JPWO2018117082A1 - Polyester polyol, reactive adhesive, and laminate - Google Patents

Abstract

Provided is a reactive adhesive that can be applied as an adhesive for laminates of various substrates, and has both high adhesiveness, excellent appearance after lamination, hydrolysis resistance, and moldability.
Polyester acid comprising polybasic acid or derivative thereof and polyhydric alcohol as essential raw materials, wherein all of the polybasic acid or derivative raw material are polybasic acid or derivative thereof having an aromatic ring, and number average molecular weight In the range of 3000 to 100,000, a reactive adhesive comprising a polyol composition (A) containing the polyester polyol and a polyisocyanate composition (B) as essential components, and first A laminate obtained by laminating an adhesive layer between the base material and the second base material, wherein the adhesive layer is the reactive adhesive described above.

Description

  The present invention relates to a reactive adhesive, a polyester polyol as one component thereof, and a laminate using the reactive adhesive.

Conventionally, laminates made by laminating various plastic films and laminating plastic films with metal-deposited films and metal foils have been used in various applications, such as packaging materials for foods, pharmaceuticals, and household goods, and barriers. Decoration for roofing materials, roofing materials, solar panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signs, stickers, etc. Used for applications.
These laminates are appropriately combined with various plastic films, metal-deposited films or metal foils according to the required properties for each application, and an adhesive is selected according to the required properties. For example, in the case of food and daily necessities, functions such as strength, resistance to cracking, retort resistance, and heat resistance are required to protect the contents from various distribution, storage such as refrigeration, and heat sterilization. . Alternatively, in outdoor industrial applications, weather resistance and hydrolysis resistance are required to maintain long-term adhesion even in open-air environments.
Furthermore, these laminates rarely circulate in the form of sheets. For example, they may be heat-sealed in the form of bags, or may be molded by thermoforming, requiring heat-sealability and moldability. Sometimes it is done.

As an adhesive used for such a laminate, a reactive adhesive (also referred to as a two-component adhesive) for reacting a hydroxyl group with an isocyanate has been conventionally known.
For example, in food applications, in an adhesive comprising a diol compound (A) having two hydroxyl groups and a polyisocyanate (B) having two or more isocyanate groups, the number average of the diol compound (A) The molecular weight (Mn) is in the range of 400 to 3000, the polyisocyanate (B) is a triisocyanate or higher polyisocyanate compound (b1), a diisocyanate compound (b2) obtained by adding an isocyanate compound to a polyester diol, Adhesives that are mixtures of these are known. (For example, see Patent Document 1)
It is an adhesive for laminate film of battery packaging materials, and contains polyurethane polyester polyol whose number average molecular weight of polyol component is 5000 or more and less than 14000, and the total content of urethane bond and isocyanate group is specified. It is known that the laminating adhesive within the range of 1 is excellent in molding processability and wet heat resistance (see, for example, Patent Document 2).

JP 2014-101422 A JP, 2006-196580, A

  The problem to be solved by the present invention can be applied as an adhesive for laminates in which various plastic films, metal vapor-deposited films or metal foils are appropriately combined, and has high adhesiveness, excellent appearance after lamination, It is an object of the present invention to provide a reactive adhesive that has hydrolysis resistance for maintaining adhesion over a long period of time even in the environment and further has moldability.

  The present inventors provide a reactive adhesive for reacting a hydroxyl group and an isocyanate, wherein the hydroxyl component is a polyester polyol having a polybasic acid or a derivative thereof and a polyhydric alcohol as essential raw materials, A reactive adhesive, which is a polyester polyol in which all of the acid or its derivative raw material is a polybasic acid having an aromatic ring or a derivative thereof and the number average molecular weight is in the range of 3000 to 100,000, solves the above problem. I found it.

  That is, the present invention is a polyester polyol having a polybasic acid or a derivative thereof and a polyhydric alcohol as essential raw materials, and all of the polybasic acid or a derivative raw material thereof is a polybasic acid having an aromatic ring or a derivative thereof. A polyester polyol having a number average molecular weight of 3000 to 100,000 is provided.

  The present invention also provides a reactive adhesive comprising a polyol composition (A) containing the polyester polyol described above and a polyisocyanate composition (B) as essential components.

  Moreover, this invention is a laminated body formed by laminating an adhesive layer between at least a first substrate and a second substrate, wherein the adhesive layer is the reactive adhesive described above. Provide the body.

  According to the present invention, a reactive adhesive having high adhesiveness can be obtained. The reactive adhesive according to the present invention can be applied to a laminating adhesive for a laminate in which various plastic films, metal-deposited films or metal foils are appropriately combined, and the obtained laminate has an appearance after laminating, Excellent hydrolysis resistance and long formability to maintain long-term adhesion even in open-air environments.

(Polyester polyol)
The polyester polyol of the present invention is a polyester polyol having a polybasic acid or a derivative thereof and a polyhydric alcohol as essential raw materials, all of the polybasic acid or a derivative raw material thereof having an aromatic ring or a polybasic acid thereof It is a derivative and has a number average molecular weight in the range of 3000 to 100,000 (hereinafter abbreviated as polyester polyol (A)). By using the polyester polyol as one component of the reactive adhesive, it is possible to achieve both hydrolysis resistance and molding processability for maintaining long-term adhesion even in an open-air environment.

Specific examples of the polybasic acid having an aromatic ring or a derivative thereof used as a raw material for the polyester polyol (A) in the present invention include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and these Examples thereof include anhydrides or ester-forming derivatives of dicarboxylic acids. Specific examples of the carboxylic acid anhydride include phthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Specific examples of these methyl ester compounds include dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylate. Here, the acid anhydride is a carboxylic acid anhydride having two or more carboxyl groups in one molecule. These can be used alone or in combination of two or more.
Among them, orthophthalic acid, isophthalic acid, terephthalic acid, trimellitic anhydride and its anhydride and its methyl ester compound are preferable, and isophthalic acid, terephthalic acid, trimellitic anhydride, its acid anhydride and its methyl ester compound are more preferable.

  Examples of the polyhydric alcohol used as a raw material for the polyester polyol (A) in the present invention include diols and trifunctional or higher functional polyols.

  Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, and 2,2-dimethyl-3-isopropyl-1,3- Propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1 Aliphatic diols such as 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohesane, 2,2,4-trimethyl-1,3-pentanediol;

  Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol;

  Modification obtained by ring-opening polymerization of the aliphatic diol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether Polyether diols;

  A lactone polyester polyol obtained by a polycondensation reaction between the aliphatic diol and various lactones such as lactanoid and ε-caprolactone;

  Bisphenols such as bisphenol A and bisphenol F;

  Examples thereof include alkylene oxide adducts of bisphenol obtained by adding ethylene oxide, propylene oxide and the like to bisphenols such as bisphenol A and bisphenol F.

  The trifunctional or higher functional polyol is an aliphatic polyol such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol;

  Modification obtained by ring-opening polymerization of the aliphatic polyol and various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether Polyether polyols;

  Examples thereof include lactone polyester polyols obtained by a polycondensation reaction between the aliphatic polyol and various lactones such as ε-caprolactone.

  In this invention, since the external appearance after a lamination process improves, it is preferable that a branched alkylene diol is included as a polyhydric alcohol.

  Specifically, the branched alkylene diol is an alkylene diol having a tertiary carbon atom or a quaternary carbon atom in its molecular structure. For example, 1,2,2-trimethyl-1,3-propanediol, 2, 2-dimethyl-3-isopropyl-1,3-propanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 2,2,4-trimethyl-1,3-pentanediol and the like can be mentioned, and these can be used alone or in combination of two or more. Of these, neopentyl glycol is preferred from the viewpoint of obtaining a polyester polyol (A) having particularly excellent hydrolysis resistance.

  In the present invention, the polyester polyol (A) comprises a polybasic acid or derivative thereof having an aromatic ring, the polyhydric alcohol, and a polyisocyanate as essential raw materials. It may be a polyester polyurethane polyol. Examples of the polyisocyanate used in this case include diisocyanate compounds and trifunctional or higher polyisocyanate compounds. These polyisocyanates may be used alone or in combination of two or more.

  Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene. Aliphatic diisocyanates such as range isocyanate;

  Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4′-diisocyanate, Alicyclic diisocyanates such as norbornane diisocyanate;

  1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate , 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate and the like.

  Examples of the tri- or higher functional polyisocyanate compound include an adduct type polyisocyanate compound having a urethane bond site in the molecule and a nurate type polyisocyanate compound having an isocyanurate ring structure in the molecule.

  The adduct type polyisocyanate compound having a urethane bond site in the molecule can be obtained, for example, by reacting a diisocyanate compound with a polyhydric alcohol. Examples of the diisocyanate compound used in the reaction include various diisocyanate compounds exemplified as the diisocyanate compound, and these may be used alone or in combination of two or more. Examples of the polyol compound used in the reaction include various polyol compounds exemplified as the polyhydric alcohol, polyester polyols obtained by reacting polyhydric alcohols and polybasic acids, and the like. Or two or more types may be used in combination.

  The nurate type polyisocyanate compound having an isocyanurate ring structure in the molecule is obtained, for example, by reacting a diisocyanate compound with a monoalcohol and / or a diol. Examples of the diisocyanate compound used in the reaction include various diisocyanate compounds exemplified as the diisocyanate compound, and these may be used alone or in combination of two or more. The monoalcohol used in the reaction includes hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n- Heptadecanol, n-octadecanol, n-nonadecanol, eicosanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol 2-octyldodecanol, 2-decyltetradecanol, and the like, and examples of the diol include the aliphatic diols exemplified for the polyhydric alcohol. These monoalcohols and diols may be used alone or in combination of two or more.

  The solid content hydroxyl value of the polyester polyol (A) of the present invention is excellent in the adhesive strength when used for adhesives, and the cross-linking density suitable for the adhesive layer after curing to obtain moldability, heat resistance and moist heat resistance. Therefore, the range is preferably 1.0 to 40.0 mgKOH / g, more preferably 1.0 to 30.0 mgKOH / g, and most preferably 3.0 to 25.0 mgKOH / g. .

The number average molecular weight (Mn) of the polyester polyol (A) of the present invention is preferably in the range of 3000 to 100,000, more preferably 3500 to 50000, because it is more excellent in adhesive strength when used for adhesive applications. 4000-20000 are still more preferable, and 5000-20000 are still more preferable. When the number average molecular weight is less than 3000, the appearance after lamination and molding processability may be inferior.
On the other hand, the weight average molecular weight (Mw) is preferably in the range of 5,000 to 300,000, and more preferably in the range of 10,000 to 200,000.

  In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8320GPC manufactured by Tosoh Corporation
Column: Tosoh Corporation TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

  The solid content acid value of the polyester polyol (A) of the present invention is not particularly limited, but is preferably 10.0 mgKOH / g or less. 5.0 mgKOH / g or less is preferable due to the heat and moisture resistance when used for adhesives. In addition, Preferably, it is 2.0 mgKOH / g or less. Most preferred is 1.8 mg KOH / g or less. Although it depends on the application, when the adhesive of the present invention is applied to, for example, a solar cell backsheet application to be described later, it is preferably 1.6 mgKOH / g or less. Such a polyester polyol (A) can be obtained by a production method described later. The lower limit is preferably as small as possible, but it is difficult to introduce hydroxyl groups at all terminals of the polyester polyol (A) from the viewpoint of reactivity, and a part of the terminals become carboxyl groups. For this reason, solid content oxidation is substantially 1.0 mgKOH / g or more, when the polybasic acid having an aromatic ring or a derivative thereof is used by controlling the reaction with an excess of polyhydric alcohol. Is often 0.5 mg KOH / g or more.

  The glass transition temperature of the polyester polyol (A) of the present invention is not particularly limited. For example, when an adhesive application is assumed, in order to suppress the protrusion of the adhesive at the time of dry lamination when producing a laminate- It is preferably 30 ° C or higher, more preferably -20 ° C or higher, and further preferably -10 ° C or higher. Moreover, in order to suppress the tunneling at the time of dry lamination, it is preferable that it is 80 degrees C or less, It is more preferable that it is 70 degrees C or less, It is further more preferable that it is 55 degrees C or less.

In addition, the glass transition temperature in this invention says the value measured as follows.
Using a differential scanning calorimeter (DSC-7000 manufactured by SII NanoTechnology Inc., hereinafter referred to as DSC), 5 mg of the sample was heated from room temperature to 200 ° C. at 10 ° C./min under a nitrogen stream of 30 mL / min. Then, it is cooled to −80 ° C. at 10 ° C./min. The DSC curve was measured by raising the temperature to 150 ° C. again at 10 ° C./min, a straight line extending the low temperature side baseline to the high temperature side in the measurement result observed in the second temperature raising step, and the glass transition step The point of intersection with the tangent drawn at the point where the slope of the curve of the shaped part is maximum is taken as the glass transition point, and the temperature at this time is taken as the glass transition temperature. Further, the temperature is raised to 200 ° C. at the first temperature rise, but this may be a temperature at which the polyester polyol (A) is sufficiently melted, and is adjusted appropriately when 200 ° C. is insufficient. Similarly, when the cooling temperature is not sufficient at −80 ° C. (for example, when the glass transition temperature is lower), it is adjusted appropriately.

  When the polyester polyol (A) of the present invention is used for an adhesive, the reason why an adhesive excellent in moldability, heat resistance, and moist heat resistance can be provided is not clear, but is presumed as follows. That is, since all of the polybasic acid or its derivative raw material is a polybasic acid having an aromatic ring or a derivative thereof, a rigid skeleton can be introduced into the polyester polyol, and its number average molecular weight (Mn) is 3000 to 100,000. By being in this range, the adhesive (adhesive layer) after reaction has a high cohesive force and can withstand deformation during molding. Further, it is considered that a rigid skeleton derived from a polybasic acid having an aromatic ring or a derivative thereof contributes to improvement of heat resistance and moist heat resistance.

  A preferred embodiment of the polyester polyol (A) of the present invention is a polyester polyol having a polybasic acid or a derivative thereof and a polyhydric alcohol as essential raw materials, and all of the polybasic acid or the derivative raw material is an aromatic ring. And polyester polyol (A) in which all of the polyhydric alcohols are dihydric alcohols.

  Another preferred embodiment of the polyester polyol (A) of the present invention is a polyester polyurethane polyol comprising a polybasic acid or a derivative thereof, a polyhydric alcohol, and a polyisocyanate as essential raw materials, the polybasic acid or a derivative raw material thereof. Polyester polyol (A) in which all are dibasic acids having an aromatic ring or derivatives thereof, all of the polyhydric alcohols are dihydric alcohols, and all of the polyisocyanates are diisocyanate compounds.

The polyol composition (A), which will be described later, contains a linear polyester polyol (A) made from such bifunctional compounds as raw materials, so that the polyol composition (A) and the polyisocyanate composition (B, which will be described later) ), The shrinkage of curing when forming a cured coating film is reduced, and distortion between the substrates is suppressed. For this reason, the reactive adhesive mentioned later is excellent in adhesive strength.
Moreover, the extensibility of a cured coating film improves because a polyol composition (A) contains such a polyester polyol (A). For this reason, the reactive adhesive which will be described later is particularly excellent in molding processability.

  Furthermore, since the polyol composition (A) contains such a polyester polyol (A), the viscosity is relatively low, the coating suitability is excellent, and a solvent-free adhesive as described below for a reactive adhesive, Alternatively, it can also be suitably used as a solvent-type adhesive having a high solid content concentration.

  In this specification, “all bifunctional compounds are used as raw materials” means that substantially all bifunctional compounds are used as raw materials. For example, when the raw material is a dihydric alcohol that is produced industrially and cannot be completely removed in the purification stage, and a monofunctional alcohol or a trihydric or higher polyol remains, the above bifunctional compounds are used as raw materials. It corresponds to the linear polyester polyol (A). The same applies to dibasic acids or derivatives thereof and diisocyanate compounds.

  As another preferred embodiment of the polyester polyol (A) of the present invention, a polyester polyol having a polybasic acid or a derivative thereof and a polyhydric alcohol as essential raw materials, all of the polybasic acid or the derivative raw material is aromatic. A polybasic acid having a group ring or a derivative thereof, wherein the polyhydric alcohol contains a branched alkylene diol, and the content of the branched alkylene diol in the polyhydric alcohol is 100 mol% to 5 mol% or more and 95 mol% or less. A certain polyester polyol (A) is mentioned.

  Another preferred embodiment of the polyester polyol (A) of the present invention is a polyester polyurethane polyol comprising a polybasic acid or a derivative thereof, a polyhydric alcohol, and a polyisocyanate as essential raw materials, the polybasic acid or a derivative raw material thereof. Is a polybasic acid having an aromatic ring or a derivative thereof, the polyhydric alcohol contains a branched alkylene diol, and the content of the branched alkylene diol in 100 mol% of the polyhydric alcohol is 5 mol% or more and 95 The polyester polyol (A) which is the mol% or less is mentioned.

  When the content of the branched alkylene diol is 5 mol% or more, when the polyester polyol (A) of the present invention is applied to a reactive adhesive described later, a crusty skin-like pattern is formed on the adhesive surface after dry lamination. It becomes easier to suppress deterioration of the appearance such as occurrence. In order to improve fluidity and wettability to the surface of the substrate and to secure initial adhesive strength, a polyol having a relatively small bulk and having no tertiary carbon atom or quaternary carbon atom in the molecular structure is used. It is preferable to use it. From the viewpoint of achieving both excellent appearance and initial adhesive strength, the content of the branched alkylene diol is preferably limited to 95 mol% or less.

  The polyester polyol (A) of the present invention may be applied to a plurality of embodiments among the preferred embodiments described above.

The reaction between the polybasic acid having an aromatic ring or a derivative thereof and the polyhydric alcohol, or the reaction between the polybasic acid having an aromatic ring or a derivative thereof, the polyhydric alcohol and the polyisocyanate is a known method. Just do it.
For example, the reaction between a polybasic acid having an aromatic ring or a derivative thereof and the polyhydric alcohol can be carried out by using a known and commonly used polycondensation using a polybasic acid having an aromatic ring or a derivative thereof, a polyhydric alcohol, and a polymerization catalyst. The reaction (or esterification reaction) can be performed. The reaction between the polybasic acid having an aromatic ring or a derivative thereof, the polyhydric alcohol and the polyisocyanate is performed by reacting the polybasic acid having an aromatic ring or a derivative thereof with the polyhydric alcohol according to the above method. The polyester polyol (A) of the present invention can be obtained by subjecting the polyester polyol and the polyisocyanate to a chain extension reaction in the presence of a known and commonly used urethanization catalyst as necessary.

  More specifically, the esterification reaction between a polybasic acid having an aromatic ring or a derivative thereof and a polyhydric alcohol comprises a polybasic acid having an aromatic ring or a derivative thereof, a polyhydric alcohol, and a polymerization catalyst. Charge to a reaction vessel equipped with a stirrer and rectifying equipment, and raise the temperature to about 130 ° C. at normal pressure while stirring. Then, the water produced | generated is distilled off, making it heat up at the rate of 5-10 degreeC in 1 hour at the reaction temperature of the range of 130-260 degreeC. After the esterification reaction for 4 to 12 hours, the polyester polyol (A) is obtained by accelerating the reaction by distilling off excess polyhydric alcohol while gradually increasing the degree of vacuum from normal pressure to 1 to 300 torr. Can be manufactured.

  The polymerization catalyst used for the esterification reaction is composed of at least one metal selected from the group consisting of Group 2, Group 4, Group 12, Group 13, Group 14, Group 15 of the periodic table, or a compound of the metal. A polymerization catalyst is preferred. Examples of the polymerization catalyst comprising such a metal or a metal compound thereof include metals such as Ti, Sn, Zn, Al, Zr, Mg, Hf, and Ge, compounds of these metals, more specifically titanium tetraisopropoxide, titanium Tetrabutoxide, titanium oxyacetylacetonate, stannous octoate, 2-ethylhexanetin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxygermanium Etc.

  Commercially available polymerization catalysts that can be used for the esterification reaction include: ORGATIX TA series, TC series, ZA series, ZC series, AL series, Matsushita Fine Chemical Co., Ltd., Nitto Kasei's organotin catalysts, inorganic metals Preferred are catalysts and inorganic tin compounds.

  The amount of these polymerization catalysts used is not particularly limited as long as the esterification reaction can be controlled and a good quality polyester polyol (A) can be obtained. As an example, a polybasic acid or a derivative thereof and a polyhydric alcohol are used. And 10 to 1000 ppm, preferably 20 to 800 ppm relative to the total amount. In order to suppress coloring of the polyester polyol (A), the content is more preferably 30 to 500 ppm.

  When the polyester polyol (A) used in the present invention is a linear polyester polyol (A), both ends are used. When the polyester polyol (A) has a branched structure, all ends are hydroxyl groups. It is preferable. In order to obtain such a polyester polyol (A), the reaction may be carried out using an excess amount of polyhydric alcohol with respect to the polybasic acid having an aromatic ring or a derivative thereof. The amount of the polyhydric alcohol charged relative to 1.0 mol of the polybasic acid having an aromatic ring or a derivative thereof is 1.0 mol (excluding 1.0 mol) to 1.4 mol, more preferably 1.0 mol. The mole (however, 1.0 mole is not included) to 1.2 mole may be used.

  Moreover, the polyester polyurethane polyol (A) used by this invention is obtained by chain-extending the polyester polyol (A) obtained by the method mentioned above with polyisocyanate. As a specific production method, a polyester polyol (A), a polyisocyanate, a chain extension catalyst, and a good solvent for the polyester polyol (A) and polyisocyanate used as needed are charged into a reaction vessel, 60 Stir at a reaction temperature of ~ 90 ° C. The reaction is carried out until the isocyanate group derived from the polyisocyanate to be used does not substantially remain to obtain the polyester polyurethane polyol (A) used in the present invention.

  As the chain extension catalyst, a known and publicly used catalyst used as a normal urethanization catalyst can be used. Specific examples include an organic tin compound, an organic carboxylic acid tin salt, a lead carboxylate, a bismuth carboxylate, a titanium compound, a zirconium compound, and the like, and these can be used alone or in combination. The chain extension catalyst may be used in an amount that sufficiently promotes the reaction between the polyester polyol (A) and the polyisocyanate. Specifically, the amount of the chain extension catalyst is based on the total amount of the polyester polyol (A) and the polyisocyanate. And 5.0% by mass or less is preferable. In order to suppress hydrolysis and coloring of the resin by the catalyst, 1.0% by mass or less is more preferable. Further, these chain extension catalysts may be used in consideration of the action as a curing catalyst of the polyester polyol (A) and the isocyanate composition (B) described later.

As a method for confirming the remaining amount of the isocyanate group, the presence or absence of an absorption peak observed in the vicinity of 2260 cm ^−1, which is an absorption spectrum derived from the isocyanate group, is determined by infrared absorption spectrum measurement, or the isocyanate group is quantified by titration. Is mentioned.

  Examples of the good solvent used for the production of the polyester polyurethane polyol (A) include ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, xylene and the like. You may use independently and may use 2 or more types together.

  The polyester polyol (A) of the present invention may be used in combination with other reaction raw materials as long as the effects of the present invention are not impaired.

(Reactive adhesive)
The reactive adhesive of the present invention comprises a polyol composition (A) containing the polyester polyol (A) and a polyisocyanate composition (B) as essential components.

(Polyisocyanate composition (B))
The polyisocyanate composition (B) used in the present invention contains an isocyanate compound (hereinafter referred to as isocyanate compound (B) in the present invention). The isocyanate compound (B) is not particularly limited as long as it is a compound having an isocyanate group in one molecule, and various compounds can be used. Specifically, various diisocyanate compounds described in the above-mentioned polyester polyol (A) raw material, adduct-modified diisocyanate compounds obtained by reacting various diisocyanate compounds and diol compounds, biuret-modified products, and allophanate-modified products. Alternatively, various trifunctional or higher polyisocyanate compounds can be used. These isocyanate compounds (B) may be used alone or in combination of two or more.

  Examples of the various diisocyanate compounds include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetra Aliphatic diisocyanate compounds such as methylxylylene diisocyanate;

  Cycloaliphatic diisocyanate compounds such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate;

  1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate And aromatic diisocyanate compounds such as 1,4-phenylene diisocyanate and tolylene diisocyanate. These may be used alone or in combination of two or more.

  Examples of the diol compound used as a reaction raw material for the adduct-modified polyisocyanate compound include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, and 2,2-dimethyl. -3-Isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5 -Pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, 2,2,4-trimethyl-1,3-pentanediol and the like. These may be used alone or in combination of two or more.

  The tri- or higher functional polyisocyanate compound is not particularly limited as long as it is a compound having three or more isocyanate groups in one molecule, and various compounds can be used. Specifically, isocyanurate-modified polyisocyanate compounds of various diisocyanate compounds, adduct-modified polyisocyanate compounds obtained by reacting various diisocyanate compounds with trifunctional or higher polyol compounds, and biuret-modified products of various diisocyanate compounds. And allophanate-modified products of various diisocyanate compounds. These polyisocyanate compounds may be used alone or in combination of two or more.

(Reactive adhesives and other ingredients)
The reactive adhesive of the present invention can be used in combination with other components as long as the effects of the present invention are not impaired. For example, the polyol composition (A) preferably contains a polycarbonate polyol compound in addition to the polyester polyol (A). At this time, since the blending ratio of the polyester polyol compound and the polycarbonate polyol compound is a reactive adhesive having high adhesion to various base materials and excellent moisture and heat resistance, the polyester polyol compound with respect to the total mass of both. Is preferably in the range of 30 to 99.5 mass%, and more preferably in the range of 60 to 99 mass%.

  The number average molecular weight (Mn) of the polycarbonate polyol compound is preferably in the range of 300 to 2,000 because it is a reactive adhesive having high adhesion to various base materials and excellent moisture and heat resistance. The hydroxyl value is preferably in the range of 30 to 250 mgKOH / g, and more preferably in the range of 40 to 200 mgKOH / g. The polycarbonate polyol compound is preferably a polycarbonate diol compound.

  Moreover, it is preferable that the said polyol composition (A) contains a polyoxyalkylene modified polyol compound other than the said polyester polyol compound. At this time, the blending ratio of the polyester polyol compound and the polyoxyalkylene-modified polyol compound is a reactive adhesive having high adhesion to various substrates and excellent in heat and moisture resistance. The polyester polyol compound is preferably in the range of 30 to 99.5% by mass, and preferably in the range of 60 to 99% by mass.

  The number average molecular weight (Mn) of the polyoxyalkylene-modified polyol compound is in the range of 300 to 2,000 because it is a reactive adhesive having high adhesion to various substrates and excellent heat and moisture resistance. Is preferred. The hydroxyl value is preferably in the range of 40 to 250 mgKOH / g, more preferably in the range of 50 to 200 mgKOH / g. The polyoxyalkylene-modified polyol compound is preferably a polyoxyalkylene-modified diol compound.

  The polyol composition (A) used in the present invention may contain other resin components in addition to the polyester polyol (A). When other resin components are used, it is preferably used at 50% by mass or less, more preferably 30% by mass or less, based on the total mass of the main agent. Specific examples of other resin components include epoxy resins. Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; biphenyl type epoxy resins such as biphenyl type epoxy resin and tetramethylbiphenyl type epoxy resin; dicyclopentadiene-phenol addition reaction Type epoxy resin and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use a bisphenol type epoxy resin because it is a reactive adhesive having high adhesion to various base materials and excellent moisture and heat resistance.

  The number average molecular weight (Mn) of the epoxy resin is preferably in the range of 300 to 2,000 because it is a reactive adhesive having high adhesion to various base materials and excellent moisture and heat resistance. Moreover, it is preferable that the epoxy equivalent is the range of 150-1000 g / equivalent.

  When the epoxy resin is used, the blending ratio of the polyester polyol (A) and the epoxy resin is a reactive adhesive that has high adhesion to various base materials and is excellent in heat and moisture resistance. The polyester polyol (A) is preferably in the range of 30 to 99.5% by mass, more preferably in the range of 60 to 99% by mass.

  The polyol composition (A) used in the present invention may contain a tackifier. Examples of the tackifier include rosin or rosin ester tackifier, terpene or terpene phenol tackifier, saturated hydrocarbon resin, coumarone tackifier, coumarone indene tackifier, and styrene resin. Examples include tackifiers, xylene resin tackifiers, phenol resin tackifiers, and petroleum resin tackifiers. These may be used alone or in combination of two or more. In addition, the tackifier can be obtained mainly having various softening points depending on the molecular weight, but compatibility, color tone, thermal stability, etc. when mixed with other resins constituting the polyol composition (A). In particular, rosin resins having a softening point of 80 to 160 ° C., preferably 90 to 110 ° C., and hydrogenated derivatives thereof are particularly preferable. Usually, the polyol composition (A) is used in the range of 1 to 30 parts by mass (solid content), particularly in the range of 5 to 20 parts by mass (solid content) with respect to 100 parts by mass of the solid content of the resin constituting the polyol composition (A). It is preferable.

  Examples of rosin or rosin ester include polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin, and glycerin esters, pentaerythritol ester, methyl ester, ethyl ester, butyl ester, ethylene glycol Examples thereof include esters, diethylene glycol esters, and triethylene glycol esters.

  Examples of the terpene system or terpene phenol system include a low polymerization terpene system, an α-pinene polymer, a β-pinene polymer, a terpene phenol system, an aromatic modified terpene system, and a hydrogenated terpene system.

  The petroleum resin system includes petroleum resin obtained by polymerizing a petroleum fraction having 5 carbon atoms obtained from pentene, pentadiene, isoprene, etc., indene, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene, etc. A petroleum resin obtained by polymerizing a petroleum fraction having 9 carbon atoms, a C5-C9 copolymerized petroleum resin obtained from the various monomers, and a petroleum resin obtained by hydrogenation of these, cyclopentadiene, petroleum resin obtained from dicyclopentadiene; Examples thereof include hydrogenated products of these petroleum resins; modified petroleum resins obtained by modifying these petroleum resins with maleic anhydride, maleic acid, fumaric acid, (meth) acrylic acid, phenol, and the like.

  As the phenol resin system, a condensate of phenols and formaldehyde can be used. Examples of the phenols include phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, and the like. These phenols and formaldehyde are subjected to a condensation reaction with an acid catalyst or an acid catalyst. The novolak obtained by this can be illustrated. Moreover, the rosin phenol resin etc. which are obtained by adding phenol to an rosin with an acid catalyst and heat-polymerizing can also be illustrated.

  Among these, a hydrogenated rosin system having a softening point of 80 to 160 ° C. is particularly preferable, and a hydrogenated rosin system having an acid value of 2 to 10 mgKOH / g and a hydroxyl value of 5 mgKOH / g or less is more preferable. .

  Moreover, the polyol composition (A) of the present invention may contain a ketone resin. Examples of the ketone resin include known and commonly used ones, and formaldehyde resins, cyclohexanone / formaldehyde resins, ketone aldehyde condensation resins, and the like can be suitably used.

  In the case of using the ketone resin, the blending ratio of the polyester polyol (A) and the ketone resin (both solid contents) is an adhesive having high adhesion to various substrates and excellent in heat and moisture resistance. The polyester polyol (A) is preferably in the range of 30 to 99.5% by mass and more preferably in the range of 60 to 99% by mass with respect to the total mass of

The adhesive of the present invention may contain a cyclic amide compound. When the adhesive of the present invention contains a cyclic amide compound, it may be added to the polyol composition (A) or may be added to the isocyanate composition (B). You may add when mixing a polyol composition (A) and an isocyanate composition (B).
By using the cyclic amide compound in combination, the heat and humidity resistance can be further improved. Examples of the cyclic amide resin include δ-valerolactam, ε-caprolactam, ω-hernantol lactam, η-capryllactam, β-propiolactam, and the like, which can be used alone or in combination of two or more. It is particularly preferred to use ε-caprolactam.

  When a cyclic amide compound is used, the blending amount is preferably 0.1 parts by mass or more, preferably 5 parts by mass or less, per 100 parts by mass in total of the polyol composition (A) and the isocyanate composition (B). It is preferable.

  In the adhesive of the present invention, as another preferred embodiment, known phosphoric acids or derivatives thereof can be used in combination. Thereby, the initial adhesiveness of the adhesive is further improved, and troubles such as tunneling can be solved.

  Examples of phosphoric acids or derivatives thereof used herein include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and hypophosphoric acid, such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid. Condensed phosphoric acids such as monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, phosphorous acid Monopropyl, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethylhexyl orthophosphate, diphenyl orthophosphate, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, Dibutyl phosphate, di-2-ethylhexyl phosphite Mono-, diesterified products such as diphenyl phosphite, mono- and diesterified products from condensed phosphoric acid and alcohols, for example, those obtained by adding an epoxy compound such as ethylene oxide, propylene oxide, etc. Examples thereof include epoxy phosphate esters obtained by adding the above phosphoric acid to an aliphatic or aromatic diglycidyl ether.

  One or more of the above phosphoric acids or derivatives thereof may be used. As a method of inclusion, it may be simply mixed.

  In the adhesive of the present invention, an adhesion promoter can be used. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, epoxy resins, and the like.

  Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ. Amino silanes such as aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycine Epoxy silanes such as Sidoxypropyltriethoxysilane; Vinylsilanes such as Vinyltris (β-methoxyethoxy) silane, Vinyltriethoxysilane, Vinyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane; Hexamethyldisilazane, γ-Mel Hept trimethoxysilane and the like.

  Examples of titanate coupling agents include tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. can be mentioned.

  Moreover, as an aluminum coupling agent, acetoalkoxy aluminum diisopropylate etc. can be mentioned, for example.

  In the reactive adhesive of the present invention, the mixing ratio of the polyol composition (A) and the polyisocyanate composition (B) is such that the total number of moles [OH] of hydroxyl groups contained in the polyol composition (A) and the polyisocyanate. By setting the ratio [NCO] / [OH] to the mole number [NCO] of the isocyanate groups contained in the composition (B) in the range of 0.5 to 30, a two-component adhesive having excellent reactivity is obtained. . Especially, it is preferable that [NCO] / [OH] is in the range of 0.8-20.

The reactive adhesive of the present invention may be in a solvent type or a solventless type. The “solvent” in the present invention refers to a highly soluble organic solvent capable of dissolving the polyol composition (A) or polyisocyanate composition (B) used in the present invention. "Solvent" refers to a form that does not contain these highly soluble organic solvents, particularly ethyl acetate or methyl ethyl ketone. Specifically, for example, esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene , Halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like. Of these, it is usually preferred to use ethyl acetate or methyl ethyl ketone alone or in combination.
In the case of a solvent type, the solvent is used as a reaction medium during the production of the polyol composition (A) or the polyisocyanate composition (B), and may further be used as a diluent during coating.
When the reactive adhesive of the present invention is a solvent type, the viscosity can be reduced by solvent dilution. Therefore, it can be used even if the polyol composition (A) or polyisocyanate composition (B) to be used has a slightly high viscosity. It is. On the other hand, in the case of the solventless type, it is important to have a low viscosity due to the characteristic of lowering the viscosity by heating, and as a means for lowering the viscosity, the polyisocyanate composition (B) has reduced the aromatic concentration contributing to the viscosity. Things are often used.

  The reactive adhesive of the present invention includes an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, an antifogging agent, a metal deactivator, and a peroxide. Various additives such as a physical decomposition agent, a flame retardant, a flame retardant, a reinforcing agent, a rust preventive, a fluorescent whitening agent, an inorganic heat absorber, and a dehydrating agent may be contained.

  The reactive adhesive of the present invention can be used for bonding various substances. The target of bonding is not only plastic film, metal vapor-deposited film or metal foil but also various materials such as paper, wood and plastic molded products. It can be suitably used as a reactive adhesive for materials.

  What is necessary is just to select the various components mentioned above suitably according to the adhesion use or adhesion object. For example, the reactive adhesive of the present invention can be suitably used as an adhesive for solar battery backsheet described later. At this time, it is preferable to use an epoxy resin, a polycarbonate polyol compound, a tackifier, and a cyclic amide compound in combination so that adhesiveness and hydrolysis resistance can be improved.

(Laminate)
The laminate of the present invention is a laminate obtained by laminating an adhesive layer between at least a first substrate and a second substrate, and the reactive adhesive of the present invention described in detail above as the adhesive layer. It is a laminate using an agent. Specifically, the adhesive of the present invention may be used as an adhesive for adhering at least two substrates. The laminated body may have two or more base materials. In this case, for example, the first base material / adhesive layer / second base material / adhesive layer / third base material... In addition, the adhesive layer also increases. In the present invention, the reactive adhesive of the present invention may be used for at least one adhesive layer, and may be used for all adhesive layers, and is not particularly limited.

The laminate is obtained by applying at least a first substrate, then laminating a second substrate on the application surface, and curing the adhesive layer.
Specifically, the reactive adhesive of the present invention is applied to the first substrate by, for example, a roll coater coating method, and then a drying process is performed for a solvent type, and a drying process is performed for a solventless type. The method of bonding another base material without passing through is mentioned. The coating condition is preferably about 500 to 2500 mPa · s in a state where it is heated to about 25 ° C. to 120 ° C. in a normal roll coater. The coating amount is preferably 0.5 to 50 g / m ² (dry mass), more preferably about 1.5 to 20 g / m ² (dry mass).

When the reactive adhesive of the present invention is used, the adhesive is cured in 6 to 168 hours at room temperature or under heating after lamination, and expresses practical physical properties.
Usually, the adhesive curing temperature is generally in the range of 15 to 60 degrees.

  Examples of the substrate include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film) and polypropylene that are widely used for food applications. Examples thereof include polyolefin films such as films (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyvinyl alcohol films, ethylene-vinyl alcohol copolymer films, and the like. These may be subjected to stretching treatment. As the stretching treatment method, it is common to perform simultaneous biaxial stretching or sequential biaxial stretching after the resin is melt-extruded by extrusion film forming method or the like to form a sheet. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used. Furthermore, a film obtained by laminating a deposition layer of a metal such as aluminum or stainless steel or a metal oxide such as silica or alumina on the film for lamination may be used.

Polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, polyvinyl alcohol, ABS resin, norbornene resin, cyclic olefin resin, polyimide, which are widely used for industrial applications Examples of the film include a resin, a polyvinyl fluoride resin, a polyvinylidene fluoride resin, and an ethylene-vinyl acetate copolymer.
In addition to films, porous substrates such as paper, paperboard, coated paper, wood, and leather can be used. In this case, the adhesive penetrates the substrate, so the amount of adhesive applied is large. There is a need to.

  The laminate obtained in this way can be used in various applications, such as packaging materials for foods and pharmaceuticals, daily necessities, barrier materials, roofing materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting. Protective materials, automotive parts, signboards, stickers, etc. for outdoor industrial use, decorative sheets used for simultaneous injection molding methods, liquid detergent for washing, liquid detergent for kitchen, liquid detergent for bath, liquid soap for bath, liquid shampoo It can be suitably used as a packaging material such as a liquid conditioner.

(Solar cell back sheet)
As described above, the reactive adhesive of the present invention can be suitably used as a solar battery back sheet adhesive used for producing a solar battery back sheet which is a member of a solar battery. Generally, a solar cell is a photovoltaic cell such as a silicon power generation element using an EVA (ethylene-vinyl acetate copolymer) film between a glass substrate as a light-receiving surface side transparent protective member and a back surface side protective member (back sheet). It is the structure which sealed. These constituent materials are laminated in the order of the light-receiving side transparent protective member, the sheet-shaped sealing resin disposed on the front surface side, the solar cell, the sheet-shaped sealing resin disposed on the back surface side, and the back sheet, A solar cell module is formed by heating and vacuum lamination.

  The back sheet requires properties such as mechanical strength, weather resistance, heat resistance, heat and humidity resistance, and light resistance, and is widely used for fluorine resin films, metal foils, polypropylene films, polyethylene terephthalate films (hereinafter referred to as PET films), etc. Often, a laminate in which a plastic film is bonded with an adhesive is used. The adhesive used at this time is required to have high adhesion to these various films, heat and humidity resistance to maintain long-term adhesion even in an open-air environment, and an excellent appearance of the laminate.

  The solar cell backsheet of the present invention is an example of the above-described laminate of the present invention, and is disposed between the first base material, the second base material, and the first base material and the second base material. And an adhesive layer that bonds the first base material and the second base material together. This adhesive layer is a cured product (reaction product) of the adhesive of the present invention described above. Furthermore, other base materials may be included. When the solar cell backsheet of the present invention further includes another substrate in addition to the first substrate and the second substrate, the first substrate or the second substrate and the other substrate are: It may be bonded using the adhesive of this invention, and it may not be so.

  Examples of the first base material, the second base material, and the other base material include paper, olefin resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, Metals such as poly (meth) acrylic resins, carbonate resins, polyamide resins, polyimide resins, polyphenylene ether resins, synthetic resin films obtained from polyphenylene sulfide resins and polyester resins, copper foil, and aluminum foil A foil or the like can be used.

  One of the first substrate and the second substrate is polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene. Preferably, the other is a metal foil or a PET film. In order to improve the adhesion between the substrate and the cured coating film, a surface treatment may be performed on the surface of the substrate on which the cured coating film is formed. Examples of the surface treatment include corona treatment, plasma treatment, ozone treatment, flame treatment, and radiation treatment.

The solar cell backsheet of the present invention is obtained by applying the adhesive of the present invention to one of the first substrate and the second substrate, then laminating the other, and curing the adhesive. When the adhesive is a solvent type, after applying the adhesive, the other substrate is laminated after a drying process. In the case of the solventless type, there is no need to provide a drying step.
As a coating method, a gravure coater method, a micro gravure coater method, a reverse coater method, a bar coater method, a roll coater method, a die coater method, or the like can be used.

When coating, the viscosity of the adhesive is adjusted to a viscosity suitable for coating. For example, when applying using a roll coater, the adhesive preferably has a viscosity of about 500 to 2500 mPa · s while being heated to about 25 ° C. to 120 ° C. The coating amount of the adhesive is preferably 5 to 15 g / ^{m 2} (dry weight), and more preferably 5 to 10 g / ^{m 2} (dry weight).

  It is preferable to provide an aging process after lamination. The adhesive cures at about 15 to 60 ° C. and about 6 to 168 hours, and exhibits practical physical properties.

  In order to improve the adhesiveness between the backsheet and the sealing resin described later, an easy-adhesive layer in which an easy-adhesive is applied and cured may be provided on the surface of the solar battery backsheet that contacts the sealing resin. Or in order to improve the weather resistance of a back sheet, you may provide the coating layer which apply | coated and hardened the coating agent for protection on the surface exposed outside.

(Solar cell module)
The solar cell module of the present invention includes a transparent protective member, a solar cell, a sealing resin that covers the entire surface of the solar cell, and a back sheet.
For example, a solar cell is formed by laminating a transparent electrode layer, an optical semiconductor layer, and a back electrode layer on a substrate, separated by separation grooves so as to form a plurality of photoelectric conversion cells, and the photoelectric conversion cells are electrically connected. Thus, the integrated solar cell elements are connected in series. As the photoelectric conversion layer in the optical semiconductor layer, silicon, thin film polycrystalline silicon, or the like can be used. Furthermore, an electrical output can be taken out of the module from the solar cell.

  As the resin used as the sealing resin, EVA, PVB (polyvinyl butyral), PIB (polyisobutylene), olefin resin (especially graft-modified polyethylene resin), ionomer resin, silicon resin, etc. can be used, and EVA is used. It is preferable. As EVA, the content of vinyl acetate is 10 to 40% by mass, and EVA is preferably crosslinked by heat or light from the viewpoint of ensuring the heat resistance and physical strength of the solar cell module.

  When performing thermal crosslinking of EVA, an organic peroxide is usually used, and one that decomposes at a temperature of 70 ° C. or higher to generate radicals is used. Usually, those having a decomposition temperature of 50 ° C. or more with a half-life of 10 hours are used, and 2,5-dimethylhexane-2,5-dihydroxyperoxide, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α '-Bis (t-butylperoxyisopropyl) benzene, n-butyl-4,4-bis- (t-butylperoxy) valerate, t-butylperoxybenzoate, benzoyl peroxide and the like are used.

  In the case of photocuring, a photosensitizer is used, and hydrogen abstraction type (bimolecular reaction type) such as benzophenone, methyl orthobenzoylbenzoate, 4-benzoyl-4′-methyldiphenyl sulfide, isopropylthioxanthone, etc. As the internal cleavage type initiator, α-hydroxyalkylphenone type such as benzoin ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl, etc. Phenyl ketone, alkylphenyl glyoxylate, diethoxyacetophenone and the like can be used. Further, as α-aminoalkylphenone type, 2-methyl-1- [4 (methylthio) phenyl] -2-morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -butanone-1 and the like, and acylphosphine oxide and the like are also used.

  A silane coupling agent is also blended in consideration of adhesion to the glass plate constituting the solar cell module, and vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, Vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropylmethoxysilane, vinyltrichlorosilane , Γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and the like.

  Furthermore, an epoxy group-containing compound may be blended for the purpose of promoting adhesion and curing. Examples of the epoxy group-containing compound include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylic glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester , Glycidyl methacrylate, butyl glycidyl ether, etc., oligomers containing epoxy groups with molecular weights of hundreds to thousands, and polymers with weight average molecular weights of thousands to hundreds of thousands. Even if that case there.

  (Meth) acrylic acid derivatives are added with an acryloxy group, methacryloxy group or allyl group-containing compound for the purpose of improving the cross-linking, adhesion, mechanical strength, heat resistance, moist heat resistance, weather resistance, etc. of the sealing resin For example, alkyl esters and amides thereof are the most common. In this case, as the alkyl group, in addition to an alkyl group such as methyl, ethyl, dodecyl, stearyl, lauryl, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, A 3-chloro-2-hydroxypropyl group and the like can be mentioned. Further, esters of (meth) acrylic acid and polyfunctional alcohols such as ethylene glycol, triethylene glycol, polyethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like are also used. A typical amide is acrylamide. Further, as the allyl group-containing compound, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, diallyl maleate and the like are blended.

  Furthermore, an inorganic compound for imparting flame retardancy, an ultraviolet absorber for imparting weather resistance, and an antioxidant for preventing oxidative degradation are variously blended. That is, EVA which comprises a solar cell module is a resin composition which mix | blended various additives in order to satisfy | fill the function requested | required as a solar cell module.

As an example of a method of integrating as a solar cell module, a vacuum laminating method can be given. This method is, for example, a solar cell in which a transparent protective member, a sealing resin on the transparent protective member side, and a wiring are provided on a dummy glass or a metal plate on a heating plate of a vacuum laminating apparatus heated to 100 to 150 ° C. The cell, the back sheet side sealing resin, and the back sheet are laminated in this order and allowed to stand. Thereafter, the vacuum laminating apparatus is closed and pressure reduction is started. After this pressure reduction state is maintained for 3 to 10 minutes, air is introduced from the air supply / exhaust pipe, and the rubber diaphragm is pressed against the solar cell backsheet by the pressure difference. Pressurize. Although depending on the type of sealing resin, the heated vacuum laminating step is completed by holding this state for 10 to 40 minutes.
The vacuum laminating method is merely an example, and a known laminating method can be applied.
By using the back sheet of the present invention, the durability of the solar cell module can be improved.

  Hereinafter, the present invention will be described in more detail with reference to specific synthesis examples and examples, but the present invention is not limited to these examples. In the following examples, “part” and “%” represent “part by mass” and “% by mass”, respectively, unless otherwise specified.

(Molecular weight measurement method)
In Examples of the present application, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) under the following conditions.
Measuring device: HLC-8320GPC manufactured by Tosoh Corporation
Column: Tosoh Corporation TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

(Acid value measurement method)
In this example, the acid value was measured by the following method.
A sample (5.0 g) was precisely weighed, 30 mL of tetrahydrofuran was added and dissolved, and titrated with a 0.1N potassium hydroxide solution (methanolic). Phenolphthalein was used as an indicator. The measurement result was converted to the amount of potassium hydroxide required to neutralize 1 g of the sample, and the unit was mgKOH / g. In addition, when the sample contained the organic solvent, the acid value measured directly by the above-mentioned measuring method was converted into the solid content acid value using the nonvolatile content value of the solution.

(Method for measuring hydroxyl value)
In this example, the hydroxyl value was measured by the following method.
4.0 g of a sample was precisely weighed, 25 mL of an acetylating agent consisting of acetic anhydride / pyridine (volume ratio 1/19) was added, sealed, and heated at 100 ° C. for 1 hour. After acetylation, 10 mL of ion exchange water and 100 mL of tetrahydrofuran were added, and titrated with a 0.5N potassium hydroxide solution (alcoholic). Phenolphthalein was used as an indicator. The measurement result was converted to the amount of potassium hydroxide required to neutralize acetic acid produced when 1 g of the sample was acetylated, and the unit was mgKOH / g. When the sample contained an organic solvent, the hydroxyl value directly measured by the above measurement method was converted to the solid content hydroxyl value using the nonvolatile content value of the solution.

(Glass transition temperature measurement method)
Using a DSC, 5 mg of a sample was heated from room temperature to 200 ° C. at 10 ° C./min under a nitrogen stream of 30 mL / min, cooled to −80 ° C. at 10 ° C./min, and again to 150 ° C. at 10 ° C. / The DSC curve was measured by raising the temperature in min. In the measurement results observed in the second heating step, a straight line with the base line on the low temperature side extended to the high temperature side, and a tangent line drawn at the point where the slope of the stepped portion of the glass transition becomes maximum The crossing point of was the glass transition point, and the temperature at this time was the glass transition temperature.

Production Example 1 Synthesis of Polyester Polyol (A-1) In a flask having a stirrer, a temperature sensor, and a rectifying tube, 790.8 parts by weight of isophthalic acid (Mitsubishi Gas Chemical Co., Ltd.), terephthalic acid (Mitsui Chemicals, Inc.) (Company) 339.4 parts by weight, trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.) 20.0 parts, 1,6-hexanediol (BASF) 738.0 parts by weight, neopentyl glycol (Mitsubishi Gas) 107.4 parts by weight of Chemical Co., Ltd.) and 4.0 parts by weight of an organic titanium compound (“Orgatechs TC-100” manufactured by Matsumoto Fine Chemical Co., Ltd.) are produced by flowing dry nitrogen into the flask while stirring. The temperature was raised to 240 ° C. while distilling off water. Thereafter, the esterification reaction was performed while increasing the degree of vacuum to 30 torr, and the reaction was stopped when the resin acid value became 1.50 mgKOH / g or less. The obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 58%, the number average molecular weight (Mn) is 7,000, the weight average molecular weight (Mw) is 23,500, and the resin hydroxyl value (in terms of solid content) is A polyester polyol (A-1) having 22.4 mgKOH / g, a resin acid value (in terms of solid content) of 1.26 mgKOH / g, and a glass transition temperature (Tg) of 2.1 ° C. was obtained.

(Production Example 2) Synthesis of Polyester Polyol (A-2) In a flask having a stirring rod, a temperature sensor, and a condenser, 75.9 parts by weight of polyester polyol (A-1), 22.9 parts by weight of ethyl acetate, hexa 1.1 parts by weight of methylene diisocyanate (“Desmodur H” manufactured by Sumika Covestrourethane Co., Ltd.) and 0.01 part by weight of an organic tin compound (“Neostan U-130” manufactured by Nitto Kasei Co., Ltd.) were added to dry nitrogen. Was allowed to flow into the flask and heated to 75 to 78 ° C. with stirring to conduct a chain extension reaction. The reaction was stopped when the isocyanate weight% was 0.05% or less, and diluted with methyl ethyl ketone to a resin solid content of 35%. The number average molecular weight (Mn) was 14,500, and the weight average molecular weight ( Polyester having a Mw) of 117,500, a resin hydroxyl value (in terms of solid content) of 5.2 mg KOH / g, a resin acid value (in terms of solid content) of 1.75 mg KOH / g, and a glass transition temperature (Tg) of 10.0 ° C. A polyol (A-2) was obtained.

Production Example 3 Synthesis of Polyester Polyol (A-3) In a flask having a stirring bar, a temperature sensor, and a condenser, 75.4 parts by weight of the polyester polyol (A-1), 23.2 parts by weight of ethyl acetate, isophorone 1.4 parts by weight of diisocyanate (manufactured by Evonic) and 0.01 part by weight of an organic tin compound were charged, dry nitrogen was introduced into the flask, and heated to 75 to 78 ° C. while stirring to carry out a chain extension reaction. The reaction was stopped when the isocyanate weight% became 0.05% or less, and diluted with methyl ethyl ketone to a resin solid content of 35%. The number average molecular weight (Mn) was 13,900, and the weight average molecular weight ( Polyester having a Mw) of 101,700, a resin hydroxyl value (in terms of solid content) of 4.9 mgKOH / g, a resin acid value (in terms of solid content) of 1.57 mgKOH / g, and a glass transition temperature (Tg) of 12.8 ° C. A polyol (A-3) was obtained.

(Production Example 4) Synthesis of Polyester Polyol (A-4) In a flask having a stirring bar, a temperature sensor, and a condenser, 74.9 parts by weight of the polyester polyol (A-1), 23.4 parts by weight of ethyl acetate, 4 , 4-Diphenylmethane diisocyanate (“rubranate MT” manufactured by Tosoh Corporation) is charged with 1.7 parts by weight and 0.01 part by weight of an organic tin compound, and dry nitrogen is introduced into the flask and heated to 75 to 78 ° C. while stirring. A chain extension reaction was performed. When the isocyanate weight% became 0.05% or less, the reaction was stopped and diluted with methyl ethyl ketone to a resin solid content of 35%. The number average molecular weight (Mn) was 12,000, the weight average molecular weight ( Polyester polyol (Mw) of 168,900, hydroxyl value (in terms of solid content) of 6.8 mg KOH / g, acid value (in terms of solid content) of 1.34 mg KOH / g, and glass transition temperature (Tg) of 14.9 ° C. A-4) was obtained.

(Production Example 5) Synthesis of polyester polyol (A-5) In a flask having a stirring bar, a temperature sensor, and a condenser, 75.8 parts by weight of the polyester polyol (A-1), 23.0 parts by weight of ethyl acetate, 1.2 parts by weight of diisocyanate (“Cosmonate T-80” manufactured by Tosoh Corporation) and 0.01 part by weight of an organic tin compound are charged, and dry nitrogen is introduced into the flask and heated to 75 to 78 ° C. while stirring. A chain extension reaction was performed. When the isocyanate weight% became 0.05% or less, the reaction was stopped, diluted with methyl ethyl ketone to a resin solid content of 35%, the number average molecular weight (Mn) was 8,900, the weight average molecular weight ( Polyester polyol (Mw) of 120,000, hydroxyl value (in terms of solid content) of 6.8 mgKOH / g, acid value (in terms of solid content) of 1.34 mgKOH / g, and glass transition temperature (Tg) of 15.4 ° C. A-4) was obtained.

Production Example 6 Synthesis of Polyester Polyol (AH-1) In a flask having a stirrer, a temperature sensor, and a rectifying tube, 310 parts by weight of sebacic acid, 420 parts by weight of isophthalic acid, 212 parts by weight of phthalic anhydride, and trimellitic anhydride Charge 11.1 parts by weight of acid, 610 parts by weight of neopentyl glycol, and 0.7 parts by weight of an organic titanium compound, let dry nitrogen flow into the flask while stirring, and raise the temperature to 240 ° C. while distilling off the generated water. did. Thereafter, the esterification reaction was performed while increasing the degree of vacuum to 30 torr, and the reaction was stopped when the acid value became 2.00 mgKOH / g or less. After cooling to 150 ° C., the resin solids content 62. When diluted to 0%, the number average molecular weight (Mn) is 6,000, the weight average molecular weight (Mw) is 17,000, the resin hydroxyl value (in terms of solid content) is 14.6 mgKOH / g, the resin acid value A polyester polyol (AH-1) having a solid content equivalent of 1.94 mg KOH / g and a glass transition temperature (Tg) of 6.0 ° C. was obtained.

(Adhesive formulation 1)
In accordance with the formulation shown in Tables 1 to 3, the polyol composition and the polyisocyanate composition were mixed together to prepare a reactive adhesive. In addition, the compounding quantity in a table | surface is a solid content mass part.

  However, [NCO] / [OH] in the table is the ratio [NCO] of the number of moles [NCO] of isocyanate groups contained in the polyisocyanate composition and the number of moles [OH] of hydroxyl groups contained in the polyol composition. ] / [OH].

(Evaluation method 1)
(Evaluation 1-1: Laminate appearance)
A 125 μm-thick PET film (“Lumirror X10S” manufactured by Toray Industries, Inc.) is used as a base material, and the reactive adhesive is applied to 4 to 6 g / m ² (dry mass), and a 30 μm-thick film is used as a bonding film. A white polyvinylidene fluoride film (“Kyner” manufactured by Arkema) was laminated to obtain an evaluation sample. The evaluation sample was subjected to evaluation after aging at 40 ° C. for 72 hours.
With the evaluation sample described above, the laminate appearance was visually evaluated from the white polyvinylidene fluoride film side.
○: The film surface is smooth △: Some craters (dents) exist on the film surface ×: Many craters (dents) exist on the film surface

(Evaluation 1-2: Adhesive strength)
Using a 30 μm thick aluminum foil (“1N30” manufactured by Toyo Aluminum Co., Ltd.) as a base material, the above reactive adhesive is applied to 4 to 6 g / m ² (dry mass) on the mat surface side of the aluminum foil, As a bonding film, a 70 μm thick CPP film (“ZK-93KM” manufactured by Toray Film Processing Co., Ltd.) was laminated to obtain an evaluation sample. The evaluation sample was subjected to evaluation after aging at 40 ° C. for 72 hours.
With the above-described evaluation sample, the strength (N / 15 mm, 180 ° peeling) at a peeling speed of 100 mm / min was evaluated as an adhesive strength with a tensile testing machine (“Autograph AGS-J” manufactured by Shimadzu Corporation).

(Evaluation 1-3: Moldability)
Using a 30 μm thick aluminum foil (“1N30” manufactured by Toyo Aluminum Co., Ltd.) as a base material, the above reactive adhesive is applied to 4 to 6 g / m ² (dry mass) on the mat surface side of the aluminum foil, A 25 μm thick stretched polyamide film (“Emblem ONBC” manufactured by Unitika Co., Ltd.) was laminated as a bonding film. Next, reactive adhesive was applied to the glossy surface of the aluminum foil at 4 to 6 g / m ² (dry mass). After coating, a stretched polyamide film was laminated in the same manner to obtain an evaluation sample, which was aged at 40 ° C. for 72 hours, and then cut into a strip of 1.5 cm width × 23 cm length for evaluation. did.
The above-described evaluation sample is held in a tensile tester (A & D Co., Ltd. “Tensilon Universal Testing Machine RTG-1210”) so that the distance between chucks becomes 10 cm, and the distance between chucks at a moving speed of 500 mm / min. The sample was evaluated until it reached 12 cm.
The appearance was visually determined from the polyamide film side of the molded evaluation sample.
○: The film surface is smooth Δ: A patchy pattern is present on the film surface, or a micro crack is generated at the end of the evaluation sample ×: The polyamide film is peeled off or the evaluation sample is broken

(Evaluation 1-4: Hydrolysis resistance of adhesive)
A PTFE film (“NITOFLON Films No. 900UL” manufactured by Nitto Denko Corporation) was used as a base material, and the above-mentioned reactive adhesive was coated with an applicator. After evaporating the solvent, the sample was aged at 40 ° C. for 72 hours to obtain an evaluation sample.
The evaluation sample was kept at 121 ° C. and 100% RH for 48 hours in a highly accelerated life test apparatus (“EMS-221M” manufactured by ESPEC Corporation) and subjected to wet heat treatment.
By the method shown below, the gel fraction of the adhesive after the initial (after aging) and after the wet heat treatment is measured, the retention of the gel fraction after the wet heat treatment with respect to the initial gel fraction is calculated, and reactive adhesion The hydrolysis resistance of the agent was evaluated.

A: Retention rate is 80% or more (particularly excellent in practical use)
A: Retention rate is 50% or more and less than 80% (practically excellent)
Δ: Retention rate of 20% to less than 50% (practical range)
X: Retention rate 0% or more and less than 20%

The gel fraction of the reactive adhesive was calculated by the measurement method described below.
About 0.2 g of the adhesive layer was collected from the evaluation sample and placed in a porous tea pack to prepare a measurement sample. Next, the mass of the measurement sample was measured and used as the mass before immersion.
Subsequently, the measurement sample was put in a 70 ml container filled with methyl ethyl ketone and stored at 23 ° C. for 24 hours. Thereafter, the measurement sample was taken out from the container and dried in a dryer at 120 ° C. for 1 hour to remove methyl ethyl ketone. Next, the mass of the measurement sample from which methyl ethyl ketone was removed was measured and taken as the mass after immersion.
And the gel fraction of the adhesive was computed from the following formula.

  (In the above formula, A is the mass after immersion, B is the mass of the tea pack, and C is the mass before immersion.)

The results are shown in Tables 1-3.

Abbreviations in each table are as follows.
Polyisocyanate B-1: “Sumijour N3300” manufactured by Sumika Covestro Urethane Co., Ltd.
Isocyanurate of hexamethylene diisocyanate
NCO group content 21.8%, solid content 100% by mass
Polyisocyanate B-2: “Death Module L75” manufactured by Sumika Covestro Urethane Co., Ltd.
Tolylene diisocyanate adduct, 13% NCO content
Ethyl acetate cut product, solid content 75% by mass
Epoxy resin A: “Epiclon 860-80SE” manufactured by DIC Corporation
Bisphenol A type epoxy resin epoxy equivalent 250g / eq,
Ethyl acetate cut product, solid content 80% by mass

  As a result, it is clear that the reactive adhesive using the polyester polyol (A) of the present invention is excellent in all of laminate appearance, adhesive strength, molding processability, and hydrolysis resistance.

(Adhesive formulation 2)
The suitability as an adhesive for a solar battery backsheet was evaluated as follows using the polyester polyol synthesized above.
(Example 2-1)
Polyester polyol (A-1) in 100 parts, polyisocyanate (B-1) nurate type hexamethylene diisocyanate (“Sumijoule N3300” manufactured by Sumitomo Covestrourethane Co., Ltd.), nonvolatile content of 35 %, Ethyl acetate was added and stirred well to produce an adhesive for solar cell backsheet.

(Example 2-2) to (Example 2-4)
An adhesive for a solar battery back sheet was produced in the same manner as in Example 2-1, with the formulation shown in Table 4.
(Comparative Example 2-1)
An adhesive for a solar battery back sheet was produced in the same manner as in Example 2-1, with the formulation shown in Table 5.
In addition, the compounding quantity in a table | surface is solid content mass ratio.

(Evaluation method 2)
(Evaluation 2-1: Laminate appearance)
After using 125 μm thick PET film (“Lumirror X10S” manufactured by Toray Industries, Inc.) as a base material, the above solar cell backsheet adhesive was applied to 10 g / m ² (dry mass) on the PET film, and the solvent was volatilized. A white polyvinylidene fluoride film (“Kyner” manufactured by Arkema) having a thickness of 30 μm was laminated as a bonding film. Then, it aged at 40 degreeC for 72 hours, and obtained the evaluation sample.
With the evaluation sample described above, the laminate appearance was visually evaluated from the white polyvinylidene fluoride film side.

○: The film surface is smooth △: Some craters (dents) exist on the film surface ×: Many craters (dents) exist on the film surface

(Evaluation 2-2: Adhesive strength)
After using 125 μm thick PET film (“Lumirror X10S” manufactured by Toray Industries, Inc.) as a base material, the above solar cell backsheet adhesive was applied to 10 g / m ² (dry mass) on the PET film, and the solvent was volatilized. A white polyvinylidene fluoride film (“Kyner” manufactured by Arkema) having a thickness of 30 μm was laminated as a bonding film. Then, it aged at 40 degreeC for 72 hours, and obtained the evaluation sample.
The evaluation sample was evaluated with a tensile tester (“Autograph AGS-J” manufactured by Shimadzu Corporation) as an adhesive strength at a peel rate of 100 mm / min (N / 15 mm, 180 ° peel). In the initial stage (after aging) and in an advanced accelerated life test apparatus (“EMS-221M” manufactured by ESPEC Corporation), the adhesive strength was measured after holding at 121 ° C. and 100% RH for 48 hours and performing wet heat treatment.

(Evaluation 2-3: Hydrolysis resistance of adhesive)
A PTFE film (“NITOFLON Films No. 900UL” manufactured by Nitto Denko Corporation) was used as a base material, and the above-mentioned adhesive for solar battery backsheet was coated with an applicator. After evaporating the solvent, the sample was aged at 40 ° C. for 72 hours to obtain an evaluation sample.
The evaluation sample was kept at 121 ° C. and 100% RH for 48 hours in the highly accelerated life test apparatus and subjected to wet heat treatment.
The gel fraction of the adhesive after the initial (after aging) and after the wet heat treatment was measured by the method shown below, and the retention rate of the gel fraction after the wet heat treatment relative to the initial gel fraction was calculated. The hydrolysis resistance of the sheet adhesive was evaluated.

A: Retention rate is 80% or more (particularly excellent in practical use)
A: Retention rate is 50% or more and less than 80% (practically excellent)
Δ: Retention rate of 20% to less than 50% (practical range)
X: Retention rate 0% or more and less than 20%

  The gel fraction of the solar cell backsheet adhesive was calculated by the measurement method described below. About 0.2 g of the adhesive layer was collected from the evaluation sample and placed in a porous tea pack to prepare a measurement sample. Next, the mass of the measurement sample was measured and used as the mass before immersion. Subsequently, the measurement sample was put in a 70 ml container filled with methyl ethyl ketone and stored at 23 ° C. for 24 hours. Thereafter, the measurement sample was taken out from the container and dried in a dryer at 120 ° C. for 1 hour to remove methyl ethyl ketone. Next, the mass of the measurement sample from which methyl ethyl ketone was removed was measured and taken as the mass after immersion. And the gel fraction of the adhesive was computed from the following formula.

（上記の式において、Ａは浸漬後質量であり、Ｂはお茶パックの質量であり、Ｃは浸漬前質量である。）

(In the above formula, A is the mass after immersion, B is the mass of the tea pack, and C is the mass before immersion.)

  The results are shown in Tables 4 and 5.

  As is clear from the examples and comparative examples, the adhesive for solar battery backsheet of the present invention is excellent in laminate appearance, adhesive strength, and hydrolysis resistance.

(Production Example 5) Synthesis of polyester polyol (A-5) In a flask having a stirring bar, a temperature sensor, and a condenser, 75.8 parts by weight of the polyester polyol (A-1), 23.0 parts by weight of ethyl acetate, 1.2 parts by weight of diisocyanate (“Cosmonate T-80” manufactured by Tosoh Corporation) and 0.01 part by weight of an organic tin compound are charged, and dry nitrogen is introduced into the flask and heated to 75 to 78 ° C. while stirring. A chain extension reaction was performed. When the isocyanate weight% became 0.05% or less, the reaction was stopped, diluted with methyl ethyl ketone to a resin solid content of 35%, the number average molecular weight (Mn) was 8,900, the weight average molecular weight ( Polyester polyol ( Mw) of 120,000, hydroxyl value (in terms of solid content) of 6.8 mgKOH / g, acid value (in terms of solid content) of 1.34 mgKOH / g, and glass transition temperature (Tg) of 15.4 ° C. A-5) was obtained.

Claims (9)

  Polyester acid comprising polybasic acid or derivative thereof and polyhydric alcohol as essential raw materials, wherein all of the polybasic acid or derivative raw material are polybasic acid or derivative thereof having an aromatic ring, and number average molecular weight Is a polyester polyol characterized by having a range of 3000 to 100,000.   The polyester polyol according to claim 1, wherein the polyhydric alcohol raw material contains a branched alkylene diol.   The polyester polyol according to claim 1 or 2, wherein the polyester polyol comprises a polybasic acid or a derivative thereof, a polyhydric alcohol, and a polyisocyanate as essential raw materials.   The polyester polyol according to any one of claims 1 to 3, wherein the polyester polyol is a reaction product of a polyester polyol and a polyisocyanate containing a polybasic acid or a derivative thereof and a polyhydric alcohol as essential raw materials.   A reactive adhesive comprising a polyol composition (A) containing the polyester polyol according to claim 1 and a polyisocyanate composition (B) as essential components.   The adhesive for solar cell backsheets in any one of Claims 1-5.   It is a laminated body formed by laminating an adhesive layer between at least a first base material and a second base material, and the adhesive layer is the reactive adhesive according to claim 5. Laminated body.   A solar battery back sheet comprising the laminate according to claim 7.   The solar cell module which bonded the solar cell backsheet and solar cell of Claim 8 through the sealing material.