KR20190011230A - Adhesive for laminated sheets - Google Patents

Abstract

(A) at least one selected from an acrylic polyol, (B) a carboxylic acid and a carboxylic acid anhydride; And (C) an isocyanate compound, wherein (B) is mixed in an amount of 0.01 to 8.0 parts by weight per 100 parts by weight of the total of (A) - (C), wherein (A) An adhesive which is obtainable by polymerizing a polymerizable monomer and has a weight average molecular weight of 10,000 to 100,000 and a hydroxyl value of 0.5 to 40 mgKOH / g is disclosed. The adhesive for the laminated sheet is excellent in coating properties, peeling strength after curing, and hydrolysis resistance for a long time at a high temperature when the laminated sheet is produced, and the adhesive for the laminated sheet does not give harmful effects to the appearance of the laminated sheet The hardenability is improved. A laminated sheet is suitably prepared using an adhesive for a laminated sheet.

Description

Adhesive for laminated sheets

Cross-reference to related application

The present application claims priority based on Japanese Patent Application No. 2016-105473, filed May 26, 2016, in Japan under the Paris Convention Article 4. This priority patent application is herein incorporated by reference in its entirety.

Technical field

The present invention relates to an adhesive for a laminated sheet. Furthermore, the present invention also relates to a laminated sheet obtainable by using the adhesive and an article (or a material) obtainable by using the laminated sheet, for example, a packing bag (a packing bag for shampoo, detergent, food, etc.) (Such as a solar cell module).

A laminate sheet (a laminate sheet) obtained by laminating a plurality of films using an adhesive, such as an outdoor material such as a barrier material, a roofing material, a solar cell module (or panel), a window material, an outdoor flooring, Or a laminate) as a constituent material. Examples of the film constituting the laminated sheet include metal foils made of metal such as aluminum, copper and steel; Metal plates and metal deposited films; And films made of plastics such as polypropylene, polyvinyl chloride, polyester, fluororesin, and acrylic resin.

As shown in Fig. 1, the laminated sheet 10 is a laminate of a plurality of films 11 and 12, and the films 11 and 12 are laminated by interposing an adhesive 13 therebetween. Since the laminate is exposed outdoors over a long period of time, the adhesive for the laminated sheet (the adhesive layer formed therefrom) must have excellent durability. Adhesives for laminated sheets, especially adhesives for solar cell applications that convert sunlight into electricity, should have a higher level of durability than conventional adhesives for laminated sheets.

3, in the case of solar cell application, the laminated sheet 10 referred to as a back sheet is attached to the solar cell module 1, the sealing material 20, the solar cell 30 and the glass plate 40 Included together.

Since the solar cell module 1 is exposed outdoors over a long period of time, sufficient durability against sunlight is required under high temperature and high humidity conditions. Particularly, in the case where the adhesive 13 has poor performance, the film 11 can be peeled off from the film 12, and therefore the appearance of the laminated sheet 10 is deteriorated. Therefore, in the production of a solar cell module, the adhesive for the laminated sheet should not undergo film peeling of the laminated sheet even if the adhesive is exposed to high temperature over a long period of time.

Patent Documents 1 and 2 disclose a urethane-based adhesive for producing a solar cell protective sheet as an example of an adhesive for a laminated sheet.

Patent Document 1 discloses an adhesive for a laminated sheet used for manufacturing a solar cell back sheet, and an adhesive for the laminated sheet includes an acrylic polyol and a polyisocyanate (see claim 1 of patent document 1) ). The acrylic polyol has a glass transition temperature of a certain range and is adjusted to have a specific range of hydroxyl values so that the adhesive has improved environmental resistance (various durability in the environment, for example, adhesion strength before and after aging, heat resistance and moisture resistance) , And the polyisocyanate is limited to have a specific structure (see [Table 1] to [Table 5] of Patent Document 1).

Patent Document 2 also discloses an adhesive for a solar cell back sheet comprising a urethane resin obtainable by reaction of an acrylic polyol and an isocyanate compound, and a solar cell back sheet and a solar cell module obtainable by using the adhesive See [Claims 1] and [Claim 5] of Patent Document 2). The adhesive for the solar cell back sheet of Patent Document 2 is excellent in hydrolysis resistance, film peel strength after aging, and yellowing by UV radiation (see [Table 1] to [Table 5] in Patent Document 2).

In recent years, the performance required for adhesives for solar cell backsheets has been increasing every year. Adhesives for the solar cell backsheet should be excellent not only in durability (hydrolysis resistance), but also in handling (or convenience) when manufacturing solar cell backsheets.

Although the adhesives of Patent Documents 1 and 2 are excellent in hydrolysis resistance, the hardenability (or solubility) of the adhesive does not completely satisfy a high level of consumer demand. Adhesives need to have improved curability to efficiently fabricate solar cell backsheets.

One of the ways to improve the curability is to add a catalyst to the adhesive. Addition of the catalyst improves the curability, but the port life is too short, which may cause some difficulties in the process of laminating the film and in appearance of the obtainable laminated sheet.

JP 5003849 B JP 2012-142349 A

The present invention has been accomplished in order to solve these problems, and its object is to provide a method for producing a laminated sheet (or a laminate), which comprises coating, peeling strength after aging (or curing) And an adhesive for laminated sheets, which is excellent in decomposability and has improved curability without exerting an adverse effect on the appearance of the laminated sheet. Furthermore, it is an object of the present invention to provide a laminated sheet (for example, a solar cell back sheet and the like) obtainable by using the above adhesive, and an article (or a material) Solar cell module, etc.).

The present inventors have intensively studied and surprisingly found that the use of a specific polyol as a raw material of a urethane resin and the addition of a specific compound further improve the coating properties in the production of a laminated sheet, the peel strength after aging, It has been found that an adhesive for a laminated sheet excellent in water-decomposability is derived, wherein the adhesive improves the curability without exerting an adverse effect on the appearance of the laminated sheet. Thus, the present invention has been completed.

In one aspect, the present invention provides a novel adhesive for a laminated sheet applied on a film to laminate (or laminate) a plurality of films, wherein the adhesive comprises (A) an acrylic polyol, (B) At least one selected from acid anhydrides, and (C) an isocyanate compound, wherein

(B) selected from a carboxylic acid and a carboxylic acid anhydride is mixed (or contained) in an amount of 0.01 to 8.0 parts by weight based on 100 parts by weight of the total weight of components (A) to (C)

The acrylic polyol (A) can be obtained by polymerizing a polymerizable monomer, and is a polymer having a weight average molecular weight of 10,000 to 100,000 and a hydroxyl value of 0.5 to 40 mgKOH / g.

In one embodiment, the present invention provides an adhesive for a laminated sheet wherein at least one (B) selected from a carboxylic acid and a carboxylic acid anhydride has a melting point of 280 DEG C or less.

In another embodiment, the present invention provides an adhesive for a laminated sheet further comprising (D) a silane compound.

In a further embodiment, the present invention provides an adhesive for a laminated sheet wherein the polymerizable monomer comprises a monomer having hydroxyl groups and other monomers, and the other monomer comprises acrylonitrile and (meth) acrylic acid ester.

In a preferred embodiment, the present invention provides an adhesive for a laminated sheet wherein the acrylic polyol (A) has a glass transition temperature of from -35 占 폚 to 20 占 폚.

In another further embodiment, the present invention relates to an adhesive for a laminated sheet wherein the silane compound (D) is included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total weight of components (A) to (C) to provide.

In another aspect, the present invention provides a laminated sheet obtainable by laminating a plurality of films through an intervening adhesive for the laminated sheet.

In a further aspect, the present invention provides an article obtainable by using a laminated sheet (outdoor material, packing bag, etc.).

In a preferred aspect,

(A) at least one selected from an acrylic polyol, (B) a carboxylic acid and a carboxylic acid anhydride, and (C) an isocyanate compound in an organic solvent, wherein

(B) selected from a carboxylic acid and a carboxylic acid anhydride is mixed (or contained) in an amount of 0.01 to 8.0 parts by weight based on 100 parts by weight of the total weight of components (A) to (C)

The acrylic polyol (A) can be obtained by polymerizing a polymerizable monomer, and is a polymer having a weight average molecular weight of 10,000 to 100,000 and a hydroxyl value of 0.5 to 40 mgKOH / g.

A method for producing an adhesive for a laminated sheet is provided.

In a more preferred aspect,

 (A) an acrylic polyol, (B) at least one selected from a carboxylic acid and a carboxylic acid anhydride, and (C) an isocyanate compound in an organic solvent to obtain a mixed solution, (Or laminating) a plurality of films, wherein

(B) selected from a carboxylic acid and a carboxylic acid anhydride is mixed (or contained) in an amount of 0.01 to 8.0 parts by weight based on 100 parts by weight of the total weight of components (A) to (C)

The acrylic polyol (A) can be obtained by polymerizing a polymerizable monomer, and is a polymer having a weight average molecular weight of 10,000 to 100,000 and a hydroxyl value of 0.5 to 40 mgKOH / g.

A method for producing an adhesive for a laminated sheet is provided.

An adhesive for a laminated sheet according to one aspect of the present invention is applied on a film to bond (or laminate) a plurality of films, wherein the adhesive comprises (A) an acrylic polyol, (B) a carboxylic acid and a carboxylic acid anhydride At least one selected, and (C) an isocyanate compound, wherein

(B) selected from a carboxylic acid and a carboxylic acid anhydride is mixed (or contained) in an amount of 0.01 to 8.0 parts by weight based on 100 parts by weight of the total weight of components (A) to (C)

The acrylic polyol (A) can be obtained by polymerizing a polymerizable monomer, and is a polymer having a weight average molecular weight of 10,000 to 100,000 and a hydroxyl value of 0.5 to 40 mgKOH / g.

Therefore, when the laminated sheet (or laminate) is produced, the adhesive is excellent in coatability, peel strength after aging, and excellent hydrolysis resistance over a long period at high temperature, and the adhesive does not exert an adverse influence on the appearance of the laminated sheet The hardenability is improved.

Therefore, a laminated sheet can be suitably produced by using such an adhesive for a laminated sheet, and an article can be manufactured using the laminated sheet.

1 is a sectional view showing one embodiment of a solar cell back sheet of the present invention.
[Fig. 2] Fig. 2 is a cross-sectional view showing another embodiment of the solar cell back sheet of the present invention.
[Fig. 3] Fig. 3 is a cross-sectional view showing one embodiment of the solar cell module of the present invention.

The adhesive for the laminated sheet of the present invention is a mixture comprising (A) an acrylic polyol, (B) at least one carboxyl group-containing compound selected from a carboxylic acid and a carboxylic acid anhydride, and (C) an isocyanate compound .

The order and method of blending the components (A) to (C) are not limited as long as an adhesive for a laminated sheet to which an embodiment of the present invention is aimed is obtainable. For example, three components: components (A) to (C) can be blended at one time. Furthermore, component (B) can be blended with component (A), and component (C) can then be added. In addition, component (B) can be blended with component (C), and component (A) can then be added.

(A) The acrylic polyol can be obtained by addition polymerization of a polymerizable monomer, and the polymerizable monomer includes " monomer having a hydroxyl group " and " other monomer ".

The " monomer having a hydroxyl group " is a radically polymerizable monomer having a hydroxyl group and an ethylene double bond, and is not particularly limited as long as an adhesive for a laminated sheet of the present invention can be obtained. The monomer having a hydroxyl group includes, for example, a hydroxyalkyl (meth) acrylate, and the hydroxyalkyl (meth) acrylate may be used alone, or a combination of two or more hydroxyalkyl (meth) Can be used. Hydroxyalkyl (meth) acrylates can also be used in combination with monomers having hydroxyl groups other than hydroxyalkyl (meth) acrylates.

Examples of "hydroxyalkyl (meth) acrylate" include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Butyl (meth) acrylate, and the like.

Examples of the polymerizable monomer having a hydroxyl group other than the hydroxylalkyl (meth) acrylate include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like.

The "other monomer" is a "radically polymerizable monomer having an ethylene double bond" other than a monomer having a hydroxyl group, and is not particularly limited as long as an adhesive for a laminated sheet of the present invention can be obtained. Other monomers preferably include acrylonitrile and (meth) acrylic acid esters, and may further comprise radically polymerizable monomers having ethylene double bonds other than acrylonitrile and (meth) acrylic acid esters. In the case where the other monomer includes acrylonitrile and (meth) acrylic acid ester, the adhesive for the laminated sheet of the present invention preferably provides a laminated sheet having excellent peel strength after aging and further improved appearance .

&Quot; Acrylonitrile " is a compound represented by the formula CH ₂ = CH-CN and is also referred to as acrylonitrile, acrylonitrile, or vinyl cyanide.

Acrylonitrile is contained in an amount of preferably 1 to 40 parts by weight, more preferably 5 to 35 parts by weight, particularly preferably 5 to 25 parts by weight, based on 100 parts by weight of the polymerizable monomer. When the acrylonitrile is contained in the amount within the above range, the coating property of the adhesive can be further improved, and an adhesive for a laminated sheet excellent in balance between peel strength after aging and hydrolysis resistance can be provided.

The "(meth) acrylic acid ester" can be obtained, for example, by a condensation reaction of (meth) acrylic acid with a monoalcohol, and has an ester bond. Although the monomer having a hydroxyl group has an ester bond, it is not included in the (meth) acrylic acid ester. Specific examples thereof include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl Dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate and the like; Glycidyl (meth) acrylate, and the like. Both linear alkyl groups and cyclic alkyl groups are included in the " alkyl group ".

The "(meth) acrylic acid ester" is preferably selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and cyclohexyl (Meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, and most preferably at least one selected from the group consisting of methyl methacrylate And both n-butyl acrylate and n-butyl acrylate.

In the present specification, acrylic acid and methacrylic acid are collectively referred to as "(meth) acrylic acid", and "acrylic acid ester and methacrylic acid ester" collectively refer to as "(meth) acrylic acid ester" Quot;

Examples of the " radically polymerizable monomer having an ethylene double bond other than acrylonitrile and (meth) acrylic acid ester " include, but are not limited to, (meth) acrylic acid, styrene, vinyltoluene and the like. The radical polymerizable monomer is not limited to these compounds as long as an adhesive for the laminated sheet of the present invention can be obtained.

As long as an adhesive for a laminated sheet for which the present invention is an object can be obtained, the polymerization method of the polymerizable monomer is not particularly limited. For example, the polymerizable monomer may be polymerized by radical polymerization of the polymerizable monomer with an appropriate catalyst or the like in an organic solvent using a common solvent polymerization method. In the present invention, the organic solvent is not particularly limited so long as the organic solvent can be used to polymerize the polymerizable monomer and does not substantially exert an adverse effect on the properties of the adhesive for the laminated sheet after the polymerization reaction. Examples of such solvents include aromatic solvents such as toluene, xylene and the like; Ester-based solvents such as ethyl acetate, butyl acetate and the like; And combinations thereof.

The acrylic polyol (A) is preferably obtained in the form of a solution containing an organic solvent or a mixture comprising an organic solvent, and can be used as a raw material for an adhesive without removing the organic solvent.

In the polymerization of the polymerizable monomer, the polymerization reaction conditions such as the reaction temperature, the reaction time, the type of the organic solvent, the type and concentration of the monomer, the stirring speed, as well as the type and concentration of the polymerization initiator, .

The polymerization initiator is preferably a compound that can accelerate polymerization of the polymerizable monomer when added in a small amount and can be used in an organic solvent. Examples of the polymerization initiator include ammonium persulfate, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile (AIBN) and 2,2-azobis (2,4-dimethylvaleronitrile) .

The chain transfer agent can be suitably used for polymerization in the present invention to adjust the molecular weight. As " chain transfer agent " it is possible to use compounds well known to those skilled in the art. Examples thereof include mercaptans such as n-dodecyl mercaptan (nDM), lauryl methyl mercaptan, mercaptoethanol and the like.

As mentioned above, acrylic polyols can be obtained by polymerizing polymerizable monomers. Considering the coating property of the adhesive and the appearance of the laminated sheet, the weight average molecular weight (Mw) of the acrylic polyol is 10,000 to 100,000, preferably 10,000 to 90,000, and most preferably 30,000 to 80,000. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) against polystyrene standards. Specifically, the value can be obtained using the following GPC apparatus and measuring method. HCL-8220GPC manufactured by TOSOH CORPORATION is used as a GPC apparatus, and RI is used as a detector. Two TSK gel super multi pores HZ-M manufactured by Tosoh Corporation are used as GPC columns. The sample was dissolved in tetrahydrofuran and the resulting solution was allowed to flow at a flow rate of 0.35 ml / min and a column temperature of 40 ° C and then measured on a calibration curve obtained using polystyrene having a monodispersed molecular weight as a standard reference material Mw is determined by conversion of the molecular weight.

The hydroxyl value of the acrylic polyol is preferably 0.5 to 40 mg KOH / g, more preferably 1 to 30 mg KOH / g, particularly preferably 4 to 20 mg KOH / g. If the hydroxyl value of the acrylic polyol is not in the above range, the adhesive for the laminated sheet can not have sufficient properties relating to the peel strength and hydrolysis resistance after aging, and it is difficult to use the adhesive as an adhesive for a laminated sheet will be.

In the present specification, the hydroxyl value is the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when acetylating 1 g of the resin.

In the present invention, the hydroxyl value is specifically calculated by the following formula (ii).

(ii): hydroxyl value = (weight of monomer having hydroxyl group / molecular weight of monomer having hydroxyl group) x mole number of hydroxyl group contained in 1 mol of monomer having hydroxyl group x chemical amount of KOH x 1,000 / Weight of polyol

The glass transition temperature of the acrylic polyol can be set by adjusting the mass fraction of the monomer to be used. The glass transition temperature of the acrylic polyol can be determined based on the glass transition temperature of the homopolymer obtainable from each monomer and the mass fraction of the homopolymer used in the acrylic polyol, using the following equation (i). It is desirable to determine the composition of the monomers of the adhesive using the glass transition temperature determined by calculation:

(i): 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn

In the formula (i), Tg represents the glass transition temperature of the acrylic polyol, and W1, W2, ..., Wn represent mass fractions of respective monomers, and Tg1, Tg2, ..., , And Tgn represent the glass transition temperature of the homopolymer corresponding to each monomer.

The values described in the literature can be used as the Tg of the homopolymer. For example, it is possible to refer to the following documents: acrylic acid ester catalog (1997 edition) of Mitsubishi Rayon Co., Ltd.; Shin Kobunshi Bunko 7, Guide to Synthetic Resin for Coating Material ", Kobunshi Kankokai, 1997, pp. 168-169; And " POLYMER HANDBOOK ", 3rd Edition, pp. 209-277, John Wiley & Sons, Inc., 1989).

In the present specification, the glass transition temperature of the homopolymer of the following monomers is as follows.

Methyl methacrylate: 105 DEG C

2-ethylhexyl acrylate: -70 占 폚

n-Butyl acrylate: -54 DEG C

Ethyl acrylate: -20 ° C

2-hydroxyethyl methacrylate: 55 占 폚

2-hydroxyethyl acrylate: -15 ° C

Glycidyl methacrylate: 41 DEG C

Acrylonitrile: 130 ° C

Styrene: 105 ℃

Cyclohexyl methacrylate: 83 DEG C

Acrylic acid: 106 ° C

In the present invention, the acrylic polyol preferably has a glass transition temperature of -35 캜 to 20 캜. In consideration of the peel strength after aging and the hydrolysis resistance, the acrylic polyol preferably has a glass transition temperature of -30 캜 to 20 캜, particularly preferably a glass transition temperature of -20 캜 to 15 캜.

When the acrylic polyol has a glass transition temperature of -35 占 폚 to 20 占 폚, the cohesive force of the adhesive for the laminated sheet is maintained, leading to improved peel strength after aging and hydrolysis resistance.

In the present specification, at least one selected from the carboxylic acid (B) and the carboxylic acid anhydride may be used either singly or as a mixture (or a combination) of the carboxylic acid and the carboxylic acid anhydride. .

Since the adhesive for the laminated sheet of the present invention contains the component (B), it is excellent in curability while maintaining an appropriate port life.

&Quot; Carboxylic acid " means an organic acid having at least one carboxyl group, and " carboxylic anhydride " means a compound having two carboxyl groups dehydrated and condensed (carboxylic acid anhydride group).

Examples of carboxylic acids include formic acid, acrylic acid, methacrylic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, But are not limited to, heptadecanoic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, 2-hydroxybutanoic acid, 2-hydroxypropanetricarboxylic acid, 3-hydroxyphenylacetic acid, glycolic acid, diphenol But are not limited to, acid, benzoic acid, 4-hydroxybenzoic acid, salicylic acid, gallic acid, cinnamic acid, phthalic acid, isophthalic acid, 2-oxopropanoic acid, dimer acid, trimer acid, 1,2,3-propanetricarboxylic acid, , Pyromellitic acid, trimellitic acid, and the like.

Examples of carboxylic anhydrides include acetic anhydride, phthalic anhydride, 4-methylhexahydrophthalic anhydride, benzoic anhydride, 4,4-oxyphthalic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, cyclohexane- 1,2,4-tricarboxylic anhydride, and the like.

In the present invention, at least one (B) selected from the carboxylic acid and the carboxylic acid anhydride preferably includes a compound having a melting point of 280 DEG C or lower. Component (B) more preferably comprises a compound having a melting point of 250 캜 or lower, and most preferably a compound having a melting point of 200 캜 or lower. When the melting point of the component (B) is in the above range, the adhesive of the present invention has improved curability and the appearance of the obtainable laminated sheet is more preferable.

In the present specification, the melting point refers to a value measured by differential scanning calorimetry (DSC). Specifically, 10 mg of a sample was weighed into an aluminum container, and the measurement was carried out at a temperature raising rate of 10 ° C / min using DSC6220 (trade name) manufactured by SII NanoTechnology Inc , And the maximum temperature of the fusion peak is referred to as melting point.

In the present invention, at least one (B) selected from a carboxylic acid and a carboxylic acid anhydride is preferably blended in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the acrylic polyol (A). When the component (B) is blended in the amount in the above range, the adhesive for the laminated sheet of the present invention will have an improved curability, but will not shorten the port life, and as a result, it will be easier to apply the adhesive.

In the present invention, component (B) is blended in an amount of 0.01 to 8.0 parts by weight per 100 parts by weight of the total of components (A) to (C). When the component (B) is blended in the amount in the above range, the adhesive for the laminated sheet of the present invention will have an improved curability, but will not shorten the port life, and as a result, it will be easier to apply the adhesive.

In the present invention, the component (B) preferably includes at least one selected from adipic acid, benzoic acid, dimer acid, azelaic acid and trimellitic acid anhydride.

When the component (B) contains at least one member selected from adipic acid, benzoic acid, dimer acid, azelaic acid and trimellitic acid anhydride, the adhesive for the laminated sheet of the present invention not only has improved curability, Both the peel strength after aging and the hydrolysis resistance are excellent.

In the present invention, examples of the isocyanate compound (C) are not particularly limited so long as the adhesive contains an aliphatic isocyanate, an alicyclic isocyanate and an aromatic isocyanate, and an adhesive for a laminated sheet to which the present invention is aimed can be obtained .

As used herein, the term " aliphatic isocyanate " refers to a compound having a chain-like hydrocarbon chain in which an isocyanate group is directly bonded to a hydrocarbon chain, and also does not have a cyclic hydrocarbon chain. Although " aliphatic isocyanate " may have an aromatic ring, the aromatic ring is not directly bonded to the isocyanate group.

In the present specification, the aromatic ring is not included in the cyclic hydrocarbon chain.

"Alicyclic isocyanate" is a compound having a cyclic hydrocarbon chain and having a chain-like hydrocarbon chain. The isocyanate group may be directly bonded to the cyclic hydrocarbon chain or may be bonded directly to the obtainable chain hydrocarbon chain. Although " alicyclic isocyanate " may have an aromatic ring, the aromatic ring is not directly bonded to the isocyanate group.

&Quot; Aromatic isocyanate " refers to a compound having an aromatic ring in which an isocyanate group is bonded directly to an aromatic ring. Therefore, a compound in which an isocyanate group is not directly bonded to an aromatic ring is classified as an aliphatic isocyanate or an alicyclic isocyanate, even though the compound has an aromatic ring in the molecule.

Thus, for example, since the 4,4'-diphenylmethane diisocyanate _{(OCN-C 6 H 4 -CH} 2 -C 6 H 4 -NCO) , the isocyanate group directly bonded to the aromatic rings correspond to the aromatic isocyanate . On the other hand, for example, xylylene diisocyanate (OCN-CH ₂ -C ₆ H ₄ -CH ₂ -NCO) is not directly bonded to the aromatic ring, and the aromatic ring is present, And therefore corresponds to an aliphatic isocyanate.

The aromatic ring may be fused with two or more benzene rings.

Examples of aliphatic isocyanates include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (also referred to below as HDI), 1,6-diisocyanine Diisocyanatohexanoic acid methyl ester (lysine diisocyanate), 1,3-bis (isocyanatomethyl) benzene (xylylene diisocyanate) And the like.

Examples of the alicyclic isocyanate include 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane (isophorone diisocyanate), 1,3-bis (isocyanatomethyl) Hexane (hydrogenated xylylene diisocyanate), bis (4-isocyanatocyclohexyl) methane (hydrogenated diphenylmethane diisocyanate), 1,4-diisocyanatocyclohexane and the like.

Examples of the aromatic isocyanates include 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, and the like. These isocyanate compounds may be used alone or in combination.

In the present invention, the isocyanate compound is not particularly limited as long as an adhesive for the laminated sheet for which the present invention is the object can be obtained. From the viewpoint of weatherability, it is preferable to select from aliphatic isocyanates and alicyclic isocyanates. HDI, isophorone diisocyanate, xylylene diisocyanate and derivatives thereof.

In the present invention, the equivalent ratio (NCO / OH) of (C) the isocyanate-based isocyanate group to the hydroxyl group based on the (A) acrylic polyol is preferably 0.5 to 4.5, more preferably 1.0 to 4.0, 1.5 to 3.5. When the equivalent ratio is in the above range, the adhesive for the laminated sheet is excellent in curability, peeling strength after aging, and hydrolysis resistance.

In this specification, the NCO / OH equivalent ratio is calculated according to the following equation (iii): < EMI ID =

(iii): NCO / OH ratio = amount of isocyanate (parts by weight) x (561 / hydroxyl value of acrylic polyol) x (NCO% / (42 x 100)

The adhesive for the laminated sheet of the present invention preferably further comprises (D) a silane compound.

Examples of the silane compound include (meth) acryloxyalkyltrialkoxysilane, (meth) acryloxyalkylalkylalkoxysilane, vinyltrialkoxysilane, vinylalkylalkoxysilane, epoxysilane, mercaptosilane and isocyanurate silane Can be used. However, the silane compound is not limited to these silane compounds.

Examples of the "(meth) acryloxyalkyltrialkoxysilane" include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 4- (meth) Ethoxy silane, and the like.

Examples of the "(meth) acryloxyalkylalkylalkoxysilane" include 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (Meth) acryloxyethylmethyldimethoxysilane, and the like.

Examples of " vinyltrialkoxysilane " include vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxyethoxysilane, vinyltri (methoxyethoxy) silane, vinyltri (ethoxymethoxy) do.

Examples of " vinylalkylalkoxysilane " include vinylmethyldimethoxysilane, vinylethyldi (methoxyethoxy) silane, vinyldimethylmethoxysilane, vinyldiethyl (methoxyethoxy) silane and the like.

For example, " epoxy silane " can be categorized as glycidyl-based silane and epoxycyclohexyl-based silane. The "glycidyl-based silane" has a glycidoxy group, and specific examples thereof include 3-glycidoxypropylmethyl diisopropenoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl tri Ethoxy silane, 3-glycidoxypropyl diethoxy silane, and the like.

"Epoxycyclohexyl-based silane" has a 3,4-epoxycyclohexyl group, and specific examples thereof include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyl triethoxysilane and the like.

Examples of " mercaptosilane " include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like.

Examples of the " isocyanurate silane " include tris (3- (trimethoxysilyl) propyl) isocyanurate and the like.

The silane compound (D) is used in an amount of preferably 1 to 10 parts by weight, more preferably 2 to 6 parts by weight, most preferably 2.5 to 5 parts by weight, based on 100 parts by weight of the total weight of components (A) By weight. When the adhesive for the laminated sheet of the present invention contains the silane compound (D) in the amount within the above range, the adhesive for the laminated sheet of the present invention is more excellent in balance between the adhesive force after aging and the hydrolysis resistance.

In the present invention, the silane compound (D) preferably comprises a glycidyl-based silane compound classified as an epoxy silane. Examples of glycidyl-based silane compounds include functional groups represented by the formula (1).

(1):

The functional group represented by the formula (1) is a glycidoxy group.

Among these glycidyl-based silane compounds, 3-glycidoxypropyltrialkoxysilane is particularly preferable. A 3-glycidoxypropyltrialkoxysilane compound is most suitable for improving the hydrolysis resistance of an adhesive for a laminated sheet and the adhesive force after aging.

The silane compound (D) preferably functions as a silane coupling agent. The silane coupling agent is composed of an organic element (or substance) and silicon, and also has an organic functional group " Y " such as an amino group, an epoxy group, a methacrylic group, a vinyl Group and a mercapto group and a hydrolyzable group " OR " such as a methoxy group, an ethoxy group and a methylcarbonyloxy group, so that the connection between the organic material and the inorganic material, ≪ / RTI >

Therefore, as the glycidyl-based silane compound, the compound acting as the silane coupling agent means a silane coupling agent containing a functional group having glycidoxy group as the organic functional group " Y ". The adhesive for the laminated sheet of the present invention exhibits a further improved initial adhesion and hydrolysis resistance by incorporating a glycidyl-based silane compound, and exhibits an improved initial adhesion and hydrolysis resistance, and an initial value between polyvinylidene fluoride (PVDF) and polyethylene terephthalate Adhesion is particularly outstanding.

The method of blending the silane compound (D) is not particularly limited as long as a desired adhesive can be obtained. For example, the silane compound (D) is obtained by reacting the acrylic polyol (A) A), or may be pre-blended with a solution and / or mixture of acrylic polyol (A) and isocyanate compound (C).

The adhesive for the laminated sheet of the present invention may contain an ultraviolet absorber for the purpose of improving long-term weatherability. As ultraviolet absorbers, it is possible to use hydroxyphenyltriazine-based compounds and other commercially available ultraviolet absorbers. The "hydroxyphenyltriazine-based compound" is a kind of a triazine derivative in which a hydroxyphenyl derivative is bonded to a carbon atom of a triazine derivative, examples of which are commercially available from BASF Corp. TINUVIN 400, TINUVIN 405, TINUVIN 479, TINUVIN 477 and TINUVIN 460 (all of which are trade names), and the like.

The adhesive for the laminated sheet may further comprise a hindered phenol-based compound. The term " hindered phenol-based compound " is generally referred to as a hindered phenol-based compound, and is not particularly limited as long as an adhesive for the intended laminated sheet of the present invention can be obtained.

Commercially available products can be used as impaired phenol-based compounds. The hindered phenol-based compounds are commercially available, for example, from BASF Corporation. Examples thereof include IRGANOX 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330 and Irganox 1520, all of which are trade names. The hindered phenol-based compound is added to the adhesive as an antioxidant and can be used in combination with, for example, a phosphite-based antioxidant, a thioether-based antioxidant, an amine-based antioxidant, and the like.

The adhesive for the laminated sheet of the present invention may further comprise a hindered amine-based compound. The term " hindered amine-based compound " is generally referred to as a hindered amine-based compound, and is not particularly limited as long as an adhesive for the intended laminated sheet of the present invention can be obtained.

Commercially available products can be used as hindered amine-based compounds. Examples of hindered amine-based compounds include, but are not limited to, Tinuvin 765, Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292 and Tinuvin 5100, all commercially available from BASF Corporation . The hindered amine-based compound is added to the adhesive as a light stabilizer and may be used in combination with, for example, a benzotriazole-based compound, a benzoate-based compound, and the like.

The adhesive for the laminated sheet of the present invention may further contain other components as long as an adhesive for the intended laminated sheet can be obtained.

As far as an adhesive for a laminated sheet to which the present invention is aimed can be obtained, the timing of adding the " other component " to the adhesive for a laminated sheet is not particularly limited. For example, the other component may be premixed with component (A), or may be added to the mixture obtained by mixing components (A) to (C).

Examples of " other components " include catalysts, pressure-sensitive adhesive resins, pigments, plasticizers, flame retardants, waxes and the like.

Examples of " catalysts " include metal catalysts and non-metal catalysts.

Examples of the " metal catalyst " include tin catalysts (trimethyltin laurate, trimethyltin hydroxide, stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate and the like) (Naphthenic acid metal salts such as cobalt naphthenate), bismuth octoate, sodium persulfate, potassium persulfate and the like, as well as catalysts (lead oleate, lead naphthenate, lead octenoate and the like)

Examples of " non-metal catalysts " preferably include amine-based catalysts. Examples of the " amine-based catalyst " include triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkene, dialkylaminoalkylamine, and the like.

Examples of the "pressure-sensitive adhesive resin" include styrene-based resins, terpene-based resins, aliphatic petroleum resins, aromatic petroleum resins, rosin esters, acrylic resins, polyester resins (excluding polyester polyols) and the like.

Examples of " pigments " include titanium oxide, carbon black, and the like.

Examples of " plasticizers " include dioctyl phthalate, dibutyl phthalate, diisononyl adipate, dioctyl adipate, mineral spirit and the like.

Examples of " flame retardants " include halogen-based flame retardants, phosphorus-based flame retardants, antimony-based flame retardants, metal hydroxide-based flame retardants and the like.

The " wax " is preferably a wax such as paraffin wax and microcrystalline wax.

The adhesive for the laminated sheet of the present invention comprises the above-mentioned components (A) to (C) and optionally comprises the component (D), and the adhesive for the laminated sheet of the present invention can be obtained by mixing these components have. The method of mixing the respective components is not particularly limited as long as an adhesive for a laminated sheet to which the present invention is aimed can be obtained. The sequence of mixing the components is also not particularly limited. The adhesive for the laminated sheet of the present invention can be produced without using a special mixing method and a special mixing sequence.

Typically, the adhesive for the laminated sheet of the present invention preferably has the form of a mixture containing an organic solvent, and may be in the form of a solution or suspension.

The adhesive for the laminated sheet of the present invention preferably has a concentration (solid component concentration) of 30 wt% or more, more preferably 30 to 40 wt% (solid component concentration).

The adhesive for the laminated sheet of the present invention preferably has a long pot life, and is excellent in coating property when a base material (film) for a laminated sheet is coated.

The port life of the adhesive for the laminated sheet of the present invention is such that the components (A) to (C) are mixed and optionally the additive (s) (D) are mixed to obtain an adhesive and the viscosity of the adhesive And determining the degree of increase in the viscosity of the adhesive. The viscosity of the adhesive for the laminated sheet was measured using a rotational viscometer (model BM manufactured by TOKIMEC Inc.). If the viscosity of the adhesive rapidly increases, the coating property of the adhesive for the laminated sheet of the present invention may be deteriorated, so that there may be some difficulties in productivity of the laminated sheet.

The adhesive for the laminated sheet of the present invention is preferably applied on a film constituting the laminated sheet, and excellent in coatability. If the adhesive has poor coating properties, a poor coating, such as a quasi-linear or linear structure, may occur. If an organic solvent is additionally added to reduce the viscosity of the adhesive in order to prevent poor coating of the adhesive for the laminated sheet, an increase in the manufacturing cost of the laminated sheet may occur.

The present invention further provides a kit for obtaining an adhesive for a laminated sheet. The kit comprises, for example, a first component comprising the above-mentioned component (A) and a second component comprising the above-mentioned component (C). Component (B) may be included in the first or second component, component (B) may be included in a third component different from the first and second components, and the third component is included in the kit . In addition, the first component, the second component and possibly the third component may optionally comprise at least one selected from component (D) and other components. It is possible to obtain an adhesive for the laminated sheet of the present invention by mixing these components.

The kit is preferably a two-part adhesive. The two-component adhesive includes a first component and a second component, for example, the first component comprises the above-mentioned component (A) and the second component comprises the above-mentioned component (C) , And component (B) and optionally component (D) and other components are included in the first or second sex component. However, not all components are necessarily included in one component.

The adhesive for the laminated sheet of the present invention is usually applied to the film constituting the laminated sheet at room temperature, and if necessary, heated to remove the solvent, thereby forming the adhesive layer. After the film is applied on the adhesive layer, it is pressurized and heated while being optionally exhausted, whereby curing proceeds to produce a laminated sheet.

The adhesive for the laminated sheet of the present invention has a long pot life and excellent coating property, and its adhesive layer maintains hydrolysis resistance at a high temperature for a long period of time, has excellent curability, and has various properties such as adhesion to a film after aging The overall balance between the two is excellent.

Therefore, the laminated sheet is produced by laminating (or joining) a plurality of adherends using the adhesive of the present invention, and the obtained laminated sheet is used for manufacturing various packing bags and various outdoor materials.

The packaging bag of the present invention means a bag-like article (or material) obtained by processing a laminated sheet to enclose foods, detergents, shampoos, rinses and the like. Examples of the outdoor material of the present invention include a barrier material, a roofing material, a solar cell module, a window material, an outdoor flooring material, a lighting protection material, an automobile member, a signboard and the like.

These packaging bags and outdoor materials include a laminated sheet obtainable by laminating a plurality of films as an adherend. Examples of films include films (metal-deposited films) on which a metal is deposited on a plastic-based material and films (plastic film) on which a metal is not deposited.

Adhesives for the manufacture of solar cell modules must have an initial adhesion and curability, especially for high levels of film, and, furthermore, hydrolysis resistance at elevated temperatures for long periods of time. The adhesive for the laminated sheet of the present invention is excellent in hydrolysis resistance at high temperatures for a long period of time, and therefore, the adhesive is suitable as an adhesive for a solar cell back sheet.

When the laminated sheet is produced, the adhesive for the laminated sheet of the present invention is applied on the film. Application can be carried out by various methods such as gravure coating, wire bar coating, air knife coating, die coating, lip coating, comma coating and the like. When an adhesive for a laminated sheet of the present invention is applied to form an adhesive layer, and thereby a plurality of films are laminated (or bonded), a laminated sheet is completed.

Although the embodiments of the laminated sheet of the present invention are shown in Figs. 1 to 3, the present invention is not limited to these embodiments.

1 is a cross-sectional view showing one embodiment of a laminated sheet of the present invention. The laminated sheet 10 is formed of two films and an adhesive layer 13 sandwiched therebetween and the two films 11 and 12 are laminated to each other with an adhesive layer 13. [ The films 11 and 12 may be made of the same or different materials. As shown in Fig. 1, the two films 11 and 12 may be laminated to each other, or three or more films may be laminated to each other.

Another embodiment of the laminated sheet of the present invention is shown in Fig. In Fig. 2, a thin film 11a is formed between the film 11 and the adhesive layer 13. For example, the figure shows an embodiment in which the metal foil 11a is formed on the surface of the film 11 when the film 11 is a plastic film. The metal thin film 11a may be formed on the surface of the plastic film 11 by vapor deposition and the laminated sheet of Fig. 2 may be formed on the film 12 (on the surface on which the metal thin film 11a is formed) And an adhesive layer 13 interposed therebetween, as shown in Fig.

Examples of the metal to be deposited on the plastic film include aluminum, steel, copper, and the like. It is possible to impart barrier properties to the plastic film by applying the film to vapor deposition. Silicon oxide or aluminum oxide is used as the vapor deposition material. The plastic film 11 as the base material may be transparent or white or black.

A plastic film made of a plastic selected from, for example, polyvinyl chloride, polyester, fluorine resin and acrylic resin is used as the film 12. Polyethylene terephthalate film and / or polybutylene terephthalate film is preferably used in order to impart heat resistance, weather resistance, rigidity and insulation properties. The films 11 and 12 may be transparent or colored.

The deposited thin film 11a and film 12 of the film 11 are laminated (or bonded together) to each other using the adhesive layer 13 of the present invention and the films 11 and 12 are often laminated Respectively.

3 shows a cross-sectional view of an exemplary solar cell module as an embodiment of the outdoor material of the present invention. 3, a glass plate 40, a sealing member 20 such as an ethylene-vinyl acetate resin (EVA), a plurality of solar cells 30 that are connected to each other to generate a desired voltage, It is possible to obtain the solar cell module 1 by overlaying the members 10, 20, 30 and 40 with the spacer 50 using the spacer 50. [

As described above, the back sheet 10 is a laminate of a plurality of films 11 and 12, so that even if the back sheet 10 is exposed outdoors for a long period of time, ) Shall not cause peeling.

The solar cell 30 is often fabricated using silicon and is sometimes fabricated using an organic resin comprising a dye. In this case, the solar cell module 1 becomes an organic-type (dye-sensitive) solar cell module. Transparent films are often used as the films 11 and 12 constituting the solar cell back sheet 10 because organic-based (dye-sensitive) solar cells are required to have colorability. Therefore, the adhesive layer 13 should exhibit little change in chrominance even when exposed to the outside for a long period of time and have excellent weatherability.

In the present invention, when the sealing material 20 is integrated with the back sheet 10, the adhesive layer 13 is not released from the film 11.

Example

The present invention is illustrated by reference to Examples and Comparative Examples, which are for the purpose of illustrating the present invention and are not intended to limit the present invention at all.

<Synthesis of Acrylic Polyol>

Synthesis Example 1 ((A1) Acrylpolyol (Polymer 1))

A four-necked flask equipped with a stirring blade, a thermometer and a reflux condenser tube was charged with 100 parts by weight of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and refluxed at about 80 캜 . To the flask, 1.0 part by weight of 2,2-azobisisobutyronitrile was added as a polymerization initiator, and a mixture of the respective monomers shown in Table 1 was continuously added dropwise over 1 hour 30 minutes. After further heating for 1 hour, 0.2 parts by weight of 2,2-azobisisobutyronitrile was added to the mixture, and the mixture was allowed to react for 1 hour. This step was repeated four times. A solution of an acrylic polyol (Polymer 1) (A1) containing 50% by weight of a non-volatile component (solids content) was obtained.

The composition of the polymerizable monomer components of the acrylic polyol (polymer 1) (A1) and the physical properties of the obtained polymer 1 are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Synthesis Examples 2 to 19

The molecular weight of each polymer is adjusted by controlling the amount of 2,2-azobisisobutyronitrile to be added, and the composition of the monomers and the like to be used for synthesizing each polymer (or polyol) is shown in Tables 1 and 2 Polymers 2 (A2) to 19 (A'19) were prepared using a method analogous to that of Synthesis Example 1, except that the polymer 2 (A2) was changed. The physical properties of the obtained polymers 2 to 19 are shown in Tables 1 and 2.

The polymerizable monomers shown in Tables 1 and 2 and other components thereof are shown below.

Methyl methacrylate (MMA): manufactured by Wako Pure Chemical Industries, Ltd.

2-ethylhexyl acrylate (2EHA): manufactured by Wako Pure Chemical Industries, Ltd.

Butyl acrylate (BA): manufactured by Wako Pure Chemical Industries, Ltd.

Ethyl acrylate (EA): manufactured by Wako Pure Chemical Industries, Ltd.

Glycidyl methacrylate (GMA): manufactured by Wako Pure Chemical Industries, Ltd.

Acrylonitrile (AN): manufactured by Wako Pure Chemical Industries, Ltd.

2-hydroxyethyl methacrylate (HEMA): manufactured by Wako Pure Chemical Industries, Ltd.

2-hydroxyethyl acrylate (HEA): manufactured by Wako Pure Chemical Industries, Ltd.

Styrene (St): Manufactured by Wako Pure Chemical Industries, Ltd.

Cyclohexyl methacrylate (CHMA): manufactured by Wako Pure Chemical Industries, Ltd.

Acrylic acid (AA): manufactured by Wako Pure Chemical Industries, Ltd.

[Table 1]

[Table 2]

&Lt; Calculation of Glass Transition Temperature (Tg) of Polymer >

The Tg of each polymer 1 (A1) to the polymer 19 (A'19) is calculated by the above-mentioned formula (i) using the glass transition temperature of the homopolymer of the " polymerizable monomer & Respectively. The literature values were used as the Tg of each homopolymer such as methyl methacrylate.

&Lt; Preparation of adhesive for laminated sheet >

Adhesives for each laminated sheet were prepared by blending component (A) shown in Tables 1 and 2 with components (B) and (C) as shown below.

(B) at least one member selected from carboxylic acid and carboxylic acid anhydride

(B1) Acetic acid (manufactured by Wako Pure Chemical Industries, Ltd., melting point: -8 캜)

(B2) hexanoic acid (manufactured by Wako Pure Chemical Industries, Ltd., melting point: -6 캜)

(B3) Stearic acid (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 63 캜)

(B4) adipic acid (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 156 占 폚)

(B5) Azela (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 104 占 폚)

(B6) oleic acid (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 2 캜)

(B7) Maleic acid (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 143 캜)

(B8) benzoic acid (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 125 캜)

(B9) isophthalic acid (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 351 DEG C)

(B10) trimellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 169 ° C)

(B11) 4,4-oxydiphthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 229 ° C)

(B12) dimer acid (Pripol 1013 (trade name), manufactured by Croda International Plc., Melting point: -47 ° C)

(B'13) methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 21 DEG C)

The melting point of the component (B) was measured using a differential scanning calorimeter (DSC) (manufactured by SIEI Nanotechnology Inc. under the trade name of DSC6620). A sample of each of (B) carboxylic acid and carboxylic acid anhydride (approximately 10 mg) was weighed into an aluminum container, the vessel placed in a DSC apparatus and cooled to -70 占 폚. The DSC curve was then measured at a rate of temperature increase of 10 DEG C / min. The maximum endothermic peak temperature shown in the obtained DSC curve was called a melting point.

(C) an isocyanate compound

(C1) isocyanate compound 1 (SUMIDULE N3300 (trade name): isocyanurate manufactured by Sumika Bayer Urethane Co., Ltd., hexamethylene diisocyanate trimer)

(C2) isocyanate compound 2 (adduct of hexamethylene diisocyanate trimer: Sumidule HT (trade name) manufactured by Sumika Bayer Urethane Co., Ltd.: trimethylol propane)

(C3) isocyanate compound 3 (xylylene diisocyanate: TAKENATE 500 (trade name) manufactured by Mitsui Chemicals, Inc.)

Example 1

As shown in Table 3, 90.1 g of Polymer 1 (A1) (180.2 g of an ethyl acetate solution of polymer 1 (50.0 wt% solids), 4.5 g of oleic acid (B6), 3.9 g of isocyanate compound 1 , 1.5 g of isocyanate compound 3 (C3) and 0.5 g of 3-glycidoxypropyltriethoxysilane (D2) produced by EVONIK Industries AG were weighed and mixed, and then the solid content Ethyl acetate was added so as to be 40% by weight to obtain an adhesive for the laminated sheet of Example 1.

Examples 2 to 19 and Comparative Examples 1 to 8

An adhesive for each laminated sheet was obtained by blending the components (A) to (C) into the respective amounts shown in Tables 3 to 5, using a method similar to that of Example 1. In Tables 3 to 5, the silane compounds as component (D) are optionally blended, wherein (D1) is 3-glycidoxypropyltrimethoxysilane prepared by Ebornic Industries AG, and (D2) Gt; 3-glycidoxypropyltriethoxysilane &lt; / RTI &gt; manufactured by Ebornic Industries AG.

[Table 3]

[Table 4]

[Table 5]

The adhesives for these laminated sheets were evaluated by the following test.

&Lt; Preparation of laminated sheet 1 >

Examples and comparative example of each of the adhesive for the laminated sheet producing the weight of the solid content by 10 g / m ² is transparent polyethylene terephthalate (PET) sheet (manufactured by Mitsubishi Polyester Film Corporation (Mitsubishi Polyester Film Corporation) to ensure that O300EW36 (trade name)) using a bar coater, and then dried at 80 DEG C for 5 minutes to form an adhesive layer. Subsequently, a surface-treated transparent polyolefin film (a linear low density polyethylene film manufactured by Futamura Chemical Co., Ltd. under the trade name of LL-XUMN # 30) was laminated on the treated polyolefin film The surface of the PET sheet was brought into contact with the surface of the PET sheet, and then the polyolefin film and the PET sheet were heated (or hot) at 80 캜 under a pressure of 0.9 MPa and a pressure of 5 m / By pressurizing using a machine, laminated sheet 1 of each of Examples and Comparative Examples was obtained.

&Lt; Preparation of laminated sheet 2 >

Examples and Comparative Example, each of the adhesive for the laminated sheet so that the weight of the solid content of 10 g / m ² transparent polyethylene terephthalate (PET) sheet (manufactured by Corporation, Mitsubishi Polyester Film O300EW36 (trade name)), the Using an EBA coater, and then dried at 80 DEG C for 5 minutes to form an adhesive layer. Subsequently, a surface-treated PET film (Shinebeam (trade name) manufactured by TOYOBO Co., Ltd.) was coated on the surface of the PET sheet with the treated surface of the PET film Placed on the surface of the PET sheet having the adhesive layer formed thereon, and then the PET film and the PET sheet were pressed using a heating (or hot) roll press machine at 80 캜 under a pressure of 0.9 MPa and a pressure of 5 m / Each of the laminated sheets 2 of Examples and Comparative Examples was obtained.

<Evaluation>

The adhesive for the laminated sheet was evaluated by the following method. The evaluation results are shown in Tables 3 to 5.

1. Evaluation of Appearance of Laminated Sheet

After aging the laminated sheet 1 at 50 占 폚 for 5 days, the surface of the laminated sheet 1 was visually observed and evaluated. The evaluation criteria are as follows.

B (Excellent): The surface of the film of the laminated sheet 1 is smooth.

C (Normal): Wrinkles or bubbles due to the shrinkage of the laminated sheet 1 are observed on a part of the surface of the laminated sheet 1.

D (defective): Wrinkles or bubbles due to the shrinkage of the laminated sheet 1 are observed in most of the surface film of the laminated sheet 1.

2. Evaluation of reaction rate (curability)

(IR) after aging at 50 캜 for 72 hours and 120 hours immediately after the pressurization using the hot rolling press of the laminated sheet 1 was measured for each of the adhesive layers (adhesive for the laminated sheet) of the laminated sheet 1 . The IR measurement was carried out using Nicolet 380 manufactured by Thermo Electron and the peak of the isocyanate group (2,270 cm ^-1 to 2,250 cm ^-1 ) to the peak of the CH stretching vibration of the hydrocarbon group (2,970 cm ^-1 to 2,940 cm ^-1 ) height was obtained at each aging time. The reaction rate can be calculated by the following equation (v).

(peak height of isocyanate group after aging for 72 hours or 120 hours / peak height of CH stretching vibration of hydrocarbon group after aging for 72 hours or 120 hours) / (pressure The peak height of isocyanate group immediately after / the peak height of CH stretching vibration of hydrocarbon group immediately after pressurization)] x 100

The evaluation criteria are as follows.

A (excellent): The reaction rate is over 95% after aging at 50 ° C for 72 hours.

B (Excellent): The reaction rate is above 80% and below 95% after aging at 50 ° C for 72 hours.

C (normal): The reaction rate is less than 80% after aging at 50 ° C for 72 hours and more than 80% after 120 hours of aging.

D (poor): the reaction rate is less than 80% after aging at 50 DEG C for 120 hours.

3. Evaluation of Adhesion to Film after Aging

After aging at 50 DEG C for 120 hours, the laminated sheet 2 was cut into pieces having a width of 15 mm to obtain evaluation samples. Using a tensile strength testing machine (manufactured by ORIENTEC Co., Ltd. under the trade name of Tensilon RTM-250), a 180 ° peel test was carried out at room temperature under a pressure of 100 mm / Test speed. The evaluation criteria are as follows.

A (excellent): Peel strength is 12 N / 15 mm or more.

B (excellent): Peel strength is 9 N / 15 mm or more and 12 N / 15 mm or less.

C (normal): Peel strength is 6 N / 15 mm or more and 9 N / 15 mm or less.

D (poor): Peel strength is 1 N / 15 mm or more and less than 6 N / 15 mm.

4. Evaluation of hydrolysis resistance

Evaluation of hydrolysis resistance was carried out by accelerating evaluation method using pressurized steam. After aging at 50 DEG C for 120 hours, the laminated sheet 2 was cut into pieces having a width of 15 mm to obtain evaluation samples. The sample was placed in a high pressure cooker (manufactured by Yamato Scientific Co., Ltd. under the trade name of Autoclave SP300) under a pressure of 0.1 MPa at 121 DEG C for 48 hours And aged at room temperature for 1 day. Then, the sample was cut into pieces having a length of 8 cm to obtain a test piece. A manual peel test was performed on the test piece.

In the manual peel test, each of the test pieces is peeled off with the base material and the adherend (or two adherends, specifically PET sheet and PET film in this test piece) with the hands of the same measurer without using a machine, And the adhesive is evaluated by considering it. When the adhesive force of the adhesive is maintained satisfactorily, the adherend or the base material is broken upon peeling of the adherend (i.e., material breakage occurs). When the adhesive force of the adhesive deteriorates, the adhesive itself is destroyed without causing material breakage of the adherend or the base material, or peeling occurs between the adhesive and the adherend or the base material. The peel length and the material breakage state of the adherend were visually observed by the measurer and the hydrolysis resistance of the adhesive for the laminated sheet was evaluated. The evaluation criteria are as follows.

A (excellent): Substance destruction is observed when the stripping length of the adherend is less than 0.5 cm.

B (Excellent): Substance destruction is observed when the peel length of the adherend is 0.5 cm or more and less than 1.5 cm.

C (normal): Substance breakdown is observed when the stripping length of the adherend is more than 1.5 cm and less than 3 cm.

D (poor): No material breakdown is observed even when the peel length of the adherend is 3 cm or more.

5. Evaluation of port life

The components (A) to (C), and optionally the component (D) were mixed to obtain an adhesive for the laminated sheet. Immediately thereafter, the adhesive for each laminated sheet was stored at 25 DEG C for 5 hours and 24 hours. Then, the solution viscosity of the adhesive for each laminated sheet was measured, and then the port lifetime was evaluated. The solution viscosity was measured at 25 캜 and a rotational speed of 30 rpm using a rotational viscometer (model BM manufactured by Toki Mec Inc.). The evaluation criteria are as follows.

A (excellent): The viscosity increase ratio after storage for 24 hours is less than 2.

B (Excellent): The viscosity increase ratio after storage for 5 hours is less than 2.

C (normal): The viscosity increase ratio after storage for 5 hours is 2 or more.

The " viscosity increase ratio " can be calculated by the following equation (iv).

(iv): viscosity increase ratio = (viscosity after storage for 5 or 24 hours) / (viscosity immediately after mixing of components)

6. Evaluation of Coating Property

In the case of the above-mentioned production of the laminated sheet 1, the adhesive for each laminated sheet was applied on a transparent polyethylene terephthalate sheet using a bar coater. Before drying the adhesive layer at 80 DEG C for 5 minutes to form the adhesive layer, it was confirmed whether or not the line structure was observed on the coated surface.

B (Excellent): The coated surface has no line structure and is smooth.

C (Good): The area in which the line structure is observed occupies less than 20% of the surface area of the coated surface.

D (poor): The area in which the line structure is observed accounts for more than 20% of the surface area of the coated surface.

As shown in Tables 3 to 5, since the adhesives for the laminated sheets of Examples 1 to 19 include components (A) to (C), they were excellent in balance between the above Ratings 1 to 6, Lt; / RTI &gt;

On the other hand, the adhesives for the laminated sheets of Comparative Examples 1 to 8 were rated " poor " with respect to any of Evaluation 1 to 6. The adhesives for the laminated sheets of Comparative Examples 1, 7 and 8 did not contain the component (B), and the adhesives for the laminated sheets of the Comparative Examples 2 to 5 did not contain the component (A). In the adhesive for the laminated sheet of Comparative Example 6, the amount of component (B) was excessive.

Mixtures containing no component (A) or (B), and mixtures comprising excess component (B) have proved to be not useful as adhesives for laminated sheets.

Particularly, while the acrylic polyol (A15) synthesized from acrylic acid as the polymerizable monomer was used and the component (A15) had a carboxyl group, the comparative example 1 was inferior in three items of the hydrolysis-resistant, Respectively.

These results indicate that, instead of introducing the carboxyl group into the acrylic polyol (A), the result of (A) at least one selected from an acrylic polyol, (B) a carboxylic acid and a carboxylic anhydride, and (C) an isocyanate compound It has been found that the mixture is excellent as an adhesive for a laminated sheet.

Industrial applicability

The present invention provides an adhesive for a laminated sheet. The adhesive for the laminated sheet of the present invention maintains a suitable port life, and the adhesive layer formed therefrom is excellent in the reaction rate and excellent in adhesion to the film after aging. The adhesive layer is also excellent in hydrolysis resistance at a high temperature for a long period of time at a high temperature and thus induces a remarkably enhanced durability against the extreme environment. Therefore, the adhesive for the laminated sheet of the present invention can be used as a packaging bag such as a shampoo, a rinse, For example as an adhesive for solar cell modules.

1: Solar module
10: laminated sheet (back sheet)
11: Film
11a: deposited thin film
12: Film
13: Adhesive layer
20: sealing material (EVA)
30: Solar cell
40: glass plate
50: Spacer

Claims (4)

(A) at least one selected from an acrylic polyol, (B) a carboxylic acid and a carboxylic acid anhydride; And (C) an isocyanate compound, wherein
At least one kind (B) selected from a carboxylic acid and a carboxylic acid anhydride is mixed in an amount of 0.01 to 8.0 parts by weight per 100 parts by weight of the total of the components (A) - (C)
The acrylic polyol (A) can be obtained by polymerizing a polymerizable monomer, and is a polymer having a weight average molecular weight of 10,000 to 100,000 and a hydroxyl value of 0.5 to 40 mgKOH / g
glue. The adhesive for a laminated sheet according to claim 1, wherein at least one (B) selected from a carboxylic acid and a carboxylic anhydride has a melting point of 280 DEG C or less. The adhesive for a laminated sheet according to claim 1 or 2, further comprising (D) a silane compound. 4. The positive resist composition according to any one of claims 1 to 3, wherein the polymerizable monomer comprises a monomer having a hydroxyl group and another monomer; And the other monomer comprises acrylonitrile and (meth) acrylic acid ester.

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