TW201943760A - Weather resistant adhesive composition - Google Patents

Abstract

Provided are a polyester polyol and a weather resistant adhesive which exhibit practical levels of adhesiveness, resistance to moist heat, and resistance to weather due to low temperature and short term aging. The polyester polyol (A) comprises a polycarboxylic acid component and a polyhydric alcohol component as copolymerization components, comprises a hydroxy pivalic acid neopentylglycol component as the polyhydric alcohol component, includes 10 mol% or less of a terephthalic acid component when the total polycarboxylic acid component is 100 mol%, and has an acid value of 20 to 150 equivalent/106 g.

Description

Weather-resistant adhesive composition

The present invention relates to a polyester polyol and a weather-resistant adhesive composition suitable for outdoor industrial applications and the like.

As a target for outdoor industrial applications, for example, a weather-resistant adhesive composition such as a building material, a solar cell surface sheet, or the like, a polyurethane-based adhesive including a polyester polyol is known.

Patent Document 1 discloses a specific polyurethane-based adhesive, and describes that it has excellent long-term humidity and heat resistance. In addition, Patent Document 2 discloses a laminate obtained by bonding a base material of at least two layers with a polyurethane-based adhesive, and describes that the laminate is excellent in weather resistance.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-43238 [Patent Document 2] Japanese Patent Laid-Open No. 2007-320218

[Questions to be solved by the invention]

In the curing reaction of polyurethane, for example, if it is applied to a metal plate and the metal plates are adhered to each other, a high temperature of approximately 200 ° C. can be applied and the curing time can be shortened. However, depending on the type and form of the bonded substrate, high temperature cannot be applied in many cases. The production of a laminate including a resin film described in Patent Literature 1 and Patent Literature 2 is a typical example of this case. In the embodiment of Patent Literature 1, curing is performed at 60 ° C for 7 days, and in Patent Literature In the example of 2 it was aged at 50 degreeC for 5 days, and the laminated body was produced. In this way, in the prior art, the aging process is generally performed at a relatively low temperature of about 50 to 60 ° C. for a long time of about 5 to 7 days. If the aging temperature can be set to the same level or lower as the current situation, and the aging time can be shortened, it is preferable from the viewpoint of saving energy, improving workability, productivity, and reducing costs.

Therefore, the subject of the present invention is to provide a weather-resistant adhesive that exhibits practical grades of adhesion, moist heat resistance, and weather resistance through low-temperature and short-term curing.
[Means for solving problems]

The present inventors made intensive studies in order to solve the above-mentioned problems, and as a result, found that an adhesive composition containing hydroxytrimethylacetic acid neopentyl glycol and a polyester polyol having a specific range of acid value and a polyisocyanate compound By aging at a relatively low temperature of about 40 to 60 ° C for a short period of about one day, good adhesion, moisture and heat resistance, and weather resistance will be exerted, and the present invention will be completed. That is, this invention includes the following structures.

A polyester polyol (A) in which a polycarboxylic acid component and a polyhydric alcohol component are used as copolymerization components, and a hydroxytrimethylacetic acid neopentyl glycol component is used as the polyol component, and a total polycarboxylic acid component is taken as 100 mol% The terephthalic acid content is 10 mol% or less, and the acid value is 20 to 150 equivalents / 10 ⁶ g.

It is preferable that the total polyol component of the polyester polyol (A) mentioned above contains 10 mol% or more of hydroxytrimethylacetic acid neopentyl glycol when 100 mol%, and further contains 3-methyl A -1,5-pentanediol component is preferred. The glass transition temperature of the polyester polyol (A) is -20 to 20 ° C, and the number average molecular weight is preferably 4,000 to 50,000.

A weather-resistant adhesive composition comprising the polyester polyol (A) and a polyisocyanate compound (B) containing an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound.

The polyisocyanate compound (B) is selected from the group consisting of an adduct of hexamethylene diisocyanate, an isotricyanate body of hexamethylene diisocyanate, a biuret body of hexamethylene diisocyanate, One or two or more of the group consisting of an adduct of phorone diisocyanate, an isotricyanate body of isophorone diisocyanate, and a biuret body of isophorone diisocyanate are preferred.

The blending ratio of the polyester polyol (A) and the polyisocyanate compound (B) is such that the polyisocyanate compound (B) is 1 to 20 parts by mass relative to 100 parts by mass of the polyester polyol (A). good.

A laminated body comprising an adhesive layer and a substrate including the weather-resistant adhesive composition according to any one of the foregoing. The substrate is preferably one or two or more films selected from the group consisting of a polyester film, a fluoropolymer film, a polyethylene film, and a vinyl acetate copolymer film.
[Effect of Invention]

The adhesive composition using the polyester polyol of the present invention exhibits good adhesion and resistance by being cured at a relatively short temperature of about 1 day at a relatively low temperature of about 40 to 60 ° C. Damp heat and weather resistance. Therefore, it becomes possible to save energy, improve workability, productivity, and reduce costs.

A polyester polyol (A) in which a polycarboxylic acid component and a polyhydric alcohol component are used as a copolymerized component, and hydroxytrimethylacetic acid neopentyl glycol is used as the polyhydric alcohol component, and the total polycarboxylic acid component is 100 mol% The terephthalic acid component is 10 mol% or less, and the acid value is 20 to 150 equivalents / 10 ⁶ g. A weather-resistant adhesive composition comprising the polyester polyol (A) and a polyisocyanate compound (B) containing an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound.

<Polyester polyol (A)>
The polyester polyol (A) of the present invention is preferably a chemical structure obtained by polycondensation of a polycarboxylic acid and a polyhydric alcohol. As the polycarboxylic acid, fats such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azalea acid, sebacic acid, tridecanedioic acid, dimer acids, and their hydrides can be used. Diprotic acids (aliphatic dicarboxylic acid), terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid and other aromatic diprotic acids (aromatic dicarboxylic acid) the above.

From the viewpoint of improving weather resistance, it is effective to suppress the copolymerization ratio of the terephthalic acid component to a low level. When the total polycarboxylic acid component is 100 mol%, the terephthalic acid component must be 10 mol% or less. . It is preferably less than 10 mol%, more preferably 5 mol% or less, even more preferably 1 mol% or less, and 0 mol% is not a problem. By setting it in the said range, favorable weather resistance can be expressed.

From the viewpoint of improving the moisture and heat resistance, as the aromatic dicarboxylic acid component, an isophthalic acid component, a phthalic acid component, or a 2,6-naphthalenedicarboxylic acid component is preferable, and the isophthalic acid component Or phthalic acid is more preferred. The total amount of the polycarboxylic acid component as 100 mol% time phthalic acid component and phthalic acid component is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 Molar% or more, particularly preferably 95 Molar% or more. It is more preferably 99 mol% or less, and more preferably 98 mol% or less. By setting it in the said range, favorable adhesiveness can be expressed.

As the aromatic dicarboxylic acid component, it is preferable to use an isophthalic acid component and a phthalic acid component in combination. The blending ratio (molar ratio) is an isophthalic acid component / phthalic acid component = 90. It is preferably from 50 to 50/10 to 50, more preferably from 80 to 60/20 to 40, and even more preferably from 75 to 65/25 to 35. By setting it in the said range, excellent adhesiveness, moist heat resistance, and weather resistance can be expressed.

The hydroxytrimethylacetic acid neopentyl glycol component must be included as the polyol component. By including a neopentyl glycol component of hydroxytrimethylacetate, excellent adhesiveness can be exhibited. When the total polyol component is 100 mol%, the hydroxytrimethylacetic acid neopentyl glycol component is preferably 1 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more. Especially good is more than 20 mol%. It is more preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 45 mol% or less. By setting it in the said range, favorable adhesiveness with a base material can be expressed.

As the polyol component other than hydroxytrimethylacetic acid neopentyl glycol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 3-methyl-1 can be used. 5,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 -Decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3- One or more kinds of aliphatic diols such as propylene glycol, alicyclic diols such as cyclohexanediol and hydrogenated diols, and diols such as diols containing aromatic rings such as diols.

An aliphatic diol component containing a long-chain aliphatic structure is preferred. From the viewpoint of moist heat resistance, it is preferred to use an aliphatic diol component having a carbon number of 5 or more, and a fat having a carbon number of 6 or more and 12 or less. Group diol components are more preferred. Among them, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol , 1,11-undecanediol, 1,12-dodecanediol, or 3-methyl-1,5-pentanediol is more preferred, and 3-methyl-1,5 is particularly preferred -Pentanediol. The aliphatic diol component containing a long-chain aliphatic structure is preferably 50 mol% or more when the total polyol component is 100 mol%, and more preferably 60 mol% or more. It is more preferably 99 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, and particularly preferably 80 mol% or less. By setting the upper limit 前述 or higher, good moisture and heat resistance can be developed, and by setting the upper limit 値 or lower, good adhesion can be developed.

When the total polyol component is 100 mol%, the total content of the hydroxytrimethylacetic acid neopentyl glycol component and the 3-methyl-1,5-pentanediol component is preferably 20 mol% or more. , More preferably 30 mol% or more, even more preferably 40 mol% or more. By setting it in the said range, excellent adhesiveness, moist heat resistance, and weather resistance can be expressed. In addition, the total of hydroxytrimethylacetic acid neopentyl glycol component, 3-methyl-1,5-pentanediol component, and other aliphatic diol components containing a long-chain aliphatic structure is 80 mol% or more. Preferably, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% is not a problem.

The tri- or higher-functional polycarboxylic acid components such as trimellitic anhydride and pyromelite dianhydride, and tri- or higher-functional polyhydric alcohol components such as trimethylolpropane are copolymerized in a small amount to introduce branching. The effect of the reactivity of the isocyanate compound (B) is a preferred embodiment. When the total polycarboxylic acid component is 100 mol%, the trifunctional or higher polycarboxylic acid component is preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 1 mol% or less. When the total polyol component is 100 mol%, the trifunctional or higher polyol component is preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 1 mol% or less. When it is too large, the branch becomes excessive, and the polyester polyol (A) may become gelatinous.

When producing the polyester polyol (A) of the present invention, a conventionally known polymerization catalyst can be used. For example, tetra-n-butyl titanate, tetra-isopropyl titanate, titanium compounds such as acetone titanylacetate, antimony compounds such as tributoxy antimony, antimony trioxide, tetra-n-butoxy germanium, germanium oxide, etc. Germanium compounds, etc. These catalysts can be used singly or in combination of two or more kinds. From the viewpoint of polymerization reactivity, a titanium compound is preferred.

The polyester polyol (A) used in the present invention has an acid value of 20 to 150 equivalents / 10 ⁶ g, preferably 50 to 120 equivalents / 10 ⁶ g, and more preferably 70 to 100 equivalents 10 ⁶ g. When the acid value is set to the above lower limit 値 or more, the effect of shortening the curing time can be exhibited, and when the acid value is set to the aforementioned upper limit 値 or less, excellent moisture and heat resistance of the adhesive layer obtained from the weather-resistant adhesive composition can be developed.

The method for adjusting the acid value of the polyester polyol (A) is not particularly limited, and the acid value can be adjusted by a method of intentionally polymerizing a large number of carboxyl terminals or by introducing a carboxyl group into the polyester polyol. The method for introducing a carboxyl group into a polyester polyol includes: a method of adding an acid anhydride to give an acid value after polymerizing the polyester polyol under normal pressure and nitrogen atmosphere; and an oligomer state before the polyester polymer is quantified. These acid anhydrides are introduced, followed by a method of polymerizing the polymer by polycondensation under reduced pressure. When the former method is used and trimellitic anhydride is used, the target acid value can be obtained particularly easily. As acid anhydrides that can be used in these reactions, in addition to the trimellitic anhydride already mentioned, phthalic anhydride, pyromelite dianhydride, succinic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1, 2-cyclohexanedicarboxylic anhydride, cyclohexane-1,2,3,4-tetracarboxylic acid-3,4-dianhydride, ethylene glycol bistrimellitic anhydride, 5- (2,5-dioxo Tetrahydro-3-furan) 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, naphthalene-1,8: 4,5-tetracarboxylic dianhydride and other aromatic carboxylic anhydrides and alicyclic rings Group carboxylic anhydrides are preferred, and one or more of these may be selected and used.

If an acid anhydride or the like is added (post-added) after the polyester is polymerized to give an acid value, the total amount of the polycarboxylic acid component may be more than 100 mole%. At this time, it is assumed that the total amount of the polycarboxylic acid component other than the components such as an acid anhydride (post-addition) is calculated as 100 mol%.

The range of the glass transition temperature of the polyester polyol (A) of the present invention is preferably -20 to 20 ° C, more preferably 0 to 10 ° C. In order to obtain such a polyester polyol, a diprotic acid or a diol having a long aliphatic chain in the copolymerization component may be introduced. In addition, in order to have both moisture and heat resistance, it is preferable to copolymerize an aliphatic diol having a carbon number of 5 or more. From the standpoint of adhesion, it is used together with hydroxytrimethylacetic acid neopentyl glycol 3- Methyl-1,5-pentanediol is particularly preferred. By setting the glass transition temperature to the aforementioned upper limit 値 or lower, good adhesion to the substrate can be exhibited, and by setting the aforementioned lower limit 値 or higher, the adhesive layer containing the weather-resistant adhesive composition does not become excessive. It is soft and exhibits excellent adhesion and moisture and heat resistance.

The number average molecular weight of the polyester polyol (A) of the present invention is not particularly limited, but is preferably 4,000 to 50,000, and more preferably 8,000 to 20,000. By setting the number average molecular weight of the polyester polyol (A) to the aforementioned lower limit 値 or higher, the molecular weight of the cross-linked ring does not become too small, and the adhesive layer containing the weather-resistant adhesive composition becomes an appropriate hardness, and can be exhibited. Good bonding strength. In addition, by setting the number average molecular weight of the polyester polyol (A) to not more than the aforementioned upper limit 値, it is possible to sufficiently react with the polyisocyanate (B), and to exhibit good moisture and heat resistance.

<Polyisocyanate compound (B)>
The polyisocyanate compound (B) used in the present invention preferably contains an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound. As the aliphatic polyisocyanate compound, an aliphatic diisocyanate compound is preferable, and specifically, a hexamethylene diisocyanate is mentioned as a suitable example. Moreover, as an alicyclic polyisocyanate compound, an alicyclic diisocyanate compound is preferable, and an isophorone diisocyanate is mentioned specifically as a suitable example. Hexamethylene diisocyanate or isophorone diisocyanate is preferred in terms of improving weather resistance.

The polyisocyanate compound (B) may be an isotricyanate body, a biuret body, or an adduct, respectively, and an isotricyanate body is particularly preferred. Specific examples include an adduct of hexamethylene diisocyanate, an isotricyanate body of hexamethylene diisocyanate, a biuret body of hexamethylene diisocyanate, and isophorone diisocyanate. Adduct, isotrione diisocyanate isotricyanate body, and isophorone diisocyanate biuret body. These can be used singly or in combination of two or more kinds.

The content of the polyisocyanate compound (B) with respect to 100 parts by mass of the polyester polyol (A) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more. Furthermore, it is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and still more preferably 15 parts by mass or less. By setting it in the said range, favorable adhesiveness can be expressed.

＜ Weather-resistant adhesive composition ＞
The weatherable adhesive composition of the present invention is preferably a composition containing the polyester polyol (A) and the polyisocyanate compound (B). In order to block the carboxyl group generated when the polyester polyol (A) is hydrolyzed, the weather-resistant adhesive composition of the present invention can be blended with carbodiimide compounds, oxazoline compounds, epoxy compounds, etc. at any ratio. Blockade. The blending amount of the terminal blocking agent is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the polyester polyol (A). By setting the blending amount as described above, a terminal blocking effect of the carboxyl group can be obtained. The content is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. By setting the blending amount as described above, good adhesiveness can be exhibited.

Examples of the carbodiimide compound include N, N'-di-o-tolylcarbodiimide, N, N'-diphenylcarbodiimide, N, N'-di-2,6-di Methylphenylcarbodiimide, N, N'-bis (2,6-diisopropylphenyl) carbodiimide, N, N'-dioctyldecylcarbodiimide, N-toluene -N'-cyclohexylcarbodiimide, N, N'-di-2,2-di-tert-butylphenylcarbodiimide, N-tolyl-N'-phenylcarbodiimide , N, N'-di-p-nitrophenylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-di-cyclohexylcarbodiimide, N, N'-di-p-tolylcarbodiimide and the like.

Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, and 2,5-dimethyl-2-oxazole Monooxazoline compounds such as phthaloline, 2,4-diphenyl-2-oxazoline, 2,2 '-(1,3-phenylene) -bis (2-oxazoline), 2,2' -(1,2-Extended ethyl) -bis (2-oxazoline), 2,2 '-(1,4-extended butyl) -bis (2-oxazoline), 2,2'-( Dioxazoline compounds such as 1,4-phenylene) -bis (2-oxazoline).

Examples of the epoxy compound include diglycidyl ethers of aliphatic diols such as 1,6-hexanediol, neopentyl glycol, and polyalkylene glycols, sorbitol, sorbitol anhydride, and polyglycerol. , Polyglycidyl ethers of aliphatic polyhydric alcohols such as neopentyl tetraol, diglycerol, glycerol, trimethylolpropane, polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol, p-benzene Diglycidyl or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as dicarboxylic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid, sebacic acid, etc. Resorcinol, bis (p-hydroxyphenyl) methane, 2,2-bis (p-hydroxyphenyl) propane, ginseng (p-hydroxyphenyl) methane, 1,1,2,2- (p-hydroxyphenyl) ) Glycidyl ether or polyglycidyl ether of polyvalent phenols such as ethane, such as N, N-glycidylaniline, N, N-glycidyltoluidine, N, N, N ', N'-tetra-glycidyl-bis (p-aminophenyl) methane amino-N-glycidyl derivative, aminophenol triglycidyl derivative, triglycidyl derivative Ginseng (2-hydroxyethyl) isotricyanate, triglycidyl isotricyanate, o-methyl Polyphenol epoxy, phenol novolac epoxy, bisphenol polyfunctional epoxy compound.

The weather-resistant adhesive composition of the present invention may contain well-known additives such as an ultraviolet absorber and an antioxidant, and may further improve weather resistance and humidity and heat resistance.

By using the weather-resistant adhesive composition of the present invention as an adhesive layer, a laminated body in which the adhesive layer and a substrate are laminated can be obtained. Examples of the substrate include one or two or more films selected from the group consisting of a polyester film, a fluoropolymer film, a polyethylene film, and a vinyl acetate copolymer film. The aforementioned laminate can be not only a three-layer laminate of film / adhesive layer / film, but also a five-layer laminate of film / adhesive layer / film / adhesive layer / film, or a stack of more layers body. The films constituting the laminate may be composed of the same material, or may be composed of different materials.

The laminated body may be a substrate that is coated with a weather-resistant adhesive composition and dried, or an adhesive layer containing a weather-resistant adhesive composition prepared in advance, and the adhesive layer is laminated on Substrate. The conditions for coating and drying the weather-resistant adhesive composition on the substrate are not particularly limited, but 40 to 250 ° C is preferred. If it is lower than 40 ° C, the drying time is time-consuming and unreasonable in terms of industrial production. In addition, the drying of the coating film may be incomplete. If it is higher than 250 ° C, a high-efficiency drying furnace is required, which is not preferable. The drying method is also not limited, and it can be applied to well-known methods such as hot air dryer, induction heating, near infrared heating, far infrared heating, and indirect heating. The thickness of the adhesive layer after drying is usually 5 to 30 μm, preferably 10 to 20 μm.

Examples of the polyester constituting the polyester film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polyethylene. Cyclohexanedimethanol-terephthalate (PCT).

The fluorine-based polymer constituting the fluorine-based polymer film refers to, for example, a fluorinated polyolefin and a polyolefin-fluorinated polyolefin copolymer, and specific examples thereof include polyvinyl fluoride (PVF), polyvinylidene fluoride ( PVDF), polychlorotrifluoroethylene (PCTFE), polyethylene tetrafluoroethylene (ETFE), polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoro Propylene copolymer (FEP) and the like.

Examples of the polymer constituting the polyethylene film include low-density polyethylene, high-density polyethylene, ultra-high molecular weight polyethylene, and various additives added thereto.

Examples of the polymer constituting the vinyl acetate copolymer film include an ethylene-vinyl acetate copolymer, and various additives added thereto.

The substrate used in the present invention may be used with or without surface treatment. In order to improve the adhesion of the coated surface and the adhesive surface, surface treatment such as corona treatment, flame treatment, and plasma treatment is preferred.

This case is based on the Japanese Patent Application No. 2018-076800 filed on April 12, 2018 and claiming priority. The entire contents of the specification of the aforementioned Japanese Patent Application No. 2018-076800 are incorporated herein by reference.
[Example]

The present invention will be described below using examples. In the examples, those simply described as "parts" represent parts by mass. In addition, each measurement item is based on the following method.

(Composition of polyester polyol (A))
The composition and composition ratio of the polyester polyol (A) were determined by ¹ H-NMR measurement (protonic nuclear magnetic resonance spectrometry) at a resonance frequency of 400 MHz. As a measuring device, a NMR device 400-MR manufactured by Varian was used, and as a solvent, deuterated chloroform was used. In addition, in the case where the acid value of the polyester polyol (A) is increased by the post-addition of the acid, the total amount of the acid components other than the acid component used in the post-added acid is 100 mol%, and the molar ratio of each component is calculated. .

(Number average molecular weight Mn)
A 4 mg sample (polyester polyol (A)) was dissolved in 4 ml of tetrahydrofuran (5 mM tetrabutylammonium chloride was added), and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a sample solution for measurement. The mobile phase was tetrahydrofuran and the device was TOSOH HLC-8220. The differential average refractometer was used to determine the number average molecular weight of polyester polyol (A) by gel permeation chromatography at a column temperature of 40 ° C and a flow rate of 1 ml / min. . The string used is Showa Denko Shodex KF-802, KF-804, and KF-806 connected in series. The number average molecular weight is calculated as a standard polystyrene conversion 値, and a low molecular weight (oligomer) portion corresponding to a molecular weight of less than 1,000 is omitted.

(Glass transition temperature (Tg))
The measurement was performed with a differential scanning calorimeter (SII, DSC-200). A 5 mg sample (polyester polyol (A)) was put into an aluminum lid-type container and sealed. First, it was cooled to -50 ° C using liquid nitrogen, and then heated to 150 ° C at 20 ° C / minute. In the endothermic curve obtained by the process, the extension line of the baseline before the endothermic peak appears (below the glass transition temperature) and the tangent to the endothermic peak (indicating the maximum slope from the peak of the peak to the peak of the peak) The temperature at the intersection of the tangent lines) is the glass transition temperature (Tg, unit: ° C).

(Acid value (AV))
A 0.2 g sample (polyester polyol (A)) was finely weighed and dissolved in 40 ml of chloroform. Next, titration was performed using a 0.01N potassium hydroxide in ethanol solution. As the indicator, phenolphthalein was used. The measurement 値 is converted into an equivalent weight per 10 ⁶ g of the sample, and the unit is set to equivalent weight / 10 ⁶ g.

Production Example of Polyester Polyol (P1) Put 415 parts of isophthalic acid, 180 parts of phthalic acid, 7 parts of trimellitic anhydride, and 333 parts of hydroxyl in a reaction vessel equipped with a stirrer, condenser, and thermometer. Trimethylacetic acid neopentyl glycol, 449 parts of 3-methyl-1,5-pentanediol, 0.03 mole% TBT as a catalyst relative to the total acid content, from 160 ° C to 230 ° C It took 4 hours for the transesterification reaction. Next, the inside of the system was decompressed slowly, and it took 20 minutes to decompress to 5 mmHg, and further, a polycondensation reaction was performed at 250 ° C. for 60 minutes under a vacuum of 0.3 mmHg or less. It was cooled to 215 ° C. under a stream of nitrogen gas, and 7 parts of trimellitic anhydride was added thereto, and a reaction was performed for 30 minutes. The obtained polyester polyol (P1) was subjected to composition analysis by NMR. As a result, the acid component was isophthalic acid / phthalic acid / trimellitic acid = 69/30/1 in terms of mole ratio, and the diol was The composition is hydroxytrimethylacetic acid neopentyl glycol / 3-methyl-1,5-pentanediol = 30/70 in terms of mole ratio. The number average molecular weight was 14,000, the glass transition temperature was 8 ° C, and the acid value was 80 equivalents / 10 ⁶ g.

The production examples of polyester polyols (P2) to (P12) are compared with the production examples of polyester polyol (P1), but the types and blending ratios of raw materials are changed to produce polyester polyols (P2) to (P12). The results are described in Table 1.

【Table 1】

Hereinafter, a hardener (polyisocyanate compound (B)) and an additive system show the following.
Hardener 1: Polyisocyanate compound, hexamethylene diisocyanate (HDI) isocyanurate "DESMODUR (registered trademark) N3300 by Sumitomo Bayer".
Hardener 2: Polyisocyanate compound, isophorone diisocyanate (IPDI) isotricyanate body "DESMODUR Z4470 manufactured by Bayer".
Hardener 3: Polyisocyanate compound, toluene diisocyanate (TDI) isocyanurate "DESMODUR IL 1351 manufactured by Bayer".
Additive (epoxy compound): a bisphenol-type polyfunctional epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation).

Example 1
(Manufacture of weather-resistant adhesive composition (1))
100 parts of resin P1, 4 parts of epoxy resin, and 382 parts of ethyl acetate were mixed and blended with 10 parts of a hardener as a weather-resistant adhesive composition (1).

(Evaluation of initial adhesion and humidity and heat resistance)
The weather-resistant adhesive composition (1) was applied to the substrate A with an applicator so that the dry film thickness (film thickness after drying) became 8 μm, and the solvent was volatilized, and then the substrate was dried using a laminator. Material B was crimped (dry laminated). The drying lamination system was performed at a roll temperature of 90 ° C., a roll load of 3 kg / cm, and a speed of the object to be bonded to be 1 m / min. Next, it aged at 50 degreeC for 1 day, and hardened the weather-resistant adhesive composition, and obtained the base material A / adhesive layer / base material B laminated body. By the same method, a substrate A / adhesive layer / substrate C laminate was obtained. In Example 1, a polyester film (TOYOBO, SHINEBEAM (registered trademark) Q1215, thickness: 250 μm) was used as the substrate A, a PVF film (25 μm, manufactured by Du Pont) was used as the substrate B, and EVA was used as the substrate C Film (manufactured by SANVIC, thickness: 300 μm).

Each of the cured laminates was cut into strips having a width of 15 mm, and the substrate A and the substrate B, and the substrate A and the substrate were measured by TENSILON (registered trademark) (manufactured by Toyo Kogyo Co., Ltd., UTM-IV). The peel strength of the material C (T-type peeling film peeling, stretching speed: 100 mm / min) was used as the initial adhesion force. The evaluation results are shown in Table 2.
Evaluation criteria: Base material A / Base material B
○: 9N / 15mm or more △: 6N / 15mm or more and less than 9N / 15mm
×: less than 6N / 15mm
Evaluation criteria: Substrate A / Substrate C
○: 8N / 15mm or more △: 6N / 15mm or more and less than 8N / 15mm
×: less than 6N / 15mm

In addition, a high-temperature and high-pressure tester (ES-315 manufactured by TOMY Industrial Co., Ltd.) was used to provide an environment of 121 ° C., 100% RH, and 90 hours to the laminate of the substrate A / adhesive layer / substrate B after curing. After the load, it was cut into strips having a width of 15 mm, and the peel strength of the substrate A and the substrate B was measured (T-type peeling film peeling, stretching speed: 100 mm / minute).
Evaluation benchmark:
○: 9N / 15mm or more △: 6N / 15mm or more, less than 9N / 15mm
×: less than 6N / 15mm

(Evaluation of Hardness)
The weather-resistant adhesive composition (1) was applied to a polyester film (Toyobo E5101, thickness 50 μm, corona-treated surface) with a coater so that the dry film thickness became 10 μm, and the solvent was evaporated, followed by drying and lamination. A polypropylene film (P2161 manufactured by Toyobo Co., Ltd., 50 μm thick, non-corona treated surface) was crimped (dry laminated) by a machine. The drying lamination system was performed at a roll temperature of 120 ° C., a roll load of 3 kg / cm, and a speed of the adherend to be 1 m / minute. Then, 50 ° C. and 48 hours of curing were performed to harden the weather-resistant adhesive composition, and the polypropylene film was further peeled to obtain a polyester film / adhesive layer laminate.

The laminated body of the cured polyester film / adhesive layer was cut into strips having a length of 2.5 cm and a width of 10 cm, and the weight was measured (this weight was set to A), and toluene / methyl ethyl ketone = 1/1 (weight ratio) The mixed solution was immersed for 1 hour. After the immersion, the laminate was taken out and dried with a hot-air drier for 1 hour, and the weight was measured (this weight was set to B). Thereafter, the adhesive layer remaining on the laminate was scraped off, and the weight of only the polyester film was measured (this weight was set to C). The number 値 calculated by the following formula is defined as the degree of hardening (%). The evaluation results are shown in Table 2.
Hardness (%) = {(AC) / (BC)} × 100
Evaluation benchmark:
○: 65% or more △: 40% or more and less than 65%
×: less than 40%

(Evaluation of weather resistance)
The weather-resistant adhesive composition (1) was applied to a polyester film (manufactured by Toyobo, SHINEBEAM (registered trademark) Q1210, thickness 50 μm) with a coater so that the dry film thickness became 20 μm, and the dried layer was used after the solvent was evaporated. The polypropylene film (P2161, manufactured by Toyobo Co., Ltd., 50 μm thick, non-corona treated surface) was crimped by a machine. The drying lamination system was performed at a roll temperature of 120 ° C., a roll load of 3 kg / cm, and a speed of the adherend to be 1 m / minute. Next, curing was performed at 40 ° C. for 24 hours to harden the weather-resistant adhesive composition, and the polypropylene film was further peeled to obtain a polyester film / adhesive layer laminate.

Ultraviolet rays were irradiated from the adhesive layer side of the laminated body of the cured polyester film / adhesive layer. Ultraviolet rays were irradiated using a UV irradiation tester (IWASAKI ELECTRIC, EYE Super UV Tester (registered trademark), SUV-W151), and the irradiation conditions were set to 60 ° C (blackboard temperature), relative humidity 60%, and only irradiation. The irradiation time was set to 24 hours. The color difference meter (ZE2000, manufactured by Nippon Denshoku Co., Ltd.) was used to measure the Co-b 値 of the polyester film / adhesive layer laminate before and after ultraviolet irradiation, and the difference between the before and after ultraviolet irradiation was used as an index of weather resistance. The larger the number, the greater the degree of yellowing, indicating poor weather resistance. The evaluation results are shown in Table 2.
Evaluation benchmark:
○: less than +15
×: +15 or more

Examples 2 to 10, Comparative Examples 1 to 3, Reference Example 1
A weather-resistant adhesive composition (1) to a weather-resistant adhesive composition (14) were produced by comparing the weather-resistant adhesive composition (1) of Example 1. Next, the weather-resistant adhesive composition and the substrate were changed as described in Table 2 and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2.

【Table 2】 [Industrial availability]

In the prior art, the aging treatment is generally performed at a relatively low temperature of about 50 to 60 ° C. for a long time of about 5 to 7 days. As long as the aging temperature can be set to the same level or lower as the current situation, and the aging time can be shortened, it is preferable from the viewpoints of saving energy, improving workability and productivity, and reducing costs.

Claims (9)

A polyester polyol (A) comprising a polycarboxylic acid component and a polyhydric alcohol component as a copolymerization component, including a hydroxytrimethylacetic acid neopentyl glycol component as a polyol component, and a total polycarboxylic acid component as 100 mol% The terephthalic acid content is 10 mol% or less, and the acid value is 20 to 150 equivalents / 10 ⁶ g. For example, the polyester polyol (A) of claim 1, wherein when the total polyol component is 100 mol%, it contains 10 mol% or more of hydroxytrimethylacetic acid neopentyl glycol component. For example, the polyester polyol (A) of claim 1 or 2 further contains a 3-methyl-1,5-pentanediol component. For example, the polyester polyol (A) of claim 1 or 2, wherein the glass transition temperature is -20 to 20 ° C and the number average molecular weight is 4,000 to 50,000. A weather-resistant adhesive composition comprising the polyester polyol (A) according to any one of claims 1 to 4, and a polyisocyanate compound containing an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound (B). The weatherable adhesive composition according to claim 5, wherein the polyisocyanate compound (B) is selected from the group consisting of an adduct of hexamethylene diisocyanate, an isotricyanate body of hexamethylene diisocyanate, Group consisting of biuret body of hexamethylene diisocyanate, adduct of isophorone diisocyanate, isotricyanate body of isophorone diisocyanate, and biuret body of isophorone diisocyanate One or more types of groups. The weatherable adhesive composition according to claim 5 or 6, wherein the blend ratio of the polyester polyol (A) and the polyisocyanate compound (B) is 100 parts by mass of the polyester polyol (A) It is 1 to 20 parts by mass of the polyisocyanate compound (B). A laminated body comprising an adhesive layer and a substrate including the weather-resistant adhesive composition according to any one of claims 5 to 7. The laminated body according to claim 8, wherein the substrate is one or two or more films selected from the group consisting of a polyester film, a fluoropolymer film, a polyethylene film, and a vinyl acetate copolymer film.