Description
Technical field
The accumulation of heat fiber, sheet and the film that the present invention relates to heat storage compound and its processing is obtained.
Background technology
The clothes that uses in the significant environment of temperature variation etc. utilizes all temps to regulate with the accumulation of heat parts.
As temperature regulation accumulation of heat parts, known have the micro-capsule near the material that has fusing point the normal temperature to be fixed on the accumulation of heat parts that obtain on the cloth inclosure, maybe will contain micro-capsule the synthetic resins spinning, make the accumulation of heat fiber that obtains form the accumulation of heat parts that cloth obtains.
As the accumulation of heat fiber, proposed to contain the conjugated fibre (patent documentation 1) of the composition of heat storage substance paraffin, polyvinyl resin as core.
In addition, proposed so that be dispersed with the composition with temp regulating function of heat storage substance exists for feature along the length direction of silk accumulation of heat fiber (patent documentation 2～4).
But these fibers are owing to mostly occurring fracture of wire when spinning, and existence can not be stablized the problem of manufacturing.
The applicant has proposed a kind of heat storage compound fiber, and this heat storage compound fiber uses the heat-storing material that will contain the heat-storing material of polymkeric substance or oligopolymer or contain their crosslinked body to be engaged in the heat storage compound (patent documentation 5) that obtains in the synthetic resins.
But, directly wait spinning condition according to silk, might can not stablize manufacturing, be necessary further to study.
Patent documentation 1: Japanese kokai publication hei 8-311716 communique
Patent documentation 2: Japanese Unexamined Patent Application Publication 2004-510068 communique
Patent documentation 3: Japanese Unexamined Patent Application Publication 2005-515317 communique
Patent documentation 4: Japanese Unexamined Patent Application Publication 2005-503497 communique
Patent documentation 5: TOHKEMY 2004-003087 communique
The present invention is in view of the above problems and proposes, and its purpose is, provide can be when spinning the heat storage compound processed of fracture of wire ground not.
Summary of the invention
According to the present invention, provide following heat storage compound etc.
1. heat storage compound, it contains temperature regulato and thermoplastic resin, wherein, the said temperature conditioning agent is the crosslinked body of polymkeric substance, oligopolymer or oligopolymer, and the fusing point of said temperature conditioning agent is that 30J/g is above, weight-average molecular weight is 5000～65000 for-10～100 ℃, latent heat.
2.1 the heat storage compound of middle record, wherein, the said temperature conditioning agent is present in the thermoplastic resin dispersedly, and the median size of temperature regulato is less than 13 μ m.
3.1 or in 2 the record heat storage compound, wherein, said temperature conditioning agent shared ratio in heat storage compound is 5～70 quality %, the ratio of above-mentioned thermoplastic resin is 30～95 quality %.
4.1 the heat storage compound of～3 any records, wherein, the weight-average molecular weight of said temperature conditioning agent is 5000～30000.
5.1 the heat storage compound of～4 any records, wherein, above-mentioned thermoplastic resin is at least a kind that is selected from acrylic resin, polyvinyl resin, vibrin, polystyrene resin, polyamide resin, ABS resin, polycarbonate resin and the ethylene-vinyl alcohol copolymer resin.
6. the accumulation of heat fiber that the heat storage compound melt-spinning of above-mentioned 1～5 any record is obtained.
7. the sheet or the film that contain the heat storage compound of above-mentioned 1～5 any record.
According to the present invention, can provide the heat storage compound of the fracture of wire in the time that spinning can being reduced.In addition, if use this heat storage compound matrix band or film, then can reduce fuzzy or variation in thickness.
Embodiment
Heat storage compound of the present invention contains temperature regulato and thermoplastic resin.
The temperature regulato that uses among the present invention is that fusing point is-10～100 ℃, the latent heat crosslinked body as the polymkeric substance more than the 30J/g, oligopolymer or oligopolymer.The weight-average molecular weight of this temperature regulato (Mw) is 5000～65000.Among the present invention,, make the temperature regulato high dispersing in thermoplastic resin by using the temperature regulato of Mw in above-mentioned scope.Thus, the fracture of wire in the time of can preventing spinning effectively.Be noted that Mw less than 5000 o'clock, temperature regulato is exuded on the surface, liquefies during use, might cause to be clamminess etc.On the other hand, if surpass 65000 owing to the dispersed variation as temperature regulato, spinning, forming process might reduce.Mw is preferably 5000～30000, and more preferably 5000～20000.
As the temperature regulato of the crosslinked body of polymkeric substance, oligopolymer and oligopolymer, can enumerate for example following (A)～(C).
(A) with constitute by the X of main chain portion, the joint portion Y shown in the formula (1) and side chain Z, side chain Z mutually the crystallinity unit of crystallization as the polymkeric substance or the oligopolymer of main composition composition.
[changing 1]
(B) with constitute by the X of main chain portion, the joint portion Y shown in the following formula (1) and side chain Z, side chain Z mutually the crystallinity unit of crystallization as the polymkeric substance or the crosslinked body of oligopolymer (crosslinking temperature conditioning agent) of main composition composition.
(C) with main chain with polyethers and mutually the unit of the side chain of crystallization as the polymkeric substance or the oligopolymer (polyethers temperature regulato) of main composition composition.
These temperature regulatos are in required temperature range, for temperature regulato (A) and (B), noncrystallineization or crystallization by side chain Z produce phase change (fuse, solidify), in addition, for temperature regulato (C), dissociating by the cohesion of side chain produces phase change (fuse, solidify), at this moment, discharges or absorb big latent heat.Therefore, fuse, rejected heat solidifies if the extraneous gas temperature reduces then by then absorption heat owing to the extraneous gas temperature raises for these temperature regulatos, therefore relaxes the change of extraneous gas temperature, easily keeps certain temperature, and performance is as the function of temperature regulato.In addition, temperature regulato (A) and (B) in because the X of main chain portion of formula (1) do not fuse in the said temperature scope, further, in temperature regulato (B), by being cross-linked to form the three dimensional network ocular structure, material monolithic does not flow out and keeps shape.In addition, these temperature regulatos (A), (B) and the length of (C) passing through to regulate side chain can easily be regulated fusing point.
At first, describe to temperature regulato (A) with (B).
Temperature regulato (A) and (B) in, the X of main chain portion of formula (1) is if not hinder the structure of the crystallization of side chain Z and then do not limit especially, is preferably to be selected from
[changing 2]
In at least a.
Joint portion Y is the part in conjunction with X of main chain portion and side chain Z, represents 1 atomic unit (1 atom ユ ニ Star ト).Side chain Z is if can crystallization then limit especially, is alkyl more than 9 but preferably contain carbonatoms, further preferably contains carbonatoms and be the straight chained alkyl more than 9.
Joint portion and side chain Y-Z be preferably and be selected from-CO-O-R ,-O-CO-R ,-O-R ,-CH
2At least a among the-R, R is that carbonatoms is the alkyl more than 9, further preferably carbonatoms is a straight chained alkyl more than 9.
The particularly preferred crystallinity unit that contains the X of main chain portion, joint portion Y and side chain Z is polymethacrylate, polyacrylate(s), polyvinylesters class, polyvinyl ether or a hydro carbons as follows.
[changing 3]
The methyl acrylic ester esters of acrylic acid
The above straight chained alkyl of straight chained alkyl R:C12 that R:C14 is above
The vinyl ester vinyl ethers
The above straight chained alkyl of straight chained alkyl R:C10 that R:C9 is above
Hydro carbons
The straight chained alkyl that R:C9 is above
Each R satisfies following formula:
A＝Z/(X+Y+Z)≥0.75
As the example of preferred temperature regulato (A), can enumerate polymethyl acrylic acid docosyl ester, polymethyl acrylic acid heneicosyl ester, polyacrylic acid eicosyl ester, polyacrylic acid nonadecyl ester, polyacrylic acid heptadecyl ester, polyacrylic acid palmityl ester, polyacrylic acid pentadecyl ester, the polyacrylic acid stearyl ester, the polyacrylic acid lauryl, the polyacrylic acid myristin, the polymethyl acrylic acid myristin, polymethyl acrylic acid pentadecyl ester, polymethyl acrylic acid palmityl ester, polymethyl acrylic acid heptadecyl ester, polymethyl acrylic acid nonadecyl ester, polymethyl acrylic acid eicosyl ester, Stearyl methacrylate homopolymer, polymethyl acrylic acid (palmityl/stearyl) ester, polyoxyethylene lauryl acid vinyl ester, poly-tetradecanoic acid vinyl ester, poly-palmitinic acid vinyl ester, poly-vinyl stearate base ester, polyoxyethylene lauryl base vinyl ether, poly-myristyl vinyl ether, poly-palmityl vinyl ether, poly-stearyl vinyl ether, poly-high ' alpha ' olefin etc.Be preferably poly-high ' alpha ' olefin especially.Wherein, it is alhpa olefin more than 10 that high ' alpha ' olefin refers to carbonatoms, and more preferably carbonatoms is 16～18 alhpa olefin.Poly-high ' alpha ' olefin contains the structural unit that derives from high ' alpha ' olefin and gets final product, and can be homopolymer, the multipolymer of high ' alpha ' olefin, so also can for the multipolymer of alkene such as ethene, propylene.
The unitary content of high ' alpha ' olefin in the poly-high ' alpha ' olefin is preferably 50 moles more than the %, is preferably 100 moles of % especially.Because by making the unitary content of high ' alpha ' olefin is 50 moles more than the %, crystallinity increases, and therefore can obtain as the effective ability of heat-storing material.
In addition, as the example of preferred temperature regulato (B), can enumerate the crosslinked body of the object lesson of said temperature conditioning agent (A).
The weight of the preferred X of main chain portion, joint portion Y and side chain Z satisfies following formula.
Z/(X+Y+Z)≥0.75
That is, side chain Z shared ratio in the crystallinity unit is more than the 75 weight %.Side chain Z is uncrystallizable during less than 75 weight %, might can not bring into play temperature regulation.
Temperature regulato (A) and (B) in the scope of not damaging its characteristic can be brought into play required function by containing other unit.
For example, temperature regulato (A) and (B) can contain hydrophilic units.These temperature regulatos are owing to have long chain hydrocarbon groups as side chain, and the hydrophobicity height still can improve wetting ability by containing hydrophilic units.In addition, when these temperature regulatos and other hydroaropic substance are used in combination, to the adaptation raising of other material.
The monomer that forms this hydrophilic units is not limited especially, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate etc. are arranged.Represent with following formula (4) by the hydrophilic units that 2-hydroxyethyl methacrylate forms.In addition, the hydrophilic units that is formed by vinylformic acid 2-hydroxy methacrylate is represented with following formula (5).
[changing 4]
The content of hydrophilic units is preferably below the 50 weight %, more preferably below the 30 weight %.If surpass 50 weight % then the crystallinity of side chain Z might reduce.
Temperature regulato (A) and preparation method (B) are not limited especially.
For example, temperature regulato (A) can prepare by forming the monomer polymerization that the unitary monomer of crystallinity maybe can form crystallinity unit and hydrophilic units.
For above-mentioned poly-high ' alpha ' olefin, preferably synthetic with the catalyzer of the homogenous system of so-called metallocene catalyst.Metallocene class catalyzer is for example on the books in the open WO03/070790 communique in the world.Wherein, C2 symmetry and the symmetric transistion metal compound of C1 that preferred especially use can the synthesing isotactic polymkeric substance.Specifically, be preferably and contain following (a) and catalyzer (b).
(a) transistion metal compound of two cross-linking types (two Bridge types)
(b): be selected from (b-1) can with the compound of the transistion metal compound or derivatives thereof reacting forming ion complex compound of above-mentioned (a) composition and (b-2) at least a composition in the aikyiaiurnirsoxan beta (ア Le ミ ノ キ サ Application)
In the presence of catalyst for polymerization, making carbonatoms is high ' alpha ' olefin polymerization more than 10.
Transistion metal compound as above-mentioned two cross-linking types, the transistion metal compound that preferably contains silicon as crosslinking group part, between part with double cross-linking type (double frame Bridge type) dicyclopentadiene radical derivative, for example can enumerate (1,2 '-dimethylated methylene is silica-based) (2,1 '-dimethylated methylene is silica-based) two (3-trimethyl silyl methyl indenyl) zirconium dichloride etc.
As (b-1) composition, can enumerate dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (ジ メ チ Le ア ニ リ ニ ウ system テ ト ラ キ ス ペ Application Off Le オ ロ Off エ ニ Le ボ レ-ト) etc.
As (b-2) composition, can enumerate chain aikyiaiurnirsoxan beta, ring-type aikyiaiurnirsoxan beta such as methylaluminoxane.
In addition, except above-mentioned (a) with (b) the composition, can use organo-aluminium compounds such as trimethyl aluminium, triisobutyl aluminium as (c) composition.
Temperature regulato (B) can prepare with the linking agent polymerization by the monomer that can form the unitary monomer of crystallinity, maybe can form crystallinity unit and hydrophilic units.
As forming crosslinked linking agent (monomer), polyoxyethylene glycol (1000) diacrylate, polyoxyethylene glycol (1000) dimethacrylate, glycol diacrylate, ethylene glycol dimethacrylate etc. are arranged, be preferably polyoxyethylene glycol (1000) dimethacrylate, ethylene glycol dimethacrylate.
The amount of linking agent is preferably 0.1～20 weight % usually with respect to the monomer that can form crystallinity unit and hydrophilic units, more preferably 0.2～3 weight %.During less than 0.1 weight %, show cross-linking effect hardly.On the other hand, even surpass also indifference almost of 20 weight % effects.
Then temperature regulato (C) is described.
Temperature regulato (C) as mentioned above, for main chain with polyethers and mutually the unit of the side chain of crystallization as the polymkeric substance or the oligopolymer of main composition composition.
In temperature regulato (C), side chain is not if can then limit especially by crystallization.
Can enumerate as concrete temperature regulato (C) and to have unitary Polyglycerine class shown in the formula (2) or to have unitary polyalkylene glycols shown in the formula (3).
[changing 5]
(in the formula, R
1Be that to be selected from carbonatoms be at least a in the alkyl more than 11, R
2Be that to be selected from carbonatoms be at least a in the alkyl more than 14.)
R
1Or R
2Be preferably straight chained alkyl with above-mentioned carbonatoms.As concrete example, can enumerate undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl etc.
Be preferably tridecyl (C13), pentadecyl (C15), heptadecyl (C17), heneicosyl (C21) especially.
For example, R
1Be that carbonatoms is 13 tridecyl, R
2Be carbonatoms when being 14 tetradecyl, temperature regulato of the present invention has the unit shown in formula (6) or the formula (7) respectively.
[changing 6]
In said structure, though main chain is non-crystallizable under the temperature of regulation, long side chain crystallization each other.
As the example of Polyglycerine class temperature regulato, can enumerate ten glycerine-lauric acid (C12) reactant, ten glycerine-tetradecanoic acid (C14) reactant, ten glycerine-palmitinic acid (C16) reactant, ten glycerine-stearic acid (C18) reactant, ten glycerine-docosoic acid (C22) reactant etc.Wherein, be preferably ten glycerine-tetradecanoic acid reactant, ten glycerine-palmitinic acid reactant, ten glycerine-stearic acid reactant, ten glycerine-docosane acid reaction.
In addition, as the example of polyalkylene glycols temperature regulato, can enumerate the polymkeric substance of oxyalkylenes such as oxidation laurylene, oxidation tetradecene, oxidation hexadecylene, oxidation octadecylene etc.Wherein, be preferably the polymkeric substance of oxidation hexadecylene, oxidation octadecylene etc.
Temperature regulato (C) can be by changing the required function of functional group's performance of side chain in the scope of not damaging its characteristic.
For example, temperature regulato (C) is owing to have long chain hydrocarbon groups as side chain and the hydrophobicity height, but by containing hydrophilic functional group such as alcohol, can improve wetting ability.Thereby when temperature regulato is applied to base material etc. and goes up, the adaptation of base material etc. is improved.
The aerial 5% weight minimizing temperature of measuring with the TG-DTA determinator of temperature regulato (C) is preferably more than 200 ℃ usually, more preferably more than 240 ℃.During less than 200 ℃, when the heating processing treatment, might evaporate.Be noted that 5% weight reduces temperature and refers to and temperature regulato (C) is heated the temperature when reducing 5 whole weight %.
Preparation method to temperature regulato (C) does not limit especially.For example, Polyglycerine class temperature regulato can prepare by using known esterification process that the hydroxyl of existence in the Polyglycerine (polyether backbone) is reacted with the carboxyl with carboxylic acid (side chain) of straight chained alkyl.
On the other hand, the polyalkylene glycols temperature regulato can be by preparing the oxyalkylene ring-opening polymerization.
Said temperature conditioning agent (A)～(C) is in the temperature range of regulation, though side chain along with big latent heat carries out the transformation mutually of reversible crystallization, noncrystallineization, main chain does not carry out above-mentionedly changing mutually.Therefore, ooze out, need not use micro-capsule owing to compare to be difficult for producing with wax etc.
The fusing point of the temperature regulato that uses among the present invention is-10～100 ℃.The lower limit of this scope is preferably 0 ℃, more preferably 10 ℃.The upper limit of this scope is preferably 80 ℃, more preferably 50 ℃, is preferably 40 ℃ especially.
If fusing point surpasses 100 ℃ then because these temperature regulatos under daily use atmosphere gas, often exist with solid state, can not utilize the character that absorbs heat of crystallization when heating up, so be difficult to give full play to function as temperature regulato.
In addition, fusing point is during less than-10 ℃, because under daily use atmosphere gas, these temperature regulatos often exist with liquid state, can not utilize the character of rejected heat when solidifying, and are difficult to give full play to the function as temperature regulato.
The fusing point of temperature regulato and the difference of zero pour are preferably in 15 ℃ usually.If greater than 15 ℃ then because the heat absorption, heat release the interval wide, be difficult to bring into play function as temperature regulato in required narrow temperature.
The latent heat of temperature regulato is more than the 30J/g in the scope of above-mentioned fusing point, is preferably more than the 50J/g, more preferably more than the 70J/g.Latent heat might be insufficient as the effect of temperature regulato during less than 30J/g.
Be noted that among the application that for fusing point, zero pour and latent heat, use differential scanning calorimeter (DSC) to measure respectively, fusing point refers to the temperature on the summit at fusion peak, zero pour refers to the temperature (JIS K 7121) on the summit of peak crystallization.Wherein, fusing point is to be heated to temperature high when once fusing the peak and finish, be cooled to specified temperature after, the temperature on the summit at the fusion peak that obtains when heating once more.
The preferred fusing point of thermoplastic resin that constitutes heat storage compound of the present invention is the thermoplastic resin more than 100 ℃.Specifically, be urethane resin, acrylic resin, polyamide resin, polyvinyl chloride (PVC) RESINS (polyvinyl chloride resin), acrylic resin, polyvinyl resin, polystyrene resin, vibrin (for example PET), polycarbonate resin, ethylene-vinyl alcohol copolymer resin, thermoplastic elastomer resin, polyphenylene sulfide, ABS resin etc.Wherein, be preferably acrylic resin, polyvinyl resin, vibrin, polystyrene resin, polyamide resin, ABS resin, polycarbonate resin and ethylene-vinyl alcohol copolymer resin.They can be used alone or be used in combination of two or more.
And thermoplastic resin also can be the distinctive resin of wet type spinning (for example artificial silk).
In the heat storage compound of the present invention, the temperature regulato high dispersing is in thermoplastic resin.Specifically, the median size of preferred temperature regulato is separated into less than 13 μ m.Among the present invention, by the smaller temperature regulato of the weight-average molecular weight of use temperature conditioning agent, can be in thermoplastic resin with the temperature regulato high dispersing.Thus, the fracture of wire in the time of can significantly reducing spinning.The median size of temperature regulato is 13 μ m when above, might produce fracture of wire during spinning.
At this, the median size of temperature regulato refers to uses transmission electron microscope observation group compound cross section to the composition before the spinning (for example particle), selects the major diameter of a plurality of temperature regulatos of dispersive to measure at random, averages the particle diameter that obtains.Be noted that in the further high dispersing of temperature regulato and might can not measure median size under the situation of compatibilized.
The median size of dispersive temperature regulato more preferably below the 10 μ m, more preferably below the 5 μ m, is preferably below the 0.5 μ m especially in the heat storage compound of the present invention.
The molecular weight that the median size of temperature regulato can be by the controlled temperature conditioning agent or the molecular weight of thermoplastic resin wait to be adjusted.
The temperature regulato in the heat storage compound of the present invention and the ratio of thermoplastic resin are preferably temperature regulato/thermoplastic resin (quality %): 5/95～70/30.Temperature regulato might can not be given full play to its temp regulating function during less than 5 quality %, might can not get sufficient dispersion when surpassing 70 quality %.5～50 quality % more preferably.
In the heat storage compound of the present invention, improve material, can cooperate the acrylic polymers that contains epoxy group(ing), allyl ethers multipolymer etc. as consistency.Thus, the consistency of thermoplastic resin and temperature regulato improves, thereby can increase the use level of temperature regulato.
In addition, in the heat storage compound of the present invention, in the scope of not damaging its characteristic, can cooperate various additives, for example, antioxidant, photostabilizer, inorganic filler (lime carbonate, talcum etc.), whipping agent (chemical foaming material etc.), age resister, antiseptic-germicide, mould inhibitor, tinting material, pigment, static inhibitor, fire retardant, processing aid, stablizer, softening agent, linking agent, reaction promotor etc.
The latent heat of heat storage compound of the present invention under-10～100 ℃, is being preferably aspect the heat accumulation function more than the 1J/g, more preferably more than the 5J/g usually.Latent heat is during less than 1J/g, and the effect of accumulation of heat might be insufficient.In addition, preferably-10～80 ℃, more preferably under 0～50 ℃, be preferably more than the 1J/g, more preferably more than the 5J/g.By this characteristic, can give full play to temp regulating function for extraneous gas temperature etc.
Heat storage compound of the present invention can by with temperature regulato and thermoplastic resin with known method, for example with mixing preparations such as mixing extruders.
In addition, can heat storage compound melt-spinning of the present invention be made the accumulation of heat fiber by known extrusion type composite spinning machine etc.Accumulation of heat fiber of the present invention is preferably core sheath structure.
Under the situation of core sheath structure, resin as constituting sheath portion can use polyamide resin, vibrin, urethane resin, ethylene vinyl acetate copolymer, polyvinylidene dichloride resin, polyvinyl chloride (PVC) RESINS, acrylic resin, polyvinyl resin, acrylic resin etc.
During spinning, preferably with respect to silk footpath (being the diameter of core in the core sheath structure), the particle diameter of temperature regulato is below 1/3, more preferably below 1/5 usually.
Spinning temperature is different and different according to the fibrous material that uses, but is generally about 180～350 ℃.
When making above-mentioned accumulation of heat fiber, in the scope of not damaging its characteristic, can suitably add moisture adsorbent, wetting agent, tinting material, stablizer, fire retardant, electrostatic agent, age resister, antioxidant, antiseptic-germicide, mould inhibitor, pigment, static inhibitor, fire retardant, processing aid, softening agent, linking agent, reaction promotor, whipping agent etc.
In addition, the cross-sectional shape of accumulation of heat fiber is not limited to circle, also can be special crosssections such as trilateral, square.
Among the present invention, the temperature regulato that uses when making the accumulation of heat fiber is because to compare molecular weight ratio higher with wax or monomer, the problem of do not have evaporation, leaking.In addition, owing to be oligopolymer or polymkeric substance, can rub (
り Write body), fibrosis, continuous spinning, inweave (
り Write body) handling ease such as.That is, the spinnability excellence of accumulation of heat fiber of the present invention is made easily.
The core of accumulation of heat fiber is owing to contain the said temperature conditioning agent, and the accumulation of heat fiber produces latent heat under the fusing point of temperature regulato.That is, under-10～100 ℃, produce above, the more preferably above latent heat of 5J/g of preferred 1J/g.Latent heat is during less than 1J/g, and the effect of accumulation of heat might be insufficient.In addition, preferably-10～80 ℃, more preferably under 0～50 ℃, preferably produce above, the more preferably above latent heat of 5J/g of 1J/g.
By this characteristic,, can give full play to temp regulating function for extraneous gas temperature etc.
In addition, be said temperature conditioning agent or thermoplastic resin by making core, the temperature regulato homogeneous can be distributed in the fiber, can suppress the unequal of spinning diameter or tensile strength.In addition, be above-mentioned thermoplastic resin by making sheath portion, can similarly form the surface of fiber with synthon in the past, the processing of woven/knitted fabrics or dyeing etc. also can be carried out processing ease with method same.
Heat storage compound of the present invention by known method, is for example carried out moulding by being equipped with sheet or film with the forcing machine of mould, can make sheet or film.
Heat storage compound of the present invention since temperature regulato high dispersing as mentioned above be difficult for producing because fuzzy (muddiness) that the bad problem of dispersion of temperature regulato is caused.
[embodiment]
By the following examples the present invention is carried out more specific description.
Embodiment 1
(1) preparation of heat storage compound
In extruding granulator (Chi Beishe system), drop into 1-hexadecylene-1-octadecylene multipolymer [(C as temperature regulato
16H
32)
m-(C
18H
36)
n] (Mw=8500) 30 quality %, as polypropylene (プ ラ イ system Port リ マ-society's system, Y2005GP) the 70 quality % of thermoplastic resin, carry out melting mixing and obtain granular composition.The prilling temperature of this moment is 280 ℃.
For said composition, as can be known, the median size of temperature regulato is 0.3 μ m after the dispersion state of usefulness infiltration type electron microscope (TEM) observation temperature regulato.
(2) spinnability evaluation
With the composition fusion of mixing extruder (KCK-80, ケ イ シ-ケ イ エ Application ジ ニ ア リ Application グ society system), be extruded into the wire rod shape from mould with preparation in above-mentioned (1).Under 240 ℃, extrude, from height 2m to the bottom surface streamline material that hangs down.Observe this wire rod and whether produce fracture of wire.Evaluation is carried out with following benchmark.The result is as shown in table 1.The silk footpath refers to the diameter of solidified wire rod.As shown in table 1, change to 1000 μ m from 7 μ m and estimate.The silk footpath is undertaken by the discharge-amount (screw rod speed of rotation etc.) of adjusting forcing machine.
Zero: the 1 minute situation of fracture of wire not
Δ: 1 minute fracture of wire is less than 10 times situation
*: the situation of 1 minute fracture of wire more than 10 times
(3) evaluation of sheet
Be shaped to the sheet of thickness 500 μ m by multilayer forcing machine (2 kind of 3 formable layer machine) (limit, field プ ラ ス チ Star Network ス machinery society system).Use the composition for preparing in above-mentioned (1) as core resin, as the resin use polypropylene (プ ラ イ system Port リ マ-society's system, E-203GV) of skin section.Mold temperature is 200 ℃, and the thickness of core is 300 μ m, and the thickness of skin section is 150 μ m.
For this sheet, its surface of visual observation is estimated with following benchmark.The result is as shown in table 1.
Zero: nothing is blured, is transparent situation on 10cm quadrate sheet
Δ: on 10cm quadrate sheet, have 5 with the fuzzy situation in interior position
*: on 10cm quadrate sheet, there are 6 with the fuzzy situation in upper part
Embodiment 2～6 comparative examples 1
Except the molecular weight Mw of change temperature regulato as shown in table 1, operation preparation similarly to Example 1, evaluation heat storage compound.The result is as shown in table 1.The rerum natura of the temperature regulato that uses in each example and the median size in granular composition are as shown in table 2.
[table 1]
[table 2]
| Molecular weight (Mw) | Fusing point (℃) | Latent heat (J/g) | Median size (μ m) | |
| Embodiment 1 | 8500 | 27～29 | 70 | 0.3 |
| Embodiment 2 | 10000 | 27～29 | 70 | 0.5 |
| Embodiment 3 | 15000 | 27～29 | 70 | 0.75 |
| Embodiment 4 | 20000 | 27～29 | 70 | 1.04 |
| Embodiment 5 | 40000 | 27～29 | 70 | 5.2 |
| Embodiment 6 | 65000 | 27～29 | 70 | 6.1 |
| Comparative example 1 | 100000 | 27～29 | 70 | 8.2 |
The evaluation of temperature regulato is carried out as follows.
(1) fusing point, latent heat
Utilize differential scanning calorimeter (DSC-7: パ-キ Application エ Le マ-ジ ヤ パ Application society system), at sample size: 3g, intensification, cooling rate: measure under 10 minutes/minute the condition.
(2) molecular weight (Mw)
Utilize GPC determinator (Japanese beam split society system) to measure.
Chromatographic column: TOSO GMHHR-H (S) HT
Detector: phase chromatography-use RI detector WATERS 150C
Measure temperature: 145 ℃
Solvent: 1,2, the 4-trichlorobenzene
Sample concentration: 2.2mg/ml
Weight-average molecular weight (Mw) is used the polystyrene conversion value of being tried to achieve by the typical curve of polystyrene standard.
(3) median size of temperature regulato
Observe, estimate the particulate cross section of composition with infiltration type electron microscope (TEM).
[preparation example]
The preparation method of the poly-high ' alpha ' olefin temperature regulato (1-hexadecylene-1-octadecylene multipolymer) that uses in the foregoing description and the comparative example below is described.
Synthesis example 1 " preparation of (1,2 '-dimethylated methylene is silica-based) (2,1 '-dimethylated methylene is silica-based) two (3-trimethyl silyl methyl indenyl) zirconium chloride (following is catalyst A) "
Under stream of nitrogen gas, in 200 milliliters Xi Laike (Schlenk) bottle, add 100 milliliters of (1,2 '-dimethylated methylene is silica-based) (2,1 '-dimethylated methylene is silica-based) two indenes 2.5g (7.2 mmole) and ether.Be cooled to-78 ℃, add the hexane solution (1.60 mol) 9.0 milliliters (14.8 mmole) of n-Butyl Lithium (n-BuLi) after, at room temperature stirred 12 hours.
Distillation removes and desolvates, and the solid with 20 milliliters of hexane wash obtain carries out drying under reduced pressure, obtains the lithium salts of (1,2 '-dimethylated methylene is silica-based) (2,1 '-dimethylated methylene is silica-based) two indenes of white solid form thus quantitatively.
Lithium salts 6.97 mmoles that obtain are dissolved in the Xi Laike bottle among 50 milliliters of the THF (tetrahydrofuran (THF)), at room temperature slowly drip 2.1 milliliters of iodomethyl trimethyl silanes (14.2 mmole), stirred 12 hours.
Distillation removes and desolvates, and adds 50 milliliters of ether, washs with saturated aqueous ammonium chloride.Behind the separatory, dry organic phase distillation removes desolvates, and obtains (1,2 '-dimethylated methylene is silica-based) (2,1 '-dimethylated methylene is silica-based) two (3-trimethyl silyl methyl indenes) 3.04g (5.9 mmole) (yield 84%) thus.
Then, under stream of nitrogen gas, in the Xi Laike bottle, add 50 milliliters of two (3-trimethyl silyl methyl indenes) 3.04g (5.9 mmole) of above-mentioned (1,2 '-dimethylated methylene is silica-based) (2,1 '-dimethylated methylene is silica-based) that obtains and ether.Be cooled to-78 ℃, add the hexane solution (1.60 mol) 7.4 milliliters (11.8 mmole) of n-Butyl Lithium (n-BuLi) after, at room temperature stirred 12 hours.
Distillation removes and desolvates, and the solid 40 milliliters of washings of hexane with obtaining obtain lithium salts 3.06g with ether affixture form thus.Ask it
1H-NMR obtains following result.
1H—NMR(90MHz、THF—d8)：δ 0.04(s，—SiMe
3，18H)，0.48(s，—Me
2Si—，12H)，1.10(t，—CH
3，6H)，2.59(s，—CH
2—，4H)，3.38(q，—CH
2-，4H)，6.2—7.7(m，Ar—H，8H)
Under stream of nitrogen gas, the above-mentioned lithium salts 3.06g that obtains is suspended in 50 milliliters of the toluene.It is cooled to-78 ℃, it is suspended in other Xi Laike bottle in 20 milliliters of the toluene, to wherein dripping the zirconium tetrachloride 1.2g (5.1 mmole) that is cooled to-78 ℃ in advance.After dripping end, at room temperature stirred 6 hours.
After the solvent of reaction soln is removed in distillation, make the residue recrystallization by methylene dichloride, obtain (1 thus, 2 '-dimethylated methylene is silica-based) the yellow crystallite 0.9g (1.33 mmole) (yield 26%) of (2,1 '-dimethylated methylene is silica-based) two (3-trimethyl silyl methyl indenyl) zirconium chloride (catalyst A).Ask it
1H-NMR obtains following result.
1H—NMR(90MHz、CDCl
3)：δ 0.0(s，—SiMe
3，18H)，1.02，1.12(s，—Me
2Si—，12H)，2.51(dd，—CH
2-，4H)，7.1—7.6(m，Ar—H，8H)
Preparation example 1
In 1 liter of autoclave of heat drying, add 180 milliliters of 1-hexadecylenes (C16), 20 milliliters of 1-octadecylenes (C18), 200 milliliters of toluene, after making polymerization temperature be 120 ℃, add 2 micromole's catalyst A, 4 micromole's dimethyl puratized agricultural sprays, four or five fluoroborates (ジ メ チ Le ア ニ リ ニ ウ system テ ト ラ キ ス ペ Application Off Le オ ロ ボ レ-ト), further import hydrogen 0.8MPa, polymerization 2 hours.Polyreaction makes the reactant post precipitation with acetone after finishing, and carries out drying treatment under heating, decompression, obtains high alpha-olefin polymkeric substance 260g thus.The Mw of the polymkeric substance that obtains is 8500.
Preparation example 2
In 1 liter of autoclave of heat drying, add 360 milliliters of 1-hexadecylenes (C16), 40 milliliters of 1-octadecylenes (C18), after making polymerization temperature be 120 ℃, add 2.0 mmole triisobutyl aluminiums, 2 micromole's catalyst A, 4 micromole's dimethyl puratized agricultural sprays, four or five fluoroborates, further import hydrogen 0.8MPa, polymerization 2 hours.Polyreaction makes the reactant post precipitation with acetone after finishing, and carries out drying treatment under heating, decompression, obtains high alpha-olefin polymkeric substance 250g thus.The Mw of the polymkeric substance that obtains is 10000.
Preparation example 3
In 1 liter of autoclave of heat drying, add 360 milliliters of 1-hexadecylenes (C16), 40 milliliters of 1-octadecylenes (C18), after making polymerization temperature be 110 ℃, add 2 micromole's catalyst A, 4 micromole's dimethyl puratized agricultural sprays, four or five fluoroborates, further import hydrogen 0.1MPa, polymerization 2 hours.Polyreaction makes the reactant post precipitation with acetone after finishing, and carries out drying treatment under heating, decompression, obtains high alpha-olefin polymkeric substance 290g thus.The Mw of the polymkeric substance that obtains is 15000.
Preparation example 4
In 1 liter of autoclave of heat drying, add 360 milliliters of 1-hexadecylenes (C16), 40 milliliters of 1-octadecylenes (C18), after making polymerization temperature be 100 ℃, add 2 micromole's catalyst A, 4 micromole's dimethyl puratized agricultural sprays, four or five fluoroborates, further import hydrogen 0.3MPa, polymerization 2 hours.Polyreaction makes the reactant post precipitation with acetone after finishing, and carries out drying treatment under heating, decompression, obtains high alpha-olefin polymkeric substance 255g thus.The Mw of the polymkeric substance that obtains is 20000.
Preparation example 5
In 1 liter of autoclave of heat drying, add 360 milliliters of 1-hexadecylenes (C16), 40 milliliters of 1-octadecylenes (C18), after making polymerization temperature be 90 ℃, add 2.0 mmole triisobutyl aluminiums, 2 micromole's catalyst A, 4 micromole's dimethyl puratized agricultural sprays, four or five fluoroborates, further import hydrogen 0.15MPa, polymerization 2 hours.Polyreaction makes the reactant post precipitation with acetone after finishing, and carries out drying treatment under heating, decompression, obtains high alpha-olefin polymkeric substance 280g thus.The Mw of the polymkeric substance that obtains is 40000.
Preparation example 6
In 1 liter of autoclave of heat drying, add 360 milliliters of 1-hexadecylenes (C16), 40 milliliters of 1-octadecylenes (C18), after making polymerization temperature be 80 ℃, add 2 micromole's catalyst A, 4 micromole's dimethyl puratized agricultural sprays, four or five fluoroborates, further import hydrogen 0.2MPa, polymerization 2 hours.Polyreaction makes the reactant post precipitation with acetone after finishing, and carries out drying treatment under heating, decompression, obtains high alpha-olefin polymkeric substance 210g thus.The Mw of the polymkeric substance that obtains is 65000.
Preparation example 7
In 1 liter of autoclave of heat drying, add 360 milliliters of 1-hexadecylenes (C16), 40 milliliters of 1-octadecylenes (C18), after making polymerization temperature be 75 ℃, add 2.0 mmole triisobutyl aluminiums, 2 micromole's catalyst A, 4 micromole's dimethyl puratized agricultural sprays, four or five fluoroborates, further import hydrogen 0.05MPa, polymerization 2 hours.Polyreaction makes the reactant post precipitation with acetone after finishing, and carries out drying treatment under heating, decompression, obtains high alpha-olefin polymkeric substance 220g thus.The Mw of the polymkeric substance that obtains is 100000.
Industrial applicability
The heat storage compound fiber that is obtained by heat storage compound of the present invention is owing to have temperature adjustment function, is suitable for and contacts around the health or noncontact is used and body temperature is carried out adjustment.
Specifically, can be used for the motion dress materials such as anorak, rainwear, cold-proof dress material, the general dress material of socks, tights, shirt, western-style clothes etc., the beddings such as cotton pad, gloves, footwear material, furniture are with, vehicle dermatine, require in the packaging for foodstuff material, building materials etc. of insulation, cold insulation, especially suitably for fibre, furniture and vehicle with leather and fur products etc.
Claims (7)
1. heat storage compound, it contains temperature regulato and thermoplastic resin, wherein,
Described temperature regulato is the crosslinked body of polymkeric substance, oligopolymer or oligopolymer,
The fusing point of described temperature regulato is that 30J/g is above, weight-average molecular weight is 5000～65000 for-10～100 ℃, latent heat.
2. heat storage compound as claimed in claim 1, wherein, described temperature regulato is present in the thermoplastic resin dispersedly, and the median size of temperature regulato is less than 13 μ m.
3. heat storage compound as claimed in claim 1 or 2, wherein, described temperature regulato shared ratio in heat storage compound is 5～70 quality %, the ratio of described thermoplastic resin is 30～95 quality %.
4. as any described heat storage compound in the claim 1～3, wherein, the weight-average molecular weight of described temperature regulato is 5000～30000.
5. as any described heat storage compound in the claim 1～4, wherein, described thermoplastic resin is at least a kind that is selected from acrylic resin, polyvinyl resin, vibrin, polystyrene resin, polyamide resin, ABS resin, polycarbonate resin and the ethylene-vinyl alcohol copolymer resin.
6. accumulation of heat fiber, it obtains any described heat storage compound melt-spinning in the claim 1～5.
7. sheet or film, it contains any described heat storage compound in the claim 1～5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006108265 | 2006-04-11 | ||
| JP108265/2006 | 2006-04-11 |
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| Publication Number | Publication Date |
|---|---|
| CN101421358A true CN101421358A (en) | 2009-04-29 |
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ID=38609416
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800133497A Pending CN101421358A (en) | 2006-04-11 | 2007-04-03 | Heat-storing composition, and heat-storing fiber, sheet and film each made of the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2007119652A1 (en) |
| KR (1) | KR20090004936A (en) |
| CN (1) | CN101421358A (en) |
| WO (1) | WO2007119652A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106459523A (en) * | 2014-04-09 | 2017-02-22 | 住友化学株式会社 | Resin composition, cross-linked product, and method for manufacturing cross-linked product |
| CN115667599A (en) * | 2020-05-29 | 2023-01-31 | 住友化学株式会社 | Heat-accumulating composition |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015034367A (en) * | 2013-08-09 | 2015-02-19 | 株式会社クラレ | Temperature adjustment fiber |
| JP6370067B2 (en) * | 2014-03-13 | 2018-08-08 | 株式会社クラレ | Core-sheath composite fiber having friction resistance and woven / knitted fabric using the same |
| DE112017003147T5 (en) * | 2016-06-22 | 2019-03-14 | Dic Corporation | Heat storage slide |
| JP2018059216A (en) * | 2016-09-30 | 2018-04-12 | Ｋｂセーレン株式会社 | Sea-island type conjugate fiber and fabric composed of the same |
| JP6736444B2 (en) * | 2016-09-30 | 2020-08-05 | Ｋｂセーレン株式会社 | Sea-island type composite fiber and cloth using the same |
| JP2018188752A (en) * | 2017-04-28 | 2018-11-29 | Ｋｂセーレン株式会社 | Composite fiber and fabric thereof |
| JP6917218B2 (en) * | 2017-07-05 | 2021-08-11 | Ｋｂセーレン株式会社 | Kaijima type composite fiber and fabric made of it |
| JP6937719B2 (en) * | 2018-03-31 | 2021-09-22 | Ｋｂセーレン株式会社 | Composite fibers and fabrics made of them |
| TWI720894B (en) | 2020-05-19 | 2021-03-01 | 財團法人紡織產業綜合研究所 | Temperature adjusting nylon fiber |
| CN117321172A (en) * | 2021-05-21 | 2023-12-29 | 住友化学株式会社 | Heat storage composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000230103A (en) * | 1999-02-08 | 2000-08-22 | Ube Ind Ltd | Trans-1,4-polybutadiene composition and heat storage material |
| JP4088178B2 (en) * | 2002-03-12 | 2008-05-21 | 出光テクノファイン株式会社 | Thermal storage film or sheet and laminate thereof |
| JP2003268359A (en) * | 2002-03-12 | 2003-09-25 | Idemitsu Kosan Co Ltd | Heat-storage material |
| JP4339006B2 (en) * | 2002-04-08 | 2009-10-07 | 出光テクノファイン株式会社 | Thermal storage composite fiber and thermal storage cloth member |
| JP2004161885A (en) * | 2002-11-13 | 2004-06-10 | Idemitsu Technofine Co Ltd | Heat storage composition and its molded article |
-
2007
- 2007-04-03 KR KR1020087024753A patent/KR20090004936A/en not_active Application Discontinuation
- 2007-04-03 JP JP2008510915A patent/JPWO2007119652A1/en active Pending
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106459523A (en) * | 2014-04-09 | 2017-02-22 | 住友化学株式会社 | Resin composition, cross-linked product, and method for manufacturing cross-linked product |
| CN106459523B (en) * | 2014-04-09 | 2019-11-19 | 住友化学株式会社 | The manufacturing method of resin combination, cross-linking agent and cross-linking agent |
| CN115667599A (en) * | 2020-05-29 | 2023-01-31 | 住友化学株式会社 | Heat-accumulating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007119652A1 (en) | 2007-10-25 |
| KR20090004936A (en) | 2009-01-12 |
| JPWO2007119652A1 (en) | 2009-08-27 |
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