CN104093760A - Resin composition, two-part laminating adhesive, laminated film, and backsheet for solar cell - Google Patents

Resin composition, two-part laminating adhesive, laminated film, and backsheet for solar cell Download PDF

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Publication number
CN104093760A
CN104093760A CN201380008286.1A CN201380008286A CN104093760A CN 104093760 A CN104093760 A CN 104093760A CN 201380008286 A CN201380008286 A CN 201380008286A CN 104093760 A CN104093760 A CN 104093760A
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Prior art keywords
molecular weight
polyester
resin
polyvalent alcohol
acid
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CN201380008286.1A
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CN104093760B (en
Inventor
海野晃生
宇野诚一
穗积正巳
秋田康二
户田哲也
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08G18/28—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/28—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • 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
    • C08G18/28—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
    • 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
    • C08G18/28—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/28—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • 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
    • B32B2457/00—Electrical equipment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electromagnetism (AREA)
  • Computer Hardware Design (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Photovoltaic Devices (AREA)
  • Hybrid Cells (AREA)

Abstract

Provided is a resin composition which can form a cured coating film exhibiting high strength, high bond strength and excellent long-term stability such that little deterioration in the bond strength is observed in a damp heat test and which can ensure excellent surface appearance of a laminate. Also provided are: a two-part laminating adhesive containing said resin composition; a laminated film having a layer made from the adhesive; and a backsheet for a solar cell. The resin composition comprises: a polyester polyurethane polyol which has a branched structure in the molecule and which has a weight-average molecular weight of 10,000 to 100,000 and a molecular weight distribution of 5.0 or more; a polyester polyol which has a branched structure in the molecule and which has a weight-average molecular weight of 10,000 to 50,000 and a molecular weight distribution of less than 5.0; a hydroxyl-containing epoxy resin which has a number-average molecular weight of 300 to 5,000; a hydroxyl-containing polycarbonate resin which has a number-average molecular weight of 300 to 3,000; and a polyisocyanate. The two-part laminating adhesive contains the composition.

Description

The backboard of resin combination, two-component-type lamination caking agent, laminated film and solar cell
Technical field
The present invention relates to the resin combination of the substrate bonding excellence under wet heat condition, the backboard of two-component-type caking agent, laminated film and solar cell for lamination.
Background technology
In recent years, as the representative of clean energy, solar electrical energy generation just attracts attention.The backboard that is arranged on the back side of solar module is for protecting the power facilities such as battery, wiring not to be subject to external environment influence and keeping the member of insulativity, is the layered product that utilizes caking agent that various functional films laminatings are formed.For the caking agent for this backboard, with high level require its have to polyester film, polyvinyl fluoride thin film etc. there is the high adhesion of the various films of different characteristics, for the also humidity resistance of long term maintenance cementability under environment in the open.
As this backboard caking agent, the host that comprises polyester polyol, polyester-polyurethane polyvalent alcohol and bisphenol-type epoxy resin and the polyurethanes caking agent (referring to patent documentation 1) of solidifying agent have been proposed to contain.
Prior art document
Patent documentation
Patent documentation 1: No. 4416047th, Japanese Patent
Summary of the invention
the problem that invention will solve
Yet there are the following problems on ageing stability for aforementioned polyurethanes caking agent: a little less than the coating strength after solidifying, and bonding strength can be deteriorated in humidity resistance test, but also have the problem of the appearance poor after lamination process.
The problem to be solved in the present invention is to provide that the coating strength after solidifying is strong, bonding strength is high, in humidity resistance test bonding strength can deteriorated such ageing stability also excellent resin combination of outward appearance after excellent and lamination process, the two-component-type lamination caking agent that contains this resin combination, has the laminated film of the layer being formed by this caking agent and the backboard of solar cell.
for the scheme of dealing with problems
The inventor etc. are in order to address the above problem, conduct in-depth research, found that, by using the resin combination of following two-pack curing, coating strength after solidifying is strong, bonding strength is high, in humidity resistance test, bonding strength is can deteriorated such ageing stability unexcellent, and the outward appearance after lamination process is also excellent, thereby completed the present invention, the resin combination of described two-pack curing is used following neccessary composition as host: in (1) molecule, have branched structure, the scope that weight-average molecular weight (Mw) is 10000～100000 and molecular weight distribution (Mw/Mn) are more than 5.0 polyester-polyurethane polyvalent alcohols (A), (2) in molecule, there is branched structure, the polyester polyol (B) that the scope that weight-average molecular weight (Mw) is 10000～50000 and molecular weight distribution (Mw/Mn) are less than 5.0, and the further hydroxyl-containing epoxy resin (C) of using the scope that compounding therein (3) number-average molecular weight (Mn) is 300～5000 as required, (4) the host composition that the hydroxyl polycarbonate resin (D) of the scope that number-average molecular weight (Mn) is 300～3000 forms and as (5) polyisocyanates (E) of its solidifying agent.
That is, the present invention relates to a kind of resin combination, it is characterized in that, it usings following compositions as neccessary composition:
(1) in molecule, having scope and the molecular weight distribution (Mw/Mn) that branched structure, weight-average molecular weight (Mw) are 10000～100000 is more than 5.0 polyester-polyurethane polyvalent alcohols (A), and
(2) in molecule, there is the polyester polyol (B) that scope that branched structure, weight-average molecular weight (Mw) are 10000～50000 and molecular weight distribution (Mw/Mn) are less than 5.0.
The invention still further relates to a kind of two-component-type lamination caking agent, it also contains (5) polyisocyanates (E) as solidifying agent on the basis of aforementioned (A) composition and aforementioned (B) composition.
The invention still further relates to a kind of laminated film, it has a kind of above film in the group of selecting free polyester film, fluorine resin film, polyolefin film, tinsel composition and the adhesive linkage being formed with caking agent by above-mentioned two-component-type lamination.
The invention still further relates to a kind of backboard of solar cell, it has the adhesive linkage being formed with caking agent by above-mentioned two-component-type lamination.
the effect of invention
With caking agent, the coating strength after solidifying is strong, bonding strength is high for resin combination of the present invention and the two-component-type lamination that contains this resin combination, in humidity resistance test bonding strength can deteriorated such ageing stability outward appearance after excellent and lamination process also excellent, therefore the caking agent as the backboard of laminated film and solar cell is useful.
Embodiment
Resin combination of the present invention contain in (1) molecule, there is branched structure, scope that weight-average molecular weight (Mw) is 10000～100000 and molecular weight distribution (Mw/Mn) be that more than 5.0 polyester-polyurethane polyvalent alcohol (A) is as neccessary composition.
Aforementioned polyester-polyurethane polyvalent alcohol (A) has branched structure in molecule, thereby final cured article becomes the material that cross-linking density is high, even if therefore also swelling not under wet heat condition can maintain high adhesion.
In addition, the scope that the weight-average molecular weight (Mw) of aforementioned polyester-polyurethane polyvalent alcohol (A) is 10000～100000.By making weight-average molecular weight (Mw) in aforementioned range, cured article demonstrates high strength, becomes the resin combination of initial bonding strength excellence.And the viscosity of resin combination is suitable for applying.The weight-average molecular weight (Mw) of aforementioned polyester-polyurethane polyvalent alcohol (A) is less than at 10000 o'clock, and the tendency that exists initial bonding strength to reduce forms the resin combination evenly applying for being difficult to because viscosity is low.
On the other hand, the weight-average molecular weight (Mw) of aforementioned polyester-polyurethane polyvalent alcohol (A) surpasses at 100000 o'clock, has the tendency of viscosity increased, therefore becomes the resin combination that is difficult to coating.Weight-average molecular weight (Mw) for this polyester-polyurethane polyvalent alcohol (A), from obtaining the also aspect of excellent resin combination of the high and substrate bonding under wet heat condition of initial bonding strength, weight-average molecular weight (Mw) is preferably 12000～90000 scope.
The molecular weight distribution (Mw/Mn) of aforementioned polyester-polyurethane polyvalent alcohol (A) is more than 5.0.By making molecular weight distribution (Mw/Mn) in aforementioned range, can bring into play the effect of adaptation raising that brought from low molecular weight compositions and base material and the cured article being brought from high molecular weight components simultaneously and become high-intensity effect, therefore become excellent, the initial high resin combination of bonding strength of substrate bonding under wet heat condition.Molecular weight distribution (Mw/Mn) is less than at 5.0 o'clock, has the tendency of the degraded appearance after lamination process.From obtaining the aspect of the more excellent resin combination of substrate bonding under wet heat condition, the molecular weight distribution (Mw/Mn) of polyester-polyurethane polyvalent alcohol (A) is preferably 5～25 scope, more preferably 5～15 scope.
In addition, from becoming the aspect that substrate bonding is excellent, viscosity is suitable for the resin combination of coating under wet heat condition, the number-average molecular weight (Mn) of aforementioned polyester-polyurethane polyvalent alcohol (A) is preferably 3000～20000 scope, more preferably 5000～10000 scope.
It should be noted that, in the present invention, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are the values that the gel permeation chromatography (GPC) by following condition is measured.
Determinator: the HLC-8220GPC that TOSOH Co., Ltd manufactures
Post: TSK-GEL SuperHZM-M * 4 that the TSK-GUARDCOLUMN SuperHZ-L+ TOSOH Co., Ltd that TOSOH Co., Ltd manufactures manufactures
Detector: RI (differential refractometer)
Data processing: the Multi station GPC-8020 model II that TOSOH Co., Ltd manufactures
Condition determination: 40 ℃ of column temperatures
Solvents tetrahydrofurane
Flow velocity 0.35ml/ minute
Standard: monodisperse polystyrene
Sample: the tetrahydrofuran solution count 0.2 quality % with microfilter to converting with resin solid composition has carried out filtering and the material (100 μ l) that obtains
In addition, from the aspect of the substrate bonding excellence under wet heat condition, the hydroxyl value of aforementioned polyester-polyurethane polyvalent alcohol (A) is preferably the scope of 5～30mgKOH/g, the more preferably scope of 7～15mgKOH/g.When the hydroxyl value of aforementioned polyester-polyurethane polyvalent alcohol (A) is greater than 30mgKOH/g, there is the tendency of wet-heat resisting cementability variation, when the hydroxyl value of aforementioned polyester-polyurethane polyvalent alcohol (A) is less than 5mgKOH/g, reduce with the reactivity of solidifying agent, have the tendency of cementability variation.
Aforementioned polyester-polyurethane polyvalent alcohol (A) for example, by obtaining polyprotonic acid (E), polyvalent alcohol (F), polyisocyanates (G) reaction.In this situation, in order to import branched structure in the molecule to polyester-polyurethane polyvalent alcohol (A), any one the above material composition in polyprotonic acid (E), polyvalent alcohol (F) and polyisocyanates (G) is used the compound that 3 officials can be above.
Aforementioned polyprotonic acid (E) can list the polyprotonic acid (E2) that diprotic acid (E1) and 3 officials can be above.
As aforementioned diprotic acid (E1), for example, can list the aliphatic dibasic acid of propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, tetradecane diacid, pentadecane diacid, Thapsic acid, pentadecane dicarboxylic acid, octadecane diacid, nonadecen diacid, octadecane dicarboxylic acid and so on; Aliphatics unsaturated dibasic acid and the acid anhydride thereof of tetrahydrophthalic acid, toxilic acid, maleic anhydride, fumaric acid, citraconic acid, methylene-succinic acid, propene dicarboxylic acid and so on; Aliphatics unsaturated dibasic acid and the acid anhydride thereof of tetrahydrophthalic acid, toxilic acid, maleic anhydride, fumaric acid, citraconic acid, methylene-succinic acid, propene dicarboxylic acid and so on; The aromatic acid of phthalic acid (Phthalic acid), Tetra hydro Phthalic anhydride, terephthalic acid, m-phthalic acid, phthalic acid (Orthophthalic acid) and so on and acid anhydride thereof etc.
Polyprotonic acid (E2) that can be above as aforementioned 3 officials, for example, can list 1,2,5-hexane tricarboxylic acid, 1,2, the aliphatics triprotic acids such as 4-hexanaphthene tricarboxylic acid; Trimellitic acid, trimellitic acid 1,2-anhydride, 1,2,5-benzene tricarbonic acid, 2,5, the aromatic series triprotic acids such as 7-naphthalene tricarboxylic acid and acid anhydride thereof etc.
At this, by using the polyprotonic acid (E2) that aforementioned 3 officials can be above, can in the molecule of polyester-polyurethane polyvalent alcohol of the present invention (A), import branched structure.
These polyprotonic acids (E) can be used alone, can also be used in combination of two or more separately.Wherein, from obtaining the excellent and viscosity of substrate bonding under wet heat condition, be suitable for the aspect of the resin combination that applies, preferably combination is used aliphatics polyprotonic acid and aromatic series polyprotonic acid, in this situation, preferred aliphat polyprotonic acid shared content in total polyprotonic acid composition is the scope that the scope of 10～30 % by mole and aromatic series polyprotonic acid are 50～90 % by mole.In addition, from becoming the aspect of the more excellent resin combination of substrate bonding under wet heat condition, the preferred hexanodioic acid of aforementioned aliphatics polyprotonic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, tetradecane diacid, pentadecane diacid, Thapsic acid, pentadecane dicarboxylic acid, octadecane diacid, nonadecen diacid, octadecane dicarboxylic acid, 1, 2, 5-hexane tricarboxylic acid, 1, 2, the aliphatics polyprotonic acid of the scope that the carbonatoms of 4-hexanaphthene tricarboxylic acid and so on is 6～20, more preferably suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, 1, 2, 5-hexane tricarboxylic acid, 1, 2, the aliphatics polyprotonic acid of the scope that the carbonatomss such as 4-hexanaphthene tricarboxylic acid are 8～13.
In addition, for adjusting the molecular weight of aforementioned polyester-polyurethane polyvalent alcohol (A), the object of viscosity, as the raw material of aforementioned polyester-polyurethane polyvalent alcohol (A), also can use the monocarboxylic acid of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, dodecylic acid, tetradecanoic acid, hexadecanoic acid, margaric acid, octadecanoic acid, phenylformic acid and so on.
Aforementioned polyvalent alcohol (F) can list the polyvalent alcohol (F2) that dibasic alcohol (F1) and 3 officials can be above.
As aforementioned dibasic alcohol (F1), for example, can list ethylene glycol, Diethylene Glycol, propylene glycol, 1,3-PD, 1,2,2-trimethylammonium-1,3-PD, 2,2-dimethyl-3-sec.-propyl-1,3-PD, BDO, 1,3-butyleneglycol, 3-methyl isophthalic acid, 3-butyleneglycol, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, neopentyl glycol, 1,6-hexylene glycol, Isosorbide-5-Nitrae-bis-(methylol) hexanaphthene, 2,2,4-trimethylammonium-1, the aliphatic diol of 3-pentanediol and so on; The ether glycol of polyoxyethylene glycol, polyoxypropylene diols and so on; The modified polyether glycol that the ring-opening polymerization of the compound containing ring-type ehter bond by aforementioned aliphatic diol and oxyethane, propylene oxide, tetrahydrofuran (THF), ethyl ether, propyl glycidyl ether, butylglycidyl ether, phenyl glycidyl ether, glycidyl allyl ether and so on obtains; The lactone polyester polyol that polycondensation by various lactone such as aforementioned aliphatic diol and 6-caprolactones obtains; The bis-phenol of dihydroxyphenyl propane, Bisphenol F and so on; The alkylene oxide adducts of the bis-phenol that the bis-phenol addition of ethylene oxide of dihydroxyphenyl propane, Bisphenol F and so on, propylene oxide etc. are obtained etc.
Polyvalent alcohol (F2) that can be above as aforementioned 3 officials, for example, can list the aliphatic polyol of trimethylolethane, TriMethylolPropane(TMP), glycerine, hexanetriol, tetramethylolmethane and so on; The modified polyether polylol that the ring-opening polymerization of the compound containing ring-type ehter bond by aforementioned aliphatic polyol and oxyethane, propylene oxide, tetrahydrofuran (THF), ethyl ether, propyl glycidyl ether, butylglycidyl ether, phenyl glycidyl ether, glycidyl allyl ether and so on obtains; Lactone polyester polyol that the polycondensation of the lactone by aforementioned aliphatic polyol and 6-caprolactone and so on obtains etc.
By using the polyvalent alcohol (F2) that aforementioned 3 officials can be above, can in the molecule of polyester-polyurethane polyvalent alcohol of the present invention (A), import branched structure.
Above-mentioned polyvalent alcohol (F) can be used alone, can also be used in combination of two or more separately.From forming the aspect of the resin combination of coating excellence, aforementioned aliphatic polyol shared content in total polyhydroxy reactant is preferably more than 40 % by mole, more preferably more than 80 % by mole.In addition, from obtaining the aspect of the more excellent resin combination of substrate bonding under wet heat condition, it is more than 5 aliphatic polyols that aforementioned aliphatic polyol is preferably carbonatoms, more preferably aforementioned aliphatic diol.
Aforementioned polyisocyanates (G) can list the polyisocyanate compound (G2) that diisocyanate cpd (G1) and 3 officials can be above
As aforementioned diisocyanate cpd (G1), for example can list butane-1,4-vulcabond, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2, the aliphatic diisocyanate of 4,4-trimethyl hexamethylene diisocyanate, xylylene vulcabond, tetramethyl-benzene dimethyl vulcabond and so on; Hexanaphthene-1,4-vulcabond, isophorone diisocyanate, lysinediisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, 1, two (isocyanic ester methyl) hexanaphthenes of 3-, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4, the alicyclic diisocyanate of 4 '-vulcabond, norbornene alkyl diisocyanate and so on; 1,5-naphthalene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-phenylbenzene dimethylmethane vulcabond, 4,4 '-dibenzyl vulcabond, dialkyl group diphenylmethanediisocyanate, tetraalkyl diphenylmethanediisocyanate, 1, the aromatic diisocyanate of 3-phenylene diisocyanate, Isosorbide-5-Nitrae-phenylene diisocyanate, tolylene diisocyanate, xylylene vulcabond, tetramethyl-benzene dimethyl vulcabond and so on etc.
Aforementioned 3 officials can polyisocyanate compound (G2) above for example can list the urea acid esters type polyisocyanate compound in the adducts type polyisocyanate compound in molecule with amino-formate bond position, molecule with isocyanuric acid ester ring structure.
The adducts type polyisocyanate compound in aforementioned molecule with amino-formate bond position for example can make diisocyanate cpd and polyol reaction and obtain.The diisocyanate cpd using in this reaction for example can list as the illustrated various diisocyanate cpds of aforementioned diisocyanate cpd (G1), and they can be used alone, can also be used in combination of two or more separately.In addition, the polyol compound using in this reaction can list as the illustrated various polyol compounds of aforementioned polyvalent alcohol (F), polyvalent alcohol be reacted and the polyester polyol that obtains etc. with polyprotonic acid, these compounds can be used alone, can also be used in combination of two or more separately.
The aforementioned urea acid esters type polyisocyanate compound in molecule with isocyanuric acid ester ring structure for example can make diisocyanate cpd and monohydroxy-alcohol and/or diol reaction and obtain.The diisocyanate cpd using in this reaction for example can list as the illustrated various diisocyanate cpds of aforementioned diisocyanate cpd, and they can be used alone, can also be used in combination of two or more separately.In addition, as the monohydroxy-alcohol using in this reaction, for example can list hexanol, 2-Ethylhexyl Alcohol, octanol, nonylcarbinol, n-undecane alcohol, n-dodecane alcohol, n-tridecane alcohol, n-tetradecanol, Pentadecane alcohol, n-heptadecane alcohol, Octadecane alcohol, NSC 77136 alcohol, eicosanol, 5-ethyl-2-nonyl alcohol, Exxal 12, 2-hexyl decyl alcohol, 3, 9-diethyl-6-tridecyl alcohol, the different hendecanol of the different heptyl of 2-, 2-Standamul G, 2-decyl tetradecanol etc., as dibasic alcohol, can list illustrative aliphatic diol etc. in aforementioned polyvalent alcohol (F).These monohydroxy-alcohols and dibasic alcohol can be used alone, can also be used in combination of two or more separately.
At this, by using the polyisocyanate compound (G2) that aforementioned 3 officials can be above, can in the molecule of polyester-polyurethane polyvalent alcohol of the present invention (A), import branched structure.
These polyisocyanates (G) can be used alone, can also be used in combination of two or more separately.Wherein, from obtaining the aspect of the resin combination of the bonding strength excellence under wet heat condition, the polyisocyanate compound (G2) that preferably aforementioned 3 officials can be above, more preferably urea acid esters type polyisocyanate compound.In addition, from easily resin combination being adjusted to the aspect that is suitable for the viscosity that applies, preferably combination is used the polyisocyanate compound (G2) that aforementioned diisocyanate cpd (G1) and aforementioned 3 officials can be above.In this situation, excellent and demonstrate the aspect of the resin combination that is suitable for the viscosity that applies from becoming substrate bonding under wet heat condition, both mass ratioes [(G1)/(G2)] are preferably 50/50～5/95 scope, more preferably 40/60～10/90 scope, is particularly preferably 30/70～15/85 scope.
3 officials that use while manufacturing aforementioned polyester-polyurethane polyvalent alcohol (A) can composition above can be any one in aforementioned polyprotonic acid (E2), aforementioned polyvalent alcohol (F2) and aforementioned polyisocyanate compound (G2), but as previously mentioned, from can obtain the bonding strength excellence under wet heat condition resin combination aspect and the aspect that can the enough shorter time manufacture easily aforementioned polyester-polyurethane polyvalent alcohol (A), preferably use polyisocyanate compound (G2).
As the method for manufacturing aforementioned polyester-polyurethane polyvalent alcohol (A), such as listing following method etc.: under the existence of esterifying catalyst, aforementioned polyprotonic acid (E) is reacted in the temperature range of 150～270 ℃ with aforementioned polyvalent alcohol (F) and obtain polyester polyol, then under the existence of urethane catalyzer, this polyester polyol is reacted in the temperature range of 50～100 ℃ with aforementioned polyisocyanates (G).
In addition, resin combination of the present invention contain in (2) molecule, there is branched structure, scope that weight-average molecular weight (Mw) is 10000～50000 and molecular weight distribution (Mw/Mn) be that polyester polyol (B) below 5.0 is as neccessary composition.
Aforementioned polyester-polyurethane polyvalent alcohol (A) has branched structure in molecule, thereby final cured article becomes the material that cross-linking density is high, even if therefore also swelling not under wet heat condition can maintain high adhesion.
Aforementioned polyester polyol (B) has branched structure in its molecule, thereby especially when for lamination caking agent, contributes to improve initial cementability and wet-heat resisting cementability.
In addition the scope that, the weight-average molecular weight (Mw) of aforementioned polyester polyol (B) is 10000～50000.By making weight-average molecular weight (Mw) in aforementioned range, cured article demonstrates high strength, becomes the resin combination of initial bonding strength excellence.And the viscosity of resin combination is suitable for applying.The weight-average molecular weight (Mw) of aforementioned polyester polyol (B) is less than at 10000 o'clock, and the tendency that exists initial bonding strength to reduce forms the resin combination evenly applying for being difficult to because viscosity is low.On the other hand, the weight-average molecular weight (Mw) of aforementioned polyester polyol (B) surpasses at 50000 o'clock, owing to existing the tendency of viscosity increased to form the resin combination applying for being difficult to.Weight-average molecular weight (Mw) for this polyester polyol (B), from obtaining the also aspect of excellent resin combination of the high and substrate bonding under wet heat condition of initial bonding strength, weight-average molecular weight (Mw) is preferably 12000～40000 scope.
The molecular weight distribution (Mw/Mn) of aforementioned polyester polyol (B) is lower than 5.0.By making molecular weight distribution (Mw/Mn) in aforementioned range, when using caking agent as two-component-type lamination, can bring into play the effect of the outward appearance excellence after lamination process.The molecular weight distribution (Mw/Mn) of aforementioned polyester polyol (B) is 5.0 when above, when use caking agent as two-component-type lamination, has the tendency of initial stage cementability reduction.The molecular weight distribution (Mw/Mn) of aforementioned polyester polyol (B) is preferably 1.0～5.0 scope, more preferably 2.0～4.0 scope.
In addition, from becoming the aspect that substrate bonding is excellent, viscosity is suitable for the resin combination of coating under wet heat condition, the number-average molecular weight (Mn) of aforementioned polyester polyol (B) is preferably 3000～20000 scope, more preferably 5000～10000 scope.
In addition, from the aspect of the substrate bonding excellence under wet heat condition, the hydroxyl value of aforementioned polyester polyol (B) is preferably the scope of 5～30mgKOH/g, the more preferably scope of 7～15mgKOH/g.
Aforementioned polyester polyol (B) for example, by making polyprotonic acid (E) react and obtain with polyvalent alcohol (F).In this situation, in order to import branched structure in the molecule to polyester polyol (B), any one the above material composition in polyprotonic acid (E) and polyvalent alcohol (F) is used the compound that 3 officials can be above.
Polyprotonic acid (E) and polyvalent alcohol (F) as the reaction raw materials of aforementioned polyester polyol (B) can be used the material same with the reaction raw materials of aforementioned polyester-polyurethane polyvalent alcohol (A).
As the method for manufacturing aforementioned polyester polyol (B), such as listing following method etc.: under the existence of esterifying catalyst, aforementioned polyprotonic acid (E) is reacted in the temperature range of 150～270 ℃ with aforementioned polyvalent alcohol (F).
Resin combination of the present invention contains above-mentioned polyester-polyurethane polyvalent alcohol (A) and polyester polyol (B) as host composition necessary in two-pack curing composition, even be that base material also can show the aspect of high adhesion from fluorine such as the PVF low to common cementability (fluorinated ethylene propylene) film, PVDF (poly(vinylidene fluoride)) films, preferably also contain the hydroxyl-containing epoxy resin (C) of the scope that number-average molecular weight (Mn) is 300～5000.The number-average molecular weight (Mn) of aforementioned epoxy resins (C) is less than at 300 o'clock, cannot obtain sufficient bonding strength; Number-average molecular weight (Mn) surpasses at 5000 o'clock, and the solvability in resin combination of the present invention reduces.Wherein, from the solvability resin combination of the present invention and the more excellent aspect of the substrate bonding under wet heat condition, number-average molecular weight (Mn) is 400～2000 scope more preferably.
As aforementioned hydroxyl-containing epoxy resin (C), for example, can list the bisphenol-type epoxy resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin and so on; The biphenyl type epoxy resin of biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin and so on; Dicyclopentadiene-phenol addition reaction-type epoxy resin etc.These hydroxyl-containing epoxy resin can be used alone, can also be used in combination of two or more separately.In the middle of these, from obtaining the aspect of the resin combination of substrate bonding under wet heat condition and initial bonding strength excellence, preferably bisphenol-type epoxy resin.
From becoming the aspect of the resin combination of the substrate bonding excellence under wet heat condition, resin combination of the present invention preferably also contains the hydroxyl polycarbonate resin (D) of the scope that number-average molecular weight (Mn) is 300～3000 on the basis of above-mentioned each composition.Number-average molecular weight (Mn) is less than at 300 o'clock, cannot obtain sufficient bonding strength; Number-average molecular weight (Mn) surpasses at 3000 o'clock, and the solvability in resin combination of the present invention reduces.Wherein, from the solvability resin combination of the present invention and the more excellent aspect of the substrate bonding under wet heat condition, the scope that more preferably number-average molecular weight (Mn) is 400～2000.
From becoming the aspect of the resin combination that solidified nature is more excellent, the hydroxyl value of aforementioned hydroxyl polycarbonate resin (D) is preferably the scope of 20～300mgKOH/g, the scope of 40～250mgKOH/g more preferably.In addition, from the aspect of the substrate bonding excellence under wet heat condition, optimization polycarbonate glycol.
Aforementioned hydroxyl polycarbonate resin (D) for example can be manufactured by the method that makes polyvalent alcohol and carbonyl agent carry out polycondensation.
As the polyvalent alcohol using in the manufacture at aforementioned hydroxyl polycarbonate resin (D), for example, can list as the illustrated various polyvalent alcohols of aforementioned polyvalent alcohol (F).
Polyvalent alcohol can be used alone, can also be used in combination of two or more separately.
The carbonyl agent of using in the manufacture of the aforementioned polycarbonate resin that contains hydroxyl (D) is such as listing ethylene carbonate, Texacar PC, methylcarbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate etc.
These can be used alone, can also be used in combination of two or more separately.
Resin combination of the present invention contains aforementioned polyester-polyurethane polyvalent alcohol (A) with following ratio, aforementioned polyester polyol (B), aforementioned hydroxyl-containing epoxy resin (C) and aforementioned hydroxyl polycarbonate resin (D), summation 100 mass parts with respect to aforementioned polyester-polyurethane polyvalent alcohol (A) with aforementioned polyester polyol (B), aforementioned hydroxyl-containing epoxy resin (C) is that scope and the aforementioned hydroxyl polycarbonate resin (D) of 5～20 mass parts is the scope of 5～20 mass parts, form thus excellent in adhesion to various base materials, even if also can maintain the resin combination of high substrate bonding under wet heat condition.
In addition, the aforementioned polyester-polyurethane polyvalent alcohol (A) in resin combination of the present invention counts with the compounding ratio of aforementioned polyester polyol (B) scope that is preferably 10:50～90:10 in mass ratio, is particularly preferably the scope of 20:80～50:50.
Resin combination of the present invention is preferably used aforementioned polyisocyanates (E) as curing agent component.This polyisocyanates (E) for example can list as the listed various polyisocyanates of aforementioned polyisocyanates (G).These polyisocyanates (E) can be used separately a kind of, also can be used in combination two or more.
In these polyisocyanates (E), from caking agent, film and be not easy to occur the aspect of xanthochromia, preferred aforementioned aliphatic diisocyanate compound.In addition, from the aspect of the base material adaptation excellence under wet heat condition, preferred aforementioned urea acid esters type polyisocyanate compound.
Resin combination of the present invention contains aforementioned polyester-polyurethane polyvalent alcohol (A), aforementioned polyester polyol (B), aforementioned hydroxyl-containing epoxy resin (C), aforementioned hydroxyl polycarbonate resin (D) and polyisocyanates (E) as neccessary composition.In the present invention, the scope that ratio [OH]/[NCO] is 1/1～1/2 of the mole number [NCO] of contained isocyanate group in the total mole number [OH] that makes hydroxyl contained in aforementioned polyester-polyurethane polyvalent alcohol (A), aforementioned polyester polyol (B), aforementioned hydroxyl-containing epoxy resin (C) and aforementioned hydroxyl polycarbonate resin (D) and aforementioned polyisocyanate compound (E), 1/1.05～1/1.5 scope more preferably, become the resin combination of solidified nature excellence thus.
Resin combination of the present invention can also contain all kinds of SOLVENTS.Aforementioned solvents for example can list the ketone compounds of acetone, methylethylketone (MEK), methyl iso-butyl ketone (MIBK) and so on, the cyclic ether compounds of tetrahydrofuran (THF) (THF), dioxolane and so on, the ester compound of methyl acetate, ethyl acetate, butylacetate and so on, the aromatic series compounds of toluene, dimethylbenzene and so on, the alcohol compound of Trivalin SF, cellosolve, methyl alcohol, Virahol, butanols, propylene glycol monomethyl ether and so on etc.These compounds can be used separately a kind of, also can be used in combination two or more.
Resin combination of the present invention can also further contain the various additives such as UV light absorber, antioxidant, silicon class additive, fluorine class additive, rheology control agent, defoamer, static inhibitor, antifogging agent.
The two-component-type lamination that resin combination of the present invention can be used as for bonding various plastics films is used aptly with caking agent.
Aforementioned various plastics film is such as listing the film being formed by polycarbonate, polyethylene terephthalate, polymethylmethacrylate, polystyrene, polyester, polyolefine, epoxy resin, melamine resin, tri acetyl cellulose resin, polyvinyl alcohol, ABS resin, norbornene resin, cyclic olefin resinoid, polyimide resin, polyfluoroethylene resin, polyvinylidene fluoride resin etc.Even the film forming be difficult to especially bonding polyfluoroethylene resin, polyvinylidene fluoride resin in above-mentioned various films, two-component-type lamination of the present invention also demonstrates high adhesion with caking agent.
When aforementioned various films are bonded to each other, two-component-type lamination of the present invention is preferably 2～10g/m by the usage quantity of caking agent 2scope.
The laminated film that uses two-component-type lamination of the present invention to obtain with bonding multiple films of caking agent has following feature: even also have between high adhesion, film and be not easy to peel off under wet heat condition.
Therefore, two-component-type lamination of the present invention with caking agent can be aptly for waiting without laminated film purposes of using under rugged environment, as this purposes, the caking agent such as can list the backboard of manufacturing solar cell time etc.
Embodiment
Below enumerate concrete synthesis example, the present invention will be described in more detail for embodiment, but the present invention is not limited to these embodiment.It should be noted that, in following example, " part " and " % " in case of no particular description, represents respectively " mass parts " and " quality % ".
It should be noted that, in the embodiment of the present application, number-average molecular weight (Mn) and weight-average molecular weight (Mw) are measured by the gel permeation chromatography (GPC) of following condition.
Determinator: the HLC-8220GPC that TOSOH Co., Ltd manufactures
Post: TSK-GEL SuperHZM-M * 4 that the TSK-GUARDCOLUMN SuperHZ-L+ TOSOH Co., Ltd that TOSOH Co., Ltd manufactures manufactures
Detector: RI (differential refractometer)
Data processing: the Multi station GPC-8020 model II that TOSOH Co., Ltd manufactures
Condition determination: 40 ℃ of column temperatures
Solvents tetrahydrofurane
Flow velocity 0.35ml/ minute
Standard: monodisperse polystyrene
Sample: the tetrahydrofuran solution count 0.2 quality % with microfilter to converting with resin solid composition filters and the material (100 μ l) that obtains
(synthesis example 1-1) [synthesizing of polyester-polyurethane polyvalent alcohol (A1)]
To having, in the flask of stirring rod, temperature sensor, bead tube, drop into 1.3 parts of 1131 parts of neopentyl glycol, 737 parts of m-phthalic acids, 342 parts of Tetra hydro Phthalic anhydrides, 534 parts of sebacic acid, 20 parts of trimellitic acid 1,2-anhydrides and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, is cooled to after 100 ℃, and by ethyl acetate, being diluted to solids component is 80%.Then, drop into isocyanurate-modified body (the SUMIDUR N-3300 of hexamethylene diisocyanate; Sumitomo Bayer Urethane Co., Ltd. manufactures) 25 parts of 124 parts, hexamethylene diisocyanate, to flask in pass into drying nitrogen and stir on one side, being heated to 70～80 ℃ carries out urethane reaction on one side.Isocyanic ester containing ratio is 0.3% stopped reaction when following, obtains number-average molecular weight and be 5700, weight-average molecular weight is 35000 and the hydroxyl value polyester-polyurethane polyvalent alcohol that is 10.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester-polyurethane polyvalent alcohol (A1).
(synthesis example 1-2) [synthesizing of polyester-polyurethane polyvalent alcohol (A2)]
To having, in the flask of stirring rod, temperature sensor, bead tube, drop into 1.3 parts of 1155 parts of neopentyl glycol, 755 parts of m-phthalic acids, 325 parts of Tetra hydro Phthalic anhydrides, 507 parts of sebacic acid, 20 parts of trimellitic acid 1,2-anhydrides and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, is cooled to after 100 ℃, and by ethyl acetate, being diluted to solids component is 80%.Then, drop into isocyanurate-modified body (the SUMIDUR N-3300 of hexamethylene diisocyanate; Sumitomo Bayer Urethane Co., Ltd. manufactures) 40 parts of 247 parts, hexamethylene diisocyanate, to flask in pass into drying nitrogen and stir on one side, being heated to 70～80 ℃ carries out urethane reaction on one side.Isocyanic ester containing ratio is 0.3% stopped reaction when following, obtains number-average molecular weight and be 7800, weight-average molecular weight is 88000 and the hydroxyl value polyester-polyurethane polyvalent alcohol that is 12.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester-polyurethane polyvalent alcohol (A2).
(synthesis example 1-3) [synthesizing of polyester-polyurethane polyvalent alcohol (A3)]
To having, in the flask of stirring rod, temperature sensor, bead tube, drop into 1.3 parts of 1144 parts of neopentyl glycol, 753 parts of m-phthalic acids, 464 parts of Tetra hydro Phthalic anhydrides, 373 parts of sebacic acid, 19 parts of trimellitic acid 1,2-anhydrides and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, is cooled to after 100 ℃, and by ethyl acetate, being diluted to solids component is 80%.Then, drop into isocyanurate-modified body (the SUMIDUR N-3300 of hexamethylene diisocyanate; Sumitomo Bayer Urethane Co., Ltd. manufactures) 13 parts of 132 parts, hexamethylene diisocyanate, to flask in pass into drying nitrogen and stir on one side, being heated to 70～80 ℃ carries out urethane reaction on one side.Isocyanic ester containing ratio is 0.3% stopped reaction when following, obtains number-average molecular weight and be 5000, weight-average molecular weight is 51000 and the hydroxyl value polyester-polyurethane polyvalent alcohol that is 17.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester-polyurethane polyvalent alcohol (A3).
(synthesis example 1-4) [synthesizing of polyester-polyurethane polyvalent alcohol (A4)]
To having in the flask of stirring rod, temperature sensor, bead tube, drop into 941 parts of neopentyl glycol, 1,1.3 parts of 201 parts of 6-hexylene glycols, 757 parts of m-phthalic acids, 301 parts of Tetra hydro Phthalic anhydrides, 68 parts of hexanodioic acids, 470 parts of sebacic acid, 19 parts of trimellitic acid 1,2-anhydrides and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, is cooled to after 100 ℃, and by ethyl acetate, being diluted to solids component is 80%.Then, drop into isocyanurate-modified body (the SUMIDUR N-3300 of hexamethylene diisocyanate; Sumitomo Bayer Urethane Co., Ltd. manufactures) 13 parts of 132 parts, hexamethylene diisocyanate, to flask in pass into drying nitrogen and stir on one side, being heated to 70～80 ℃ carries out urethane reaction on one side.Isocyanic ester containing ratio is 0.3% stopped reaction when following, obtains number-average molecular weight and be 5500, weight-average molecular weight is 32000 and the hydroxyl value polyester-polyurethane polyvalent alcohol that is 11.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester-polyurethane polyvalent alcohol (A4).
(synthesis example 2-1) [synthesizing of polyester polyol (B1)]
To having, in the flask of stirring rod, temperature sensor, bead tube, drop into 1.0 parts of 828 parts of neopentyl glycol, 588 parts of m-phthalic acids, 274 parts of Tetra hydro Phthalic anhydrides, 407 parts of sebacic acid, 15 parts of trimellitic acid 1,2-anhydrides and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, obtains number-average molecular weight and be 6700, weight-average molecular weight is 22000 and the hydroxyl value polyester polyol that is 12.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester polyol (B1).
(synthesis example 2-2) [synthesizing of polyester polyol (B2)]
To having, in the flask of stirring rod, temperature sensor, bead tube, drop into 1.0 parts of 1114 parts of neopentyl glycol, 717 parts of m-phthalic acids, 456 parts of Tetra hydro Phthalic anhydrides, 407 parts of sebacic acid, 19 parts of trimellitic acid 1,2-anhydrides and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, obtains number-average molecular weight and be 6200, weight-average molecular weight is 23000 and the hydroxyl value polyester polyol that is 15.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester polyol (B2).
(synthesis example 2-3) [synthesizing of polyester polyol (B3)]
To having in the flask of stirring rod, temperature sensor, bead tube, drop into 985 parts of neopentyl glycol, 1,1.3 parts of 70 parts of 6-hexylene glycols, 600 parts of m-phthalic acids, 144 parts of terephthalic acids, 349 parts of Tetra hydro Phthalic anhydrides, 25 parts of hexanodioic acids, 514 parts of sebacic acid, 19 parts of trimellitic acid 1,2-anhydrides and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, obtains number-average molecular weight and be 6000, weight-average molecular weight is 20000 and the hydroxyl value polyester polyol that is 13.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester polyol (B3).
(relatively synthesis example 1-1) [synthesizing of polyester-polyurethane polyvalent alcohol (a1)]
To having, in the flask of stirring rod, temperature sensor, bead tube, drop into 1.2 parts of 1130 parts of neopentyl glycol, 759 parts of m-phthalic acids, 342 parts of Tetra hydro Phthalic anhydrides, 534 parts of sebacic acid and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, is cooled to after 100 ℃, and by ethyl acetate, being diluted to solids component is 80%.Then, drop into 108 parts of hexamethylene diisocyanates, to flask in pass into drying nitrogen and stir on one side, being heated to 70～80 ℃ carries out urethane reaction on one side.Isocyanic ester containing ratio is 0.3% stopped reaction when following, obtains number-average molecular weight and be 10000, weight-average molecular weight is 22000 and the hydroxyl value polyester-polyurethane polyvalent alcohol that is 9.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester-polyurethane polyvalent alcohol (a1).
(relatively synthesis example 1-2) [synthesizing of polyester-polyurethane polyvalent alcohol (a2)]
To having, in the flask of stirring rod, temperature sensor, bead tube, drop into 1.2 parts of 1210 parts of neopentyl glycol, 679 parts of m-phthalic acids, 346 parts of Tetra hydro Phthalic anhydrides, 539 parts of hexanodioic acids, 20 parts of trimellitic acid 1,2-anhydrides and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, is cooled to after 100 ℃, and by ethyl acetate, being diluted to solids component is 80%.Then, drop into isocyanurate-modified body (the SUMIDUR N-3300 of hexamethylene diisocyanate; Sumitomo Bayer Urethane Co., Ltd. manufactures) 25 parts of 132 parts, hexamethylene diisocyanate, to flask in pass into drying nitrogen and stir on one side, being heated to 70～80 ℃ carries out urethane reaction on one side.Isocyanic ester containing ratio is 0.3% stopped reaction when following, obtains number-average molecular weight and be 5500, weight-average molecular weight is 32000 and the hydroxyl value polyester-polyurethane polyvalent alcohol that is 12.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester-polyurethane polyvalent alcohol (a2).
(relatively synthesis example 2-1) [synthesizing of polyester polyol (b1)]
To having, in the flask of stirring rod, temperature sensor, bead tube, drop into 1.2 parts of 1088 parts of neopentyl glycol, 727 parts of m-phthalic acids, 336 parts of Tetra hydro Phthalic anhydrides, 524 parts of sebacic acid, 19 parts of trimellitic acid 1,2-anhydrides and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, obtains number-average molecular weight and be 2300, weight-average molecular weight is 5000 and the hydroxyl value polyester polyol that is 50.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester polyol (b1).
(relatively synthesis example 2-2) [synthesizing of polyester polyol (b1)]
To having, in the flask of stirring rod, temperature sensor, bead tube, drop into 1.2 parts of 1105 parts of neopentyl glycol, 898 parts of m-phthalic acids, 421 parts of Tetra hydro Phthalic anhydrides, 272 parts of hexanodioic acids, 19 parts of trimellitic acid 1,2-anhydrides and organic titanic compounds, in flask, pass into drying nitrogen and stir on one side, Yi Bian be heated to 230～250 ℃, carrying out esterification.Acid number is 1.0mgKOH/g stopped reaction when following, obtains number-average molecular weight and be 7200, weight-average molecular weight is 21000 and the hydroxyl value polyester polyol that is 15.It is obtained to solids component with ethyl acetate dilution is 62% resin solution, as polyester polyol (b2).
The epoxy resin (C) using in embodiments of the invention and comparative example is below shown.
Epoxy resin (C1): the bisphenol A type epoxy resin of number-average molecular weight (Mn) 470, epoxy equivalent (weight) 245g/eq (" EPICLON 860 " that Dainippon Ink Chemicals manufactures) epoxy resin (C2): the bisphenol A type epoxy resin of number-average molecular weight (Mn) 900, epoxy equivalent (weight) 475g/eq (" JER1001 " that Mitsubishi chemical Co., Ltd manufactures)
The polycarbonate resin (D) using in embodiments of the invention and comparative example is below shown.
Polycarbonate polyol (D1): the polycarbonate diol of number-average molecular weight (Mn) 1000, hydroxyl value 10mgKOH/g (" DURANOL T5651 " that Asahi Kasei Corporation manufactures)
The polyisocyanates (E) using in embodiments of the invention and comparative example is below shown
Polyisocyanates (E1): the isocyanurate-modified body of hexamethylene diisocyanate (Sumitomo Bayer Urethane Co., " SUMIDURN3300 " that Ltd. manufactures)
(embodiment 1)
10 parts of 90 parts of polyester polyol (B1) solution, 10 parts of aforementioned epoxy resins (C1), the aforementioned polycarbonate polyols (C1) of gained in 10 parts of polyester-polyurethane polyvalent alcohol (A1) solution of gained in aforementioned Production Example 1-1, aforementioned Production Example 2-1 are obtained by mixing to resin combination with 10 parts of aforementioned polyisocyanates (D1), by following main points, make assess sample, by method shown below, evaluate.The results are shown in table 1.
(making of assess sample)
Using the thick PET film of 125 μ m (" X10S " that Dongli Ltd. manufactures) as base material, it is 5～6g/m that the resin combination of gained in above-described embodiment 1 be take to the quality of the solids component after solvent seasoning 2the mode of scope carry out application, the thick fluorine resin film of 25 μ m of then fitting (" AFLEX 25PW " that Asahi Glass Co., Ltd manufactures) and obtain laminated film.By its slaking 72 hours at 50 ℃, obtain assess sample.
(evaluate 1): outward appearance is for the assess sample of making of preceding method, from fluorine resin film side with visual valuation lamination outward appearance.
Zero: the level and smooth △ of film surface: film surface exist a small amount of arc crater *: there are a plurality of arc craters (depression) in film surface
(evaluating 2): the mensuration of the bonding force under wet heat condition is for the assess sample of making of preceding method, use tensile testing machine (" AGS500NG " that SHIMADZU Co., Ltd. manufactures), under the condition of peeling rate 300mm/min, intensity N/15mm, carry out T-shaped stripping test, its intensity is evaluated as bonding force.The initial bonding force of evaluation of measuring sample, and the bonding force that exposes the sample after 25 hours, 50 hours, 75 hours under 121 ℃, humidity 100% environment.
(evaluate 3): the initial bonding force of the assess sample that the evaluation comparison of humidity resistance is measured in aforementioned evaluation 2 and expose the bonding force of the sample after 75 hours under 121 ℃, humidity 100% environment, more than 60% sample that is initial bonding force by the bonding force after exposure is evaluated as zero, by more than 40% and lower than 60% sample be evaluated as △, the sample lower than 40% be evaluated as *.
(embodiment 2～14)
Except by the formula change of resin combination, be as shown in table 1～2, assess sample is made in operation similarly to Example 1, and evaluates.Evaluation result is shown in table 1～2.
(comparative example 1～10), except the formula of resin combination is changed into as shown in table 3～4, assess sample is made in operation similarly to Example 1, and evaluates.Evaluation result is shown in table 3～4.
[table 1]
[table 2]
[table 3]
[table 4]

Claims (16)

1. a resin combination, is characterized in that, it usings following compositions as neccessary composition:
(1) in molecule, having scope and the molecular weight distribution (Mw/Mn) that branched structure, weight-average molecular weight (Mw) are 10000～100000 is more than 5.0 polyester-polyurethane polyvalent alcohols (A), and
(2) in molecule, there is the polyester polyol (B) that scope that branched structure, weight-average molecular weight (Mw) are 10000～50000 and molecular weight distribution (Mw/Mn) are less than 5.0.
2. resin combination according to claim 1, wherein, described polyester-polyurethane polyvalent alcohol (A) can react and obtain by polyisocyanate compound (G2) above polyprotonic acid (E), polyvalent alcohol (F) and 3 officials as neccessary composition.
3. resin combination according to claim 1, wherein, described polyester-polyurethane polyvalent alcohol (A) is polyisocyanates (G) to be reacted and the polyester-polyurethane polyvalent alcohol that obtains as neccessary composition, and described polyisocyanates (G) be take scope that both mass ratio (G1)/(G2) is 50/50～5/95 and contained the polyisocyanate compound (G2) that diisocyanate cpd (G1) and 3 officials can be above.
4. resin combination according to claim 3, wherein, the scope of the hydroxyl value of described polyester-polyurethane polyvalent alcohol (A) is 5～30mgKOH/g.
5. resin combination according to claim 2, wherein, be necessary that, described polyprotonic acid (E) is to contain the dicarboxylic acid component that carbonatoms is 50～90 % by mole of 10～30 % by mole of more than 8 aliphatic dibasic acids and aromatic acids, and it is 40～100 % by mole of more than 5 aliphatic polyols that described polyvalent alcohol (F) contains carbonatoms.
6. resin combination according to claim 1, wherein, described polyester-polyurethane polyvalent alcohol (A) can react and obtain by polyisocyanate compound (G2) above 3 officials as neccessary composition.
7. resin combination according to claim 1, wherein, described polyester polyol (B) is by dicarboxylic acid component and 40～100 % by mole of polyester polyols that form of more than 5 aliphatic polyol of carbonatoms of containing 50～90 % by mole of 10～30 % by mole of more than 8 aliphatic dibasic acids of carbonatoms and aromatic acids.
8. resin combination according to claim 6, wherein, the scope of the hydroxyl value of described polyester polyol (B) is 5～30mgKOH/g.
9. resin combination according to claim 1, it also contains the hydroxyl-containing epoxy resin (C) of the scope that (3) number-average molecular weight (Mn) is 300～5000 on the basis of described (A) composition and described (B) composition.
10. resin combination according to claim 9, it also contains the hydroxyl polycarbonate resin (D) of the scope that (4) number-average molecular weight (Mn) is 300～3000 on the basis of described (A) composition, described (B) composition and described (C) composition.
11. according to the resin combination described in claim 9 or 10, and it also contains (5) polyisocyanates (E) as solidifying agent on the basis of described (A) composition and described (B) composition.
12. resin combinations according to claim 11, wherein, the scope that ratio [OH]/[NCO] is 1/1～1/2 of the mole number [NCO] of contained isocyanate group in the total mole number [OH] of contained hydroxyl and described polyisocyanate compound (E) in described polyester-polyurethane polyvalent alcohol (A), described polyester polyol (B), described epoxy resin (C) and described polycarbonate resin (D).
13. resin combinations according to claim 10, wherein, summation 100 mass parts with respect to described polyester-polyurethane polyvalent alcohol (A) with described polyester polyol (B), scope with 5～20 mass parts contains described epoxy resin (C), and contains described polycarbonate resin (D) with the scope of 5～20 mass parts.
14. 1 kinds of two-component-type lamination caking agents, it contains the resin combination described in claim 11.
15. 1 kinds of laminated films, it has a kind of above film in the group of selecting free polyester film, fluorine resin film, polyolefin film and tinsel composition and the adhesive linkage being formed by the caking agent described in claim 14.
The backboard of 16. 1 kinds of solar cells, it has the adhesive linkage being formed by the caking agent described in claim 14.
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