CN103842463B - Heat ray shielding adhesive composition and heat ray shielding bonding sheet - Google Patents
Heat ray shielding adhesive composition and heat ray shielding bonding sheet Download PDFInfo
- Publication number
- CN103842463B CN103842463B CN201280048422.5A CN201280048422A CN103842463B CN 103842463 B CN103842463 B CN 103842463B CN 201280048422 A CN201280048422 A CN 201280048422A CN 103842463 B CN103842463 B CN 103842463B
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- Prior art keywords
- heat ray
- ray shielding
- adhesive composition
- group
- bonding sheet
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- WQDGUYZIAJKLAB-UHFFFAOYSA-N octan-2-yl nitrite Chemical compound CCCCCCC(C)ON=O WQDGUYZIAJKLAB-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910021509 tin(II) hydroxide Inorganic materials 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- ITAKKORXEUJTBC-UHFFFAOYSA-L vanadium(ii) chloride Chemical compound Cl[V]Cl ITAKKORXEUJTBC-UHFFFAOYSA-L 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
The problem of the present invention is effectively to shield infrared spectral range and the heat ray of near infrared range.The present invention provides the heat ray shielding adhesive composition containing (A) metal particle, (B) acrylic adhesive, (C) dispersant and (D) near infrared absorption pigment, and uses the heat ray shielding bonding sheet of said composition.
Description
Technical field
The present invention relates to be fitted in the heat ray shielding adhesive composition of the enterprising enforcements such as glass pane and employ
The heat ray shielding bonding sheet of said composition, can be with high-efficiency shielding heat ray.
Background technology
In recent years, from the standpoint of energy-conservation, global environmental problems etc., it is desirable to alleviate the load of air-conditioning equipment.Such as exist
House, automobile field in, seek to be attached to the heat ray shielding material that can shield the heat ray from sunlight
On glass pane, thus the temperature in indoor, car is suppressed to rise.The material with heat ray shielding is varied,
Patent Document 1 discloses a kind of binding agent imparting heat ray shielding and bonding sheet thereof.This bonding sheet is to compose
The binding agent having given heat ray shielding is processed into lamellar, and it has following feature: can be pre-machined into and appoint
Meaning shape, there is the re-workability that can re-expand.But, this imparts the heat of bonding sheet of heat ray shielding
Shielding is insufficient, it is desirable to be further improved.
Prior art literature
Patent documentation
Patent documentation 1: flat No. 10-8010 of Japanese Patent Application
Summary of the invention
The problem that invention is to be solved
The problem of the present invention be to provide a kind of with conventional heat ray shielding bonding sheet compared with heat ray shielding obtain
To the heat ray shielding adhesive composition greatly improved and heat ray shielding bonding sheet.
Means for solving the above
Heat ray shielding bonding sheet that the present inventor is greatly improved to obtain heat ray shielding and carry out
Further investigation, it was found that by containing with tin-doped indium oxide as representative metal particle, near infrared absorption pigment,
Dispersant and binding agent, can obtain can high-efficiency shielding heat ray heat ray shielding adhesive composition and should
Compositions is processed into the heat ray shielding bonding sheet of lamellar, thus completes the present invention.
That is, the present invention relates to
" (1) a kind of heat ray shielding adhesive composition, its contain (A) metal particle, (B) acrylic adhesive,
(C) dispersant and (D) near infrared absorption pigment,
(2) the heat ray shielding adhesive composition as described in (1), it is characterised in that described (A) metal particle is choosing
Autoxidation stannum, Indium sesquioxide., zinc oxide group in a kind of metal particle,
(3) the heat ray shielding adhesive composition as described in any one of (1) or (2), it is characterised in that described (B)
Acrylic adhesive be the ratio containing carboxyl or the monomeric building blocks of anhydride be the total monomer structure list in polymer
The polymer of 1%～the 5% of unit,
(4) the heat ray shielding adhesive composition as described in any one of (1) to (3), it is characterised in that described (B)
The weight average molecular weight of acrylic adhesive is 100000～1200000,
(5) the heat ray shielding adhesive composition as described in any one of (1) to (4), it is characterised in that described (D)
Near infrared absorption pigment is phthalocyanine based compound, naphthalene phthalocyanine based compound and/or diimmonium based compound,
(6) the heat ray shielding adhesive composition as described in (5), it is characterised in that described (D) near infrared absorption color
Element is the naphthalene phthalocyanine based compound represented with formula (1),
[chemical formula 1]
In formula (1), M represents metallic atom, metal-oxide, metal hydroxides or metal halide or hydrogen
Atom, X represent low alkyl group, lower alkoxy, substituted-amino, nitro, halogen, hydroxyl, carboxyl, sulfonic group,
Sulfophenyl, A represents the crosslinking group of bivalence, and Y represents the nitrogen-atoms of sulfonic group, carboxyl, primary amino radical or secondary amino group up
Except removing the residue of at least 1 hydrogen on the residue of at least 1 hydrogen or nitrogenous heterocyclic nitrogen-atoms, m and n is flat
Average, and m, n be respectively more than 0 and less than 12, and m's Yu n and more than 0 and less than 12.
(7) the heat ray shielding adhesive composition as described in (6), wherein, the M in formula (1) be VO, A be carbon
Atomic number is the alkylidene of 1～3, and Y is to have substituent group or do not have the phthaloyl imino of substituent group,
(8) the heat ray shielding adhesive composition as described in (6), wherein, the M in formula (1) be Cu, A be carbon
Atomic number is the alkylidene of 1～3, and Y is to have substituent group or do not have the phthaloyl imino of substituent group,
(9) a kind of heat ray shielding bonding sheet, it is coating heat ray shielding bonding described in any one of (1) to (8)
Agent compositions.
Invention effect
According to the present invention, by using dispersant by the metal particle with tin-doped indium oxide as representative and near infrared absorption
Obtained heat ray shielding adhesive composition, in acrylic adhesive, is processed into lamellar by pigment dispersion,
A kind of heat ray shielding bonding sheet can be provided, can press down further compared with conventional heat ray shielding bonding sheet
Heat the temperature rising that ray causes.Thus can suppress house, the temperature of vapour interior space rises, and can subtract
The load of light air-conditioning equipment, therefore the present invention can be that energy-conservation, solution global environmental problems contributes.
Detailed description of the invention
The present invention is described in detail.The adhesive composition that the heat ray shielding bonding sheet of the present invention is formed
It is characterised by, uses dispersant the metal particle with tin-doped indium oxide as representative and near infrared absorption pigment dispersion to be existed
In acrylic adhesive, this adhesive composition can also be processed into lamellar.
It is little, to near-infrared extremely that the metal particle used in heat ray shielding adhesive composition is preferably visible absorption
The light in far infrared region has the material of good absorption characteristic.As this material, can enumerate near infrared region
There is the conductive metal oxide of plasma wavelength.Specifically, stannum oxide, Indium sesquioxide., oxygen can be exemplified
Change zinc, tungsten oxide, chromium oxide, molybdenum oxide etc..Wherein, particularly preferably at the oxygen that the light absorption of visible region is little
Change stannum, Indium sesquioxide., zinc oxide.
It addition, for the electric conductivity improving these oxides, particularly preferably doping the 3rd composition.As for the purpose
Alloy, Sb, V, Nb, Ta etc. are selected for stannum oxide, for Indium sesquioxide. select Zn, Al, Sn, Sb,
Ga, Ge etc., select Al, Ga, In, Sn, Sb, Nb etc. for zinc oxide.
For the preparation method of metal particle, as long as it is the most special to obtain the material that particle diameter is below 100nm
Limit, it is possible to use the known method such as gas phase synthesis method, liquid phase synthesizing method.Such as Indium sesquioxide. microgranule,
The method disclosed in Japanese Unexamined Patent Publication 6-227815 can be utilized.That is, alkali is utilized to neutralize containing special metal microgranule
The aqueous solution of the salt of element, filters obtained precipitate, cleans, and at high temperature carries out heat treated, thus obtains
Method to metal particle.It addition, for tin oxide particles, zinc oxide fine particles, Japan can be exemplified respectively
Unexamined Patent 2-105875, Japanese Unexamined Patent Publication 6-234522.
Method in organic solvent is disperseed, it is possible to use conventional method as by metal particle.I.e., it is possible to according to
Regulation ratio hybrid metal microgranule and organic solvent, be added as needed on dispersant, surfactant in the mixture
Deng, use the dispersal devices such as sand mill, grater, ball mill, homogenizer, roller mill to be disperseed by mixture.
For the metal particle of the present invention, XRD figure spectrum the half-peak of the first main peak that obtains a width of 0.01 °～
0.8 °, and if a width of less than 0.01 ° of half-peak, then primary particle size increases, thus is difficult to ensure that the transparency.If it addition, half
Peak width more than 0.8 °, then is difficult to show sufficient heat shielding.It addition, the half-peak breadth of above-mentioned metal particle is preferred
Lower limit is 0.1 °, preferred upper limit is 0.8 °, preferred lower limit is 0.2 °, the preferred upper limit is 0.5 °.
The specific surface area with BET method mensuration of the metal particle used in the present invention is preferably 5m3/ g～200m3/ g,
More preferably 10m3/ g～150m3/ g, particularly preferably 10m3/ g～100m3/g.Specific surface area based on BET method
Less than 5m3The primary particle size of the metal particle of/g is big, therefore in the feelings making sheet material, film, coating or resin combination
Under condition, finished surface is the most unsmooth.Further, it is possible to produce the shortcomings such as the transparency cannot be expected.The opposing party
Face, BET specific surface area is more than 200m3The metal particle of/g needs special technology in the mill, and likely obtains
Less than sufficient degree of crystallinity, heat ray shielding is impaired.It should be noted that BET method is on powder granule surface
Molecule or ion known to absorption size, the method measuring the specific surface area of test portion according to its adsorbance.
Near infrared absorption pigment be absorb in infrared ray closest to visibility region near infrared ray (wavelength be about 780nm～
The general name of pigment 2000nm), as the kind of near infrared absorption pigment can enumerate azo system, ammonium system, anthraquinone system,
Cyanines system, diimmonium system, dithiol metal complex system, side acid inner salt (squalirium) be, phthalocyanine system, naphthalene phthalocyanine
System etc..From improving from the viewpoint of durability, preferably phthalocyanine system, naphthalene phthalocyanine system, diimmonium system, and from efficiently screen
From the viewpoint of covering heat ray, preferably naphthalene phthalocyanine system, the compound particularly preferably represented with above-mentioned formula (1).?
In above-mentioned formula (1), M represents hydrogen atom, metallic atom, metal-oxide, metal hydroxides or metal halide.
M be beyond hydrogen atom in the case of, this M means that the naphthalene phthalocyanine ring in formula (1) has so-called central metal.Separately
Outward, in the case of M is hydrogen atom, it is meant that this naphthalene phthalocyanine ring does not has central metal.
As the concrete example of metallic atom in above-mentioned M, can enumerate such as Li, Na, K, Mg, Ti, Zr, V,
Nb、Ta、Cr、Mo、W、Mn、Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt、Cu、Ag、Au、
Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi etc..
As metal-oxide, VO, GeO etc. can be enumerated.As metal hydroxides, can enumerate such as
Si(OH)2、Cr(OH)2、Sn(OH)2, AlOH etc..As metal halide, such as SiCl can be enumerated2、VCl、
VCl2, VOCl, FeCl, GaCl, ZrCl, AlCl etc..Wherein, preferably Fe, Co, Cu, Ni, Zn,
The metal hydroxidess etc., more preferably Cu, VO such as the metal-oxide such as metallic atom, VO, AlOH such as Al, V.
To use above-mentioned M be Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe,
Co、Ni、Ru、Rh、Pd、Os、Ir、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Si、
The heat ray shielding bonding sheet that the toluene dispersion liquid of the naphthalene phthalocyanine based compound of Ge, Sn, Pb, Sb, Bi makes exists
The temperature inside the box making the case used in test in heat ray shielding test declines, it is shown that good heat ray shielding
Effect.It addition, during especially with the naphthalene phthalocyanine based compound that M is Cu, make the temperature inside the box be remarkably decreased, display
Excellent heat ray heat shielding effect, thus be preferred.During the naphthalene phthalocyanine based compound using M to be VO,
Also make the temperature inside the box be remarkably decreased, it is shown that excellent heat ray heat shielding effect, thus be preferred.
X represent low alkyl group, lower alkoxy, substituted-amino, nitro, halogen, hydroxyl, carboxyl, sulfonic group or
Sulfophenyl.A is the crosslinking group of bivalence, can enumerate alkylidene ,-CO that such as carbon number is 1～32-,
-SO2-,-SO2NH(CH2)a-(herein, a represents 0～4), but preferably carbon number is the alkylene of 1～3
Base, a are the-SO of 02NH-, more preferably carbon number are the alkylidene of 1～3.Y represents sulfonic group, carboxylic
Remove on the nitrogen-atoms of base, primary amino radical or secondary amino group remove on the residue of at least 1 hydrogen or nitrogenous heterocyclic nitrogen-atoms to
The residue of few 1 hydrogen, can enumerate such as carboxyl, sulfonic group, have substituent group or do not have the adjacent benzene two of substituent group
Formyl imino group, there is substituent group or not there is the 1-piperazinyl of substituent group, there is substituent group or not there is substituent group
Piperidino etc., preferably carboxyl, sulfonic group, there is substituent group or not there is the phthaloyl imino of substituent group,
More preferably there is substituent group or not there is the phthaloyl imino of substituent group.It should be noted that as Y
For there is substituent group or not there is the phthaloyl imino of substituent group, there is substituent group or not there is substituent group
1-piperazinyl, substituent group when having substituent group or do not have the piperidino of substituent group, can illustrate hydrogen atom, low
Level alkyl, lower alkoxy, substituted-amino, nitro, halogen, sulfonic group, preferably hydrogen atom, halogen.
Being not particularly limited for substituted-amino in the present invention, it includes such as with the substituted amino of low alkyl group.Separately
Outward, low alkyl group, lower alkoxy refer respectively to the alkyl that carbon number is 1～4 and the alkane of straight-chain or branched
Epoxide.As by near infrared absorption pigment dispersion method in organic solvent, it is possible to use conventional method.That is,
Ratio can mix near infrared absorption pigment and organic solvent according to the rules, be added as needed on dispersion in the mixture
Agent, surfactant etc., use the dispersal devices such as sand mill, grater, ball mill, homogenizer, roller mill to mixed
Compound disperses.
It is dispersed with metal particle and near-infrared is inhaled the heat ray shielding adhesive composition of pigment and said composition added
The heat ray shielding bonding sheet of work slabbing is comprised with shielding sunlight for being attached on glass pane
The purpose of the heat ray composition in wavelength, therefore good weatherability is its most important condition.Therefore, this embodiment makes
Binder resin be preferably the acrylic copolymer system binder resin of good weatherability.Acrylic copolymer system bonds
Agent generally can be by main monomer that the glass transition temperature of polymer the is low copolymerization list high with glass transition temperature
The copolymerization of body manufactures.
As the monomer as main constituent of acrylic copolymer system binding agent, glass transition temperature can be enumerated low
And alkyl acrylate that the carbon number of alkyl is 2～14 or the metering system that carbon number is 4 to 16 of alkyl
Acid alkyl ester, and glass transition temperature higher than they and the monomer of copolymerization can be carried out with them can be together with main monomer
Use.
As the alkyl acrylate monomer that glass transition temperature is low, ethyl acrylate, acrylic acid can listed just
Propyl ester, isopropyl acrylate, methoxyethyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, acrylic acid are secondary
Butyl ester, 2-EHA, n-octyl, Isooctyl acrylate monomer, acrylic acid different nonyl ester, acrylic acid are different
Stearyl etc..
It addition, as the low alkyl methacrylate monomer of glass transition temperature, methacrylic acid can be exemplified
2-Octyl Nitrite, n octyl methacrylate, the positive Lauryl Ester of methacrylic acid etc..
It addition, as the monomer of copolymerization can be carried out, can exemplify vinyl acetate, acrylonitrile, acrylamide,
Styrene, methyl methacrylate, acrylic acid methyl ester. etc..
In addition to above-mentioned monomer, in order to obtain required bond properties, as containing monomer, it be also possible to use
(methyl) acrylic acid, itaconic acid, (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate, (methyl) acrylic acid two
Methylamino ethyl ester, acrylamide, n-methylolacrylamide, DMAA, glycidyl methacrylate,
Maleic anhydride etc..
It addition, molecular weight can significantly affect metal particle and the dispersibility of near infrared absorption pigment, therefore acrylic acid series glues
The weight average molecular weight of mixture is preferably 100000～1200000.More preferably 200000～800000.
Constitute the degree of cross linking of macromolecular material of binding agent because of each bars such as the kind of binding agent (adhesive composition), compositions
Part and different, there is no particular limitation as to it.Adhesive composition can also contain plasticizer as required.As this plasticising
Agent, can enumerate phthalic acid ester, trimellitate, pyromellitic acid ester, adipate ester, sebacate, phosphoric acid
The esters such as three esters or glycol ester；Operation oil, liquid polyethers, liquid polyterpenes or other liquid resins；Etc., can
One kind or two or more be used in mixed way in them.This type of plasticizer is preferably the plasticising good with the compatibility of binding agent
Agent.It addition, in addition to above-mentioned plasticizer, adhesive composition can contain such as UV absorbent as required
Or the various additives such as antioxidant.
As dispersant, representative is soap (soap), alpha-sulfo fatty acid ester salt (MES), alkylbenzene
Sulfonate (ABS), linear alkylbenzene sulfonate (LAS) (LAS), alkyl sulfate (AS), alkyl ether sulphate salts (AES),
Low molecule anion (anion) the property compound of alkylsurfuric acid three ethanol ester etc；Fatty acid ethanol amide, polyoxyethylene
The low molecule nonionic of alkyl ether (AE), polyoxyethylene alkyl phenyl ether (Α Ρ Ε), Sorbitol, sorbitol anhydride etc
Based compound；Alkyl trimethyl ammonium salt, chlorination dialkyl dimethyl ammonium, alkylpyridinium chlorides etc low molecule sun from
Son (cation) property compound；The low molecule both sexes system chemical combination of alkyl carboxyl glycine betaine, sulfobetaines, lecithin etc
Thing；Formaldehyde condensation products, poly styrene sulfonate, polyacrylate, vinyl compound and carboxylic acid with naphthalene sulfonate
Be the copolymer salt of monomer, carboxymethyl cellulose, polyvinyl alcohol etc. be representative macromolecule water system dispersant；Polypropylene
The macromolecule non-water system dispersant of acid moieties Arrcostab, polyalkylene polyamine etc；Polymine, methacrylic acid
The macromolecule cation system dispersant of aminoalkyl ester copolymer etc, but as long as the present invention can be highly suitable for
Granule, be just not excluded for the dispersant with the structure beyond the material of form illustrated herein.
As dispersant, if enumerating specific name, it is known that following material.I.e. can enumerate Flowlen DOPA-15B,
Flowlen DOPA-17 (Kyoeisha Chemical Co., Ltd.'s system), Solplus AX5, Solplus TX5, Solsperse9000,
Solsperse12000、Solsperse17000、Solsperse20000、Solsperse21000、Solsperse24000、
Solsperse26000、Solsperse27000、Solsperse28000、Solsperse32000、Solsperse35100、
Solsperse54000, SOLTHIX250 (Lubrizol Japan company system), EFKA4008, EFKA4009,
EFKA4010、EFKA4015、EFKA4046、EFKA4047、EFKA4060、EFKA4080、EFKA7462、
EFKA4020、EFKA4050、EFKA4055、EFKA4400、EFKA4401、EFKA4402、EFKA4403、
EFKA4300、EFKA4330、EFKA4340、EFKA6220、EFKA6225、EFKA6700、EFKA6780、
EFKA6782, EFKA8503 (EFKA Additives company system), AJISPER PA111, AJISPER PB711,
AJISPER PB821、AJISPER PB822、AJISPER PN411、FAMEX L-12(Ajinomoto
Fine-Techno company system), TEXAPHOR-UV21, TEXAPHOR-UV61 (Cognis Japan company system),
DisperBYK101、DisperBYK102、DisperBYK106、DisperBYK108、DisperBYK111、
DisperBYK116、DisperBYK130、DisperBYK140、DisperBYK142、DisperBYK145、
DisperBYK161、DisperBYK162、DisperBYK163、DisperBYK164、DisperBYK166、
DisperBYK167、DisperBYK168、DisperBYK170、DisperBYK171、DisperBYK174、
DisperBYK180、DisperBYK182、DisperBYK192、DisperBYK193、DisperBYK2000、
DisperBYK2001、DisperBYK2020、DisperBYK2025、DisperBYK2050、DisperBYK2070、
DisperBYK2155、DisperBYK2164、BYK220S、BYK300、BYK306、BYK320、BYK322、
BYK325、BYK330、BYK340、BYK350、BYK377、BYK378、BYK380N、BYK410、
BYK425, BYK430 (BYK-Chemie Japan company system), DISPARLON1751N, DISPARLON
1831、DISPARLON1850、DISPARLON1860、DISPARLON1934、DISPARLON
DA-400N、DISPARLON DA-703-50、DISPARLON DA-725、DISPARLON DA-705、
DISPARLON DA-7301、DISPARLON DN-900、DISPARLON NS-5210、DISPARLON
NVI-8514L、HIPLAAD ED-152、HIPLAAD ED-216、HIPLAAD ED-251、HIPLAAD
ED-360 (nanmu this chemical conversion Co., Ltd. system), FTX-207S, FTX-212P, FTX-220P, FTX-220S,
FTX-228P、FTX-710LL、FTX-750LL、FTERGENT212P、FTERGENT220P、FTERGENT
222F、FTERGENT228P、FTERGENT245F、FTERGENT245P、FTERGENT250、
FTERGENT251、FTERGENT710FM、FTERGENT730FM、FTERGENT730LL、
FTERGENT730LS, FTERGENT750DM, FTERGENT750FM (NEOS company system),
AS-1100, AS-1800, AS-2000 (Toagosei Co., Ltd's system), KAOCER2000, KAOCER2100,
KDH-154、MX-2045L、HOMOGENOL L-18、HOMOGENOL L-95、RHEODOL
SP-010V, RHEODOL SP-030V, RHEODOL SP-L10, RHEODOL SP-P10 (flower king's strain formula meeting
Society's system), EPAN U103, SHALLOL DC902B, NOIGEN EA-167, PLYSURF A219B,
PLYSURF AL (Di-ichi Kogyo Seiyaku Co., Ltd.'s system), MEGAFAC F-477, MEGAFAC480SF,
MEGAFAC F-482 (DIC company system), Silface SAG503A, Dynol604 (Nishin Chemical Industry Co. Lt
System), SN SPERSE2180, SN SPERSE2190, SN Leveller S-906 (SAN NOPCO company system),
The material of S-386, S-420 (AGC SEIMI CHEMICAL company system) etc.
Generally, the RED (relative energy is poor: Relative Enelgy Difference) of metal particle and dispersant is the least then
Dispersibility is the best, and preferably RED is the combination of less than 1.5.As the RED with metal particle be less than 1.5 point
Powder, can enumerate DISPERBYK-116, DISPERBYK-142, DISPERBYK-145,
DISPERBYK-163、DISPERBYK-2000、DSPERBYK-2155、BYK-P105、ANTI-TERRAU、
EFKA-4010、DOPA-17HF。
(Hansen is in view of the solubility parameter of Hildebrand can to use the solubility parameter that represents in mathematical expression 1
(δ) relevant dispersion force, dipole-dipole interaction, the effect of hydrogen bond and propose), (dispersion force brings to calculate δ D
Contribution；Its London forces or Van der Waals force produced by the dipole by being induced by molecular collision is formed known is carried
Come contribution), the δ P (contribution that polar interaction is brought；In the presence of it refers to that molecule is in the solution, subject molecule is produced
The contribution that raw permanent dipole brings), the δ H (contribution that hydrogen bond brings；It represents specific and interacts, such as table
Show that hydrogen bond, acid/base combine and donor/acceptor combines the contribution brought), use mathematical expression 2 to calculate further and interact
Radius R0, HSP spacing Ra, mathematical expression 3, R0, Ra (relative energy is poor: Relative Enelgy to calculate RED
Difference)。
[mathematical expression 1]
δ2=δD 2+δp 2+δH 2
[mathematical expression 2]
(Ra)2=4(δD2-δD1)2+(δp2-δP1)2+(δH2-δH1)2
[mathematical expression 3]
RED=Ra/RO
Heat ray shielding adhesive composition can utilize known method to make.Such as by metal particle, the reddest
Outer absorption pigment dispersion, in the monomer of the main constituent as acrylic acid series copolymer system binding agent, then brings it about poly-
Close, it is hereby achieved that target heat ray shielding adhesive composition.It addition, also have the most pre-
First make metal particle, the dispersion liquid of near infrared absorption pigment, bring it about after it is mixed with monomer be polymerized thus must
Method to subject adhesives.Further, as easier method, inhale also by by metal particle, near-infrared
Receive the direct method mixing with binding agent thus obtaining subject adhesives compositions of dispersion liquid of pigment.It addition, by metal
Microgranule and near infrared absorption pigment and dispersant, be then dispersed in binding agent, it is also possible to obtain binding agent
Compositions.
In the manufacture of heat ray shielding bonding sheet, the coating process for binding agent is not particularly limited, and can make
With comma coating machine, bar coater, spin coater, flush coater, roll coater, gravure coater, knife type coater or other
Various apparatus for coating.
Metal particle and near infrared absorption pigment are relative to the monomer of acrylic acid series copolymer system binding agent or binding agent
Dispersion ratio is determined by coating thickness and the shielding properties of adhesive layer.As the film being coated with heat ray shielding binding agent
Optical property, it is generally desirable to visible light transmissivity is high, solar transmittance is low, but generally both has proportionate relationship,
Optical property can be determined by the performance of one party emphatically.
This is coated with on the actual glass pane being pasted to building and automobile of film of heat ray shielding binding agent, respectively
Measuring summer and the effect in winter, result is reached to draw a conclusion: in order to obtain sufficient cooling in summer effect, can make
Solar transmittance is less than 80%, in order to make the Min. that rises to of the heating cost in illumination cost and winter, permissible
Making visible light transmissivity is more than 50%.Therefore, the optical characteristics of the film being coated with heat ray shielding binding agent is preferred
For visible light transmissivity be more than 50% and solar transmittance is less than 80%.
Generally, it is contemplated that with the tracing ability of joined face and bonding force and economy, the coating thickness of adhesive layer is usual
Use 10 μm～the thickness of 50 μm, as the amount of the microgranule giving above-mentioned heat ray shielding in this range, excellent
Elect as (metal particle+near infrared absorption pigment): the scope of resin solid content=3:97～1:1 (weight ratio).This
Be due to, the ratio of heat ray shielding agent microgranule less than this ratio time, need to obtain required heat ray shielding
Want the thickness of more than 50 μm, in contrast, during higher than this ratio, it is seen that light transmission rate becomes too small.Further,
The haze value of film should not damage the transparency of glass, can be less than 8%, can be more preferably less than 3%.
Embodiment
Enumerate following embodiment and comparative example illustrates the present invention, but the invention is not restricted to these examples.
Synthesis example 1 (metal particle)
By stannic chloride (SnCl4·5H2O) 5.9g and indium chloride (InCl3) 75.9g is dissolved in water 4000ml, expends 58
Adding minute wherein the ammonia of 2%, finally making pH is 7.85, so that the hydrate of stannum oxide and Indium sesquioxide. is sent out
Raw co-precipitation.During this, liquid temperature maintains 5 DEG C.Then, it is dried after this co-precipitation thing is cleaned, further with 900 DEG C
Fire 2 hours, obtained stanniferous Indium sesquioxide. (ITO) micropowder (metal particle).
Synthesis example 2 (near infrared absorption pigment)
2,3-naphthalene ranadylic phthalocyanine (vanadyl2,3-naphthalocyanine) (Aldrich is added in polyphosphoric acid 40 parts
System) 3.9 parts, phthalimide (Tokyo chemical conversion industry society system) 5.0 parts, paraformaldehyde 1.0 parts, stir at 140 DEG C
Mix 8 hours, be injected in 300 parts of water, filter the solid separated out, resulting in naphthalene phthalocyanine based compound 7.5 parts.
Manufacture example 1 (metal particle dispersion liquid)
Toluene solution 7ml adds in synthesis example 1 obtain ITO synthesis granule 1.12g, acetylacetone,2,4-pentanedione 0.7g,
Dispersant DisperBYK1400.175g, is put into batch-type bead mill apparatus (T.K.Fill Mix30-25 type, primix
Company's system) crushing container in.The zirconium oxide bead that broken pearl uses mean diameter to be 30 μm, fills to crushing container
35% filling of volume.For broken, the mode with peripheral speed as 6.8m/s sets motor, with broken
Time is that the condition of 10 minutes is carried out.It addition, use the centrifugal separator (Himac that Hitachi Koki Co., Ltd manufactures
CR18) with revolution 5000rpm, obtained dispersion (metal particle dispersion liquid) 15 minutes centrifugal treating have been carried out.
Manufacture example 2 (near infrared absorbing coloring matter dispersion liquid 1)
Near infrared absorption pigment 0.21g, the dispersant obtained in synthesis example 2 is added in toluene solution 7ml
DisperBYK1400.21g, is put into batch-type bead mill apparatus (T.K.Fill Mix30-25 type, primix company system)
Crushing container in.The zirconium oxide bead that broken pearl uses mean diameter to be 30 μm, fills to the 70% of crushing container volume
Fill.For broken, the mode with peripheral speed as 10m/s sets motor, is 30 points with the broken time
The condition of clock is carried out.It addition, use centrifugal separator (the Himac CR18 that Hitachi Koki Co., Ltd manufactures) to turn
Number 5000rpm carries out 15 minutes centrifugal treating to obtained dispersion, resulting near infrared absorption pigment and divides
Dissipate liquid 1.
Manufacture example 3 (near infrared absorbing coloring matter dispersion liquid 2)
The near infrared absorption pigment obtained in synthesis example 2 is replaced with 2,3-naphthalene phthalocyanine (Aldrich system), except this with
Outward, near-infrared colorant dispersing liquid 2 has been obtained in the same manner as manufacturing example 2.
Synthesis example 3 (acrylic adhesive A)
N-butyl acrylate 291g and acrylic acid 9g as monomer is dissolved in toluene 366g, adds azo two
Isopropyl cyanide 0.15g, makes these monomers be polymerized 6 hours with 70 DEG C under nitrogen flowing, thus has obtained acrylic resin
Copolymer (weight average molecular weight: Mw=320000).It is diluted with toluene further, has obtained solid constituent ratio
Be 29.36%, viscosity be the acrylic resin copolymer solution of 2700mPas.
Make heat ray shielding binding agent and heat ray shielding bonding sheet
(embodiment 1)
By synthesis example 3 obtains acrylic adhesive A100 weight portion (butyl acrylate: acrylic acid=97:
3), manufacture in toluene dispersion liquid 144 weight portion of the stanniferous Indium sesquioxide. (ITO) obtained in example 1, manufacture example 2 and obtain
The toluene dispersion liquid 14.7 weight portion mixed dissolution of the near infrared absorption pigment arrived, to uniformly, has obtained heat ray shielding
Property binding agent.It addition, the polyester film utilizing comma coating machine to be coated on release sheet (was implemented to have on one side side
Machine silicon processes) (lintec company manufacture 3811, thickness: 38 μm) upper and be dried, with the polyester film of release sheet (
Implemented on one side side organosilicon process) (lintec company manufacture 3801 thickness: 38 μm) cover, thus make
Make heat ray shielding bonding sheet (thickness: 15 μm).
(embodiment 2)
The toluene dispersion liquid of near infrared absorption pigment is replaced with and manufactures the dispersion liquid made in example 3, in addition, with
Embodiment 1 has similarly made heat ray shielding binding agent and heat ray shielding bonding sheet.
Comparative example 1
The toluene dispersion liquid of the most unmixed near infrared absorption pigment, employs and manufactures in example 1 containing of obtaining
Toluene dispersion liquid 144 weight portion of the Indium sesquioxide. (ITO) of stannum and acrylic adhesive A100 weight portion, except this with
Outward, heat ray shielding bonding sheet (thickness: 15 μm) has been made similarly to Example 1.
(embodiment 3)
With the method shown in hereafter, the heat ray shielding of making in embodiment 1, embodiment 2 and comparative example 1 is glued
Close sheet and implement heat ray shielding test.Its result is listed in table 1.
Test method
Experimental enviroment: prepare internal diameter width 150mm × length 235mm × highly 110mm has the shielding of outer temperature
Property and bubble-tight proof box, at the center of top portion of this proof box, high 40cm in above-mentioned proof box top
Position arranges infrared lamp (100V, 250W: Toshiba Corporation), constitutes heat shielding evaluation assay device.
Then, proof box top section arranges made heat ray shielding bonding sheet, utilize adhesive tape surrounding to be attached
Fixing.It addition, thermometer can not be provided with in the way of directly striking at the central part within this proof box by light.It
After, put bright light, within every 10 seconds, measure a temperature, determine the test the temperature inside the box after 30 minutes.Need explanation
, above-mentioned proof box is arranged in the room of about 25 DEG C.In this experiment, to using making in comparative example
The temperature inside the box during the heat ray shielding bonding sheet of heat ray shielding bonding sheet and the present invention compares, if using
The temperature inside the box of the heat ray shielding bonding sheet of the present invention is low, then explanation heat ray shielding effect improves.Need
Bright, the computational methods of the temperature inside the box difference are: by from using the heat ray shielding bonding sheet made in comparative example
The temperature inside the box in deduct and use the temperature inside the box of heat ray shielding bonding sheet of the present invention to obtain.
[table 1]
Table 1. heat ray shielding is tested
| Heat ray shielding bonding sheet | The temperature inside the box | Poor with the temperature inside the box of comparative example 1 |
| Embodiment 1 | 68.4℃ | -4.1℃ |
| Embodiment 2 | 68.0℃ | -4.5℃ |
| Comparative example 1 | 72.5℃ | - |
As shown in table 1, the temperature inside the box during heat ray shielding bonding sheet made in use comparative example 1 is
72.5℃.On the other hand, the heat ray shielding bonding sheet made in embodiments of the invention 1, embodiment 2 is used
Time the temperature inside the box be respectively 68.4 DEG C, 68.0 DEG C.It is to say, embodiments of the invention 1, embodiment 2 are made
The temperature inside the box of the heat ray shielding bonding sheet made is respectively than the heat ray shielding bonding sheet made in a comparative example
The temperature inside the box low 4.1 DEG C, 4.5 DEG C.Thus result understands, the heat ray of the heat ray shielding bonding sheet of the present invention
Shield effectiveness improves.
Industrial applicibility
By the present invention in that makes heat ray shielding metal particle and near infrared absorption pigment dispersion in bonding with dispersant
In agent, compared with conventional heat ray shielding bonding sheet, the temperature that heat ray can be suppressed to cause rises.Thus,
The present invention can suppress house, the temperature of vapour interior space rises, and alleviates the load of air-conditioning equipment, for energy-conservation, the earth
Environmental problem contributes.
Claims (5)
1. a heat ray shielding adhesive composition, its contain (A) metal particle, (B) acrylic adhesive,
(C) dispersant and (D) near infrared absorption pigment, wherein,
A width of 0.01 °～0.8 ° of the half-peak of first main peak obtained by XRD figure spectrum of described (A) metal particle,
The weight average molecular weight of described (B) acrylic adhesive is 100000～1200000,
Described (D) near infrared absorption pigment is the naphthalene phthalocyanine based compound represented with formula (1),
[chemical formula 1]
In formula (1), M represent VO, X represent low alkyl group, lower alkoxy, substituted-amino, nitro, halogen,
Hydroxyl, carboxyl, sulfonic group, sulfophenyl, A represents the crosslinking group of bivalence, and Y represents sulfonic group, carboxyl, primary amino radical
Or remove on the nitrogen-atoms of secondary amino group and remove at least 1 hydrogen on the residue of at least 1 hydrogen or nitrogenous heterocyclic nitrogen-atoms
Residue, m and n is meansigma methods, and m, n are respectively more than 0 and less than 12, and m's Yu n and
More than 0 and less than 12.
2. heat ray shielding adhesive composition as claimed in claim 1, it is characterised in that described (A) metal
Microgranule be selected from stannum oxide, Indium sesquioxide., zinc oxide group in a kind of metal particle.
3. the heat ray shielding adhesive composition as described in any one of claim 1 or 2, it is characterised in that
Described (B) acrylic adhesive be the ratio containing carboxyl or the monomeric building blocks of anhydride be the total monomer in polymer
The 1% of construction unit～the polymer of 5%.
4. heat ray shielding adhesive composition as claimed in claim 1, wherein, in formula (1), A is that carbon is former
Subnumber is the alkylidene of 1～3, and Y is to have substituent group or do not have the phthaloyl imino of substituent group.
5. a heat ray shielding bonding sheet, it is coating heat ray screen described in any one of Claims 1-4
Covering property adhesive composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-239956 | 2011-11-01 | ||
| JP2011239956 | 2011-11-01 | ||
| PCT/JP2012/077972 WO2013065662A1 (en) | 2011-11-01 | 2012-10-30 | Heat ray shielding adhesive composition and heat ray shielding adhesive sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103842463A CN103842463A (en) | 2014-06-04 |
| CN103842463B true CN103842463B (en) | 2016-11-30 |
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