CN103842463A - Heat ray shielding adhesive composition and heat ray shielding adhesive sheet - Google Patents

Heat ray shielding adhesive composition and heat ray shielding adhesive sheet Download PDF

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Publication number
CN103842463A
CN103842463A CN201280048422.5A CN201280048422A CN103842463A CN 103842463 A CN103842463 A CN 103842463A CN 201280048422 A CN201280048422 A CN 201280048422A CN 103842463 A CN103842463 A CN 103842463A
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heat ray
ray shielding
binder composition
group
metal
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CN103842463B (en
Inventor
樋下田贵大
仓田高明
高桥知宏
有福达治
原幸广
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Nippon Kayaku Co Ltd
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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
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2231—Oxides; Hydroxides of metals of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The issue of the invention is to efficiently shield heat rays not only in the infrared region but also in the near-infrared region. The present invention provides: a heat ray shielding adhesive composition which contains (A) fine metal particles, (B) an acrylic adhesive, (C) a dispersant and (D) a near-infrared absorbing dye; and a heat ray shielding adhesive sheet which uses the heat ray shielding adhesive composition.

Description

Heat ray shielding binder composition and heat ray shielding pressure-sensitive adhesive sheet
Technical field
The heat ray shielding pressure-sensitive adhesive sheet that the present invention relates to be fitted in the heat ray shielding binder composition of the enterprising enforcement use such as window glass and used said composition, can high-efficiency shielding invisible heat.
Background technology
In recent years, from the viewpoint of energy-conservation, global environment problem etc., require to alleviate the load of conditioning unit.For example, in the field of house, automobile, seek to shield from the heat ray shielding material of the invisible heat of sunlight being attached on window glass, thereby suppress the temperature rise in indoor, car.The material with heat ray shielding is varied, discloses a kind of tackiness agent and adhesive sheet thereof of having given heat ray shielding in patent documentation 1.This adhesive sheet is the tackiness agent of having given heat ray shielding to be processed into sheet form, and it has following feature: can be processed in advance arbitrary shape, have the re-workability that can again stretch.But this thermoshield of adhesive sheet of having given heat ray shielding is insufficient, expects to be further improved.
Prior art document
Patent documentation
Patent documentation 1: flat No. 10-8010 of Japanese Patent Application
Summary of the invention
The problem that invention will solve
Problem of the present invention is to provide heat ray shielding binder composition and the heat ray shielding pressure-sensitive adhesive sheet that heat ray shielding is greatly improved compared with a kind of heat ray shielding pressure-sensitive adhesive sheet with in the past.
For the means of dealing with problems
The inventor is for the heat ray shielding pressure-sensitive adhesive sheet that obtains heat ray shielding and be greatly improved and conduct in-depth research, found that, by containing metal particle, near infrared absorption pigment, dispersion agent and the tackiness agent taking tin-doped indium oxide as representative, can obtain heat ray shielding binder composition that can high-efficiency shielding invisible heat and said composition is processed into the heat ray shielding pressure-sensitive adhesive sheet that sheet forms, thereby having completed the present invention.
, the present invention relates to
" (1) a kind of heat ray shielding binder composition, it contains (A) metal particle, (B) acrylic adhesive, (C) dispersion agent and (D) near infrared absorption pigment,
(2) the heat ray shielding binder composition as described in (1), is characterized in that, described (A) metal particle is a kind of metal particle being selected from the group of stannic oxide, Indium sesquioxide, zinc oxide,
(3) the heat ray shielding binder composition as described in (1) or (2) any one, it is characterized in that, described (B) acrylic adhesive is to be 1%～5% polymkeric substance of total monomer structural unit in polymkeric substance containing the ratio of the monomer structure unit of carboxyl or acid anhydrides
(4) the heat ray shielding binder composition as described in (1) to (3) any one, is characterized in that, the weight-average molecular weight of described (B) acrylic adhesive is 100000～1200000,
(5) the heat ray shielding binder composition as described in (1) to (4) any one, it is characterized 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 binder composition as described in (5), is characterized in that, described (D) near infrared absorption pigment is the naphthalene phthalocyanine based compound representing with formula (1),
[Chemical formula 1]
Figure BDA0000485495390000021
In formula (1), M represents atoms metal, metal oxide, metal hydroxides or metal halide, or hydrogen atom, X represents low alkyl group, lower alkoxy, substituted-amino, nitro, halogen, hydroxyl, carboxyl, sulfonic group, sulfahydantoin, A represents the crosslinking group of divalence, Y represents sulfonic group, carboxyl, on the nitrogen-atoms of primary amino or secondary amino group, on the residue of at least 1 hydrogen of removal or nitrogenous heterocyclic nitrogen-atoms, remove the residue of at least 1 hydrogen, m and n are mean value, and m, n is respectively more than 0 and below 12, and m and n's and more than 0 and below 12.
(7) the heat ray shielding binder composition as described in (6), wherein, the M in formula (1) is VO, and A is that carbonatoms is 1～3 alkylidene group, and Y is for having substituting group or not having substituent phthaloyl imino,
(8) the heat ray shielding binder composition as described in (6), wherein, the M in formula (1) is Cu, and A is that carbonatoms is 1～3 alkylidene group, and Y is for having substituting group or not having substituent phthaloyl imino,
(9) a heat ray shielding pressure-sensitive adhesive sheet, it is that the heat ray shielding binder composition of coating described in (1) to (8) any one forms.
Invention effect
According to the present invention, by using dispersion agent that the metal particle taking tin-doped indium oxide as representative and near infrared absorption pigment are dispersed in acrylic adhesive, obtained heat ray shielding binder composition is processed into sheet, a kind of heat ray shielding pressure-sensitive adhesive sheet can be provided, can further suppress the temperature rise that invisible heat causes compared with heat ray shielding pressure-sensitive adhesive sheet in the past.Can suppress thus the temperature rise of house, vapour interior space, and can alleviate the load of conditioning unit, therefore the present invention can contribute for energy-conservation, solution global environment problem.
Embodiment
The present invention is described in detail.The binder composition that heat ray shielding pressure-sensitive adhesive sheet of the present invention forms use is characterised in that, use dispersion agent that the metal particle taking tin-doped indium oxide as representative and near infrared absorption pigment are dispersed in acrylic adhesive, this binder composition also can be processed into sheet.
The metal particle using in heat ray shielding binder composition is preferably the material that visible absorption is little, near infrared is had to good absorption characteristic to the light in far infrared region.As this material, can enumerate the conductive metal oxide near infrared region with plasma wavelength.Specifically, can exemplify stannic oxide, Indium sesquioxide, zinc oxide, Tungsten oxide 99.999, chromic oxide, molybdenum oxide etc.Wherein, particularly preferably in the little stannic oxide of the light absorption of visible region, Indium sesquioxide, zinc oxide.
In addition, in order to improve the electroconductibility of these oxide compounds, the 3rd composition particularly preferably adulterates.As the hotchpotch for this object, select Sb, V, Nb, Ta etc. for stannic oxide, select Zn, Al, Sn, Sb, Ga, Ge etc. for Indium sesquioxide, select Al, Ga, In, Sn, Sb, Nb etc. for zinc oxide.
For the method for making of metal particle, be that material below 100nm is just not particularly limited as long as can obtain particle diameter, can use the known method such as gas phase synthesis method, liquid phase synthesizing method.For example, for Indium sesquioxide particulate, can utilize disclosed method in Japanese kokai publication hei 6-227815., the aqueous solution of the salt that utilizes alkali to neutralize to contain special metal particulate element, filters obtained throw out, clean, and at high temperature carries out heat treated, obtains thus the method for metal particle.In addition, for stannic oxide particulate, zinc oxide fine particles, can exemplify respectively Japanese kokai publication hei 2-105875, Japanese kokai publication hei 6-234522.
As metal particle being dispersed in to the method in organic solvent, can use method in the past.That is, ratio hybrid metal particulate and organic solvent according to the rules adds as required dispersion agent, tensio-active agent etc. in this mixture, uses the diverting devices such as sand mill, masher, ball mill, homogenizer, roller mill that mixture is disperseed.
For metal particle of the present invention, the peak width at half height of being composed the first main peak obtaining by XRD figure is 0.01 °～0.8 °, and if peak width at half height is below 0.01 °, primary particle size increases, thereby is difficult to guarantee the transparency.In addition, if peak width at half height exceedes 0.8 °, be difficult to show sufficient thermoshield.In addition, the preferred lower limit of the peak width at half height of above-mentioned metal particle is that 0.1 °, preferred upper limit are 0.8 °, are limited to 0.2 ° under preferred, are limited to 0.5 ° on preferred.
The specific surface area of measuring with BET method of the metal particle using in the present invention is preferably 5m 3/ g～200m 3/ g, more preferably 10m 3/ g～150m 3/ g, is particularly preferably 10m 3/ g～100m 3/ g.Specific surface area based on BET method is less than 5m 3the primary particle size of the metal particle of/g is large, and therefore, in the situation that making sheet material, film, coating or resin combination, finished surface is likely unsmooth.Further, likely produce shortcomings such as cannot expecting the transparency.On the other hand, BET specific surface area is greater than 200m 3the metal particle of/g needs special technology in the mill, and likely can not get sufficient degree of crystallinity, and heat ray shielding is impaired.It should be noted that, BET method is molecule or the ion known in powder granule surface adsorption size, measures the method for the specific surface area of test portion according to its adsorptive capacity.
Near infrared absorption pigment is to absorb the general name that approaches the pigment of the near infrared ray (wavelength is about 780nm～2000nm) of visibility region in infrared rays most, as the kind of near infrared absorption pigment can enumerate azo system, ammonium system, anthraquinone system, cyanines system, diimmonium system, dithiol metal complexing system, just sour inner salt (squalirium) be, phthalocyanine system, naphthalene phthalocyanine system etc.From improving the viewpoint of weather resistance, preferably phthalocyanine system, naphthalene phthalocyanine system, diimmonium system, and from the viewpoint of high-efficiency shielding invisible heat, be preferably naphthalene phthalocyanine system, be particularly preferably the compound representing with above-mentioned formula (1).In above-mentioned formula (1), M represents hydrogen atom, atoms metal, metal oxide, metal hydroxides or metal halide.M is that in the situation beyond hydrogen atom, this M means that the naphthalene phthalocyanine ring in formula (1) has so-called central metal.In addition, in the situation that M is hydrogen atom, mean that this naphthalene phthalocyanine ring does not have central metal.
As the concrete example of atoms metal 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, can enumerate VO, GeO etc.As metal hydroxides, can enumerate for example Si (OH) 2, Cr (OH) 2, Sn (OH) 2, AlOH etc.As metal halide, can enumerate for example SiCl 2, VCl, VCl 2, VOCl, FeCl, GaCl, ZrCl, AlCl etc.Wherein, be preferably the metal hydroxidess such as the metal oxide such as atoms metal, VO, AlOH such as Fe, Co, Cu, Ni, Zn, Al, V etc., more preferably Cu, VO.
Use the heat ray shielding pressure-sensitive adhesive sheet that the toluene dispersion liquid of the naphthalene phthalocyanine based compound that above-mentioned M is 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 is made in heat ray shielding is tested, to make the temperature inside the box of the case using in test decline, shown good heat ray shielding effect.In addition, while especially using the naphthalene phthalocyanine based compound that M is Cu, the temperature inside the box is significantly declined, has shown excellent invisible heat thermoshield effect, because of but preferred.When to use M be VO naphthalene phthalocyanine based compound, also make the temperature inside the box significantly decline, shown excellent invisible heat thermoshield effect, because of but preferably.
X represents low alkyl group, lower alkoxy, substituted-amino, nitro, halogen, hydroxyl, carboxyl, sulfonic group or sulfahydantoin.A is the crosslinking group of divalence, can enumerate alkylidene group ,-CO that for example carbonatoms is 1～3 2-,-SO 2-,-SO 2nH (CH 2) a-(herein, a represents 0～4), but be preferably carbonatoms be 1～3 alkylidene group, a be 0-SO 2nH-, the alkylidene group that more preferably carbonatoms is 1～3.Y represents sulfonic group, carboxyl, on the nitrogen-atoms of primary amino or secondary amino group, on the residue of at least 1 hydrogen of removal or nitrogenous heterocyclic nitrogen-atoms, remove the residue of at least 1 hydrogen, can enumerate for example carboxyl, sulfonic group, there is substituting group or do not there is substituent phthaloyl imino, there is substituting group or do not there is substituent 1-piperazinyl, there is substituting group or do not there is substituent piperidino etc., be preferably carboxyl, sulfonic group, there is substituting group or do not there is substituent phthaloyl imino, more preferably there is substituting group or do not there is substituent phthaloyl imino.It should be noted that, be the substituting group when thering is substituting group or not thering is substituent phthaloyl imino, there is substituting group or do not there is substituent 1-piperazinyl, there is substituting group or do not there is substituent piperidino as Y, hydrogen atom, low alkyl group, lower alkoxy, substituted-amino, nitro, halogen, sulfonic group can be shown, be preferably hydrogen atom, halogen.
Be not particularly limited for substituted-amino in the present invention, it comprises the amino for example replacing with low alkyl group.In addition, low alkyl group, lower alkoxy refer to respectively alkyl and the alkoxyl group that the carbonatoms of straight chain shape or a chain is 1～4.As near infrared absorption pigment is dispersed in to the method in organic solvent, can use method in the past.; ratio is mixed near infrared absorption pigment and organic solvent according to the rules; in this mixture, add as required dispersion agent, tensio-active agent etc., use the diverting devices such as sand mill, masher, ball mill, homogenizer, roller mill to disperse mixture.
Being dispersed with that metal particle and near infrared inhale the heat ray shielding binder composition of pigment and said composition is processed into heat ray shielding pressure-sensitive adhesive sheet that sheet forms is that therefore good weatherability is its most important condition for what be attached on window glass with the object of the invisible heat composition of the shielding wavelength that sunlight was comprised.Therefore the acrylic copolymer that the binder resin, using in this embodiment is preferably good weatherability is binder resin.Acrylic copolymer is that tackiness agent can be manufactured by the copolymerization of the low main monomer of the second-order transition temperature of polymkeric substance and the high comonomer of second-order transition temperature conventionally.
It is the monomer as principal constituent of tackiness agent as acrylic copolymer, the carbonatoms that can enumerate alkyl acrylate that second-order transition temperature carbonatoms low and alkyl is 2～14 or alkyl is 4 to 16 alkyl methacrylate, and second-order transition temperature can use higher than them and the monomer that can carry out copolymerization with them together with main monomer.
As the low alkyl acrylate monomer of second-order transition temperature, can list ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, vinylformic acid methoxyl group ethyl ester, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, 2-EHA, vinylformic acid n-octyl, Isooctyl acrylate monomer, vinylformic acid ester in the different ninth of the ten Heavenly Stems, vinylformic acid iso stearyl ester etc.
In addition, as the low alkyl methacrylate monomer of second-order transition temperature, can exemplify 2-Ethylhexyl Methacrylate, n octyl methacrylate, the positive Lauryl Ester of methacrylic acid etc.
In addition, as the monomer that can carry out copolymerization, can exemplify vinyl-acetic ester, vinyl cyanide, acrylamide, vinylbenzene, methyl methacrylate, methyl acrylate etc.
Except above-mentioned monomer, in order to obtain needed bond properties, as containing monomer, also can use (methyl) vinylformic acid, methylene-succinic acid, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) dimethylaminoethyl acrylate, acrylamide, n-methylolacrylamide, DMAA, glycidyl methacrylate, maleic anhydride etc.
In addition, molecular weight can significantly affect the dispersiveness of metal particle and near infrared absorption pigment, and therefore the weight-average molecular weight of acrylic adhesive is preferably 100000～1200000.More preferably 200000～800000.
The degree of crosslinking of the macromolecular material of formation tackiness agent is different because of each condition such as kind, composition of tackiness agent (binder composition), and there is no particular limitation as to it.Binder composition also can contain softening agent as required.As this softening agent, can enumerate the ester classes such as phthalic acid ester, trimellitate, Pyromellitic Acid ester, adipic acid ester, sebate, phosphotriester or glycol ester; Process oil, liquid polyethers, liquid polyterpene or other liquid resins; Etc., can mix and use one kind or two or more in them.This type of softening agent is preferably the softening agent good with the consistency of tackiness agent.In addition, except above-mentioned softening agent, binder composition can contain various additives such as such as UV light absorber or antioxidant etc. as required.
As dispersion agent, representative is low molecular anion (anion) the property compound of soap (soap), alpha-sulfo fatty acid ester salt (MES), alkylbenzene sulfonate (ABS), linear alkylbenzene sulfonate (LAS), alkyl-sulphate (AS), alkyl ether sulphate salts (AES), alkylsurfuric acid three ethanol esters and so on; The low molecule nonionic based compound of fatty acid ethanol amide, Voranol EP 2001 (AE), polyoxyethylene alkyl phenyl ether (Α Ρ Ε), Sorbitol Powder, sorbitol anhydride and so on; Low molecular weight cationic (cation) the property compound of alkyl trimethyl ammonium salt, chlorination dialkyl dimethyl ammonium, kelene yl pyridines and so on; The low molecule both sexes based compound of alkyl carboxyl trimethyl-glycine, sultaine, Yelkin TTS and so on; It is the polymer water system dispersion agent as representative such as copolymer salt, carboxymethyl cellulose, polyvinyl alcohol of monomer taking formaldehyde condensation products, poly styrene sulfonate, polyacrylate, vinyl compound and the carboxylic acid of naphthalenesulfonate; The non-water system dispersion agent of polymer of polyacrylic acid part alkyl ester, polyalkylene polyamine and so on; The macromolecule cation of polymine, amino alkyl methacrylate multipolymer and so on is dispersion agent, as long as but can be applicable to well particle of the present invention, just do not get rid of the dispersion agent of the structure beyond the material with exemplified form here.
As dispersion agent, if enumerate concrete title, known following material.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, DISPARLON1831, DISPARLON1850, DISPARLON1860, DISPARLON1934, DISPARLONDA-400N, DISPARLON DA-703-50, DISPARLON DA-725, DISPARLON DA-705, DISPARLON DA-7301, DISPARLON DN-900, DISPARLON NS-5210, DISPARLONNVI-8514L, HIPLAAD ED-152, HIPLAAD ED-216, HIPLAAD ED-251, HIPLAADED-360 (nanmu originally changes into Co., Ltd.'s system), FTX-207S, FTX-212P, FTX-220P, FTX-220S, FTX-228P, FTX-710LL, FTX-750LL, FTERGENT212P, FTERGENT220P, FTERGENT222F, 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, RHEODOLSP-010V, RHEODOL SP-030V, RHEODOL SP-L10, RHEODOL SP-P10 (Kao Corp'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's system), SN SPERSE2180, SN SPERSE2190, SN Leveller S-906 (SAN NOPCO company system), S-386, the material of S-420 (AGC SEIMI CHEMICAL company system) and so on.
Conventionally, the less dispersiveness of the RED of metal particle and dispersion agent (relative energy is poor: Relative Enelgy Difference) is better, and preferably RED is the combination below 1.5.As with the RED of metal particle be the dispersion agent below 1.5, can enumerate DISPERBYK-116, DISPERBYK-142, DISPERBYK-145, DISPERBYK-163, DISPERBYK-2000, DSPERBYK-2155, BYK-P105, ANTI-TERRAU, EFKA-4010, DOPA-17HF.
Can use the solubility parameter (Hansen considers that the effect of the relevant London force of the solubility parameter (δ) of Hildebrand, dipole-dipole interaction, hydrogen bond proposes) representing in mathematical expression 1, calculate the δ D (contribution that London force brings; The known contribution that it brings for form the London force that produce or Van der Waals force by the dipole of being induced by molecular impact), the δ P (contribution that polar interaction is brought; It refers to when molecule exists in solution, the contribution that the permanent dipole that subject molecule produces brings), the δ H (contribution that hydrogen bond brings; It represents specific interaction, for example represent that hydrogen bond, the combination of acid/alkali and donor/acceptor are in conjunction with the contribution bringing), further use mathematical expression 2 to calculate interaction radius R 0, HSP spacing Ra, calculate RED (relative energy is poor: Relative Enelgy Difference) by mathematical expression 3, R0, Ra.
[mathematical expression 1]
δ 2=δ D 2+δ p 2+δ H 2
[mathematical expression 2]
(R a) 2=4(δ D2-δ D1) 2+(δ p2-δ P1) 2+(δ H2-δ H1) 2
[mathematical expression 3]
RED=R a/R O
Heat ray shielding binder composition can utilize known method to make.For example metal particle, near infrared absorption pigment being dispersed in as acrylic copolymer is in the monomer of principal constituent of tackiness agent, then makes it that polymerization occurs, and can obtain thus target heat ray shielding binder composition.In addition, also make in advance like that the dispersion liquid of metal particle, near infrared absorption pigment just like patent documentation 1, thereby after it is mixed with monomer, make its generation polymerization obtain the method for target tackiness agent.Further, as easier method, thereby also have by the dispersion liquid of metal particle, near infrared absorption pigment is directly mixed to the method that obtains target binder composition with tackiness agent.In addition, by metal particle and near infrared absorption pigment and dispersant, be then dispersed in tackiness agent, also can be obtained binder composition.
In the manufacture of heat ray shielding pressure-sensitive adhesive sheet, be not particularly limited for the coating process of tackiness agent, can use comma coating machine, excellent painting machine, spin coater, spraying machine, roller coating machine, intaglio plate coating machine, knife coater or other various apparatus for coating.
Metal particle and near infrared absorption pigment are that the monomer of tackiness agent or the dispersion ratio of tackiness agent are determined by coating thickness and the shielding properties of bonding coat with respect to acrylic copolymer.As the optical property of film that is coated with heat ray shielding tackiness agent, it is desirable to that visible light transmissivity is high, day light transmission rate is low, but the two has proportionlity conventionally, can decide optical property by the performance of one party emphatically.
This is coated with on the actual window glass that is pasted to buildings and automobile of film of heat ray shielding tackiness agent, measure respectively the effect in summer and winter, result is reached to draw a conclusion: in order to obtain sufficient cooling in summer effect, can make daylight transmitance is below 80%, for make illumination cost and winter heating cost rise to inferior limit, it is more than 50% can making visible light transmissivity.Therefore it is more than 50% that the optical characteristics that, is coated with the film of heat ray shielding tackiness agent is preferably visible light transmissivity and a day light transmission rate is below 80%.
Conventionally, consider and the tracing ability and bounding force and the economy that are engaged face, the coating thickness of bonding coat adopts the thickness of 10 μ m～50 μ m conventionally, as the amount of giving the particulate of above-mentioned heat ray shielding in this scope, be preferably (metal particle+near infrared absorption pigment): the scope of resin solid composition=3:97～1:1 (weight ratio).This is due to, the ratio of heat ray shielding agent particulate during lower than this ratio, and in order to obtain thickness more than needed heat ray shielding sexual needs 50 μ m, in contrast, during higher than this ratio, it is too small that visible light transmissivity becomes.Further, the haze value of film should not damage the transparency of glass, can be below 8%, can be more preferably below 3%.
Embodiment
Enumerate following embodiment and comparative example and illustrate the present invention, but the invention is not restricted to these examples.
Synthesis example 1 (metal particle)
By tin chloride (SnCl 45H 2o) 5.9g and indium chloride (InCl 3) 75.9g is dissolved in water 4000ml, expends 58 minutes and adds therein 2% ammoniacal liquor, finally making pH is 7.85, thereby makes the hydrate generation co-precipitation of stannic oxide and Indium sesquioxide.During this, liquid temperature maintains 5 DEG C.Then, dry after this coprecipitate is cleaned, further fire 2 hours with 900 DEG C, obtain stanniferous Indium sesquioxide (ITO) micro mist (metal particle).
Synthesis example 2 (near infrared absorption pigment)
In 40 parts of Tripyrophosphoric acid, add 2,3-naphthalene ranadylic phthalocyanine (vanadyl2,3-naphthalocyanine) (Aldrich company system) 3.9 parts, 5.0 parts of phthalic imidines (Tokyo changes into industrial society system), 1.0 parts of paraformaldehydes, stir 8 hours at 140 DEG C, be injected in 300 parts of water, the solid that filtration is separated out, has obtained 7.5 parts of naphthalene phthalocyanine based compounds thus.
Production Example 1 (metal particle dispersion liquid)
In toluene solution 7ml, add the ITO obtaining in synthesis example 1 synthetic particle 1.12g, methyl ethyl diketone 0.7g, dispersion agent DisperBYK1400.175g, dropped in the crushing container of batch-type bead mill apparatus (T.K.Fill Mix30-25 type, primix company system).It is the zirconium oxide bead of 30 μ m that broken pearl is used median size, is filled to 35% of crushing container volume and fills.For fragmentation, the mode taking circumferential speed as 6.8m/s is set electric motor, carries out taking the broken time as the condition of 10 minutes.In addition, use separating centrifuge (HimacCR18 that Hitachi Koki Co., Ltd manufactures), with revolution 5000rpm, the dispersion being obtained (metal particle dispersion liquid) has been carried out to 15 minutes centrifugal treating.
Production Example 2 (near infrared absorbing coloring matter dispersion liquid 1)
In toluene solution 7ml, add the near infrared absorption pigment 0.21g, the dispersion agent DisperBYK1400.21g that in synthesis example 2, obtain, dropped in the crushing container of batch-type bead mill apparatus (T.K.Fill Mix30-25 type, primix company system).It is the zirconium oxide bead of 30 μ m that broken pearl is used median size, is filled to 70% of crushing container volume and fills.For fragmentation, the mode taking circumferential speed as 10m/s is set electric motor, carries out taking the broken time as the condition of 30 minutes.In addition, use separating centrifuge (the Himac CR18 that Hitachi Koki Co., Ltd manufactures), with revolution 5000rpm, the dispersion being obtained is carried out to 15 minutes centrifugal treating, obtained thus near infrared absorption colorant dispersing liquid 1.
Production Example 3 (near infrared absorbing coloring matter dispersion liquid 2)
The near infrared absorption pigment obtaining in synthesis example 2 is replaced with to 2,3-naphthalene phthalocyanine (Aldrich company system), in addition, similarly obtained near infrared colorant dispersing liquid 2 with Production Example 2.
Synthesis example 3 (acrylic adhesive A)
N-butyl acrylate 291g and vinylformic acid 9g as monomer are dissolved in toluene 366g, add Diisopropyl azodicarboxylate 0.15g, under nitrogen gas stream, make these monomers with 70 DEG C of polymerizations 6 hours, thereby obtained acrylic resin multipolymer (weight-average molecular weight: Mw=320000).Further dilute the acrylic resin copolymer solution that obtained solids component ratio and be 29.36%, viscosity is 2700mPas with toluene.
Make heat ray shielding tackiness agent and heat ray shielding pressure-sensitive adhesive sheet
(embodiment 1)
The toluene dispersion liquid 14.7 weight part mixed dissolutions of the near infrared absorption pigment obtaining in toluene dispersion liquid 144 weight parts of the stanniferous Indium sesquioxide (ITO) obtaining in the acrylic adhesive A100 weight part (butyl acrylate: vinylformic acid=97:3) obtaining in synthesis example 3, Production Example 1, Production Example 2, to evenly, have been obtained to heat ray shielding tackiness agent.In addition, utilize comma coating machine be coated on release sheet polyester film (implementing organosilicon processing in one side side) (lintec company manufacture 3811, thickness: 38 μ m) go up and are dried, with polyester film (implementing organosilicon processing in one side side) (3801 thickness that lintec company manufactures: 38 μ m) cover, and have made thus heat ray shielding pressure-sensitive adhesive sheet (thickness: 15 μ m) of release sheet.
(embodiment 2)
The toluene dispersion liquid of near infrared absorption pigment is replaced with to the dispersion liquid of making in Production Example 3, in addition, made similarly to Example 1 heat ray shielding tackiness agent and heat ray shielding pressure-sensitive adhesive sheet.
Comparative example 1
The toluene dispersion liquid of unmixed near infrared absorption pigment in embodiment 1, toluene dispersion liquid 144 weight parts and the acrylic adhesive A100 weight part of the stanniferous Indium sesquioxide (ITO) obtaining in Production Example 1 are used, in addition, made similarly to Example 1 heat ray shielding pressure-sensitive adhesive sheet (thickness: 15 μ m).
(embodiment 3)
With the method below, the heat ray shielding pressure-sensitive adhesive sheet of making in embodiment 1, embodiment 2 and comparative example 1 is implemented to heat ray shielding test.It the results are shown in table 1.
Test method
Testing circumstance: for preparing internal diameter width 150mm × length 235mm × height 110mm has outer temperature shielding and a bubble-tight proofing box, at the place of center of top portion of this proofing box, in above-mentioned proofing box top, the position of high 40cm arranges infrared lamp (100V, 250W: Toshiba Corporation), has formed thermoshield evaluation testing apparatus.Then, the heat ray shielding pressure-sensitive adhesive sheet of made is set on proofing box top section, utilizes adhesive tape that surrounding is attached fixing.The mode that can not directly shine with light at the central part of this proofing box inside in addition, is provided with thermometer.Afterwards, some bright light, measures one time temperature every 10 seconds, has measured the test the temperature inside the box after 30 minutes.It should be noted that, above-mentioned proofing box is arranged in the room of 25 DEG C of left and right.In this test, the temperature inside the box during to the heat ray shielding pressure-sensitive adhesive sheet of making in use comparative example and heat ray shielding pressure-sensitive adhesive sheet of the present invention compares, if use the temperature inside the box of heat ray shielding pressure-sensitive adhesive sheet of the present invention low, illustrate that heat ray shielding effect has improved.It should be noted that, the poor method of calculation of the temperature inside the box are: use the temperature inside the box of heat ray shielding pressure-sensitive adhesive sheet of the present invention to obtain by deducting from the temperature inside the box that uses the heat ray shielding pressure-sensitive adhesive sheet of making comparative example.
[table 1]
The test of table 1. heat ray shielding
Heat ray shielding pressure-sensitive adhesive 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 while using the heat ray shielding pressure-sensitive adhesive sheet of making in comparative example 1 is 72.5 DEG C.On the other hand, the temperature inside the box while using the heat ray shielding pressure-sensitive adhesive sheet of making in embodiments of the invention 1, embodiment 2 is respectively 68.4 DEG C, 68.0 DEG C.That is to say, in embodiments of the invention 1, embodiment 2 make heat ray shielding pressure-sensitive adhesive sheet the temperature inside the box respectively lower 4.1 DEG C than the temperature inside the box of the heat ray shielding pressure-sensitive adhesive sheet of making in comparative example, 4.5 DEG C.Result is known thus, and the heat ray shielding effect of heat ray shielding pressure-sensitive adhesive sheet of the present invention has improved.
Industrial applicibility
The present invention, by using dispersion agent that heat ray shielding metal particle and near infrared absorption pigment are dispersed in tackiness agent, compared with heat ray shielding pressure-sensitive adhesive sheet in the past, can suppress the temperature rise that invisible heat causes.Thus, the present invention can suppress the temperature rise of house, vapour interior space, alleviates the load of conditioning unit, for energy-conservation, global environment problem contribute.

Claims (9)

1. a heat ray shielding binder composition, it contains (A) metal particle, (B) acrylic adhesive, (C) dispersion agent and (D) near infrared absorption pigment.
2. heat ray shielding binder composition as claimed in claim 1, is characterized in that, described (A) metal particle is a kind of metal particle being selected from the group of stannic oxide, Indium sesquioxide, zinc oxide.
3. the heat ray shielding binder composition as described in claim 1 or 2 any one, it is characterized in that, described (B) acrylic adhesive is to be 1%～5% polymkeric substance of total monomer structural unit in polymkeric substance containing the ratio of the monomer structure unit of carboxyl or acid anhydrides.
4. the heat ray shielding binder composition as described in claims 1 to 3 any one, is characterized in that, the weight-average molecular weight of described (B) acrylic adhesive is 100000～1200000.
5. the heat ray shielding binder composition as described in claim 1 to 4 any one, is characterized in that, described (D) near infrared absorption pigment is phthalocyanine based compound, naphthalene phthalocyanine based compound and/or diimmonium based compound.
6. heat ray shielding binder composition as claimed in claim 5, is characterized in that, described (D) near infrared absorption pigment is the naphthalene phthalocyanine based compound representing with formula (1),
[Chemical formula 1]
Figure FDA0000485495380000011
In formula (1), M represents atoms metal, metal oxide, metal hydroxides or metal halide, or hydrogen atom, X represents low alkyl group, lower alkoxy, substituted-amino, nitro, halogen, hydroxyl, carboxyl, sulfonic group, sulfahydantoin, A represents the crosslinking group of divalence, Y represents sulfonic group, carboxyl, on the nitrogen-atoms of primary amino or secondary amino group, on the residue of at least 1 hydrogen of removal or nitrogenous heterocyclic nitrogen-atoms, remove the residue of at least 1 hydrogen, m and n are mean value, and m, n is respectively more than 0 and below 12, and m and n's and more than 0 and below 12.
7. heat ray shielding binder composition as claimed in claim 6, wherein, the M in formula (1) is VO, and A is that carbonatoms is 1～3 alkylidene group, and Y is for having substituting group or not having substituent phthaloyl imino.
8. heat ray shielding binder composition as claimed in claim 6, wherein, the M in formula (1) is Cu, and A is that carbonatoms is 1～3 alkylidene group, and Y is for having substituting group or not having substituent phthaloyl imino.
9. a heat ray shielding pressure-sensitive adhesive sheet, it is that heat ray shielding binder composition described in coating claim 1 to 8 any one forms.
CN201280048422.5A 2011-11-01 2012-10-30 Heat ray shielding adhesive composition and heat ray shielding bonding sheet Expired - Fee Related CN103842463B (en)

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CN106590471A (en) * 2016-11-01 2017-04-26 常州斯威克光伏新材料有限公司 Infrared shielded EVA photovoltaic film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH108010A (en) * 1996-06-28 1998-01-13 Sumitomo Osaka Cement Co Ltd Heat ray blocking tacky agent, its production and heat ray blocking transparent sheet
WO2011024787A1 (en) * 2009-08-24 2011-03-03 積水化学工業株式会社 Intermediate film for laminated glass, and laminated glass

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH108010A (en) * 1996-06-28 1998-01-13 Sumitomo Osaka Cement Co Ltd Heat ray blocking tacky agent, its production and heat ray blocking transparent sheet
WO2011024787A1 (en) * 2009-08-24 2011-03-03 積水化学工業株式会社 Intermediate film for laminated glass, and laminated glass

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106590471A (en) * 2016-11-01 2017-04-26 常州斯威克光伏新材料有限公司 Infrared shielded EVA photovoltaic film

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