CN104169387B - Sealant, the duplexer employing it and solar module - Google Patents

Sealant, the duplexer employing it and solar module Download PDF

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Publication number
CN104169387B
CN104169387B CN201380014083.3A CN201380014083A CN104169387B CN 104169387 B CN104169387 B CN 104169387B CN 201380014083 A CN201380014083 A CN 201380014083A CN 104169387 B CN104169387 B CN 104169387B
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China
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mentioned
resin
sealant
urethane resin
mass parts
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CN201380014083.3A
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CN104169387A (en
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栗山千里
千代延一彦
北田满
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DIC Corp
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Dainippon Ink and Chemicals 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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    • 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
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • C09J7/00—Adhesives in the form of films or foils
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    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/042—PV modules or arrays of single PV cells
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    • H01—ELECTRIC ELEMENTS
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract

Problem to be solved by this invention is, provides a kind of can formation all have excellent adaptation to arbitrary base material and possess the sealant that can not be caused the heat sealing layer of the humidity resistance of the level of the reduction of adaptation by heat, water mitigation.The present invention relates to following sealant: containing urethane resin (A), polyolefin resin (B), linking agent (C) and aqueous medium (D), urethane resin (A) is the urethane resin that makes to have isocyanate group and be selected from the compound with primary amino, there is at least a kind of reaction of the compound of hydrazide group and hydrazine and obtain, linking agent (C) is containing alkylated methylol groups melamine resin (c1) and epoxy compounds (c2), any one or both of urethane resin (A) and polyolefin resin (B) have the functional group with epoxy reaction.

Description

Sealant, the duplexer employing it and solar module
Technical field
The present invention relates to the bonding sealant that may be used for various component, particularly polar element and nonpolar component.
Background technology
As the component used in the manufacture of auto parts or household appliances, solar power generating device etc., used the excellence such as weathering resistance, water tolerance widely, the component comprising vinyl acetate resins, polyolefin resin of easy plasticity, recyclability excellence in the past always.
Above-mentioned vinyl acetate resins is in general easily deteriorated because being exposed in heat, water (moisture), not enough in humidity resistance.Thus, as a rule, in most of the cases, make composite component by the component laminating glass that comprises vinyl acetate resins to above-mentioned or polyethylene terephthalate base material, thus vinyl acetate resins base material is given to the humidity resistance that can suppress the level of above-mentioned deterioration.
But, because in general the base material comprising vinyl acetate resins etc. is the base material that surface polarity is low, even if laminatings such as the base material therefore such as wanting to use caking agent to comprise vinyl acetate resins by above-mentioned and above-mentioned glass, also be easy to peel off at the interface on the above-mentioned surface and bond layer that comprise the base material of vinyl acetate resins, even if or can be temporarily bonding, also because of heat, water mitigation and make bond layer deterioration, thus can have and pass in time and cause the situation of stripping.
On the other hand, by adjusting the composition of above-mentioned caking agent, the caking agent of the closing force excellence of the non-polar substrate for above-mentioned vinyl acetate resins etc. can be manufactured.But, not enough to the adaptation of above-mentioned glass, polyethylene terephthalate base material isopolarity base material with the caking agent of the excellent adhesion of above-mentioned non-polar substrate, therefore the adaptation of above-mentioned polar substrates and bond layer reduces, and still has and passes in time and cause the situation of stripping.
Said, technically, be difficult to find out the caking agent arbitrary base material in non-polar substrate and polar substrates all being possessed to excellent closing force.
As the caking agent possessing excellent adaptation, the such as known caking agent be made up of the aqueous dispersion containing acid-modified polyolefin resin, urethane resin, fatty acid amide and terpenic series Tackifier materials with specified proportion in water-medium is known if this caking agent is then for the excellent adhesion (such as with reference to patent documentation 1) of thermoplastic resin base material.
But above-mentioned caking agent is not material non-polar substrate and polar substrates to excellent closing force, therefore, there is the situation of passing in time and occurring at the interface of any one base material and bond layer to peel off.
In addition, above-mentioned caking agent is easily deteriorated because being exposed in heat, water (moisture), therefore can because of the impact of heat, water etc., passes in time and causes deterioration, the stripping of above-mentioned bond layer, consequently, the situation of the deterioration causing above-mentioned base material self is had.
But, when using foregoing caking agent to carry out the laminating of base material, as a rule, in most of the cases, before being about to fit, at any one substrate surface coating adhesive, the stacked another kind of base material in bond layer surface with adhesion sense then before this bond layer solidifies completely, make it solidification, thus they are fitted.
But the method needs to carry out coating adhesive in the operation site of the laminating carrying out base material or remove the operation of solvent contained in this caking agent etc., therefore, has the situation of the production efficiency reducing above-mentioned composite component significantly.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-235289 publication
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is, a kind of sealant is provided, it can form following heat sealing layer, namely, for the arbitrary base material in polar substrates and non-polar substrate, all there is excellent adaptation, and possess the heat sealing layer that can not cause the humidity resistance of the level of the reduction of adaptation because of the impact of heat, water (moisture).
In addition, to be solved by this inventionly to be problematic in that, a kind of sealant is provided, it can form following heat sealing layer, namely, for any one base material in polar substrates and non-polar substrate, all there is excellent adaptation, and possess can not because of heat, the impact of water (moisture) and cause the heat sealing layer of the humidity resistance of the level of the reduction of deterioration or adaptation, and by being coated with above-mentioned sealant in advance at a kind of substrate surface and drying, thus define through crosslinked heat sealing layer, then by loading another kind of base material and heat on this heat sealing layer, thus can by these substrate bondings.
For the method for dealing with problems
The present inventor etc. are studied based on resin combination urethane resin and polyolefin resin combined, found that, by the urethane resin and polyolefin resin with specific end structure are combinationally used, and specific crosslinker combination is used, can solve the problem thus.
Namely, the present invention relates to a kind of sealant, it is characterized in that, containing urethane resin (A), polyolefin resin (B), the sealant of linking agent (C) and aqueous medium (D), above-mentioned urethane resin (A) is the urethane resin that makes to have isocyanate group and be selected from the compound with primary amino, at least a kind of compound of the compound and hydrazine with hydrazide group reacts and obtains, above-mentioned linking agent (C) is containing alkylated methylol groups melamine resin (c1) and epoxy compounds (c2), and any one or both of above-mentioned urethane resin (A) and polyolefin resin (B) have and the functional group of epoxy reaction [X].
The effect of invention
Sealant of the present invention is not only for comprising the widely used base material comprising vinyl acetate resins or polyolefin-based resins in industrial circle, and for the base material comprising polyethylene terephthalate etc., all there is excellent adaptation, therefore, may be used in the laminating of non-polar substrate, polar substrates, in the surface coverage of these base materials etc.
In addition, sealant of the present invention can also improve significantly by stacked for various base material and the duplexer (composite component), the particularly solar module that obtain production efficiency.
Embodiment
The feature of sealant of the present invention is, containing urethane resin (A), polyolefin resin (B), the sealant of linking agent (C) and aqueous medium (D), above-mentioned urethane resin (A) is the urethane resin that makes to have isocyanate group and be selected from the compound with primary amino, at least a kind of compound of the compound and hydrazine with hydrazide group reacts and obtains, above-mentioned linking agent (C) is containing alkylated methylol groups melamine resin (c1) and epoxy compounds (c2), and any one or both of above-mentioned urethane resin (A) and polyolefin resin (B) have and the functional group of epoxy reaction [X].
Abovementioned alkyl melamine methylol resin (c1) can utilize self-crosslinking reaction to form crosslinking structure.In addition, when generating the functional groups such as hydroxyl when the functional group [X] that above-mentioned urethane resin (A) and said polyolefins resin (B) have reacts with above-mentioned epoxy compounds (c2), this hydroxyl and abovementioned alkyl melamine methylol resin (c1) react and form crosslinking structure.
Herein, even use abovementioned alkyl melamine methylol resin (c1) as above-mentioned linking agent (C), also differ and solve problem of the present invention surely.Even if be used alone abovementioned alkyl melamine methylol resin (c1) as above-mentioned linking agent (C), be sometimes also difficult to the adaptation taking into account excellent humidity resistance and the excellence to various base material.
In the present invention, abovementioned alkyl melamine methylol resin (c1) and epoxy compounds (c2) are combinationally used be used as above-mentioned linking agent (C).
The functional group [X] that any one or both of above-mentioned epoxy compounds (c2) and above-mentioned urethane resin (A) and said polyolefins resin (B) have reacts and forms crosslinking structure.Thus, the sealant possessing excellent humidity resistance and the adaptation to the excellence of various base material can be obtained.
In addition, as the urethane resin (A) combinationally used with above-mentioned linking agent (C) and said polyolefins resin (B), use have can with the particularly resin of the functional group [X] of epoxy reaction that has of epoxy compounds (c2) in above-mentioned linking agent (C).As the functional group that above-mentioned epoxy compounds (c2) has, can specifically list the hydrolyzable silyl group such as alkoxysilyl or silanol group, epoxy group(ing).
As above-mentioned functional group [X], such as, can enumerate carboxyl, hydroxyl, amino etc.And, when using the urethane resin and polyolefin resin with hydrophilic radicals such as anionic property group, cationic groups to make above-mentioned urethane resin (A) and said polyolefins resin (B) stably exist in aqueous medium (D), as the carboxyl of this hydrophilic radical or by using it, with basic cpd neutralization, the carboxylic acid ester groups that formed plays a role as above-mentioned functional group [X] when above-mentioned crosslinking reaction, can react with a part for above-mentioned linking agent (C).Therefore, as above-mentioned functional group [X], also can use can as hydrophilic radical described later play a role by basic cpd and after the anionic property such as carboxylic acid ester groups, sulfonate group group, by acidic cpd and after the cationic groups such as amino.As above-mentioned functional group [X], in above-mentioned, be preferably carboxyl, carboxylic acid ester groups.
Particularly, when using carboxyl as above-mentioned functional group [X], as above-mentioned urethane resin (A), preferred use has the resin of the acid number of 5 ~ 70, more preferably the resin with the acid number of 5 ~ 50 is used, from the viewpoint of the adaptation further improved for various base material, preferably use has the resin of the acid number of 5 ~ 35 further.In addition, as said polyolefins resin (B), preferably use the resin with the acid number of 5 ~ 300, more preferably use the resin with the acid number of 10 ~ 250.
Above-mentioned urethane resin (A) and said polyolefins resin (B) preferably separately disperse or dissolve in above-mentioned aqueous medium (D), even if their part combines and forms resin particle, the composite resin particles of so-called core-shell-type also can be formed.
Wherein, above-mentioned urethane resin (A) and said polyolefins resin (B) preferably separately can form resin particle, are scattered in above-mentioned aqueous medium (D).
From the viewpoint of the smoothness improving the film formed, the median size of the above-mentioned resin particle preferably roughly scope of 10nm ~ 500nm.Median size mentioned here refers to the median size of the volume reference utilizing dynamic light scattering determination.
Above-mentioned urethane resin (A) is preferably the scope of 9/1 ~ 2/8 with the mass ratio " urethane resin (A)/polyolefin resin (B) " of said polyolefins resin (B), be more preferably the scope of 8/2 ~ 3/7, from the viewpoint of taking into account more excellent humidity resistance and the adaptation for the excellence of various base material, the more preferably scope of 8/2 ~ 5/5.
In addition, from the viewpoint of can the good dispersion stabilization of maintenance heat sealing agent and painting work, preferably relative to the total amount of sealant of the present invention in the scope of 5 quality % ~ 70 quality % containing above-mentioned urethane resin (A) and said polyolefins resin (B).
In addition, from the viewpoint of the good dispersion stabilization given in above-mentioned aqueous medium (D), above-mentioned urethane resin (A) and said polyolefins resin (B) also can have hydrophilic radical.As above-mentioned hydrophilic radical, such as, can use anionic property group, cationic groups and the polyoxyethylene structure as nonionic group, wherein, more preferably use anionic property group.
As above-mentioned anionic property group, such as can use carboxyl, carboxylic acid ester groups, sulfonic group, sulfonate group etc., wherein, from the viewpoint of manufacturing, there is the urethane resin (A) of good water dispersible and polyolefin resin (B), preferably use part or all neutralized by basic cpd and the carboxylic acid ester groups, the sulfonate group that are formed.
In addition, as above-mentioned cationic groups, such as can use uncle amino, used in acidic cpd, quaternary salt agent and after functional group.
In addition, as above-mentioned nonionic group, such as, can use polyoxyethylene groups, polyoxypropylene base, polybutylene base, poly-(oxygen ethene-oxypropylene) polyoxyalkylenes such as base and PULLRONIC F68 base.
Above-mentioned urethane resin (A) is the resin with above-mentioned functional group [X], from the viewpoint of obtain can be formed take into account excellent humidity resistance and for the heat sealing layer of the adaptation of the excellence of various base material sealant and used.
As above-mentioned urethane resin (A), use have the isocyanate group that had by urethane resin be selected from there is primary amino compound, there is hydrazide group that the compound of hydrazide group and at least a kind of hydrazine has, the urethane resin of urea key that nitrogen-atoms that primary amino, hydrazine have reacts and formed.Thus, the adaptation for various base material can significantly be improved.The adaptation of the outer excellence that particularly surface exhibits of the base material of the polar substrates (E) implementing corona treatment etc. etc. acted improperly.Infer that it is that this carbonyl forms key with the nitrogen-atoms forming above-mentioned urea key because generate carbonyl by above-mentioned corona treatment etc. at above-mentioned substrate surface.
Improving in the adaptation of base material further, overall relative to urethane resin (A), above-mentioned urea key preferably exists in the scope of 50mmol/kg ~ 2000mmol/kg.
As above-mentioned urethane resin (A), possess relative in the adaptation of excellence of polar substrates (E), non-polar substrate (F) and the heat sealing layer of weather resistance in formation, preferred use has the urethane resin of the weight-average molecular weight of the scope of 5000 ~ 200000, more preferably uses the urethane resin of the scope of 50000 ~ 20000.
As above-mentioned urethane resin (A), the urethane resin with isocyanate group, and above-mentioned at least a kind of being selected from the compound with primary amino, the compound with hydrazide group and hydrazine of the use urethane resin that reacts and manufacture that will such as obtain by polyvalent alcohol (a1) and polymeric polyisocyanate (a2) will be made react can be used.
As above-mentioned polyvalent alcohol (a1), such as, individually or and polyester polyol, polycarbonate polyol, polyether glycol, polyolefin polyhydric alcohol etc. can be used with two or more ground.
Wherein, due to the adaptation for non-polar substrate (F) can be improved further, so preferably use polyether glycol.
As above-mentioned polyether glycol operable in above-mentioned polyvalent alcohol (a1), such as can to use in the compound of the active hydrogen atom with more than 2 one kind or two or more makes epoxy alkane addition polymerization and the polyether glycol obtained as initiator.
As above-mentioned initiator, such as, can make spent glycol, glycol ether, triglycol, propylene glycol, 1,3-PD, 1,3 butylene glycol, BDO, 1,6-hexylene glycol, dihydroxyphenyl propane, glycerine, trimethylolethane, TriMethylolPropane(TMP) etc.
As above-mentioned epoxy alkane, such as, can use oxyethane, propylene oxide, butylene oxide ring, Styrene oxide 98min., Epicholorohydrin, tetrahydrofuran (THF) etc.
As operable polyether glycol in above-mentioned polyvalent alcohol (a1), preferably use the polyoxytetramethylene glycol that tetrahydrofuran (THF) open loop is formed specifically.
As above-mentioned polyether glycol, improving further for consideration in the adaptation of polar substrates (E), non-polar substrate (F), preferably use the polyether glycol of number-average molecular weight 500 ~ 3000.
Overall relative to the polyvalent alcohol (a1) used when manufacturing above-mentioned urethane resin (A), above-mentioned polyether glycol preferably uses in the scope of 50 quality % ~ 99.7 quality %, more preferably uses in the scope of 50 quality % ~ 90 quality %.
In addition, as the polyester polyol that can use in the above-mentioned polyvalent alcohol (a1), such as, the material that low-molecular-weight polyvalent alcohol and poly carboxylic acid can be used to carry out esterification and obtain, the cyclic ester compounds such as 6-caprolactone are made to carry out ring-opening polymerization and the polyester, their copolyesters etc. that obtain.
As above-mentioned low-molecular-weight polyvalent alcohol, such as can use molecular weight be about 50 ~ 300 ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1, the polyvalent alcohols containing aromatic structure such as bisphenol cpd and their alkylene oxide adducts such as aliphatic polyol, the cyclohexanedimethanols etc. such as 6-hexylene glycol, glycol ether, neopentyl glycol, the 1,3 butylene glycol polyvalent alcohol containing aliphatics ring structures, dihydroxyphenyl propane or Bisphenol F.
In addition, as above-mentioned poly carboxylic acid operable in the manufacture of above-mentioned polyester polyol, such as can use the aliphatic polycarboxylic acids such as succinic acid, hexanodioic acid, sebacic acid, dodecanedioic acid, the aromatic series poly carboxylic acid such as terephthalic acid, m-phthalic acid, phthalic acid, naphthalene diacid, and their acid anhydrides or carboxylate etc.
As above-mentioned polyester polyol, preferably use the polyester polyol with the number-average molecular weight of the scope of 200 ~ 5000.
In addition, as operable polycarbonate polyol in above-mentioned polyvalent alcohol (a1), such as, can use carbonic ether and polyol reaction and the polycarbonate polyol obtained, carbonyl chloride and dihydroxyphenyl propane etc. be reacted and the polycarbonate polyol obtained.
As above-mentioned carbonic ether, methyl carbonate, methylcarbonate, ethyl-carbonate, diethyl carbonate, cyclic carbonate ester, diphenyl carbonate etc. can be used.
As can with the polyvalent alcohol of above-mentioned carbonate reaction, such as can make spent glycol, glycol ether, 1,2-propylene glycol, dipropylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, Isosorbide-5-Nitrae-cyclohexanediol, 1,6-hexylene glycol, cyclohexanedimethanol equimolecular quantity are roughly the glycol, polyoxyethylene glycol, polypropylene glycol, poly-hexanodioic acid hexylene glycol ester etc. of the lower molecular weight of 50 ~ 2000.
As above-mentioned polycarbonate polyol, do not damage excellent humidity resistance, in the adaptation comprising the non-polar substrate such as vinyl acetate resins, polypropylene (F), preferably use the polycarbonate polyol with the number-average molecular weight of the scope of 500 ~ 4000.
In addition, as said polyolefins polyvalent alcohol operable in above-mentioned polyvalent alcohol (a1), such as, can use polyethylene polyols, polypropylene polyvalent alcohol, polyisobutene polyol, hydrogenation (hydrogenation) polybutadiene polyol, hydrogenation (hydrogenation) polyisoprene polyol.
In addition, as above-mentioned polyvalent alcohol (a1), give good dispersion stability from the viewpoint of to above-mentioned urethane resin (A), except above-mentioned material, the polyvalent alcohol containing hydrophilic radical can be combinationally used.
As the above-mentioned polyvalent alcohol containing hydrophilic radical, such as, can use containing the polyvalent alcohol of anionic property group, the polyvalent alcohol containing cationic groups and containing the polyvalent alcohol of nonionic group beyond above-mentioned polyvalent alcohol.Wherein, preferably use the polyvalent alcohol containing anionic property group or the polyvalent alcohol containing cationic groups, more preferably use the polyvalent alcohol containing anionic property group.
As the above-mentioned polyvalent alcohol containing anionic property group, such as, can use the polyvalent alcohol containing carboxyl, containing sulfonic polyvalent alcohol.
As the above-mentioned polyvalent alcohol containing carboxyl, such as can use 2,2 '-dimethylol propionic acid, 2,2 '-dimethylolpropionic acid, 2,2 '-dihydroxymethyl valeric acid etc., wherein, preferably use 2,2 '-dimethylol propionic acid.In addition, the polyester polyol containing carboxyl that the above-mentioned polyvalent alcohol containing carboxyl and various poly carboxylic acid also can be used to react and obtain.
As above-mentioned containing sulfonic polyvalent alcohol, such as can use dicarboxylic acid or their salt such as 5-sulfoisophthalic acid, sulfoterephthalic, 4-sulfosalicylic phthalate, 5 [4-sulfophenoxy] m-phthalic acid, and to react as the low molecular weight polyols that can be used for going out illustrated in the material of the manufacture of the above-mentioned polyester polyol containing aromatic structure and the polyester polyol that obtains.
Above-mentioned polyvalent alcohol containing carboxyl or containing the preferably use the scope that the acid number of above-mentioned urethane resin (A) is 10 ~ 70 in of sulfonic polyvalent alcohol, more preferably use in the scope reaching 10 ~ 50, preferably further to use in the scope reaching 10 ~ 35.And said acid number is the usage quantity of the compound containing acidic group such as the polyvalent alcohol containing carboxyl used in manufacture based on above-mentioned urethane resin (A) and the theoretical value that calculates in the present invention.
From the viewpoint of showing good water dispersible, preferably basic cpd is utilized to neutralize part or all of above-mentioned anionic property group.
As above-mentioned basic cpd, such as, the boiling points such as ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine can be used to be the organic amine of more than 200 DEG C; The metal hydroxidess such as sodium hydroxide, potassium hydroxide, lithium hydroxide.From the viewpoint of the dispersion stability of the sealant of raising gained, preferably in the scope of basic cpd/anionic property group=0.5 ~ 3.0 (mol ratio), use above-mentioned basic cpd, more preferably use in the scope of 0.9 ~ 2.0 (mol ratio).
In addition, as the above-mentioned polyvalent alcohol containing cationic groups, such as can use the polyvalent alcohol containing tertiary amino, specifically, the polyvalent alcohol etc. that N-metil-diethanolamine, the compound in 1 molecule with 2 epoxy group(ing) and secondary amine react and obtains can be used.
Preferably by acidic cpd neutralizations such as part or all use formic acid, acetic acid, propionic acid, succinic acid, pentanedioic acid, tartrate, hexanodioic acids of above-mentioned cationic groups.
In addition, preferably using part or all quaternary salt in addition of the tertiary amino as above-mentioned cationic groups.As above-mentioned quaternary salt agent, such as, can use methyl-sulfate, ethyl sulfate, methyl chloride, monochloroethane etc., preferably use methyl-sulfate.
In addition, as the above-mentioned polyvalent alcohol containing nonionic group, the polyvalent alcohol etc. with polyoxyethylene structure can be used.
Preferably relative to the polyvalent alcohol (a1) used in the manufacture of above-mentioned urethane resin (A) total amount in the scope of 0.3 quality % ~ 10.0 quality %, use the above-mentioned polyvalent alcohol containing hydrophilic radical.
In addition, as above-mentioned polyvalent alcohol (a1), except above-mentioned polyvalent alcohol, other polyvalent alcohol can also be used as required.
As other polyvalent alcohol above-mentioned, such as, can make spent glycol, glycol ether, 1,2-PD, dipropylene glycol, 1,4-butyleneglycol, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, 1, the polyvalent alcohol of the lower molecular weights such as 4-cyclohexanediol, 1,6-hexylene glycol, cyclohexanedimethanol.
In the present invention, in the adaptation improving sealant and various base material further, preferably neopentyl glycol etc. is used.
As the polymeric polyisocyanate (a2) that can react with above-mentioned polyvalent alcohol (a1), such as can use 4, 4 '-diphenylmethanediisocyanate, 2, 4 '-diphenylmethanediisocyanate, carbodiimide modified diphenylmethanediisocyanate, thick diphenylmethanediisocyanate, phenylene diisocyanate, tolylene diisocyanate, the aromatic poly-isocyanates such as naphthalene diisocyanate, hexamethylene diisocyanate, lysinediisocyanate, xylylene diisocyanate, the aliphatic polymeric isocyanates such as tetramethyl-xylylene diisocyanate, cyclohexyl diisocyanate, dicyclohexyl methane diisocyanate, the polymeric polyisocyanate containing aliphatics ring structures such as isophorone diisocyanate.
Above-mentioned urethane resin (A) such as can manufacture as follows, namely, under the existence of solvent-free lower or organic solvent, the urethane resin with isocyanate group is produced by making above-mentioned polyvalent alcohol (a1) and above-mentioned polymeric polyisocyanate (a2) react, then, when there is hydrophilic radical in above-mentioned urethane resin, as required part or all of this hydrophilic radical is neutralized, the material mixing of gained is thus carried out Water-borne modification in aqueous medium (D), now, the compound with primary amino is selected from above-mentioned, there is the compound of hydrazide group and at least a kind of mixing of hydrazine, the isocyanic ester radical reaction had with above-mentioned urethane resin, thus manufacture above-mentioned urethane resin (A).
The equivalents ratio of the hydroxyl that the reaction such as preferred isocyanate group had at above-mentioned polymeric polyisocyanate (a2) of above-mentioned polyvalent alcohol (a1) and polymeric polyisocyanate (a2) has relative to above-mentioned polyvalent alcohol (a1) be 0.8 ~ 2.5 scope in carry out, more preferably carry out in the scope of 0.9 ~ 1.5.
In addition, as operable organic solvent during manufacture above-mentioned urethane resin (A), such as can by the ketone such as acetone, methylethylketone; The ethers such as tetrahydrofuran (THF), diox; The acetate esters such as ethyl acetate, butylacetate; The nitriles such as acetonitrile; The acid amides such as dimethyl formamide, N-Methyl pyrrolidone is used alone or will wherein two or more is also used.
In addition, the compound that being selected from of using when manufacturing in the present invention urethane resin (A) used has primary amino, there is the compound of hydrazide group and at least a kind of hydrazine for giving the adaptation of the excellence to various base material.Wherein, preferably hydrazine is used further raising in humidity resistance.In addition, as above-mentioned hydrazine, the hydrazine hydrate of the monohydrate of hydrazine can be used as.
As the above-mentioned compound with primary amino, thanomin etc. can be used.
As the above-mentioned compound with hydrazide group, such as dicarboxyl acid dihydrazide, carbohydrazide, 1,3-two (Hydrazinocarbonyl ethyl)-5-sec.-propyl glycolylurea etc. can be used, preferably use dicarboxyl acid dihydrazide or carbohydrazide.
As above-mentioned dicarboxyl acid dihydrazide, can a kind or use such as acid dihydrazide, succinic acid hydrazide ii, adipic dihydrazide, penta acid dihydrazide, sebacic dihydrazide, isophthalic dihydrazide with combining two or more; Beta-amino ureido propionic acid hydrazides etc.Wherein in the adaptation of giving excellence, preferably use adipic dihydrazide.
Above-mentioned be selected from there is primary amino compound, there is the compound of hydrazide group and at least a kind of hydrazine uses in following ranges: the equivalence ratio of the isocyanate group that the total amount of the nitrogen-atoms that its primary amino had, hydrazide group and hydrazine have has with the urethane resin making above-mentioned polyvalent alcohol (a1) and polymeric polyisocyanate (a2) react and obtain is preferably in the scope of less than 1 (equivalence ratio), is more preferably in the scope of 0.3 ~ 1 (equivalence ratio).
In addition, such as, the Water-borne modification of the urethane resin (A) that following method can be utilized to carry out utilizing aforesaid method to manufacture.
Part or all of the hydrophilic radical of the urethane resin that (method 1) will obtain polyvalent alcohol (a1) and polymeric polyisocyanate (a2) will be made to react neutralizes or after quaternary salt, drop in water and make it water-dispersion, thereafter by using above-mentioned at least a kind of being selected from the compound with primary amino, the compound with hydrazide group and hydrazine to carry out chain extension, thus urethane resin (A) is made to carry out the method for water-dispersion.
The urethane resin that (method 2) obtains making polyvalent alcohol (a1) and polymeric polyisocyanate (a2) react and the above-mentioned compound with primary amino, the compound with hydrazide group and hydrazine at least a kind of being selected from disposable or add in batches in reaction vessel, urethane resin (A) is manufactured by making it to carry out chain extension reaction, then, after by part or all neutralization of the hydrophilic radical in the urethane resin (A) of gained or quaternary salt, the method making it water-dispersion in water is dropped into.
In above-mentioned (method 1) ~ (method 2), also emulsifying agent can be used as required.In addition, when water dissolution or water-dispersion, also the machineries such as homogenizer can be used as required.
As mentioned emulsifier, such as, can enumerate the nonionic system emulsifying agents such as ethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, Polyoxyethylene sorbitol tetraoleate, poloxalkol; The negatively charged ion system emulsifying agents such as the soaps such as sodium oleate, alkyl sulfuric ester salt, alkylbenzene sulfonate, salts of alkyl sulfosuccinates salt, naphthalenesulfonate, laureth sulfate, alkane sulfonic acid sodium salt, alkyl diphenyl base salt; The positively charged ion system emulsifying agents such as alkylamine salt, alkyl trimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt.Wherein, from the viewpoint of the storage stability of the excellence of maintenance sealant of the present invention, the emulsifying agent of anionic property or nonionic is substantially preferably used.
For the urethane resin utilizing aforesaid method to obtain (A) being scattered in for urethane resin (A) water dispersion that obtains in aqueous medium (D), improve the easness of manufacture of sealant of the present invention and preparation take into account excellent humidity resistance and for the adaptation of the excellence of various base material sealant in, preferably relative to the total amount of this water dispersion in the scope of 10 ~ 50 containing above-mentioned urethane resin (A).
Above-mentioned urethane resin (A) water dispersion also can be the material be obtained by mixing by the different urethane resin of more than two kinds of composition.Specifically, urethane resins different for the composition of the polyvalent alcohol used in the manufacture of urethane resin (a1) can be combinationally used two or more.
Below, the polyolefin resin (B) used in the manufacture to sealant of the present invention is described.
As the polyolefin resin used in the present invention (B), such as, can use the material with functional group [X] that the homopolymer, multipolymer etc. of ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene etc. are central.
As said polyolefins resin (B), specifically, in the middle of polyethylene, polypropylene, polyhutadiene, ethylene-propylene copolymer, natural rubber, the different acrylic rubber of synthesis, vinyl-vinyl acetate copolymer etc., can use have have with above-mentioned linking agent (C) epoxy group(ing), isocyanic ester radical reaction the material of functional group [X].When said polyolefins resin (B) is multipolymer, both can be random copolymers, also can be segmented copolymer.
As the functional group [X] that said polyolefins resin (B) has, the functional group [X] that can have with above-mentioned urethane resin (A) enumerates such as carboxyl in the same manner.And above-mentioned functional group [X] also can be the functional group identical with the hydrophilic radical that polyolefin resin (B) has.Specifically, when being used as carboxyl, the carboxylic acid ester groups of anionic property group as above-mentioned hydrophilic radical, above-mentioned carboxyl etc. also can play a role as above-mentioned functional group [X] when crosslinking reaction.
As the polyolefin resin (B) had as the carboxyl of above-mentioned functional group [X], the so-called modified polyolefin hydrocarbon system resins such as the resin after the resin preferably making said polyolefins resin and unsaturated carboxylic acid react and obtain, the resin making said polyolefins resin and vinyl monomer react and obtain, chlorination.
The polyolefin resin of carboxyl as above-mentioned functional group [X] can be had by making the unsaturated dicarboxylic acids such as such as polyolefin resin and toxilic acid (acid anhydride) react to manufacture.
As above-mentioned unsaturated dicarboxylic acid, such as can enumerate toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid and their acid anhydrides, unsaturated dicarboxylic acid ester class (butyl maleate, dibutyl maleinate, itaconic acid n-butyl etc.), their more than a kind can be used.Wherein be preferably maleic anhydride.
From the deterioration of resin-cured layer (heat sealing layer) prevented because the impact of heat, water (moisture) causes, prevent the aspect of the reduction of the adaptation for various base material from considering, by above-mentioned unsaturated carboxylic acid-modified after polyolefin resin (B) preferably there is the acid number of the scope of 5 ~ 250.
The modification of said polyolefins resin such as can by heat the unsaturated dicarboxylic acids such as foregoing polyolefin resin and toxilic acid etc. etc. and to make it reaction to carry out.
In addition, as said polyolefins resin (B), from the viewpoint of the deterioration of the resin-cured layer (heat sealing layer) that causes of impact prevented because of heat, water (moisture), the reduction preventing the adaptation for various base material, preferably use has the resin of the weight-average molecular weight of 20000 ~ 500000.And above-mentioned weight-average molecular weight refers to the value using gel permeation chromatography (GPC) method to measure.
Below, the linking agent used in the present invention (C) is described.
In the present invention, as above-mentioned linking agent (C), for obtaining the object taking into account excellent humidity resistance and the sealant for the adaptation of the excellence of various base material, abovementioned alkyl melamine methylol resin (c1) and above-mentioned epoxy compounds (c2) are combinationally used.
As abovementioned alkyl melamine methylol resin (c1), such as, can use methylolated melamine resin, react and the resin that obtains with the lower alcohol such as methyl alcohol or butanols (alcohol of carbonatoms 1 ~ 6).Specifically, the alkylated methylol groups melamine resin containing imino-can be used, containing amino alkylated methylol groups melamine resin etc.
As above-mentioned methylolated melamine resin, such as can use trimeric cyanamide and formaldehyde condensation are obtained containing amino methylol type melamine resin, methylol type melamine resin, trimethoxy methylol type melamine resin, hexa methoxy methylol type melamine resin etc. containing imino-, preferably use trimethoxy methylol type melamine resin, hexa methoxy methylol type melamine resin.
In addition, as above-mentioned epoxy compounds (c2), the compound that preferably there are 2 ~ 5, more preferably there are 3 ~ 4 epoxy group(ing) can be used.
As above-mentioned epoxy compounds (c2), such as can use the epoxy resin of bisphenol A/epichlorohydrin type, ethene glycidyl ether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, T 55,1,6-hexylene glycol glycidyl ether, TriMethylolPropane(TMP) polyglycidyl ether, diglycidylaniline, diamines glycidyl group amine, N, N, N ', N '-four glycidyl group-xylylene diamine, 1, two (N, N '-diamines glycidyl-amino methyl) hexanaphthenes of 3-etc.
Wherein, as above-mentioned epoxy compounds (c2), from the viewpoint of giving weather resistance, epoxy equivalent (weight) is preferably 100 ~ 300, specifically, more than a kind that is selected from TriMethylolPropane(TMP) polyglycidyl ether and T 55 is preferably used.
In addition, as above-mentioned epoxy compounds (c2), also preferably use the epoxy compounds with hydrolyzable silyl group.
As the above-mentioned epoxy compounds with hydrolyzable silyl group, such as can use 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxyl silane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane etc.
Preferably in the scope of 3 quality % ~ 50 quality %, use abovementioned alkyl melamine methylol resin (c1) relative to the total quality of above-mentioned urethane resin (A) and said polyolefins resin (B), more preferably use in the scope of 3 quality % ~ 30 quality %.Thus, the impact of heat, water (moisture) can not cause the deterioration of above-mentioned heat sealing layer, the reduction of closing force, can take into account more excellent humidity resistance and the more excellent adaptation for various base material.
With regard to the usage quantity of abovementioned alkyl melamine methylol resin (c1), taking into account in more excellent humidity resistance and the adaptation to the excellence of various base material, preferably using in the scope of 10 quality % ~ 30 quality % relative to the total quality of above-mentioned urethane resin (A) and said polyolefins resin (B).
In addition, as above-mentioned linking agent (C), the ratio (the total amount of substance (mole number) of amount of substance (the mole number)/functional group [X] of epoxy group(ing)) of the total amount of substance (mole number) of the above-mentioned functional group [X] that the amount of substance (mole number) of the epoxy group(ing) preferably had at above-mentioned epoxy compounds (c2) has relative to above-mentioned urethane resin (A) and said polyolefins resin (B) be 5/1 ~ 1/5 scope in use above-mentioned epoxy compounds (c2).Thus, utilize heating etc., the heat sealing layer of more firmly cross-linking density is defined when can be formed in solidification, therefore the impact of heat, water (moisture) can not cause the deterioration of above-mentioned heat sealing layer, the reduction of closing force, can take into account more excellent humidity resistance and the more excellent adaptation for various base material.
Taking into account preferred above-mentioned usage ratio in more excellent humidity resistance and the adaptation to the excellence of various base material (the total amount of substance of the amount of substance/functional group [X] of epoxy group(ing)) preferably in the scope of 2/1 ~ 1/5.
In addition, having concurrently in more excellent humidity resistance and the adaptation to the excellence of various base material, preferably in the scope of mass ratio (abovementioned alkyl melamine methylol resin (c1)/above-mentioned epoxy compounds (c2))=7/1 ~ 1/4, use abovementioned alkyl melamine methylol resin (c1) and above-mentioned epoxy compounds (c2), more preferably use in the scope of 5/1 ~ 1/4.
As above-mentioned linking agent (C), except abovementioned alkyl melamine methylol resin (c1), beyond above-mentioned epoxy compounds (c2), also can be used together other linking agent as required, such as tolylene diisocyanate can be used, chlorophenylene diisocyanates, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, the isocyanate-monomers such as the diphenylmethanediisocyanate after hydrogenation, or make the alkylol cpd etc. of they and TriMethylolPropane(TMP) etc. more than 2 yuan carry out addition reaction and the isocyanate compound obtained or isocyanuric acid carboxylate, the isocyanate compounds such as biuret form compound.
Below, the aqueous medium used in the present invention (D) is described.
As the aqueous medium used in the present invention (D), such as, can enumerate water, the organic solvent miscible with water and their mixture.As the organic solvent miscible with water, such as, can enumerate the alcohols such as methyl alcohol, ethanol, n-propyl alcohol and Virahol; The ketone such as acetone, methylethylketone; The polyalkylene glycols such as ethylene glycol, glycol ether, propylene glycol; The alkyl ether of polyalkylene glycol; The lactams etc. such as METHYLPYRROLIDONE.In the present invention, also only can use water, also can use the mixture of water and the organic solvent miscible with water in addition, can also only use the organic solvent miscible with water.From the viewpoint of security, to the burden that environment causes, be preferably only the mixture of water or water and the organic solvent miscible with water, be particularly preferably only water.
Preferably relative to the total amount of sealant of the present invention, containing above-mentioned aqueous medium (D) in the scope of 10 quality % ~ 90 quality %, from the viewpoint of taking into account the raising of painting work etc. of sealant of the present invention and adaptation, humidity resistance, preferably in the scope of 30 quality % ~ 85 quality % containing above-mentioned aqueous medium (D).
Sealant of the present invention such as can by by the water dispersion of the water dispersion of the urethane resin utilizing aforesaid method to obtain (A), said polyolefins resin (B) and above-mentioned linking agent (C) disposable or supply in batches, mixing and being manufactured.With regard to above-mentioned linking agent (C), both abovementioned alkyl melamine methylol resin (c1) and above-mentioned epoxy compounds (c2) can be pre-mixed, also can by their water dispersions respectively to urethane resin (A), the water dispersion supply of said polyolefins resin (B), remix.
The sealant of the present invention utilizing aforesaid method to obtain, as required also can containing other additive etc. except above-mentioned composition.
As above-mentioned additive, such as, can use antioxidant, photostabilizer, softening agent, membrane producing promoter, flow agent, whipping agent, thickening material, tinting material, fire retardant, other water-base resin, various weighting agents etc. in the scope not damaging effect of the present invention.
In addition, as above-mentioned additive, from the viewpoint of the dispersion stabilization improving sealant of the present invention further, such as, tensio-active agent can be used.But, because tensio-active agent has the adaptation of tunicle, the situation of water tolerance reducing gained, therefore relative to total 100 mass parts of urethane resin (A) and polyolefin resin (B), use in scope preferably below 20 mass parts, preferably do not use as far as possible.
Sealant of the present invention can form the heat sealing layer of excellent adhesion for base material and humidity resistance excellence.Especially, sealant of the present invention, owing to all having excellent closing force for any one in polar substrates and non-polar substrate, therefore goes for polar substrates with the bonding sealant of non-polar substrate.Specifically, can use suitably with the bonding sealant of the polar substrates (backsheet layer) comprising polyethylene terephthalate, polycarbonate or polymeric amide etc. as the non-polar substrates such as vinyl-vinyl acetate copolymer, polyvinyl butyral acetal, glass that comprise formed with the sensitive surface opposing face forming solar cell.In addition, can as forming and the comprising the non-polar substrates such as vinyl-vinyl acetate copolymer, polyvinyl butyral acetal, glass, use suitably with the bonding sealant of the non-polar substrate (backsheet layer) comprising acrylic resin etc. of the sensitive surface opposing face of formation solar cell.
As the base material that can form above-mentioned heat sealing layer, such as various plastics or its film, metal, glass, paper, timber etc. can be enumerated.
As polar substrates, polyethylene terephthalate base material, polycarbonate substrate, polyamide substrate etc. can be enumerated.
As non-polar substrate, such as, can enumerate the base material comprising vinyl-vinyl acetate copolymer, polyvinylidene fluoride resin, polyfluoroethylene resin, ethylene-vinyl alcohol copolymer, polyvinyl butyral acetal, glass etc.
Surface treatment can be implemented in advance to the surface of above-mentioned base material, preferably implement corona treatment specifically.Infer and utilize corona treatment, when being formed with carbonyl isoreactivity group on the surface of above-mentioned base material, forming key with the urea key of the above-mentioned urethane resin (A) comprised in sealant of the present invention, consequently, adaptation can be improved further.
In addition, sealant of the present invention is by coating the surface of above-mentioned base material and dry and can be formed and be cross-linked to a certain degree and the resin layer that formed.Surface due to above-mentioned resin layer there is no adhesion sense before heating, and therefore, also can carry out keeping etc. under the stacked state having the component being provided with above-mentioned resin layer in advance of substrate surface.
Then, if load other base materials, heating on the surface of above-mentioned resin layer, then above-mentioned resin layer melting, and the reactions such as the hydrolyzable silyl group of the hydroxyl generated by above-mentioned crosslinking reaction and above-mentioned epoxy compounds (c2), form that show can by the heat sealing layer of closing force bonding securely for two base materials thus.The humidity resistance of the heat sealing layer formed after above-mentioned crosslinking reaction is also excellent, therefore can prevent heat, the deterioration of this heat sealing layer that the impact of water (moisture) causes.
As method sealant of the present invention being coated on substrate surface, such as, can enumerate spray method, heavy curtain coating method, flow coat method, rolling method, spread coating, pickling process etc.
Particularly, when above-mentioned sealant of plastic basis material surface coated etc. such as polyethylene terephthalate films, following streamline coating (inlinecoating) method can be adopted, namely, plastic basis material is being carried out in the way of biaxial stretch-formed operation under the condition of about about 200 DEG C, by also dry in the above-mentioned sealant of this plastic basis material surface coated, make it crosslinking reaction occurs, thus form heat sealing layer.
In addition, when above-mentioned sealant of plastic basis material surface coated etc. such as polyethylene terephthalate films, following off-line coating (offlinecoating) method can be adopted, namely, once will be wound on roller etc. by carrying out above-mentioned biaxial stretch-formed obtained plastic basis material, then, from this roller, pull out plastic basis material, in the above-mentioned sealant of its surface coated.
Above-mentioned off-line coating method, in order to not damage the dimensional stability of above-mentioned plastic basis material, carries out drying etc. at the temperature preferably below roughly 150 DEG C.
Utilize above method, can be formed at substrate surface and make above-mentioned sealant crosslinking curing and the heat sealing layer that formed.
In addition, by being coated with sealant of the present invention at a substrate surface by above-mentioned method, dry, thus when above-mentioned substrate surface arranges resin layer, by loading other base material on the surface of above-mentioned resin layer, then, under the state reduced pressure or pressurize, be heated to roughly 100 DEG C ~ 160 DEG C, thus can obtain the duplexer of they laminatings.
The humidity resistance of above-mentioned duplexer is also excellent, therefore such as may be used for forming solar power generating device solar module or with automobile interior trim material be representative various uses in.
Above-mentioned solar module in general mostly possess form with the face of sunlight sensitive surface opposition side comprise on the face of vinyl-vinyl acetate copolymer etc., for preventing the objects such as its deterioration, and be provided with the stepped construction of the backsheet layer comprising polyethylene terephthalate, acrylic resin etc.
As above-mentioned solar module, specifically, the solar module possessing following structure can be enumerated: be laminated with in the face comprising vinyl-vinyl acetate copolymer of the opposing face of the sensitive surface of formation solar module the heat sealing layer using above-mentioned sealant to be formed, be laminated with the structure of the layer comprising polyethylene terephthalate base material, polypropylene base, polycarbonate substrate or polyamide substrate on the surface of above-mentioned heat sealing layer.
As the method manufacturing above-mentioned solar module, such as following method can be enumerated.
First, be coated with above-mentioned sealant in advance on the surface of polyethylene terephthalate base material, polypropylene base, polycarbonate substrate or polyamide substrate, manufacture to possess and heat and the lamination sheets of the heat sealing layer of formation.
Then, load in the mode that the heat sealing layer of above-mentioned lamination sheets contacts with the face of vinyl-vinyl acetate copolymer of the opposing face comprising the sensitive surface being formed solar module, heating, thus that above-mentioned polyethylene terephthalate base material etc. is mutually bonding with the face comprising above-mentioned vinyl-vinyl acetate copolymer.Thus, solar module can be manufactured.
Even if the solar module utilizing this kind of method to obtain is when using out of doors for a long time, the weather resistance such as humidity resistance are also excellent.
Embodiment
Below, embodiment and comparative example is utilized to carry out more specific description to the present invention.
[preparation example 1]
Possessing stirrer, reflux condensing tube, temperature is taken into account nitrogen and is blown in 4 neck flasks of pipe, under nitrogen flowing, add polyoxytetramethylene glycol (weight-average molecular weight: 2000) 1000 mass parts, dimethylol propionic acid 79.8 mass parts, methylethylketone 672.7 mass parts, after Homogeneous phase mixing, add tolylene diisocyanate 255.6 mass parts, then dibutyltin dilaurate 0.1 mass parts is added, reaction about 4 hours are made it at 80 DEG C, (isocyanate group is relative to the mass ratio (isocyanate group content) of above-mentioned polyurethane prepolymer to obtain having the polyurethane prepolymer of isocyanate group at end thus, 2.1 quality %) methyl ethyl ketone solution.
Then, add triethylamine 69.3 mass parts in the solution after the methyl ethyl ketone solution of the polyurethane prepolymer obtained by aforesaid method is cooled to 40 DEG C, thus by the carboxyl neutralization in above-mentioned polyurethane prepolymer.
Then, add ion exchanged water 3079.2 mass parts, add 80 quality % hydrazine hydrates (monohydrate of hydrazine is hydrazine relative to overall 80 quality %) 20.97 mass parts and make it reaction.
After reaction terminates, under reduced pressure distillation removing methylethylketone, by being that the mode of 35 quality % adds ion exchanged water and obtains composition (I) with its nonvolatile component.
[preparation example 2]
Possessing stirrer, reflux condensing tube, temperature take into account nitrogen and be blown in 4 neck flasks of pipe, under nitrogen flowing, add polyoxytetramethylene glycol (weight-average molecular weight: 2,000) 1000 mass parts, dimethylol propionic acid 79.8 mass parts, methylethylketone 672.7 mass parts, after Homogeneous phase mixing, add tolylene diisocyanate 255.6 mass parts, then dibutyltin dilaurate 0.1 mass parts is added, make it reaction about 4 hours at 80 DEG C, obtain the polyurethane prepolymer (isocyanate group content at end with isocyanate group thus; 2.1 quality %) methyl ethyl ketone solution.
Then, add triethylamine 69.3 mass parts in the solution after the methyl ethyl ketone solution of the polyurethane prepolymer obtained by aforesaid method is cooled to 40 DEG C, by the carboxyl neutralization in above-mentioned polyurethane prepolymer.
Then, add ion exchanged water 3130.9 mass parts, add adipic dihydrazide 116.7 mass parts and make it reaction.
After reaction terminates, under reduced pressure distillation removing methylethylketone, by being that the mode of 35 quality % adds ion exchanged water and obtains composition (II) with its nonvolatile component.
[preparation example 3]
Possessing stirrer, reflux condensing tube, temperature take into account nitrogen and be blown in 4 neck flasks of pipe, under nitrogen flowing, add polyoxytetramethylene glycol (weight-average molecular weight: 2000) 1000 mass parts, dimethylol propionic acid 79.8 mass parts, methylethylketone 672.7 mass parts, after Homogeneous phase mixing, add tolylene diisocyanate 255.6 mass parts, then dibutyltin dilaurate 0.1 mass parts is added, make it reaction about 4 hours at 80 DEG C, obtain the polyurethane prepolymer (isocyanate group content at end with isocyanate group thus; 2.1 quality %) methyl ethyl ketone solution.
Then, add triethylamine 69.3 mass parts in the solution after the methyl ethyl ketone solution of the polyurethane prepolymer obtained by aforesaid method is cooled to 40 DEG C, by the carboxyl neutralization in above-mentioned polyurethane prepolymer.
Then, add ion exchanged water 3149.2 mass parts, add 80 quality % hydrazine hydrates (monohydrate of hydrazine is hydrazine relative to overall 80 quality %) 93.2 mass parts and make it reaction.
After reaction terminates, under reduced pressure distillation removing methylethylketone, by being that the mode of 35 quality % adds ion exchanged water and obtains composition (III) with its nonvolatile component.
[preparation example 4]
Possessing stirrer, reflux condensing tube, temperature is taken into account nitrogen and is blown in 4 neck flasks of pipe, under nitrogen flowing, add polyoxytetramethylene glycol (weight-average molecular weight: 2000) 1000 mass parts, 1, 4-butyleneglycol 21.2 mass parts, dimethylol propionic acid 87.1 mass parts, methylethylketone 784.9 mass parts, after Homogeneous phase mixing, add isophorone diisocyanate 336.0 mass parts, then dibutyltin dilaurate 0.1 mass parts is added, reaction about 4 hours are made it at 80 DEG C, obtain the polyurethane prepolymer (isocyanate group content at end with isocyanate group thus, 2.1 quality %) methyl ethyl ketone solution.
Then, the methyl ethyl ketone solution of the polyurethane prepolymer obtained by aforesaid method and thanomin 13.6 mass parts, methylethylketone 189 mass parts mixed and makes it reaction, obtaining the methyl ethyl ketone solution at end with the urethane resin of primary amino thus.
Then, triethylamine 69.0 mass parts is added in solution after the methyl ethyl ketone solution of the urethane resin obtained by aforesaid method is cooled to 40 DEG C, by in the carboxyl in above-mentioned urethane resin and after, under reduced pressure distillation removing methylethylketone, by being that the mode of 35 quality % adds ion exchanged water and obtains composition (IV) with its nonvolatile component.
[preparation example 5]
In the reactor possessing thermometer, nitrogen ingress pipe, stirrer, importing nitrogen limit in limit adds 1000 mass parts POLESTARVS-1236 (Nippon PMC K. K.'s system, maleic anhydride modified polyolefinic water dispersion, weight-average molecular weight 70000), within 3 hours, melting is made it 80 DEG C of stirrings, then 50 DEG C are cooled to, add after triethylamine 180 mass parts neutralizes, add water 2153 mass parts and carry out water-solubleization, obtain the composition (V) of nonvolatile component 30 quality % thus.
[preparation example 6]
Possessing stirrer, reflux condensing tube, temperature take into account nitrogen and be blown in 4 neck flasks of pipe, under nitrogen flowing, add polyoxytetramethylene glycol (weight-average molecular weight: 2000) 1000 mass parts, dimethylol propionic acid 79.8 mass parts, methylethylketone 672.7 mass parts, after Homogeneous phase mixing, add tolylene diisocyanate 255.6 mass parts, then dibutyltin dilaurate 0.1 mass parts is added, make it reaction about 4 hours at 80 DEG C, obtain the polyurethane prepolymer (isocyanate group content in molecular end with isocyanate group thus; 2.1 quality %) methyl ethyl ketone solution.
Then, add triethylamine 69.3 mass parts in the solution after the methyl ethyl ketone solution of the polyurethane prepolymer obtained by aforesaid method is cooled to 40 DEG C, by the carboxyl neutralization in above-mentioned polyurethane prepolymer.
Then, add ion exchanged water 3122.6 mass parts, add carbohydrazide 60.3 mass parts and make it reaction.
After reaction terminates, under reduced pressure distillation removing methylethylketone, by being that the mode of 35 quality % adds ion exchanged water and obtains composition (VI) with its nonvolatile component.
[embodiment 1]
By composition (V) the 78 mass parts mixing obtained in the composition obtained in preparation example 1 (I) 100 mass parts and preparation example 5.Then, add BECKAMINEM-3 (Dainippon Ink Chemicals's system, trimethoxy methylol type melamine resin, nonvolatile component 80 quality %) 5 mass parts and DenacolEX-321 (NagaseChemtex Co., Ltd. system, TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) 4 mass parts, stir, add water, obtain the sealant (X-1) of the aqueous resin composition (X-1) comprising nonvolatile component 20 quality % thus.
[embodiment 2]
Except composition (I) 100 mass parts replacing obtaining in preparation example 1 except using composition (II) 100 mass parts obtained in preparation example 2, obtain the sealant (X-2) comprising aqueous resin composition (X-2) in the same manner as in Example 1.
[embodiment 3]
Except composition (I) 100 mass parts replacing obtaining in preparation example 1 except using composition (III) 100 mass parts obtained in preparation example 3, obtain the sealant (X-3) comprising aqueous resin composition (X-3) in the same manner as in Example 1.
[embodiment 4]
Except composition (I) 100 mass parts replacing obtaining in preparation example 1 except using composition (IV) 100 mass parts obtained in preparation example 4, obtain the sealant (X-4) comprising aqueous resin composition (X-4) in the same manner as in Example 1.
[embodiment 5]
Except by BECKAMINEM-3 (the trimethoxy methylol type melamine resin of Dainippon Ink Chemicals, nonvolatile component 80 quality %) usage quantity change to beyond 23 mass parts from 5 mass parts, obtain the sealant (X-5) comprising aqueous resin composition (X-5) in the same manner as in Example 1.
[embodiment 6]
Except by DenacolEX-321 (NagaseChemtex Co., Ltd. system, TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) usage quantity change to beyond 42 mass parts from 4 mass parts, obtain the sealant (X-6) comprising aqueous resin composition (X-6) in the same manner as in Example 1.
[embodiment 7]
Except by DenacolEX-321 (NagaseChemtex Co., Ltd. system, TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) usage quantity change to beyond 1 mass parts from 4 mass parts, obtain the sealant (X-7) comprising aqueous resin composition (X-7) in the same manner as in Example 1.
[embodiment 8]
Except the usage quantity of the composition (V) preparation example 5 recorded changes to 175 mass parts from 78 mass parts, by BECKAMINEM-3 (the trimethoxy methylol type melamine resin of Dainippon Ink Chemicals, nonvolatile component 80 quality %) usage quantity change to beyond 7 mass parts from 5 mass parts, and by DenacolEX-321 (NagaseChemtex Co., Ltd. system, TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) usage quantity change to beyond 8 mass parts from 4 mass parts, obtain the sealant (X-8) comprising aqueous resin composition (X-8) in the same manner as in Example 1.
[embodiment 9]
Except using BECKAMINEJ-101 (Dainippon Ink Chemicals's system, hexa methoxy methylol type melamine resin, nonvolatile component 80 quality %) 5 mass parts replacement BECKAMINEM-3 (the trimethoxy methylol type melamine resins of Dainippon Ink Chemicals, nonvolatile component 80 quality %) beyond, obtain the sealant (X-9) comprising aqueous resin composition (X-9) in the same manner as in Example 1.
[embodiment 10]
Except composition (I) 100 mass parts replacing obtaining in preparation example 1 except using composition (VI) 100 mass parts obtained in preparation example 6, obtain the sealant (X-10) comprising aqueous resin composition (X-10) in the same manner as in Example 1.
[comparative example 1]
By composition (V) the 78 mass parts mixing obtained in the composition obtained in preparation example 1 (I) 100 mass parts and preparation example 5, stir, add water, obtain the sealant (X '-1) of the aqueous resin composition (X '-1) comprising nonvolatile component 20 quality % thus.
[comparative example 2]
Composition (V) 78 mass parts obtained in the composition obtained in preparation example 1 (I) 100 mass parts and preparation example 5 is mixed and stirs, then, mixing DenacolEX-321 (NagaseChemtex Co., Ltd. system, TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) 4 mass parts, add water, obtain the sealant (X '-2) of the aqueous resin composition (X '-2) comprising nonvolatile component 20 quality % thus.
[comparative example 3]
Composition (V) the 78 mass parts portion obtained in the composition obtained in preparation example 1 (I) 100 mass parts and preparation example 5 is mixed and stirs, then, mixing BECKAMINEM-3 (the trimethoxy methylol type melamine resin of Dainippon Ink Chemicals, nonvolatile component 80 quality %) 5 mass parts, add water, obtain the sealant (X '-3) of the aqueous resin composition (X '-3) comprising nonvolatile component 20 quality % thus.
[comparative example 4]
Add composition (I) 100 mass parts, BECKAMINEM-3 (the trimethoxy methylol type melamine resin of Dainippon Ink Chemicals that obtain in preparation example 1, nonvolatile component 80 quality %) 3 mass parts and DenacolEX-321 (NagaseChemtex Co., Ltd. system, TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) 0.2 mass parts, stir, add water, obtain the sealant (X '-4) of the aqueous resin composition (X '-4) comprising nonvolatile component 20 quality % thus.
[comparative example 5]
Add composition (V) 100 mass parts, BECKAMINEM-3 (the trimethoxy methylol type melamine resin of Dainippon Ink Chemicals that obtain in preparation example 5, nonvolatile component 80 quality %) 2 mass parts and DenacolEX-321 (NagaseChemtex Co., Ltd. system, TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) 4 mass parts, stir, add water, obtain the sealant (X '-5) of the aqueous resin composition (X '-5) comprising nonvolatile component 20 quality % thus.
[comparative example 6]
Except using AQUANATE210 (Nippon Polyurethane Industry Co., Ltd.'s system, water-dispersible polyisocyanates linking agent, nonvolatile component 100 quality %) 7 mass parts replacement DenacolEX-321 (NagaseChemtex Co., Ltd. systems, TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) beyond, obtain the sealant (X '-7) comprising aqueous resin composition (X '-7) in the same manner as in Example 1.
[comparative example 7]
Except using AQUANATE210 (Nippon Polyurethane Industry Co., Ltd.'s system, water-dispersible polyisocyanates linking agent, nonvolatile component 100 quality %) 7 mass parts replacement BECKAMINEM-3 (Dainippon Ink Chemicals's systems, trimethoxy methylol type melamine resin, nonvolatile component 80 quality %) beyond, obtain the sealant (X '-8) comprising aqueous resin composition (X '-8) in the same manner as in Example 1.
[comparative example 8]
Except using HydranAssisterCS-7 (Dainippon Ink Chemicals's system, water dispersible carbodiimide compound, nonvolatile component 40 quality %) 28 mass parts replacement DenacolEX-321 (NagaseChemtex Co., Ltd. systems, TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) beyond, obtain the sealant (X '-9) comprising aqueous resin composition (X '-9) in the same manner as in Example 1.
[comparative example 9]
Except using AQUANATE210 (Nippon Polyurethane Industry Co., Ltd.'s system, water-dispersible polyisocyanates linking agent, nonvolatile component 100 quality %) 7 mass parts replacement BECKAMINEM-3 (Dainippon Ink Chemicals's systems, trimethoxy methylol type melamine resin, nonvolatile component 80 quality %), and use HydranAssisterCS-7 (Dainippon Ink Chemicals's system, water dispersible carbodiimide compound, nonvolatile component 40 quality %) 10 mass parts replacement DenacolEX-321 (NagaseChemtex Co., Ltd. systems, TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) beyond, obtain the sealant (X '-10) comprising aqueous resin composition (X '-10) in the same manner as in Example 1.
[evaluation method for the adaptation of polar substrates and non-polar substrate]
On the surface comprising the film of polyethylene terephthalate as polar substrates, in the mode making dry film thickness become 5 μm, be coated with the sealant obtained in above-described embodiment and comparative example, drying 5 minutes under the condition of 150 DEG C, thus obtain the duplexer being provided with the resin layer through being cross-linked on above-mentioned film surface.
The film (vertical 5cm × wide 1cm) comprising ethane-acetic acid ethyenyl ester as non-polar substrate is loaded by the surface of the above-mentioned resin layer at above-mentioned duplexer, then use vacuum compressing device by their crimping 15 minutes at 150 DEG C, thus obtain the film comprising polyethylene terephthalate and the film comprising ethane-acetic acid ethyenyl ester by the bonding duplexer of above-mentioned resin-cured layer (heat sealing layer).
(test method of adaptation)
The adaptation of the duplexer just produced for utilizing aforesaid method, uses tensile testing machine (Shimadzu Scisakusho Ltd Autograph), utilizes T-shaped stripping test (1000Ncell) to evaluate.Based on the adaptation between heat sealing layer and the above-mentioned film comprising ethane-acetic acid ethyenyl ester, have rated above-mentioned adaptation.
The duplexer that the stripping strength measured utilizing aforesaid method is roughly more than 30N/cm is evaluated as the duplexer of excellent adhesion, the duplexer for more than 35N/cm is evaluated as the duplexer that adaptation is excellent especially.
(evaluation of humidity resistance)
The duplexer obtained in above-mentioned is left standstill 72 hours in the constant temperature and humidity machine of condition being set as 120 DEG C × 100%RH and has carried out humid heat test.Method same as described above is utilized to measure and the closing force of duplexer after have rated above-mentioned leaving standstill.
The duplexer that the stripping strength measured utilizing aforesaid method is roughly more than 25N/cm is evaluated as the duplexer of excellent adhesion, the duplexer for more than 35N/cm is evaluated as the duplexer that adaptation is excellent especially.
In addition, the stripping strength of the duplexer after above-mentioned hot resistance test is evaluated as the duplexer of humidity resistance excellence relative to the duplexer that the ratio (conservation rate) of the stripping strength of the duplexer just produced is roughly more than 50%, the duplexer for more than 75% is evaluated as the duplexer that humidity resistance is excellent especially.
[table 1]
[table 2]
[table 3]
[table 4]
" content [quality %] of alkylated methylol groups melamine resin " in table represents the mass ratio of alkylated methylol groups melamine resin relative to the total quality of urethane resin (A) and polyolefin resin (B).
In addition, the ratio of the total amount of substance of the functional group [X] that the amount of substance (mole) of epoxy group(ing) that (the total amount of substance of the amount of substance/functional group [X] of epoxy group(ing)) representative ring oxygen compound (c2) has has with urethane resin (A) and polyolefin resin (B).
" M-3 " in table represents the BECKAMINEM-3 (trimethoxy methylol type melamine resin, nonvolatile component 80 quality %) of Dainippon Ink Chemicals.
" EX-321 " in table represents the DenacolEX-321 (TriMethylolPropane(TMP) polyglycidyl ether, nonvolatile component 100 quality %) of NagaseChemtex Co., Ltd..
" AQUANATE210 " in table represents the AQUANATE210 (water-dispersible polyisocyanates linking agent, nonvolatile component 100 quality %) of Nippon Polyurethane Industry Co., Ltd..
" WSA-950 " in table represents the WATERSOLWSA-950 (having the epoxy compounds of hydrolyzable silyl group, nonvolatile component 100 quality %) of Dainippon Ink Chemicals.
" CS-7 " in table represents the HydranAssisterCS-7 (water dispersible carbodiimide compound, nonvolatile component 40 quality %) of Dainippon Ink Chemicals.
The sealant that the embodiment 1 using above-mentioned hydrazine to obtain is recorded possesses excellent adaptation and humidity resistance.In addition, the sealant that the embodiment 2 and 10 using above-mentioned adipic dihydrazide or carbohydrazide to obtain is recorded possesses excellent adaptation and good humidity resistance.
In addition, the good humidity resistance that the sealant that the embodiment 3 employing excessive above-mentioned hydrazine is recorded also possesses excellent adaptation and reaches to a certain degree.In addition, the sealant using thanomin to obtain possesses good adaptation and humidity resistance.
In addition, change the usage ratio of alkylated methylol groups melamine resin and epoxy compounds, sealant that the embodiment 5 ~ 7 and 9 of kind is recorded possesses excellent adaptation and good humidity resistance.In addition, change the sealant obtained in the embodiment 9 of the mass ratio of urethane resin and polyolefin resin and possess excellent adaptation and humidity resistance.
On the other hand, linking agent is not used and sealant that the comparative example 1 that obtains is recorded is insufficient in adaptation.In addition, although do not use the above-mentioned sealant of any one comparative example obtained as linking agent 2 and 3 of alkylated methylol groups trimeric cyanamide or epoxy compounds to have good adaptation, after hot resistance test, the obvious reduction of adaptation is caused.In addition, any one of urethane resin or polyolefine tree is not used and sealant that the comparative example 4 and 5 that obtains is recorded is insufficient in adaptation.
In addition, although the sealant that the comparative example 6 ~ 9 that the linking agent combinationally using other replaces the combination of alkylated methylol groups trimeric cyanamide and epoxy compounds to be used as linking agent and obtains is recorded has good adaptation, after hot resistance test, cause the obvious reduction of adaptation.

Claims (6)

1. a sealant, is characterized in that, is the sealant containing urethane resin (A), polyolefin resin (B), linking agent (C) and aqueous medium (D),
Described urethane resin (A) is that the urethane resin by making to have isocyanate group reacts with at least a kind of being selected from the compound with primary amino, the compound with hydrazide group and hydrazine and obtains, and it is overall relative to described urethane resin (A), there is urea key in the scope of 50mmol/kg ~ 2000mmol/kg
Described linking agent (C) is containing alkylated methylol groups melamine resin (c1) and epoxy compounds (c2), and any one or both in described urethane resin (A) and polyolefin resin (B) have and the functional group of epoxy reaction [X].
2. sealant according to claim 1, wherein,
Contain described alkylated methylol groups melamine resin (c1) with the scope being 5 quality % ~ 50 quality % relative to the total quality of described urethane resin (A) and described polyolefin resin (B), the amount of substance of the epoxy group(ing) that described epoxy compounds (c2) has is 5/1 ~ 1/5 relative to the total amount of substance of the ratio of the total amount of substance of described functional group [X] and the amount of substance/functional group [X] of epoxy group(ing).
3. sealant according to claim 1, wherein,
Described functional group [X] is selected from more than a kind of carboxyl, hydroxyl and amino.
4. sealant according to claim 1, wherein,
Described epoxy compounds (c2) is selected from least a kind of TriMethylolPropane(TMP) polyglycidyl ether and T 55.
5. a solar module, is characterized in that, possesses following structure:
Be laminated with the heat sealing layer using the sealant according to any one of claim 1 ~ 4 to be formed in the face comprising vinyl-vinyl acetate copolymer of the opposing face of the sensitive surface of formation solar module, be laminated with the layer comprising polyethylene terephthalate base material, polypropylene base, polycarbonate substrate or polyamide substrate on the surface of described heat sealing layer.
6. a manufacture method for solar module, is characterized in that,
The mode that lamination sheets contacts with the face comprising vinyl-vinyl acetate copolymer of opposing face of the sensitive surface being formed solar module with the heat sealing layer of described lamination sheets is loaded, heats, thus carry out bonding,
Described lamination sheets possesses the sealant according to any one of the surface coated Claims 1 to 4 of polyethylene terephthalate base material, polypropylene base, polycarbonate substrate or polyamide substrate, then the heat sealing layer carrying out heating and formed.
CN201380014083.3A 2012-03-15 2013-01-28 Sealant, the duplexer employing it and solar module Active CN104169387B (en)

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CN104169387A (en) 2014-11-26
JPWO2013136861A1 (en) 2015-08-03
TW201341467A (en) 2013-10-16
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JP5418742B1 (en) 2014-02-19
TWI563032B (en) 2016-12-21

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