CN107343383A

CN107343383A - The manufacture method of solar cell sealing film, solar cell sealing film roll and solar module

Info

Publication number: CN107343383A
Application number: CN201680008453.6A
Authority: CN
Inventors: 室伏贵信; 德弘淳; 德武昌道
Original assignee: Mitsui Chemicals Tohcello Inc
Current assignee: Mitsui Chemicals Tohcello Inc
Priority date: 2015-02-04
Filing date: 2016-02-02
Publication date: 2017-11-10
Also published as: WO2016125793A1; JPWO2016125793A1; KR20170101257A

Abstract

A kind of film (10), it has multiple recesses (100) at least one face with clathrate arrangement form.Moreover, the mean depth of multiple recesses (100) is less than more than 50 μm 200 μm.In addition, at least one face, surface is set to S for the apparent surface product in the case of flat_a, and the area for the upper surface (110) for not forming multiple recesses (100) is set to S_tWhen, by S_t/S_aThe area occupation ratio for the upper surface (110) that × 100 (%) are represented is less than 10%.

Description

Solar cell sealing film, solar cell sealing film roll and solar cell The manufacture method of module

Technical field

The present invention relates to the system of solar cell sealing film, solar cell sealing film roll and solar module Make method.

Background technology

Recorded in patent document 1 and implemented being formed by ethylene-vinyl acetate copolymer resin film for Embossing processing Sealing films for solar cell.In patent document 1, film is provided with recess by Embossing processing, the per unit area of film Total volume V of recess_HAnd unit area is multiplied by the apparent volume V of film obtained by maximum gauge_APercentage V_H/V_A× 100% is 5~80%.Thus, during the heating processing of the sealing process in the making of solar cell, buffering is granted to film Property, prevents the breakage of unit for solar cell, and it is bad etc. to prevent from deaerating.

Prior art literature

Patent document

Patent document 1：No. 3473605 publications of Japanese Patent No.

The content of the invention

Invent problem to be solved

However, in patent document 1, on and the depth of recess formed, being paid attention to by Embossing processing relative to film most Big thickness t_maxDepth rate, describe the purport that depth rate is preferably 20~95%.Therefore, if the thickness of film becomes big, for The specific voidage of holding, the area shared by recess necessarily diminish.Moreover, it specify that according to the research of inventor etc., patent In the case where being taken care of as film roll etc., the film surface to contact with each other sometimes sticks together such film described in document 1 each other.

The present invention provide be not susceptible to convey, keeping when the mutual adhesion of film surface, in the manufacture of solar module The excellent solar cell sealing film of middle out gassing.

Means for solving the problems

The present inventor etc. have made intensive studies to solve above-mentioned problem, as a result find, by suitably adjusting recess The area occupation ratio of the upper surface of mean depth and film, can obtain be not susceptible to convey, keeping when the mutual adhesion of film surface, too The excellent solar cell sealing film of out gassing in the manufacture of positive energy battery module, so that complete the present invention.

That is, according to the present invention, there is provided solar cell sealing film as shown below.

[1]

A kind of solar cell sealing film, it has multiple recesses at least one face with clathrate arrangement form,

The mean depth of above-mentioned multiple recesses is less than more than 50 μm 200 μm,

In above-mentioned at least one face, surface is set to S for the apparent surface product in the case of flat_a, will not formed The area for stating the upper surface of multiple recesses is set to S_tWhen, by S_t/S_aThe area occupation ratio of above-mentioned upper surface that × 100 (%) are represented is Less than 10%.

[2]

According to the solar cell sealing film described in above-mentioned [1], cycle of the arrangement of above-mentioned multiple recesses for 500 μm with Upper less than 2000 μm of scope.

[3]

According to the solar cell sealing film described in above-mentioned [1] or [2], above-mentioned upper surface is with forming above-mentioned multiple recesses Face it is intersecting with less than more than 30 ° 60 °.

[4]

According to the solar cell sealing film any one of above-mentioned [1]~[3], above-mentioned multiple recesses are when overlooking For square, rectangle, rhombus, parallelogram, triangle or hexagon, and be separated from each other certain distance and fill it is above-mentioned extremely A few face.

[5]

A kind of solar cell sealing film roll, it is close as the solar cell any one of above-mentioned [1]~[4] Envelope is around in what core formed with film roll.

[6]

A kind of manufacture method of solar module, it includes following processes：

Preparatory process, prepare solar cell sealing film, and

Sealing process, by face side transparent protection member, the first solar cell sealing film, solar cell list Member, the second solar cell sealing are stacked gradually with film and rear side protection component and form layered product, and to above-mentioned Layered product is heated and pressurizeed and integrated,

Above-mentioned first and second solar cell sealings film has with clathrate arrangement form multiple recessed at least one face Portion,

The effect of invention

According to the present invention it is possible to provide be not susceptible to convey, keeping when the mutual adhesion of film surface, in solar cell mould The excellent solar cell sealing film of out gassing in the manufacture of block.

Brief description of the drawings

Above-mentioned purpose and other purposes, feature and advantage by the preferred embodiment of following record and are appended hereto it The following drawings and further clearly.

Fig. 1 is the figure for the structure for showing solar cell sealing film of the present embodiment.

Fig. 2 is section obtained from from the direction that arrow represents along figure of the section of the single dotted broken line A-A shown in Fig. 1 Figure.

Fig. 3 shows that recess is triangle, is arranged in the example of the structure of the solar cell sealing film of positive triangle clathrate The figure of son.

Fig. 4 is the section for the example for showing structure of the recess comprising the solar cell sealing film in the case of curved surface Figure.

Fig. 5 is used for being cut from by solar cell sealing solar cell sealing obtained by web-like is made in film with film roll Go out the figure that the example of the position of diaphragm illustrates.

Fig. 6 is the section signal that the processing of the manufacture method for the solar module being related to embodiment illustrates Figure.

Embodiment

Hereinafter, on embodiments of the present invention, illustrated using accompanying drawing.In addition, in whole accompanying drawings, to same Inscape encloses same symbol, suitably omits the description.

In addition, on "~", as long as no specializing, then it represents that with up to following.

Fig. 1 is the structure of display solar cell sealing film 10 of the present embodiment (hereinafter referred to as " film 10 ") Figure.This figure is the figure for overlooking film 10, and the single dotted broken line A-A's shown in Fig. 1 observed in the direction that Fig. 2 is towards in figure shown in arrow Sectional view obtained from section.

Film 10 of the present embodiment, there are multiple recesses 100 at least one face with clathrate arrangement form.Moreover, The mean depth of multiple recesses 100 is less than more than 50 μm 200 μm.It is being flat by surface in addition, at least one face In the case of apparent surface product be set to S_a, and the area for the upper surface 110 for not forming multiple recesses 100 is set to S_tWhen, by S_t/S_aThe area occupation ratio for the upper surface 110 that × 100 (%) are represented is less than 10%.It is described further below.

Film 10 as such as film 10 be wound in the solar cell sealing that core forms conveyed with film roll, keeping.Separately Outside, film 10 is not limited to web-like, can also be laminated and be conveyed, keeping.

The one or both sides of film 10 are provided with multiple recesses 100.Multiple recesses 100 are arranged with clathrate, are separated from each other Certain distance and fill surface.Here, so-called clathrate, however it is not limited to square lattice, can be to follow oblique cage, trigonal lattice The arrangement of the grid such as son, hexagonal lattice.From the viewpoint of effectively the mutual adhesion of film surface is suppressed, preferably recess 100 is in film Formed in 10 at least one face throughout whole face.

The shape of multiple recesses 100 is not particularly limited, but from the viewpoint of efficiently fill surface and from recess 100 It is square, rectangle, rhombus, parallelogram, triangle or six preferably when overlooking from the viewpoint of the easiness of formation Side shape.In addition, in the case where recess 100 is triangle, more preferably equilateral triangle or isosceles triangle.Here, it is so-called recessed Shape of the portion 100 when overlooking, is that line, the i.e. exterior contour 104 of recess 100 intersected by recess 100 with upper surface 110 determines Shape.

Here, so-called upper surface 110, it is not form recess 100 in the surface of the side for foring recess 100 of film 10 Region, become the top surface of convex protrusion.Be wound into film roll 20 or overlapping film 10 the part of upper surface 110 with it is adjacent Film surface contact.

Fig. 1 shows recess 100 as square, the example arranged with square lattice shape.

On the other hand, Fig. 3 is to show that recess 100 is equilateral triangle as variation, the film arranged with triangular lattice shape The figure of the example of 10 structure.

In film 10, the mean depth of multiple recesses 100 is less than more than 50 μm 200 μm, more preferably more than 80 μm 200 Below μm, more preferably less than more than 100 μm 200 μm.Here, the depth d of each recess 100 is relative to upper surface 110 Recess 100 depth capacity, the mean depths of multiple recesses 100 is depth d average value.In the system of solar module In making, solar cell sealing with after other inscapes are laminated on film, are heated and pressurizeed and during the processing of integration, Sometimes air remains in recess and produces bubble in layered product.If mean depth is below the above-mentioned upper limit, bumps are by adding Heat is squeezed bad when with pressurizeing, and air is not easy to be captured, i.e. out gassing is excellent, and bubble is reduced.It is if in addition, average deep Spend for below the above-mentioned upper limit, then when being formed as film roll etc., it is possible to reduce its internal useless space, transfer efficiency improve. On the other hand, if mean depth is more than above-mentioned lower limit, the bottom surface of recess 100 is not easy to contact with adjacent film surface, can be with Effectively suppress the mutual adhesion of film surface.In addition, the mean depth of recess 100 is the maximum gauge no more than film 10 described later t_maxScope, preferably film 10 maximum gauge t_maxLess than 50%, the more preferably maximum gauge t of film 10_max40% with Under.

In Fig. 2, display recess 100 is inclined-plane and the example of the structure of bottom surface with plane.In this case, by outside The shape for the recess 100 that profile 104 is formed, can be with identical with the shape formed by the exterior contour 102 of bottom surface, or it is mutual The shape differed.

On the other hand, Fig. 4 is to show the example of the structure of the film 10 when recess 100 is formed by curved surface as variation Sectional view.In this case, the depth d of each recess 100 can be defined relative to the maximum of the recess 100 of upper surface 110 deeply Degree.

The mean depth of recess 100 can be for example, by carrying out cross-section to ask with electron microscope to the diaphragm of film 10 Go out.

Fig. 5 is used for (hereinafter referred to as " the film of solar cell sealing film roll 20 obtained by web-like is made from by film 10 Volume 20 ".) cut out diaphragm 200 position the figure that illustrates of example.The width of film roll 20 is represented in this figure with single dotted broken line The Central Line in direction.Specifically, first, it is inner in the center of film roll 20 and both ends away from width as this figure This at the 10cm of side cuts out 20mm × 20mm square diaphragm 200 at 3.Moreover, seen by using the section of electron microscope The depth d for examining each recess 100 for being pointed to these diaphragms 200 is measured, and is determined 10 depth d to every 1 diaphragm 200, is calculated Go out their average value, so as to obtain the mean depth of multiple recesses 100.

Next, returning to Fig. 1 and Fig. 2, the area occupation ratio of upper surface 110 is illustrated.There is recess 100 in the formation of film 10 Face in, the area occupation ratio of upper surface 110 is less than 10%, more preferably less than 8%.If the area occupation ratio be the above-mentioned upper limit with Under, then the mutual contact area of opposed film surface can be reduced, therefore can effectively suppress the mutual adhesion of film surface.The opposing party Face, the area occupation ratio of upper surface 110 can be such as more than 1%, preferably more than 2%, more preferably more than 4%.

Here, the area occupation ratio of so-called upper surface 110, it is to be set on surface for the apparent surface product in the case of flat S_a, and the area for the upper surface 110 for not forming multiple recesses 100 is set to S_tWhen, by S_t/S_aThe value that × 100 (%) are represented.That is, So-called apparent surface accumulates S_a, it is the value that the width of film is multiplied by the length of film and obtained, the area S of so-called upper surface 110_t, it is Fig. 1 With the area in the region of the upper surface 110 shown in Fig. 2.The area occupation ratio of upper surface 110 can be by adjusting mutual point of recess 100 Width of distance or upper surface 110 etc. is opened to adjust.

The area occupation ratio of upper surface 110 can be for example, by being observed to ask the diaphragm 200 of film 10 with light microscope Go out.Specifically, first, in the same manner as the evaluation of the mean depth of recess 100,10mm × 10mm is cut out at 3 shown in Fig. 5 Square diaphragm 200.It is then possible to the surface configurations of light microscope determining these diaphragms 200 and calculate upper surface 110 area occupation ratio, obtained using the average value of 3 diaphragms 200 as the area occupation ratio of upper surface 110.

The period p of the arrangement of multiple recesses 100 is preferably less than more than 500 μm 2000 μm of scope, more preferably 500 μm The scope of scope below 1500 μm of the above, more preferably less than more than 500 μm 1200 μm.In addition, period p need not be It is all identical in whole film 10.If period p is below the above-mentioned upper limit, the bottom of recess 100 is not easy to contact with adjacent film surface. Therefore, it is possible to effectively suppress adhesion.On the other hand, if period p is more than above-mentioned lower limit, as the film that out gassing is excellent 10。

Here, as shown in figures 1 and 3, so-called period p, be 1 recess 100 and recess 100 adjacent thereto center of gravity between Distance.It is the center of gravity of the shape of the recess 100 determined by exterior contour 104 in addition, the center of gravity of so-called recess 100.Relative to 1 recess 100, exist between the center of gravity of multiple and adjacent recesses 100 in the case of distance, distance is in upper between minimum center of gravity In the range of stating, but between further preferably minimum center of gravity between the center of gravity of distance and maximum distance all in above range.

Period p can be for example, by being obtained with the diaphragm 200 of observation by light microscope film 10.Specifically, first, with The evaluation of the mean depth of recess 100 similarly, cuts out 5mm × 5mm square diaphragm 200 at 3 shown in Fig. 5.So Afterwards, with the surface configurations of light microscope determining these diaphragms 200 and the cycle can be determined, is confirmed whether to be in above range.

Preferably intersected with forming the face of multiple recesses 100 with less than more than 30 ° 60 ° the upper surface 110 of film 10.That is, with In the cross sectional shape of the vertical recess 100 of film surface, preferably at the point that recess 100 intersects with upper surface 110, what they were formed Angle r is less than more than 30 ° 60 °.Specifically, for example, what the recess 100 shown in Fig. 2 and Fig. 4 was formed with upper surface 110 Angle r is preferably in above range.As shown in Figure 2, in the case of the inclined-plane in recess 100 with plane, angle r is upper table The angle that face 110 is formed with inclined-plane.On the other hand, as shown in Figure 4, in the case where recess 100 is formed by curved surface, angle r The angle formed for tangent line at the point that intersects in recess 100 with upper surface 110, the curved surface with upper surface 110.If angle It is below the above-mentioned upper limit to spend r, then formation yield rate of the recess 100 on film 10 improves.On the other hand, if above-mentioned lower limit with On, then it can effectively suppress adhesion.

Angle r can be for example, by carrying out cross-section to obtain with electron microscope to the diaphragm 200 of film 10.It is specific and Speech, first, in the same manner as the evaluation with the mean depth of recess 100, cuts out 20mm × 20mm square at 3 shown in Fig. 5 Diaphragm 200.Furthermore, it is possible to by using the cross-section of electron microscope be pointed to each recesses 100 of these diaphragms 200 with it is upper The angle r on surface 110 is measured, and is determined 10 angle r to every 1 diaphragm, is confirmed whether to be in above range.

Out gassing when being manufactured from solar module and from the viewpoint of the balance of resiliency, in film 10, film Total volume V of the recess of per unit area_HWith the apparent volume V of film_APercentage V_H/V_AVoidage P shown in × 100 (%) is preferably 3~30%, and more preferably 10~28%.In addition, the apparent volume V of film_AFilm can be multiplied by by unit area 10 maximum gauge obtains.

Voidage P can be obtained by being calculated as below.The apparent volume V of film formed with recess_A(mm³), film can be passed through Maximum gauge t_max(mm) with unit area (such as 1m²=1000 × 1000=10⁶mm²) product, calculated as following formula (3) Go out.

V_A(mm³)=t_max(mm)×10⁶(mm²) (3)

On the other hand, the actual volume V of the film of the unit area₀(mm³) can be by the way that the ratio of the resin combination of film will be formed Weight ρ (g/mm³) and film per unit area (1m²) actual weight W (g) substitute into following formula (4) and calculate.

V₀(mm³)=W/ ρ (4)

For total volume V of the recess of the per unit area of film_H(mm³), can be by from " film as shown in following formula (5) Apparent volume V_A" subtract " actual volume V₀" calculate.

V_H(mm³)=V_A-V₀=V_A-(W/ρ) (5)

Therefore, voidage (%) can be obtained as follows.

Voidage P (%)=V_H/V_A×100

=(V_A-(W/ρ))/V_A×100

=1-W/ (ρ V_A)×100

=1-W/ (ρ t_max·10⁶)×100

Voidage (%) can be obtained by above-mentioned calculating formula, can also cutting by the actual film of microscope photographing Face, the face formed with recess, image procossing etc. is carried out to obtain.

Here, the maximum gauge t of so-called film_max, in the case of in a face of film formed with recess, represent from one Upper surface in the case of in two faces of film formed with recess, represents to (thickness direction of the film) distance in another face (film thickness direction) distance from a upper surface to another upper surface.

The maximum gauge t of film 10_maxPreferably 0.01mm~2mm, more preferably 0.1~1mm, more preferably 0.3~ 0.8mm.If the maximum gauge t of solar cell sealing film_maxFor the table being laminated in process in the range of this, then can be suppressed The breakage of surface side transparent protection member, solar battery cell, rear side protection component etc., can also enter even in lower temperature Row solar module it is laminated into type, therefore preferably.In addition, film 10 is able to ensure that sufficient light transmittance, it is used Solar module there is high light generated energy.

Thermoplastic resin composition can be molded and manufacture by film 10.Thermoplastic resin composition is not particularly limited, but Preferably clear is high.In thermoplastic resin composition, comprising thermoplastic resin, further as needed comprising crosslinking agent, crosslinking Accelerator, coupling agent, light stabilizer, ultra-violet absorber, antioxidant etc..

As thermoplastic resin, the ethene-α-alkene for example formed by the alpha-olefin of ethene and carbon number 3~20 can be enumerated Hydrocarbon copolymer, high density ethylene system resin, low density ethylenic resin, Midst density vinylite, ultra-low density polyethylene system tree Fat, propylene (co) polymer, 1- butylene (co) polymer, 4-methyl-1-pentene (co) polymer, ethylene-cyclic olefin copolymerization Thing, ethene-alpha-olefin-cyclic olefin copolymer, ethylene/alpha-olefin/unconjugated polyene copolymer, ethene-alpha-olefin-conjugation are more The olefin-based resins such as alkene copolymer, ethylene/aromatic vinyl copolymer, ethene-alpha-olefin-aromatic vinyl copolymer, Ethene-unsaturated carboxylic acid anhydride copolymer, ethene-alpha-olefin-unsaturated carboxylic acid anhydride copolymer, ethene-insatiable hunger containing epoxy radicals With compound copolymer, the ethene-alpha-olefin-unsaturated compound copolymer containing epoxy radicals, ethylene-vinyl acetate c Thing；Ethene-the copolymers of unsaturated carboxylic acids such as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid The ethene such as methacrylate copolymers, ethylene methyl methacrylate copolymer-unsaturated carboxylic acid ester copolymer, esters of unsaturated carboxylic acids (co) polymer, (methyl) acrylate (co) polymer, ethylene-propylene acid metal salt copolymer, ethylene-methyl methacrylate gold Belong to salt copolymer plasma key resin, carbamate system resin, silicon-type resin, acrylic resin, methacrylic acid Be resin, cyclic olefin (co) polymer, alpha-olefin-aromatic ethenyl compound-aromatic polyene copolymer, ethene-α- Alkene-aromatic ethenyl compound-aromatic polyene copolymer, ethylene/aromatic vinyl compound-aromatic polyene are common Polymers, phenylethylene resin series, acrylonitrile-butadiene-styrene copolymer, styrene-conjugated diene copolymer, acrylonitrile-benzene Ethylene copolymer, acrylonitrile-vinyl-alpha-olefin-nonconjugated polyene-styrol copolymer, acrylonitrile-vinyl-alpha-olefin-conjugation Polyenoid-styrol copolymer, methacrylic acid-styrol copolymer, ethylene glycol terephthalate resin, fluororesin, polyester Carbonic ester, polyvinyl chloride, Vingon, polyolefin thermoplastic elastomer (TPE), polystyrene thermoplastic elastomer (TPE), polyurethane Based thermoplastic elastomer, 1,2 polybutadiene based thermoplastic elastomers, trans-polyisoprene based thermoplastic elastomer, chlorination gather Ethene based thermoplastic elastomer, liquid crystalline polyester, PLA etc..

Wherein, it is the ethene-alpha-olefin copolymer that is preferably formed by the alpha-olefin of ethene and carbon number 3~20, low close It is (common) poly- to spend vinylite, Midst density vinylite, ultra-low density polyethylene system resin, propylene (co) polymer, 1- butylene Compound, 4-methyl-1-pentene (co) polymer, ethylene-cyclic olefin copolymer, ethene-alpha-olefin-cyclic olefin copolymer, Ethylene/alpha-olefin/unconjugated polyene copolymer, ethene-alpha-olefin-conjugated polyene copolymer, ethylene/aromatic vinyl copolymerization The olefin-based resins such as thing, ethene-alpha-olefin-aromatic vinyl copolymer, ethene-unsaturated carboxylic acid anhydride copolymer, ethene-α- Alkene-unsaturated carboxylic acid anhydride copolymer, ethene-unsaturated compound copolymer, ethene-alpha-olefin containing epoxy radicals-contain Ethene-the insatiable hungers such as the unsaturated compound copolymer of epoxy radicals, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer With polymers of carboxylic acid, ethylene-ethyl acrylate copolymer, esters of unsaturated carboxylic acids (co) polymer, (methyl) acrylate (common) The ethene such as polymer, ethylene methyl methacrylate copolymer-unsaturated carboxylic acid ester copolymer, ethylene-propylene acid metal salt are total to Polymers, ethylene-methyl methacrylate metal salt copolymer plasma key resin, cyclic olefin (co) polymer, alpha-olefin-aromatic series Vinyl compound-aromatic polyene copolymer, ethene-alpha-olefin-aromatic ethenyl compound-aromatic polyene copolymerization Thing, ethylene/aromatic vinyl compound-aromatic polyene copolymer, acrylonitrile-butadiene-styrene copolymer, benzene second Alkene-conjugated diene copolymer, acrylonitritrile-styrene resin, acrylonitrile-vinyl-alpha-olefin-nonconjugated polyene-styrene are common Polymers, acrylonitrile-vinyl-alpha-olefin-conjugated polyene-styrol copolymer, methacrylic acid-styrol copolymer.

Further, the ethene-alpha-olefin copolymer more preferably formed by the alpha-olefin of ethene and carbon number 3~20. Above-mentioned thermoplastic resin composition can be modified by silane compound.

In addition, ethene-alpha-olefin copolymer preferably meets following important document a1)~a4).

A1) content ratio of Component units from ethene be 80~90mol%, and derive from carbon number 3~ The content ratio of the Component units of 20 alpha-olefin is 10~20mol%.

A2) according to ASTM D1238, the MFR determined under conditions of 190 DEG C, 2.16kg load is 0.5~50g/10 points Clock.

A3) density determined according to ASTM D1505 is 0.865~0.884g/cm³。

A4) Xiao A hardness determined according to ASTM D2240 is 60~85.

Hereinafter, to important document a1)~a4) illustrate.

(important document a1)

For the alpha-olefin from carbon number 3~20 contained in ethene-alpha-olefin copolymer Component units (with Under, be also denoted as " alpha-olefin unit ") ratio, from the viewpoint of the transparency, the balance of flexibility and manufacture efficiency, be preferably 10~20mol%, more preferably 12~20mol%, more preferably 13~18mol%.

In addition, in ethene-alpha-olefin copolymer, unconjugated polyene can also be included.As unconjugated polyene, can not have Limitation ground uses the compound with more than 2 non-conjugated unsaturated bonds.Specifically, as unconjugated polyene, can use Any of non-conjugated Cyclic Polyene, non-conjugated chain polyenoid, it is more can also to be applied in combination two or more non-conjugated ring-types Alkene and non-conjugated chain polyenoid.In addition, as unconjugated polyene, can use can be polymerize in carbon-to-carbon double bond by catalyst Carbon-to-carbon double bond can be polymerize by the catalyst in the unconjugated polyene and carbon-to-carbon double bond that 1 intramolecular only exists 1 Carbon-to-carbon double bond in 1 intramolecular in the presence of any of 2 unconjugated polyene.Wherein, the carbon-to-carbon double bond that can polymerize is 1 Only existed in molecule in the unconjugated polyene of 1, be vinyl (CH without two ends₂=CH-) chain polyenoid.Such In the case of more than 2 carbon-to-carbon double bonds being present in unconjugated polyene, it is preferred that only 1 carbon-to-carbon double bond is made in molecular end Exist for vinyl, and other carbon-to-carbon double bonds (C=C) in strand (comprising main chain and side chain) with internal alkene structures Form exist.In addition, in the concept of non-conjugated Cyclic Polyene, non-conjugated chain polyenoid, can also polymerize including above-mentioned Carbon-to-carbon double bond only exists what can be polymerize by the catalyst in the unconjugated polyene and carbon-to-carbon double bond of 1 in 1 molecule The unconjugated polyene of 2 in 1 intramolecular be present in carbon-to-carbon double bond.In addition, as conjugation chain polyenoid, also comprising conjugated triene or Tetraene.

As the concrete example of unconjugated polyene, the paragraph in No. 2005/105867 pamphlet of International Publication No. can be enumerated 0061~0084 and Japanese Unexamined Patent Publication 2008-308696 publications paragraph 0026~0035 described in compound.

Particularly, the unconjugated polyene of 1 is only existed in 1 molecule as the carbon-to-carbon double bond that can polymerize, can be enumerated Following polyenoid, the polyenoid is by the alicyclic moiety with 1 carbon-to-carbon double bond (unsaturated bond) and with alkylidene Etc. (alkylidene) it is not polymerize by metalloscene catalyst or the chain of the internal alkene key (carbon-to-carbon double bond) of polymerism difference Shape part is formed.Specifically, 5- ethylidene -2- ENBs (ENB), 5- propylidene -2- ENBs and 5- can be enumerated Butylidene -2- ENBs etc..In addition, have 2 in 1 intramolecular as the carbon-to-carbon double bond that can polymerize in above-mentioned carbon-to-carbon double bond The concrete example of individual unconjugated polyene, 5- vinyl -2- ENBs (VNB), 5- pi-allyl -2- ENBs etc. can be enumerated 5- alkenyl -2- ENBs；2,5- norbornadienes, bicyclopentadiene (DCPD), Fourth Ring [4.4.0.1^2,5.1^7,10] 12 carbon- The Alicyclic polyenes such as 3,8- diene；The α, ω-diene etc. such as 1,7- octadienes, 1,9- dodecylenes.

It is when as ethylene/alpha-olefin/unconjugated polyene copolymer, from unconjugated polyene Component units (with Under, be also denoted as " unconjugated polyene unit ") ratio be 0.01~5.0mol%, preferably 0.01~4.5mol%, further Preferably 0.05~4.0mol%.If the content ratio of unconjugated polyene unit is more than 0.01mol%, crosslinking feature is excellent It is different.On the other hand, if the content ratio of unconjugated polyene unit is below 5.0mol%, film can be suppressed and produce gel Foreign matter.

(important document a2)

For according to ASTM D1238, the ethene-alpha-olefin copolymer determined under conditions of 190 DEG C, 2.16kg load Melt flow rate (MFR) (MFR), from manufacture efficiency, insulaion resistance, penetrability, flat with the adaptation of glass etc. and heat resistance From the viewpoint of weighing apparatus, preferably 0.5~50g/10 minutes, more preferably 10~45g/10 minutes, more preferably 10~ 40g/10 minutes.Polymerization temperature, polymerization pressure when the MFR of ethene-alpha-olefin copolymer can be by adjusting above-mentioned polymerisation The monomer concentration of ethene and alpha-olefin in power and polymerization system and the molar ratio of hydrogen concentration etc. adjust.

(important document a3)

For the density of the ethene-alpha-olefin copolymer determined according to ASTM D1505, from the transparency, manufacture efficiency, From the viewpoint of the balance of flexibility and heat resistance, preferably 0.865~0.884g/cm³, more preferably 0.865~0.880g/ cm³.The density of ethene-alpha-olefin copolymer can pass through the content ratio and the content ratio of alpha-olefin unit of ethylene unit Balance to adjust.That is, if improve ethylene unit content ratio if crystallinity uprise, can obtain the high ethene-α of density- Olefin copolymer.On the other hand, the crystallinity step-down if the content ratio for reducing ethylene unit, can obtain low density second Alkene-alpha olefin copolymer.

(important document a4)

For the Xiao A hardness of the ethene-alpha-olefin copolymer determined according to ASTM D2240, from manufacture efficiency, resistance to From the viewpoint of hot, transparent and flexibility balance, preferably 60~85, more preferably 60~83, more preferably 65~80.The Xiao A hardness of ethene-alpha-olefin copolymer can be by controlling the ethylene unit of ethene-alpha-olefin copolymer Content ratio, density adjust.That is, for the ethene-alpha-olefin copolymer that the content ratio of ethylene unit is high, density is high, Xiao A hardness uprises.On the other hand, with regard to the content ratio of ethylene unit is low, for low density ethene-alpha-olefin copolymer, Xiao A hardness step-down.

By comprising meeting above-mentioned important document a1)~a4) the thermoplastic resin composition of ethene-alpha-olefin copolymer formed Film, it is prone to adhesion, air residual, but be effectively improved by the present invention.

As the film as described above for including ethene-alpha-olefin copolymer, can use in International Publication No. 2012/ Film described in No. 2012/046456 No. 60086 pamphlets, International Publication No. pamphlet.

(vinylite composition)

For solar cell sealing film of the present embodiment, preferably comprising vinylite group Compound, the vinylite composition contain the above-mentioned parts by weight of ethene-alpha-olefin copolymer 100 and ethene unsaturated silane The parts by weight of crosslinking agent 0.1~3 such as the parts by weight of the silane couplers such as compound 0.1~5 and organic peroxide.

Further, in vinylite composition, second is contained preferably with respect to the parts by weight of ethene-alpha-olefin copolymer 100 The parts by weight of alkene unsaturated silane compound 0.1~4 and the parts by weight of organic peroxide 0.2~3, particularly preferably relative to second The parts by weight of alkene-alpha olefin copolymer 100 contain the parts by weight of ethene unsaturated silane compound 0.1~3, organic peroxide 0.2~2.5 parts by weight.

(ethene unsaturated silane compound)

If ethene unsaturated silane compound is more than 0.1 parts by weight, cementability can be improved.The opposing party Face, if ethene unsaturated silane compound is below 4 parts by weight, can make the cost of solar cell sealing film with The balance of performance is good, furthermore it is possible to reduce for making ethene unsaturated silane in the lamination of solar module Compound carries out the addition of the organic peroxide of graft reaction with ethene-alpha-olefin copolymer.Therefore, it is possible to suppress the sun Can cell sealing film extrusion mechanism film-like and gelation when obtaining.Therefore, because the torque of extruder reduces, therefore Film shaping can be made to become easy.Further, since can suppress to produce jello in extruder, therefore can suppress in film Surface produces unnecessary bumps, can suppress the deterioration of outward appearance.

In addition, if jello inside film be present, then crack, insulation breakdown are produced on jello periphery upon application of a voltage Voltage reduces, but by making the content of ethene unsaturated silane compound be below 4 parts by weight, can suppress insulation breakdown electricity The reduction of pressure.In addition, it is easy to moisture-inhibiting at jello interface if it jello be present inside film, but by making ethene unsaturated The content of silane compound is below 4 parts by weight, can suppress the reduction of penetrability.

Ethene unsaturated silane compound can use known compound, be not particularly limited.Specifically, Can use VTES, vinyltrimethoxy silane, vinyl three ('beta '-methoxy Ethoxysilane), γ-glycidoxypropyltrime,hoxysilane, γ aminopropyltriethoxy silane, γ-methacryloxypropyl three Methoxy silane etc..Preferably, the good γ of cementability-glycidoxypropyl group methoxy silane, gamma-amino propyl group can be enumerated Triethoxysilane, γ-methacryloxypropyl trimethoxy silane, VTES.

(organic peroxide)

When organic peroxide is used as the graft modification of ethene unsaturated silane compound and ethene-alpha-olefin copolymer Radical initiator, be further used as ethene-alpha-olefin copolymer solar module it is laminated into type when crosslinking Radical initiator during reaction.By by ethene unsaturated silane compound graft modification in ethene-alpha-olefin copolymer, It can obtain good too with the cementability of face side transparent protection member, solar battery cell, rear side protection component etc. Positive energy battery module.Further, by the way that ethene-alpha-olefin copolymer is crosslinked, heat resistance, excellent in adhesion can be obtained Solar module.

It is preferred that as long as the organic peroxide used can be by ethene unsaturated silane compound graft modification in second The organic peroxide of alkene-alpha olefin copolymer or the organic peroxide that ethene-alpha-olefin copolymer can be crosslinked , productivity ratio and solar module when being molded from extruded film it is laminated into type when the balance of crosslinking rate consider, 1 minute half life temperature of organic peroxide is 100~170 DEG C.If 1 minute half life temperature of organic peroxide is More than 100 DEG C, then it can prevent from being produced with film by the solar cell sealing that resin combination obtains when extruded film is molded and coagulate Glue, and because the torque of extruder reduces, therefore film shaping can be made to become easy.Further, since extruder can be suppressed Interior generation jello, therefore can suppress to produce unnecessary bumps on the surface of film, the deterioration of outward appearance can be suppressed.

In addition, if jello inside film be present, then crack, insulation breakdown are produced on jello periphery upon application of a voltage Voltage reduces, but is more than 100 DEG C by making 1 minute half life temperature of organic peroxide, can suppress insulation breakdown electricity The reduction of pressure.In addition, it is easy to moisture-inhibiting at jello interface if it jello be present inside film, but by making organic peroxide 1 minute half life temperature be more than 100 DEG C, additionally it is possible to suppress the reduction of penetrability.

On the other hand, if 1 minute half life temperature of organic peroxide is less than 170 DEG C, the sun can be suppressed Can battery module it is laminated into type when crosslinking rate reduction, therefore the drop of the productivity ratio of solar module can be prevented It is low.Additionally it is possible to prevent the reduction of the heat resistance of solar cell sealing film, cementability.

As organic peroxide, known organic peroxide can be used.It is 100 as 1 minute half life temperature The preferred concrete example of the organic peroxide of~170 DEG C of scope, dilauroyl peroxide, 1,1,3,3- tetramethyl fourth can be enumerated Base peroxidating -2 ethyl hexanoic acid ester, dibenzoyl peroxide, peroxidating tertiary pentyl -2 ethyl hexanoic acid ester, tert-butyl hydroperoxide - 2 ethyl hexanoic acid ester, tert-butyl hydroperoxide isobutyrate, peroxidating Malaysia tert-butyl acrylate, 1,1- bis- (t-amyl peroxy) -3, 3,5- trimethyl-cyclohexanes, 1,1- bis- (t-amyl peroxy) hexamethylene, t-amyl peroxy isononoate, t-amyl peroxy Caprylic acid ester, (the tert-butyl hydroperoxide) -3,3,5- of 1,1- bis- trimethyl-cyclohexanes, 1,1- bis- (tert-butyl hydroperoxide) hexamethylene, T-butylperoxyisopropyl carbonic ester, tert-butyl hydroperoxide -2- ethylhexyl carbonates, (the benzene first of 2,5- dimethyl -2,5- two Acyl peroxidating) hexane, tertiary pentyl-peroxide benzoate, tert-butyl hydroperoxide acetic acid esters, tert-butyl hydroperoxide isononoate, 2,2- bis- (tert-butyl hydroperoxide) butane, tert butyl peroxy benzoate etc..It is preferred that dilauroyl peroxide, tertiary fourth can be enumerated Base isopropyl peroxide carbonic ester, tert-butyl hydroperoxide acetic acid esters, tert-butyl hydroperoxide isononoate, tert-butyl hydroperoxide -2- Ethylhexyl carbonate, tert butyl peroxy benzoate etc..

(ultra-violet absorber, light stabilizer, heat-resisting stabilizing agent)

In vinylite composition, preferably comprise selected from by ultra-violet absorber, light stabilizer and heat-resisting stabilizing agent group Into at least one of group additive.The use level of these additives relative to the parts by weight of ethene-alpha-olefin copolymer 100, It is respectively preferably 0.005~5 parts by weight.Further, at least two additives in above-mentioned three kinds are preferably comprised, it is especially excellent Choosing contains above-mentioned three kinds of whole.If the use level of above-mentioned additive is above range, raising pair can be fully ensured Hot and humid patience, the patience of thermal cycle, the effect of weathering stability and heat-resistant stability, further, it is possible to prevent solar energy The transparency of cell sealing film and face side transparent protection member, solar battery cell, rear side protect the viscous of component etc. The reduction of connecing property, therefore preferably.

As ultra-violet absorber, specifically, 2- hydroxyl -4- n-octyl epoxides benzophenone, 2- hydroxyls -4 can be used Methoxy benzophenone, 2,2- dihydroxy -4- methoxy benzophenones, 2- hydroxyl -4- methoxyl group -4- carboxyl benzophenones, 2- The benzophenone series such as hydroxyl -4- oxy-octyl benzophenones；2- (2- hydroxyl -3,5- di-t-butyls phenyl) BTA, 2- The enumerate BTA systems such as (2- hydroxy-5-methyl bases phenyl) BTA；Phenyl salicylate, salicylic acid are to salicylic acids such as octyl phenyl esters The ultra-violet absorber of ester system.

As light stabilizer, preferably using double (2,2,6,6- tetramethyl -4- piperidyls) sebacates, it is poly- [6- (1,1, 3,3- tetramethyl butyls) amino -1,3,5- triazine -2,4- diyls } { (2,2,6,6- tetramethyl -4- piperidyls) imino group } six Asia Methyl { (2,2,6,6- tetramethyl -4- piperidyls) imino group }] etc. the light stabilizer such as amine system of being obstructed, hindered piperidine based compound.

As heat-resisting stabilizing agent, specifically, three (2,4- di-t-butyl phenyl) phosphite esters, double [2,4- can be enumerated Double (1,1- dimethyl ethyls) -6- aminomethyl phenyls] ethyl ester phosphorous acid, four (2,4- di-t-butyls phenyl) [1,1- biphenyl] -4, The phosphite ester system such as 4'- diyls biphosphinate and double (2,4- di-t-butyls phenyl) pentaerythritol diphosphites is heat-resisting steady Determine agent；The lactone system heat-resisting stabilizing agents such as the reaction product of 3- hydroxyls -5,7- di-t-butyl -s furans -2- ketone and ortho-xylene； 3,3', 3 ", 5,5', 5 "-six-tert-butyl group-a, a', a "-(bases of methylene -2,4,6- three) three-paracresol, 1,3,5- trimethyls - 2,4,6- tri- (3,5- di-t-butyl -4- hydroxy phenyls) benzyl benzene, [3- (the 3,5- di-t-butyl -4- hydroxy benzenes of pentaerythrite four Base) propionic ester], octadecyl -3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester, the double [3- (3,5- of thiodiethylene Di-t-butyl -4- hydroxy phenyls) propionic ester] etc. hindered phenol series heat-resisting stabilizing agent；Sulphur system heat-resisting stabilizing agent；Amine system Heat-resistant stable Agent etc..In addition, they can be used alone or can also be applied in combination two or more.Wherein, preferably phosphite ester system Heat-resisting stabilizing agent and hindered phenol series heat-resisting stabilizing agent.

(other additives)

In the vinylite composition for forming solar cell sealing film, the purpose of the present invention can not damaged Scope, suitably containing the various composition beyond each composition described in detail above.For example, it can enumerate beyond ethene-alpha-olefin copolymer Various polyolefin, polystyrene, ethene based block copolymer, acrylic polymer etc..They are relative to above-mentioned ethene-α-alkene The parts by weight of hydrocarbon copolymer 100,0.0001~50 parts by weight, preferably 0.001~40 parts by weight can be contained.It is furthermore, it is possible to suitable Various resins beyond containing polyolefin and/or selected from various rubber, plasticizer, filler, pigment, dyestuff, antistatic additive, One or more of antiseptic, mould inhibitor, fire retardant, crosslinking coagent and dispersant etc. additive.

Particularly, in the case of containing crosslinking coagent, if the use level of crosslinking coagent is total to relative to ethene-alpha-olefin The parts by weight of polymers 100 are 0.05~5 parts by weight, then can have the cross-linked structure of appropriateness, it is possible to increase heat resistance, mechanical thing Property, cementability, therefore preferably.

As crosslinking coagent, the known crosslinking coagent used general to olefin-based resin can be used.It is such Crosslinking coagent is the compound for having more than two double bonds in intramolecular.Specifically, tert-butyl acrylate, acrylic acid can be enumerated Lauryl Ester, acrylic acid spermaceti base ester, stearyl acrylate base ester, acrylic acid 2- methoxy ethyls ester, ethyl carbitol acrylic acid The mono acrylic esters such as ester, methoxyl group tripropylene glycol acrylate；Tert-butyl Methacrylate, lauryl methacrylate, first Base acrylic acid spermaceti base ester, stearyl methacrylate, methoxyl group glycolmethacrylate, methoxy poly (ethylene glycol) first The monomethacrylates such as base acrylate；1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, 1,9- nonyls two Alcohol diacrylate, neopentylglycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, poly- second two The diacrylates such as alcohol diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate；1,3 butylene glycol diformazan Base acrylate, 1,6-HD dimethylacrylate, 1,9- nonanediols dimethylacrylate, neopentyl glycol dimethyl propylene It is olefin(e) acid ester, ethylene glycol dimethacrylate, dimethacrylate, TEGDMA, poly- The dimethylacrylates such as ethylene glycol dimethacrylate；Trimethylolpropane trimethacrylate, tetramethylol methane 3 third The triacrylates such as olefin(e) acid ester, pentaerythritol triacrylate；Trimethylol-propane trimethacrylate, trimethylolethane The trimethyl acrylic esters such as trimethyl acrylic ester；Tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate etc. four Acrylate；The di vinyl aromatic compounds of group such as divinylbenzene, two-isopropenylbenzene；Triallyl cyanurate, isocyanide urea The cyanurates such as sour triallyl；The diallyl compounds such as diallyl phthalate；Triallyl compound：Paraquinones two The oximes such as oxime, p-p'- dibenzoyl quininie dioximes：The maleimides such as phenyl maleimide.It is preferred in these crosslinking coagents It is diacrylate, dimethylacrylate, di vinyl aromatic compounds of group, trimethylolpropane trimethacrylate, four hydroxyls The triacrylates such as methylmethane triacrylate, pentaerythritol triacrylate；Trimethylol-propane trimethacrylate, The trimethyl acrylic esters such as trimethylolethane trimethacrylate methacrylate；Tetramethylol methane tetraacrylate, tetramethylol methane four The cyanurates such as the tetraacrylates such as acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate The diallyl compounds such as propyl ester；Triallyl compound：The oximes such as paraquinonedioxime, p-p'- dibenzoyl quininie dioximes：Phenyl Malaysia The maleimides such as acid imide.Triallyl isocyanurate, the solar energy after lamination are further particularly preferably in them The bubble of cell sealing film produces, the balance of crosslinking feature is most excellent.

Here, tensile modulus of elasticity at 23 DEG C of film 10 is preferably 6~13MPa.The tensile modulus of elasticity is for example with such as Under type determines.First, the film by forming the thickness 1mm formed with the identical of film 10 is prepared.Then, by the film according to JIS K7113 is punched into dumb-bell shape, utilizes Auto-graph (Shimadzu Seisakusho Ltd.'s company systems：AGS-J), between fixture：40mm, stretching speed Degree：1mm/min is measured.Now, the temperature of determination of the environment is 23 DEG C, humidity 50%Rh.

Film 10 with tensile modulus of elasticity as described above is prone to adhesion, air residual, but has by the present invention Effect ground is improved.

As the manufacture method of film 10 of the present embodiment, commonly used approach can be utilized, but preferably pass through Melt blending is carried out using kneader, Banbury mixer, extruder etc. to manufacture.Particularly preferably using being capable of quantity-produced Extruder manufactures.

Solar cell sealing is not particularly limited with the forming method of film 10, can use known various forming methods (cast molding, extruded film shaping, inflation shaping, injection moulding, compression forming etc.).It is particularly following to obtain solar-electricity like that Pond film for sealing is most preferred embodiment.That is, for example, being blended in the bags such as polybag with manpower, or prosperous house is used The stirring mixers such as your mixer, rotating cylinder, high-speed mixer are by ethene-alpha-olefin copolymer, ethene unsaturated silane chemical combination Thing, organic peroxide, ultra-violet absorber, light stabilizer, heat-resisting stabilizing agent and other additives as needed blending, are obtained Obtain composition.Then, the composition of gained is put into the hopper of extruded film shaping, extruded while melting mixing Film is molded, and obtains solar cell sealing film.As extrusion temperature scope, extrusion temperature is 100~130 DEG C.If make to squeeze Go out temperature for more than 100 DEG C, then can improve the productivity ratio of solar cell sealing film.If it is 130 to make extrusion temperature Below DEG C, then with extruder, by solar cell sealing, the vinylite composition used in film carries out membranization and obtained too Gelation is not susceptible to when positive energy cell sealing is with film.It is therefore prevented that extruder torque rise, can easily carry out film into Type.Further, since being not easy that unnecessary bumps occur on the surface of piece, therefore the deterioration of outward appearance can be prevented.Furthermore it is possible to press down System produces crack when applying voltage inside film, therefore can prevent the reduction of breakdown voltage.Further, additionally it is possible to suppress The reduction of penetrability.

Further, film 10 can be with the sheet form that is cut according to solar module size or with can The roll form cut before it will make solar module according to size uses.

Film 10 can include hard conating, adhesive linkage, anti-reflection layer, gas barrier layer, the stain-proofing layer for surface or back-protective Deng.If classified by material, the layer comprising uv curing resin, the layer comprising thermosetting resin can be enumerated, included It is the layer of vistanex, the layer comprising carboxyl acid modified vistanex, the layer comprising fluorine resin, (common) poly- comprising cyclic olefin The layer of compound, layer comprising inorganic compound etc..

Film 10 of the surface formed with recess can carry out Embossing processing to make by using the dandy roll with given shape Make.Dandy roll can for example prepare as follows：Using the intermetallic composite coating according to prior art, formed on the surface of metal roller with Want to be formed at the convex portion pattern that the recess of film accordingly designs.In this case, the convex of roller surface is embossed by adjusting The size in portion, shape, position, depth etc., the shape, mean depth, upper surface of the recess 100 for being formed at film roll 20 can be adjusted 110 area occupation ratio, period p, angle r etc..

For solar cell sealing film as described above, the mutual adhesion of film surface is suppressed, and can be obtained defeated Send the solar cell sealing film of keeping efficiency high.If in addition, solar cell sealing as described above is used for film The manufacture of solar module, then it can suppress the generation of the bubble caused by air is involved in.

The method that solar module is manufactured using film 10 of the present embodiment is illustrated below.

Fig. 6 is that the section that the processing to the manufacture method of solar module of the present embodiment illustrates shows It is intended to.

The manufacture method of solar module of the present embodiment includes preparatory process and sealing process.Beam worker In sequence, prepare solar cell sealing film 10.In sealing process, by face side transparent protection member 40, the first solar-electricity Pond film for sealing 120, solar battery cell 30, the second solar cell sealing with film 140 and rear side protect component 42 according to Secondary stacking and form layered product, and layered product heated and pressurizeed and integrated.It is explained in detail below.

Layered product is for example by face side transparent protection member 40, the first solar cell sealing film 120, solar-electricity Pool unit 30, the second solar cell sealing film 140 and rear side protection component 42 are stacked gradually and obtained.

Face side transparent protection member 40 is not particularly limited, but due to positioned at the most top layer of solar module, because This preferably has headed by weatherability, water proofing property, stain resistance, mechanical strength, for ensuring solar module in outdoor The performance of long-term reliability during exposure.In addition, in order to effectively utilize sunshine, preferably optical loss is small, the transparency is high Piece.

As the material of face side transparent protection member 40, can enumerate comprising polyethylene terephthalate (PET) etc. The resin of polyester resin, fluororesin, acrylic resin, cyclic olefin (co) polymer, vinyl-vinyl acetate copolymer etc. Film, glass substrate etc..In the case of using glass substrate, the full light of 350~1400nm of wavelength of glass substrate light is saturating The rate of mistake is preferably more than 80%, and more preferably more than 90%.As such glass substrate, typically lacked using the absorption in infrared portion Blank glass, even if being blue or green glass sheet, as long as thickness is below 3mm, to the shadow of the output characteristics of solar module Ring also few.In addition, in order to improve the mechanical strength of glass substrate, strengthened glass can be obtained by being heat-treated, but can also make With the float glass of no heat treatment.In addition it is also possible to carry out antireflection in the light surface side of glass substrate to suppress reflection Coating.

Rear side protection component 42 is not particularly limited, but due to positioned at the most top layer of solar module, therefore with Above-mentioned face side transparent protection member 40 is similarly, it is desirable to each characteristic such as weatherability, mechanical strength.Therefore, can use and table The same material of surface side transparent protection member 40 forms rear side protection component 42.That is, the transparent guarantor of face side will can also be used as The above-mentioned various materials for protecting component 40 and using are used as rear side protection component 42.Especially it is possible to it is preferred that use polyester resin And glass.In addition, rear side protects component 42 due to premised on, therefore being not necessarily required not by sunshine to face side The transparency required by transparent protection member 40.Therefore, in order to increase the mechanical strength of solar module, or in order to prevent Strain, warpage, can also put up enhancing plate as caused by temperature change.Strengthen plate can preferably using such as steel plate, plastic plate, FRP (fiberglass reinforced plastics) plate etc..

At least one face in the first solar cell sealing with the solar cell sealing film 140 of film 120 and second, with Clathrate arrangement form has multiple recesses 100.The mean depth of multiple recesses 100 is less than more than 50 μm 200 μm, upper surface 110 area occupation ratio is less than 10%.First solar cell sealing film 120 and the second solar cell sealing film 140 can Think identical film, or mutually different film.That is, the shape of recess 100, arrangement, recess 100 mean depth, on At least one among the area occupation ratio on surface 110, period p, angle r, resin composition etc. can be with different.

In sealing process, by face side transparent protection member 40, the first solar cell sealing film 120, solar-electricity Pool unit 30, the second solar cell sealing film 140 and rear side protection component 42 stack gradually and form layered product, and Layered product is heated and pressurizeed and be integrated.By being heated and being pressurizeed in this process, so as to form the tree of film 10 Fat flows and the recess 100 of film 10 disappears.

In the layered product of the process sealed, the direction of film is not particularly limited, but preferably with the first solar-electricity The formation that the formation of pond film for sealing 120 has the face 120A and the second solar cell sealing film 140 of recess 100 has recessed The face 140A in portion 100, the mode opposed with solar battery cell 30 are laminated and form layered product.In addition it is also possible to with The mode that the face of recess connects with solar battery cell 30 is laminated, and forms layered product.By in this way, entering to layered product Row heating and pressurization and during the processing of integration, played because recess is squeezed bad as the function of buffering, application can be mitigated In the pushing force of solar battery cell.As a result, it is possible to suppress the breakage of solar battery cell.

In addition, layered product is heated and pressurizeed and integration processing when, recess formed air passage, degassing Property improve.Therefore, can suppress to deaerate bad.

Further, layered product is heated and pressurizeed and during the processing of integration, be heated and as can flow The resin of state can be flowed into recess, therefore the bad shape that such resin is spilt into outside layered product can be suppressed Condition.

In addition, in sealing process by the process of layered product integration, preferably by heating and as can flow First solar cell sealing of dynamic state is not overflowed with the solar cell sealing film 140 of film 120 and second from layered product Pressurizeed and heated under the conditions of such.

In addition, in sealing process by layered product integration process in, layered product can be placed in hot plate 50 In the state of upper, layered product is pressurizeed.

In addition, in sealing process by layered product integration process in, can by atmospheric pressure to layered product carry out Pressurization.

In addition, in sealing process by layered product integration process in, can be by using soft 60 and hot plate 50 Layered product is surrounded, layered product is put on to be pressurizeed by inner pressure relief and by atmospheric pressure.

For example, as shown in fig. 6, mounting stacks gradually rear side protection component 42, second sun from top on hot plate 50 Can cell sealing film 140, solar battery cell 30, the first solar cell sealing film 120, the transparency protected structure of face side Layered product obtained by part 40.

In addition, in layered product, one or more solar battery cells 30 can be included.In example illustrated, multiple sun Energy battery unit 30 is included in layered product.Moreover, multiple solar battery cells 30 using electrode (not shown) the company of series connection Connect.Here, the composition of electrode and material are not particularly limited, but in specific example, have nesa coating and metal film Stepped construction.Nesa coating includes SnO₂, ITO, ZnO etc..Metal film include silver, gold, copper, tin, aluminium, cadmium, zinc, mercury, chromium, The metals such as molybdenum, tungsten, nickel, vanadium.These metal films can be used alone, alloy that can also be as Composite and use.It is transparent Conducting film and metal film the methods of CVD, sputtering, evaporation by forming.

In addition, the first solar cell sealing film 120 and the second solar cell sealing film 140 can mutually divide From the first solar cell sealing can also be formed with the solar cell sealing film of film 120 and second by a film 10 140.For example, it is also possible to a film is bent by way of bag solar battery cell 30 within, so as to realize that diagram is such The first solar cell sealing of use film 120 and the second solar cell sealing film 140 sandwich solar battery cell 30 State.

By layered product as described above as illustrated with after soft 60 covering, will be wrapped by soft 60 and hot plate 50 The inner space decompression enclosed.As a result, layered product can be pressurizeed by atmospheric pressure.Now, hot plate 50 is heated to predetermined temperature, By the heat, the first solar cell sealing is also heated with the solar cell sealing of film 120 and second with film 140.

In addition, one as condition now, hot plate temperature is less than more than 70 DEG C 170 DEG C, and vacuum time is 1 minute Below the above 10 minutes, pressing pressure is more than 0.1 air pressure below 1 air pressure, and pressing time is less than 20 minutes more than 1 minute.

In addition, solar module is not limited to above-mentioned composition, can be in the range of the purpose of the present invention not be damaged It is appropriately arranged with layer other than the above.As layer other than the above, for example, adhesive linkage, impact absorbing layer, coating layer, anti- Reflecting layer, the back side reflecting layer and light diffusion layer etc. again.These layers are not particularly limited, it may be considered that set purpose, the spy of each layer Property is arranged at appropriate location.

More than, according to the system for the solar module for having used solar cell sealing film of the present embodiment Make method, can solve the problem that the crackle of solar battery cell, by sealing when the bad caused air of degassing be involved in, resin group Spilling from compound to layered product end face the problems such as.

Next, the effect and effect to present embodiment illustrate.

Solar cell sealing film of the present embodiment, be not susceptible to convey, keeping when film surface it is mutual viscous Even, the out gassing in the manufacture of solar module is excellent.

In addition, the present invention is not limited to above-mentioned embodiment, deformation in the range of it can realize the purpose of the present invention, Improvement etc. is contained in the present invention.

Embodiment

Hereinafter, the present invention is specifically described by embodiment.In addition, present embodiment is not by the record of these embodiments Any restriction.

(embodiment 1)

[synthesis of ethene-alpha-olefin copolymer]

To a supply mouth of the continuous polymerization device for the internal volume 50L for possessing stirring vane, using as the first of co-catalyst The toluene solution of base aikyiaiurnirsoxan beta using 8.0mmol/hr, be used as double (1,3- dimethylcyclo-pentadienyls) zirconium dichlorides of major catalyst Hexane slurry supplied with the hexane solution of 0.025mmol/hr, triisobutyl aluminium with 0.5mmol/hr ratio, and continuously supply The n-hexane that the dehydration that the n-hexane refined to dehydration is used using causing as catalyst solution and polymer solvent refines adds up to As 20L/hr.Simultaneously to polymerizer other supply mouths, by ethene with 3kg/hr, 1- butylene with 15kg/hr, hydrogen with 5NL/hr Ratio continuously supply, 90 DEG C of polymerization temperature, stagnation pressure 3MPaG, under conditions of 1.0 hours holdup times carry out successive soln gather Close.For n-hexane/toluene mixed solution of the ethene-alpha-olefin copolymer generated in polymerizer, via being arranged at polymerizer The outlet of bottom is continuously discharged, and is guided to chuck portion by 3~25kg/cm²Connecting tube that steam is heated so that N-hexane/toluene mixed solution of ethene-alpha-olefin copolymer turns into 150~190 DEG C.In addition, reach connecting tube it is tight before Place, be attached to supply mouth of the injection as the methanol of catalyst deactivator, with about 0.75L/hr speed inject methanol make its with The n-hexane of ethene-alpha-olefin copolymer/toluene mixed solution interflow.Insulation is in about in the connecting tube with steam jacket N-hexane/toluene mixed solution of 190 DEG C of ethene-alpha-olefin copolymer, in a manner of maintaining about 4.3MPaG, pass through setting Flash tank is continuously fed in the aperture adjustment of the pressure-control valve of connecting tube terminal part.In addition, into flash tank In transfer, carry out solution temperature and pressure-regulating valve aperture is set so that the pressure in flash tank maintains about 0.1MPaG, and makes sudden strain of a muscle The temperature for steaming the steam portion in groove maintains about 180 DEG C.Then, by being 180 DEG C of single axle extruding machine by mold temperature set, profit Strands are cooled down with tank, strands is cut off using pelleter, obtains the ethene-alpha-olefin copolymer as particle.Yield is 2.2kg/hr。

[evaluation of ethene-alpha-olefin copolymer]

The content ratio ＞ of ＜ ethylene units and alpha-olefin unit

The solution for dissolving by heating sample 0.35g to obtain in hexachlorobutadiene 2.0ml is subjected to glass filter (G2) mistake After filter, deuterated benzene 0.5ml is added, is encased in internal diameter 10mm NMR pipes.Use the JNM GX-400 types of Japan Electronics Corporation NMR determines device, in 120 DEG C of progress¹³C-NMR is determined.Cumulative number is set to more than 8000 times.According to gained¹³C-NMR light Spectrum, quantify the content ratio of ethylene unit and the content ratio of alpha-olefin unit in copolymer.As a result, the present embodiment The content ratio of the alpha-olefin unit of ethene-alpha-olefin copolymer is 14mol%.

[MFR]

According to ASTM D1238, the MFR of measure ethene-alpha-olefin copolymer under conditions of 190 DEG C, 2.16kg load. As a result, the MFR of the ethene-alpha-olefin copolymer of the present embodiment is 20g/10 minutes.

[density]

According to ASTM D1505, the density of ethene-alpha-olefin copolymer is determined.As a result, ethene-the α of the present embodiment- The density of olefin copolymer is 0.870g/cm³。

[Xiao A hardness]

By ethene-alpha-olefin copolymer with 190 DEG C, heating 4 minutes, after 10MPa pressurizeed, with 10MPa pressurizations cooling 5 Minute until normal temperature, obtains the thick pieces of 3mm.Piece obtained by use, ethene-alpha-olefin copolymerization is determined according to ASTM D2240 The Xiao A hardness of thing.As a result, the Xiao A hardness of the ethene-alpha-olefin copolymer of the present embodiment is 70.

[manufacture of solar cell sealing film]

Relative to the parts by weight of ethene-alpha-olefin copolymer 100 of gained, cooperation is used as ethene unsaturated silane compound The parts by weight of γ-methacryloxypropyl trimethoxy silane 0.5,1 minute half-life period temperature as organic peroxide Spend the parts by weight of tert-butyl hydroperoxide -2- ethylhexyl carbonates 1.0 for 166 DEG C, the isocyanuric acid triolefin as crosslinking coagent The parts by weight of propyl ester 1.2, the parts by weight of 2- hydroxyl -4- n-octyl epoxides benzophenone 0.4 as ultra-violet absorber, as freedom The parts by weight of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate 0.2 of base agent for capturing (light stabilizer) and conduct are heat-resisting The parts by weight of three (2,4- di-t-butyls phenyl) phosphite ester 0.1 of stabilizer 1, the octadecyl -3- as heat-resisting stabilizing agent 2 The parts by weight of (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester 0.1, obtain resin combination A.

Clothes hanger is installed on the single axle extruding machine (screw diameter 20mm φ, L/D=28) of Thermoplastics company systems Formula T-shaped mould has (die lip shape：270 × 0.8mm), under conditions of 100 DEG C of mold temperature, with 30 DEG C of roll temperature, winding speed 1.0m/min, it is molded for the first chill roll using dandy roll, obtains the graining film (solar-electricity of 500 μm of thickness Pond film for sealing).In addition, the surface of the dandy roll used in the present embodiment, has been made like with multiple on whole face It is the convex pattern of square convex portion when overlooking.

(embodiment 2~7,9 and comparative example 1~3)

The convex pattern dandy roll different from embodiment 1 has been used, in addition, has operated, obtains similarly to Example 1 Solar cell sealing film.In any embodiment and comparative example, on the surface of used dandy roll, all one on whole face Sample formed with the convex pattern with multiple convex portions.

(embodiment 8)

Instead of resin combination A, used as resin combination B vinyl-vinyl acetate copolymer (VA28%, MFR15g/10min), in addition, operate similarly to Example 1, obtain solar cell sealing film.

[evaluation of solar cell sealing film]

Following evaluation is carried out with film to the solar cell sealing obtained in each embodiment and each comparative example, by its result It is summarized in table 1.

[table 1]

The shape ＞ of ＜ recesses

With the shape of the recess of observation by light microscope solar cell sealing film.As a result, embodiment 1~5,7, 8th, 9 and comparative example 1~3 in, as shown in Figure 1, have multiple square recesses with square lattice shape arrangement form.In embodiment 6, As shown in Figure 3, there is the recess of multiple equilateral triangles with triangular lattice shape arrangement form.

The mean depth ＞ of ＜ recesses

Determine the mean depth of the recess of solar cell sealing film.Specifically, center is being rolled up and away from volume in width The both ends spent on direction at this at 10cm 3, cut out 20mm × 20mm square diaphragm, by using electronic display in the inner part The cross-section of micro mirror determines the depth for each recess for being present in these diaphragms, determines 10 depth to every 1 diaphragm, obtains Mean depth.Due in each embodiment and each comparative example using the dandy roll that convex pattern is made like on whole face, because This average value so obtained is considered as being averaged for entirety.

＜ upper surfaces and the angle ＞ of recess

Determine the upper surface of solar cell sealing film and the angle of recess.Specifically, in the average depth with recess Evaluating at same 3 for degree, cuts out 20mm × 20mm square diaphragm, comes by using the cross-section of electron microscope Measure is present in each recess of these diaphragms and the angle of upper surface, and 10 angles are determined to every 1 diaphragm.Determine obtained angle Spend about the same, 45 ± 1 ° of scope is in embodiment 1~6,8,9 and comparative example 1~3.In addition, the angle is in embodiment 7 In be in 25 ± 1 ° of scope.In addition, for convenience, median is recorded in table 1.

The area occupation ratio ＞ of ＜ upper surfaces

Determine the area occupation ratio of upper surface.Specifically, 10mm × 10mm is cut out at same 3 from evaluating for mean depth Square diaphragm, by the surface configurations of light microscope determining these diaphragms and the area occupation ratio of upper surface is calculated, by 3 The average value of diaphragm is obtained as the area occupation ratio of the upper surface of film.Due in each embodiment and each comparative example use in whole face On be made like the dandy roll of convex pattern, therefore the area occupation ratio so obtained is considered as the area of the overall upper surface of film Rate.

＜ cycles ＞

Determine the period p of the arrangement of recess.Specifically, from the evaluation with mean depth it is same 3 at cut out 5mm × 5mm square diaphragm, the surface configuration of these diaphragms is determined to determine the cycle by light microscope.Cycle almost one Sample, 1030 ± 5 μm of scope is in embodiment 1.In addition, for convenience, table 1 describes median.In any embodiment, ratio Compared with example, scope of the cycle all in central value ± 5 μm.

＜ voidages ＞

Determine the voidage P [%] of solar cell sealing film.Specifically, cut out 10cm × 10cm's from volume center The diaphragm of square, from the weight W [g] of their total quality determination per unit area.In addition, separately obtain the maximum film of film Thick t_maxProportion ρ [the g/mm of [mm] and membrane material³], based on P (%)=1-W/ (ρ t_max·10⁶The relation of) × 100, obtains sky Gap rate P.Here, maximum film thickness t_maxSeen by the same section of the cross-section carried out during evaluation with the mean depth of recess Examine to determine.In addition, the proportion ρ of membrane material uses the technique same with the present embodiment, obtained using without Embossing processing Film determine.

＜ tensiles modulus of elasticity ＞

In addition, the tensile modulus of elasticity of measure solar cell sealing film.Prepare to include and used with solar cell sealing The thickness 1mm of film identical composition film.Moreover, the film is punched into dumb-bell shape according to JIS K7113, Auto- is utilized Graph (Shimadzu Seisakusho Ltd.'s company systems：AGS-J), between fixture：40mm, draw speed：1mm/min is measured.Now, survey The temperature for determining environment is set to 23 DEG C, and humidity is set to 50%Rh.As a result, on tensile modulus of elasticity, in embodiment 1~7,9 It is 8MPa with the resin combination A used in comparative example 1~3, the resin combination B used in embodiment 8 is 15MPa.

The rejection ＞ of ＜ adhesions

Solar cell sealing the film roll wide 250mm of gained is stood into 1 week post-tensioning membrane at 35 DEG C, will now be pulled out Situation of the intensity less than 1kgf is evaluated as zero, 1kgf is evaluated as into △ less than 1.5kgf situation, by more than 1.5kgf Situation be evaluated as ×.

[manufacture of solar module]

Solar cell sealing film obtained by use, the small mould for being connected in series Unit 18 is made using monocrystalline unit Block, evaluated.For face side transparent protection member, use the Asahi Glass fabritech for cutting into 24 × 21cm public Take charge of the heat-treated glass with embossing of the blank float glass 3.2mm thickness of system.System of crystallization unit (Shinsung monocrystalline Unit) use the unit that 5 × 3cm is cut into using the busbar silver electrode of light surface side as center.Using in copper foil surface It is coated with the copper strips electrode of eutectic solder and the unit is connected in series Unit 18.As tergite (rear side protection component), make With the PET systems tergite comprising silica steam plating PET, cut in a part for tergite from the taking-up position of unit with cutter Enter about 2cm otch, take out the plus end and negative terminal of unit obtained from being connected in series Unit 18, use vacuum laminator (NPC systems：LM-110x160-S solar energy) is laminated with 150 DEG C of hot plate temperature, vacuum time 4 minutes, 15 minutes pressing times Cell sealing film.Then, the solar cell sealing film stretched out from glass, tergite are cut, end face is assigned to glass edge Sealing material, after installing aluminium chassis, to assigning RTV organosilicons from the cutting part for the terminal part that tergite takes out and making its solidification.

[evaluation of solar module]

＜ out gassing ＞

Observed across the glass of the solar module of gained, confirmed when will be observed by light microscope Situation less than bubble is evaluated as zero, and bubble will be confirmed when will be observed by light microscope but is confirmed with visual less than gas Bubble, △ is evaluated as the situation that product quality has no problem, will the available situation for visually confirming bubble be evaluated as ×.

As shown in table 1, in embodiment 1~9, confirm adhesion rejection and out gassing is all excellent.On the other hand, recess Mean depth less than 50 μm comparative example 1 and upper surface area occupation ratio more than 10% comparative example 3 in, adhesion rejection Difference.In addition, in comparative example 2 of the mean depth of recess more than 200 μm, out gassing is poor.

This application is advocated preferential based on 2 months 2015 Japanese publication Patents filed in 4 days 2015-020253 Power, this is incorporated in by its entire disclosure.

Claims

1. a kind of solar cell sealing film, it has multiple recesses at least one face with clathrate arrangement form,

The mean depth of the multiple recess is less than more than 50 μm 200 μm,

In at least one face, surface is set to S for the apparent surface product in the case of flat_a, and will not formed described more The area of the upper surface of individual recess is set to S_tWhen, by S_t/S_a× 100 (%) represent the upper surface area occupation ratio for 10% with Under.

2. solar cell sealing film according to claim 1, cycle of the arrangement of the multiple recess for 500 μm with Upper less than 2000 μm of scope.

3. solar cell sealing film according to claim 1 or 2, the upper surface is with forming the multiple recess Face is intersecting with less than more than 30 ° 60 °.

4. according to solar cell sealing film according to any one of claims 1 to 3, the multiple recess is when overlooking Square, rectangle, rhombus, parallelogram, triangle or hexagon, and be separated from each other certain distance and fill it is described at least One face.

5. a kind of solar cell sealing film roll, used by solar cell sealing according to any one of claims 1 to 4 Film roll is around in what core formed.

6. a kind of manufacture method of solar module, it includes following processes：

Preparatory process, prepare solar cell sealing film, and

Sealing process, by face side transparent protection member, the first solar cell sealing film, solar battery cell, Second solar cell sealing is stacked gradually with film and rear side protection component and forms layered product, and to the stacking Body is heated and pressurizeed and integrated,

In the first and second solar cell sealings film, have at least one face with clathrate arrangement form multiple recessed Portion,

The mean depth of the multiple recess is less than more than 50 μm 200 μm,

In at least one face, surface is set to S for the apparent surface product in the case of flat_a, will not formed the multiple The area of the upper surface of recess is set to S_tWhen, by S_t/S_aThe area occupation ratio for the upper surface that × 100 (%) are represented is less than 10%.