JP2018109150A - Polyester-based adhesive composition, polyester-based adhesive, adhesive sheet, and optical member with adhesive layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester-based adhesive composition capable of giving an adhesive which has high-level blister resistance even when exposed to a high-temperature and high-humidity environment.SOLUTION: The polyester-based adhesive composition contains a polyester-based resin (I) obtained from: a polycarboxylic acid component (A) in which the content ratio of an aromatic dicarboxylic acid (a1) is 50 mol% or more; and a polyol component (B) containing a diol compound (b1) having a hydrocarbon group in a side chain. The content ratio of isophthalic acid to the whole aromatic dicarboxylic acid (a1) is 60 mol% or more. The polyester-based resin (I) has a glass transition temperature of -20 to +30°C.SELECTED DRAWING: None

Description

  The present invention relates to a polyester-based pressure-sensitive adhesive composition, a polyester-based pressure-sensitive adhesive using the same, a pressure-sensitive adhesive sheet, and an optical member with a pressure-sensitive adhesive layer.

  Conventionally, polyester resins have excellent heat resistance, chemical resistance, durability, and mechanical strength, so they are used in a wide range of applications such as films, PET bottles, fibers, toners, electrical parts, adhesives, and adhesives. However, in recent years, polyester-based pressure-sensitive adhesives have been used particularly as pressure-sensitive adhesives when bonding optical members.

  On the other hand, in recent years, display devices such as a liquid crystal display (LCD) and input devices used in combination with the display device such as a touch panel have been widely used in various fields. In, a transparent pressure-sensitive adhesive sheet, for example, a substrate-less double-sided pressure-sensitive adhesive sheet, is used for bonding optical members such as an optical film and a base material.

  Here, a transparent base material is required for an optical member constituting an optical device such as a touch panel, and conventionally, a glass base material such as a protective cover made of glass or a glass substrate has been used. From the viewpoint of weight reduction, a plastic substrate such as a polycarbonate resin, an acrylic resin, or a (cyclic) olefin resin is used instead of a glass substrate.

  However, when such a plastic substrate is used, there is a problem that foaming or peeling occurs between the plastic substrate and the pressure-sensitive adhesive layer due to gas or moisture generated from the plastic substrate, leading to a decrease in visibility. there were.

  Therefore, the pressure-sensitive adhesive used for bonding optical members is required to have a performance (hereinafter referred to as blister resistance) capable of suppressing such foaming and peeling.

  For example, Patent Document 1 discloses a pressure-sensitive adhesive that contains a polyester-based resin that exhibits a sufficient adhesive force at a pressure of about a finger pressure and can be developed in a wide range of applications having excellent adhesiveness, heat resistance, and mechanical strength. As a polycondensation of a carboxylic acid component containing 10 mol% or more and less than 50 mol% of an aromatic dicarboxylic acid and a polyhydric alcohol component containing 5 mol% or more of a glycol having a hydrocarbon group in the side chain, and A pressure-sensitive adhesive composition containing a polyester resin having a number average molecular weight of 5000 or more is described, and it is also described that it can be used as a pressure-sensitive adhesive for an optical member.

  In addition, Patent Document 2 has various properties such as excellent surface tackiness, adhesive strength, heat resistance, moisture resistance, creep resistance, etc. both in the initial stage and after wet heat aging, and an excellent adhesive layer. As a pressure-sensitive adhesive composition that can be formed, a polyester-based resin having a hydroxyl group and / or carboxyl group in the side chain and containing 5 to 50 mol% of an aromatic ring structure, having a glass transition temperature in the range of −80 to 0 ° C. A pressure-sensitive adhesive composition comprising a cyclic diterpene compound and a reactive compound capable of reacting with a hydroxyl group and / or a carboxyl group in the resin is described.

JP 2007-45914 A JP 2009-7419 A

  However, since the pressure-sensitive adhesive described in Patent Document 1 uses a polyester-based resin using a polyvalent carboxylic acid component with a small content of aromatic dicarboxylic acid, the glass transition temperature of the polyester-based resin is low. Therefore, the adhesive strength at high temperatures (especially 80 ° C. or more) tends to decrease, and the blister resistance under high temperature and high humidity conditions is poor.

  Also in Patent Document 2, the pressure-sensitive adhesive actually disclosed uses a polyester-based resin having a low glass transition temperature, and does not have sufficient adhesive strength under high-temperature and high-humidity conditions. The high level of blister resistance that can be achieved is not obtained.

  The present invention has been made in view of the above-described conventional circumstances, and can provide a pressure-sensitive adhesive having a high level of blister resistance even when exposed to a high-temperature and high-humidity environment. The purpose is to provide.

  As a result of intensive research in view of such circumstances, the present inventor is a polyester-based resin having a glass transition temperature in a specific range higher than that of a resin generally used in a pressure-sensitive adhesive composition. A polyester-based resin obtained from a polyvalent carboxylic acid component having an aromatic dicarboxylic acid as a main component and containing 60 mol% or more of isophthalic acid as an aromatic dicarboxylic acid, and a specific polyol component having a side chain structure By using it, it was found that a pressure-sensitive adhesive exhibiting a very high level of blister resistance was obtained, and the present invention was completed.

That is, the present invention relates to the following <1> to <9>.
<1> Polyol component (B) containing a polycarboxylic acid component (A) having an aromatic dicarboxylic acid (a1) content of 50 mol% or more and a diol compound (b1) having a hydrocarbon group in the side chain A polyester resin (I) obtained from the following, a polyester resin (I) having a content of isophthalic acid of 60 mol% or more with respect to the whole aromatic dicarboxylic acid (a1) and a glass transition temperature of −20 to + 30 ° C. A polyester-based pressure-sensitive adhesive composition comprising I).
<2> Furthermore, 0.01-10 mass parts of hydrolysis inhibitors (II) are contained with respect to 100 mass parts of the said polyester-type resin (I), The polyester adhesive as described in <1> characterized by the above-mentioned. Agent composition.
<3> The polyester-based pressure-sensitive adhesive composition according to <1> or <2>, further comprising a crosslinking agent (III).
<4> A polyester-based pressure-sensitive adhesive, wherein the polyester-based pressure-sensitive adhesive composition according to <3> is crosslinked with a crosslinking agent (III).
<5> A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer containing the polyester-based pressure-sensitive adhesive according to <4>.
<6> The pressure-sensitive adhesive sheet according to <5>, including a base material, wherein the pressure-sensitive adhesive layer is provided on at least one side of the base material.
<7> The pressure-sensitive adhesive sheet according to <5>, which is a substrate-less type having no substrate.
<8> The pressure-sensitive adhesive sheet according to any one of <5> to <7>, which is used for bonding an optical member.
<9> An optical member with an adhesive layer, comprising an adhesive layer and an optical member containing the polyester adhesive according to <4>.

According to the present invention, it is possible to provide a polyester-based pressure-sensitive adhesive composition capable of obtaining a pressure-sensitive adhesive having a high level of blister resistance even when exposed to a high temperature and high humidity environment.
The pressure-sensitive adhesive can be suitably used for bonding optical members, and in particular, can be suitably used for bonding optical members made of plastic materials.

Hereinafter, although this invention is explained in full detail, these show an example of a desirable embodiment, and this invention is not specified by these content.
In the present invention, the term “carboxylic acid” includes, in addition to carboxylic acid, carboxylic acid derivatives such as carboxylic acid salts, carboxylic acid anhydrides, carboxylic acid halides, and carboxylic acid esters, These carboxylic acid derivatives are referred to as “ester-forming derivatives”.
The same applies to specific carboxylic acids such as isophthalic acid.
In the present invention, the “sheet” conceptually includes a sheet, a film, and a tape.

<Polyester adhesive composition>
The polyester-based pressure-sensitive adhesive composition of the present invention comprises a polyvalent carboxylic acid component (A) having an aromatic dicarboxylic acid (a1) content of 50 mol% or more, and a diol compound (b1) having a hydrocarbon group in the side chain. Polyester-based resin having a content ratio of isophthalic acid with respect to the whole aromatic dicarboxylic acid (a1) of 60 mol% or more and a glass transition temperature of -20 to + 30 ° C. Containing I).

[Polyester resin (I)]
The polyester resin (I) used in the present invention needs to have a glass transition temperature of -20 to + 30 ° C, preferably -15 to + 25 ° C, more preferably -10 to + 20 ° C, still more preferably. It is −8 to + 15 ° C., particularly preferably −5 to + 10 ° C.

When the glass transition temperature exceeds the upper limit, the flexibility of the polyester resin (I) is lost, the initial adhesiveness of the pressure-sensitive adhesive (adhesiveness when bonded to the adherend) is reduced, Since it becomes difficult to exhibit sufficient adhesive force with pressure, workability is reduced.
On the other hand, when the glass transition temperature is lower than the lower limit value, the cohesive force of the pressure-sensitive adhesive is lowered and the peeling off easily occurs, so that the object of the present invention cannot be achieved.

  The glass transition temperature (Tg) of the polyester resin is a value measured using a differential scanning calorimeter DSC Q20 manufactured by TA Instruments. The measurement temperature range is from -90 ° C to + 100 ° C, and the temperature increase rate is 10 ° C / min.

  The polyester resin (I) used in the present invention is obtained by copolymerizing (condensation polymerization) a copolymer component containing a polyvalent carboxylic acid component (A) and a polyol component (B) as constituent raw materials.

(Polyvalent carboxylic acid component (A))
Examples of the polyvalent carboxylic acid component (A) include divalent carboxylic acids such as aromatic dicarboxylic acid (a1), aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid, and trivalent or higher polyvalent carboxylic acids. be able to.

  Examples of the aromatic dicarboxylic acid (a1) include isophthalic acid, terephthalic acid, benzylmalonic acid, diphenic acid, 4,4′-oxydibenzoic acid, naphthalenedicarboxylic acid and the like.

  Examples of the aliphatic dicarboxylic acid include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid. Examples include acids, itaconic acid, thiodipropionic acid, diglycolic acid and the like.

  Examples of the alicyclic carboxylic acid include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 2,5-norbornanedicarboxylic acid. Examples include acids and adamantane dicarboxylic acids.

Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid, pyromellitic acid, adamantanetricarboxylic acid, and trimesic acid.
These may be used individually by 1 type, or may use 2 or more types together.

  In the present invention, the polyvalent carboxylic acid component (A) needs to contain 50 mol% or more of the aromatic dicarboxylic acid (a1), preferably 55 to 100 mol%, more preferably 55 to 90 mol%, More preferably, it is 60-85 mol%, Most preferably, it is 60-80 mol%.

When the content is too small, the cohesive force of the pressure-sensitive adhesive is lowered, and the float and peeling are likely to occur, and the object of the present invention cannot be achieved.
Moreover, when there is too much this content rate, the softness | flexibility of polyester-type resin (I) will be lost, and there exists a tendency for the initial stage adhesiveness of an adhesive to fall.

  Furthermore, in the present invention, the aromatic dicarboxylic acid (a1) contains isophthalic acid, and the content of isophthalic acid relative to the whole aromatic dicarboxylic acid (a1) needs to be 60 mol% or more, preferably Is 62 mol% or more, more preferably 65 mol% or more, still more preferably 70 mol% or more, and particularly preferably 80 mol% or more.

  If the content is too small, the crystallinity of the polyester resin (I) becomes high and the solvent solubility is lowered, so that the object of the present invention cannot be achieved.

  In the present invention, as the polyvalent carboxylic acid component (A) other than the aromatic dicarboxylic acid (a1), from the viewpoint of improving the initial adhesiveness of the pressure-sensitive adhesive, the number of carbon atoms (including carbon of the carboxyl group) is 4 or more. Aliphatic dicarboxylic acids are preferable, and aliphatic dicarboxylic acids having 9 to 12 carbon atoms (including carbon of a carboxyl group) such as azelaic acid and sebacic acid are more preferable.

  Moreover, it is preferable to contain an aliphatic dicarboxylic acid from the viewpoint of imparting tackiness, particularly preferably an aliphatic dicarboxylic acid having 4 to 12 carbon atoms (including carbon of a carboxyl group), and more preferably. Sebacic acid.

  The content ratio of the aliphatic dicarboxylic acid is preferably less than 50 mol%, particularly preferably 10 to 45 mol%, more preferably 20 to 40 mol, based on the entire polyvalent carboxylic acid component (A). %.

  If the content is too low, the glass transition temperature of the polyester-based resin (I) tends to be high, and sufficient adhesive force tends to be not obtained. There exists a tendency for the adhesive force to a to-be-adhered body to fall.

  In the present invention, for the purpose of increasing the branch point in the polyester resin (I), a trivalent or higher polyvalent carboxylic acid may be used, and in particular, the gelation is relatively difficult to occur during the production. Therefore, it is preferable to use trimellitic acid.

  The content ratio of the trivalent or higher polyvalent carboxylic acid is preferably 10 mol% or less, more preferably 0.1%, based on the whole polyvalent carboxylic acid component (A), from the viewpoint of cohesive strength of the pressure-sensitive adhesive. When it is ˜5 mol% and the content ratio is too large, gelation tends to occur during the production of the polyester resin (I).

(Polyol component (B))
In the present invention, the polyol component (B) needs to contain a diol compound (b1) having a hydrocarbon group in the side chain.

Examples of the diol compound (b1) having a hydrocarbon group in the side chain include dipropylene glycol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-methyl-2-ethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2- Branched structures such as ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, etc. Aliphatic diol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Glycol, tricyclodecanedimethanol, adamantanediol, mention may be made of alicyclic diols such as 2,2,4,4-tetramethyl-1,3-cyclobutanediol.
These may be used individually by 1 type, or may use 2 or more types together.

  Among these, a diol compound having a hydrocarbon group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms is preferable, and more preferably, from the viewpoint of preventing crystallization while maintaining mechanical strength and heat resistance. Neopentyl glycol, 2-methyl-2-ethyl-1,3-propanediol.

  The content ratio of the diol compound (b1) having a hydrocarbon group in the side chain is preferably 5 mol% or more, more preferably 15 to 90 mol%, more preferably, based on the entire polyol component (B). Preferably it is 30-80 mol%.

  If the content is too small, the polyester resin (I) crystallizes and the initial adhesiveness of the pressure-sensitive adhesive tends to decrease. If the content is too large, the reaction during the production of the polyester resin (I) is likely to occur. Tend to decrease.

  In addition to the above, the polyol component (B) other than the diol compound (b1) having a hydrocarbon group in the side chain used in the present invention, for example, an aliphatic diol having a linear structure, an aromatic diol, etc. And dihydric alcohols and trihydric or higher polyhydric alcohols.

  As the aliphatic diol having a linear structure, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4- Linear aliphatic diols such as butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and ethylene oxides thereof, Examples include propylene oxide adducts.

  Examples of the aromatic diol include 4,4'-thiodiphenol, 4,4'-methylenediphenol, bisphenol S, bisphenol A, bisphenol fluorene, 4,4'-dihydroxybiphenyl, o-, m- and p. -Aromatic diols such as dihydroxybenzene, 2,5-naphthalenediol and p-xylenediol, and their ethylene oxide and propylene oxide adducts.

Examples of the trihydric or higher polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6-hexanetriol, adamantanetriol, and the like.
These may be used individually by 1 type, or may use 2 or more types together.

  Among these, it is preferable to use an aliphatic diol having a linear structure in terms of excellent adhesion, and in particular, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are used. In addition, it is preferable to use 1,4-butanediol and 1,6-hexanediol from the viewpoint that the crystallinity of the polyester resin (I) is lowered and the adhesiveness is more excellent.

  The content ratio of the aliphatic diol having a linear structure is preferably 5 to 95 mol%, more preferably 10 to 85 mol%, still more preferably 20 to 70, based on the entire polyol component (B). Mol%.

  If the content is too high, the polyester resin (I) crystallizes and the initial adhesiveness of the pressure-sensitive adhesive tends to decrease. If it is too low, the reactivity during the production of the polyester resin (I) decreases. Tend.

  In the present invention, it is preferable to use a trihydric or higher polyhydric alcohol from the viewpoint of forming a reactive site with a crosslinking agent (III) described later in the polyester resin (I) and increasing the cohesive force, Of these, trimethylolpropane is preferably used because it is relatively difficult to generate a gel.

  The content ratio of the trihydric or higher polyhydric alcohol is preferably 10 mol% or less, more preferably 0.1 to 5 mol% with respect to the entire polyol component (B).

  When there is too much this content rate, polyester-type resin (I) will gelatinize at the time of manufacture, and there exists a tendency for manufacture to become difficult.

(Production method)
The polyester resin (I) used in the present invention can be produced by polycondensation reaction of a polyvalent carboxylic acid component (A) and a polyol component (B) by a known method in the presence of a catalyst.

  At that time, the mixing ratio of the polyvalent carboxylic acid component (A) and the polyol component (B) is preferably 1 to 2 equivalents of the polyol component (B) per equivalent of the polyvalent carboxylic acid component (A). Particularly preferred is 1.1 to 1.7 equivalents. If the content ratio of the polyol component (B) is too low, the acid value tends to be high and it is difficult to increase the molecular weight, and if the content ratio of the polyol component (B) is too high, the yield tends to decrease. .

In the polycondensation reaction, first, an esterification reaction is performed, and then a polycondensation reaction is performed.
Examples of the catalyst used in the esterification reaction include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate, antimony-based compounds such as antimony trioxide, germanium-based catalysts such as germanium dioxide, zinc acetate, manganese acetate, A dibutyltin oxide etc. can be mentioned. These may be used individually by 1 type, or may use 2 or more types together.

  Among these, it is preferable to use antimony trioxide, tetrabutyl titanate, germanium dioxide, and zinc acetate from the viewpoint of high catalytic activity and hue.

The blending amount of the catalyst is preferably 1 to 10,000 ppm, more preferably 10 to 5,000 ppm, and still more preferably 10 to 3,000 ppm with respect to the polyvalent carboxylic acid component (A).
If the blending amount is too small, the polymerization reaction tends not to proceed sufficiently. If the blending amount is too large, there is no advantage such as shortening the reaction time, and a side reaction tends to occur.

About the reaction temperature at the time of esterification reaction, 160-280 degreeC is preferable, More preferably, it is 180-270 degreeC, More preferably, it is 200-260 degreeC.
If the reaction temperature is too low, the reaction tends not to proceed sufficiently, and if it is too high, side reactions such as decomposition tend to occur. Moreover, the pressure at the time of reaction should just be under normal pressure normally.

  About reaction time of esterification reaction, 1-48 hours are preferable, More preferably, it is 1.5-24 hours, More preferably, it is 2-12 hours.

After the esterification reaction is performed, a polycondensation reaction is performed.
As the reaction conditions for the polycondensation reaction, a catalyst similar to that used in the esterification reaction is further blended in the same amount, and the reaction temperature is preferably 220 to 280 ° C. (more preferably 230 to 270 ° C.). It is preferable to gradually reduce the pressure and finally react at 5 hPa or less.
If the reaction temperature is too low, the reaction tends not to proceed sufficiently, and if it is too high, side reactions such as decomposition tend to occur.

  About the reaction time of a polycondensation reaction, 1-48 hours are preferable, More preferably, it is 1.5-24 hours, More preferably, it is 2-12 hours.

(Physical properties)
The number average molecular weight of the polyester resin (I) used in the present invention is preferably 5,000 or more, more preferably 10,000 to 150,000, and further preferably 15,000 to 80,000.

  If the number average molecular weight is too low, sufficient cohesive force as a pressure-sensitive adhesive cannot be obtained, and heat resistance and mechanical strength tend to decrease, and if the number average molecular weight is too high, flexibility is lost, There exists a tendency for the initial adhesiveness of an adhesive to fall.

In addition, the number average molecular weight in this specification is a number average molecular weight in terms of standard polystyrene molecular weight, and the column: TSKgel SuperMultipore HZ-M (exclusion) is used for high performance liquid chromatography (“HLC-8320GPC” manufactured by Tosoh Corporation). The molecular weight is 2 × 10 ⁶ , the number of theoretical plates: 16,000 plates / line, the filler material: styrene-divinylbenzene copolymer, and the particle size of filler particle: 4 μm). is there.

  The acid value of the polyester resin (I) used in the present invention is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, still more preferably 1 mgKOH / g or less, particularly preferably 0.5 mgKOH. / G or less.

  If the acid value is too high, the pressure-sensitive adhesive layer made of the polyester-based pressure-sensitive adhesive composition of the present invention tends to be hydrolyzed and the durability tends to decrease. Moreover, when it becomes the structure used as the metal oxide thin film layer on one surface of an adhesive layer, there exists a tendency for corrosion to occur and the electroconductivity of a metal oxide film to fall.

The acid value of the polyester resin (I) is neutralized based on JIS K 0070 by dissolving 10 g of the polyester resin (I) in a mixed solvent of 7/3 (toluene / methanol (volume ratio)) of toluene and methanol. It is obtained by titration.
In addition, in this invention, the acid value of polyester-type resin (I) means content of the carboxyl group in resin.

[Hydrolysis inhibitor (II)]
The polyester-based pressure-sensitive adhesive composition of the present invention preferably contains a hydrolysis inhibitor (II) in addition to the polyester-based resin (I), particularly from the viewpoint of improving durability under high temperature and high humidity. .

As the hydrolysis inhibitor (II), conventionally known ones can be used, and examples thereof include compounds that react with and bind to the carboxylic acid end groups of the polyvalent carboxylic acid component (A). Includes compounds having a functional group such as a carbodiimide group, an epoxy group, and an oxazoline group.
Among these, a carbodiimide group-containing compound is preferable in that it has a high effect of eliminating the catalytic activity of protons derived from carboxyl group end groups.

  As the carbodiimide group-containing compound, a known carbodiimide having one or more carbodiimide groups (—N═C═N—) in the molecule may be used, but it is preferable to improve durability under higher temperature and humidity. It is preferable to use polycarbodiimide having 2 or more carbodiimide groups in the molecule, particularly preferably 3 or more, more preferably 5 or more, and particularly preferably 7 or more. It is preferable.

  In addition, when 30 or more are contained, the molecular structure becomes excessively large, which tends to be undesirable. It is also preferable to use a high molecular weight polycarbodiimide produced by decarboxylation condensation reaction of diisocyanate in the presence of a carbodiimidization catalyst.

  Examples of the high molecular weight polycarbodiimide include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction.

Examples of the diisocyanate include 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, and 4,4′-. Diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4, Examples thereof include 4′-dicyclohexylmethane diisocyanate and tetramethylxylylene diisocyanate, and these can be used alone or in combination of two or more.
Such a high molecular weight polycarbodiimide may be synthesized or a commercially available product may be used.

  Examples of commercially available carbodiimide group-containing compounds include Carbodilite (registered trademark) series manufactured by Nisshinbo Chemical Co., Ltd. Among them, Carbodilite (registered trademark) V-01, V-02B, V-03, V -05, V-07, V-09, and V-09GB are preferable in terms of excellent compatibility with organic solvents.

  As said epoxy group containing compound, a glycidyl ester compound, a glycidyl ether compound, etc. are preferable.

  Specific examples of glycidyl ester compounds include, for example, glycidyl benzoate, t-Bu-glycidyl benzoate, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, pelargonic acid glycidyl ester, stearic acid glycidyl ester, lauric acid Glycidyl ester, palmitic acid glycidyl ester, behenic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, behenolic acid glycidyl ester, stearolic acid glycidyl ester, terephthalic acid diglycidyl ester, Isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalenedicarboxylic acid diglyceride Diglycidyl ester, methyl terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, Examples include dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, and pyromellitic acid tetraglycidyl ester. These can use 1 type (s) or 2 or more types.

  Specific examples of the glycidyl ether compound include, for example, phenylglycidyl ether, o-phenylglycidyl ether, 1,4-bis (β, γ-epoxypropoxy) butane, 1,6-bis (β, γ- Epoxypropoxy) hexane, 1,4-bis (β, γ-epoxypropoxy) benzene, 1- (β, γ-epoxypropoxy) -2-ethoxyethane, 1- (β, γ-epoxypropoxy) -2-benzyl Oxyethane, 2,2-bis- [р- (β, γ-epoxypropoxy) phenyl] propane and 2,2-bis- (4-hydroxyphenyl) propane and 2,2-bis- (4-hydroxyphenyl) Examples thereof include bisglycidyl polyether obtained by the reaction of bisphenol such as methane and epichlorohydrin. These can use 1 type (s) or 2 or more types.

Examples of the oxazoline group-containing compound include bisoxazoline compounds.
Specific examples of the bisoxazoline compound include, for example, 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4,4- Dimethyl-2-oxazoline), 2,2′-bis (4-ethyl-2-oxazoline), 2,2′-bis (4,4′-diethyl-2-oxazoline), 2,2′-bis (4 -Propyl-2-oxazoline), 2,2'-bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2-oxazoline), 2,2'-bis (4-phenyl) -2-oxazoline), 2,2′-bis (4-cyclohexyl-2-oxazoline), 2,2′-bis (4-benzyl-2-oxazoline), 2,2′-p-phenylenebis (2- Oxazoline), 2,2′-m-phenylenebis (2-oxa Phosphorus), 2,2'-o-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4 -Dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4,4-dimethyl-2-oxazoline), 2, 2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2- Oxazoline), 2,2′-decamethylenebis (2-oxazoline), 2,2′-ethylenebis (4-methyl-2-oxazoline), 2,2′-tetramethylenebis (4,4-dimethyl-2) -Oxazoline) 2,2′-9,9′-diphenoxyethanebis (2-oxazoline), 2,2′-cyclohexylenebis (2-oxazoline), 2,2′-diphenylenebis (2-oxazoline), etc. Can be mentioned. These can use 1 type (s) or 2 or more types.

  Among these, 2,2'-bis (2-oxazoline) is preferable from the viewpoint of reactivity with polyester.

As the hydrolysis inhibitor (II), it is preferable to use one having a high weight average molecular weight from the viewpoint of hydrolysis resistance and blister resistance.
The weight average molecular weight of the hydrolysis inhibitor (II) is preferably 500 or more, more preferably 2,000 or more, and further preferably 5,000 or more. The upper limit of the weight average molecular weight is usually 50,000.

  When the weight average molecular weight of the hydrolysis inhibitor (II) is too small, hydrolysis resistance and blister resistance tend to be lowered. Moreover, when a weight average molecular weight is too large, there exists a tendency for compatibility with a polyester resin to fall.

In addition, the weight average molecular weight in this specification is a weight average molecular weight in terms of standard polystyrene molecular weight, and the column: TSKgel SuperMultipore HZ-M (exclusion) is used for high performance liquid chromatography (“HLC-8320GPC” manufactured by Tosoh Corporation). The molecular weight is 2 × 10 ⁶ , the number of theoretical plates: 16,000 plates / line, the filler material: styrene-divinylbenzene copolymer, and the particle size of filler particle: 4 μm). is there.

  The content of the hydrolysis inhibitor (II) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, more preferably 100 parts by mass of the polyester resin (I). Preferably it is 0.2-3 mass parts.

  When the content is too large, the compatibility with the polyester resin (I) is lowered, and the pressure-sensitive adhesive tends to be turbid. When the content is too small, sufficient durability tends to be difficult to obtain.

  Further, the blending amount of the hydrolysis inhibitor (II) is preferably optimized according to the acid value of the polyester resin (I), and the acid of the polyester resin (I) in the polyester pressure-sensitive adhesive composition is preferably optimized. The molar ratio ((y) / (x)) of the total (x) of the valence and the total (y) of the functional group amount of the hydrolysis inhibitor (II) in the polyester-based tree adhesive composition is 0.5. It is preferable that ≦ (y) / (x), particularly preferably 1 ≦ (y) / (x) ≦ 1,000, and more preferably 1.5 ≦ (y) / (x) ≦ 100.

  Inclusion of the total amount (y) of functional groups of the hydrolysis inhibitor (II) in the polyester-based resin adhesive composition relative to the total acid value (x) of the polyester-based resin (I) in the polyester-based adhesive composition When the ratio increases, the compatibility with the polyester resin (I) tends to decrease, or the adhesive strength, cohesive strength, and durability performance tend to decrease, and the content ratio of (y) to (x) decreases. There is a tendency for the moisture and heat resistance performance to decrease.

[Crosslinking agent (III)]
The polyester pressure-sensitive adhesive composition of the present invention preferably further contains a crosslinking agent (III).
By crosslinking the polyester resin (I) with the crosslinking agent (III), the polyester resin (I) becomes excellent in cohesive force, and the performance as an adhesive can be further improved.

The crosslinking agent (III) may be any compound having a functional group contained in the polyester resin (I), for example, a functional group that reacts with a hydroxyl group and / or a carboxyl group. For example, a polyisocyanate compound or a polyepoxy compound. Etc.
Among these, a polyisocyanate compound is preferable because the initial adhesiveness of the pressure-sensitive adhesive, mechanical strength, and heat resistance can be balanced.

  Examples of the polyisocyanate compound include polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, and hydrogenated xylylene diisocyanate. Further, there may be mentioned tolylene diisocyanate adducts of trimethylolpropane, isocyanate adducts such as hexamethylene diisocyanate adducts and isophorone diisocyanate adducts.

In addition, the said polyisocyanate compound can also use what the isocyanate part was blocked by phenol, lactam, etc.
One of these crosslinking agents (III) may be used alone, or two or more thereof may be mixed and used.

  The content of the crosslinking agent (III) can be appropriately selected depending on the amount of the functional group contained in the polyester resin (I), the molecular weight of the polyester resin (I) and the purpose of use. The reactive group contained in the crosslinking agent (III) contains the crosslinking agent (III) at a ratio of 0.2 to 10 equivalents with respect to 1 equivalent of the hydroxyl group and / or carboxyl group contained in Preferably, it is 0.5-8 equivalent, More preferably, it is 1-5 equivalent.

  If the number of equivalents of reactive groups contained in the cross-linking agent (III) is too small, the cohesive strength of the pressure-sensitive adhesive tends to be insufficient and sufficient heat resistance tends not to be obtained, and if it is too large, the flexibility of the pressure-sensitive adhesive decreases. The initial tackiness tends to decrease, and a sufficient adhesive force tends not to be exhibited at a pressure of about the finger pressure.

[Urethaneization catalyst (IV)]
The polyester-based pressure-sensitive adhesive composition of the present invention preferably further contains a urethanization catalyst (IV) from the viewpoint of curing speed. By containing the urethanization catalyst (IV), curing is accelerated, the aging time is shortened, and a stable coating film is easily formed.
Examples of the urethanization catalyst (IV) include organometallic compounds and tertiary amine compounds.
Examples of organometallic compounds include zirconium compounds, iron compounds, tin compounds, titanium compounds, lead compounds, cobalt compounds, zinc compounds, and the like.

Examples of the zirconium-based compound include zirconium naphthenate and zirconium acetylacetonate.
Examples of iron-based compounds include iron acetylacetonate and iron 2-ethylhexanoate.
Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dilaurate, and the like.
Examples of titanium compounds include dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and the like.
Examples of the lead-based compound include lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate and the like.
Examples of cobalt compounds include cobalt 2-ethylhexanoate and cobalt benzoate.
Examples of the zinc-based compound include zinc naphthenate and zinc 2-ethylhexanoate.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, 1,8-diazabixic mouth- (5,4,0) -undecene-7, and the like.

Among these, a zirconium-based compound is preferable in terms of the reaction rate and the pot life of the pressure-sensitive adhesive layer.
Moreover, only 1 type may be sufficient as a urethanization catalyst (IV), and 2 or more types may be sufficient as it.

It is preferable that content of a urethanization catalyst (IV) is 0.001-0.1 mass part with respect to 100 mass parts of polyester-type resin (I), More preferably, it is 0.005-0.08 mass. Part, more preferably 0.01 to 0.05 part by weight.
If the content is too small, the curing rate tends to be slow and it tends to be difficult to form a stable coating film. If the content is too large, the pot life tends to be short and the coatability tends to decrease.

[Catalytic action inhibitor (V)]
The polyester-based pressure-sensitive adhesive composition of the present invention preferably contains a catalytic action inhibitor (V) in the urethanization catalyst (IV) in terms of extending the pot life and improving the coatability.
Examples of the catalyst inhibitor (V) include β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, acetylacetone, and 2,4-hexanedione. And β-diketones such as benzoylacetone. These are ketoenol tautomeric compounds, and by protecting the urethanization catalyst (IV), the catalyst activity in the solution state of the urethanization catalyst (IV) is reduced, and the pressure-sensitive adhesive composition after mixing is excessive. An increase in viscosity and gelation can be suppressed, and the pot life of the pressure-sensitive adhesive composition can be extended.

Among these, from the viewpoint of the balance between pot life and curing rate, a catalytic action inhibitor (V
) Is preferably acetylacetone. These catalytic action inhibitors (V) can be used alone or in combination of two or more.

The content ratio (mass ratio) of the catalyst inhibitor (V) and the urethanization catalyst (IV) is within the range of the catalyst action inhibitor (V): the urethanization catalyst (IV) = 0.001: 1 to 15: 1. It is preferable that there is, more preferably 0.005: 1 to 13: 1, and particularly preferably 0.01: 1 to 10: 1. If the content of the catalytic action inhibitor (V) is too small relative to the content of the urethanization catalyst (IV), the pot life tends to be short and the coating property tends to decrease, and if too large, the curing rate tends to decrease. There is.

[Antioxidant (VI)]
The polyester-based pressure-sensitive adhesive composition of the present invention preferably further contains an antioxidant (VI) from the viewpoint of improving heat resistance. By containing an acid value inhibitor (VI),
The molecular weight reduction of the polyester resin (I) in a heat resistant environment is suppressed, and the adhesive residue preventing property to the adherend is excellent.
As the antioxidant (VI), an antioxidant having a hindered phenol structure is preferable.
As an antioxidant having a hindered phenol structure, for example, a group having a large steric hindrance such as a tertiary butyl group is bonded to at least one of the adjacent carbon atoms on the aromatic ring to which the OH group of phenol is bonded. Any appropriate antioxidant can be adopted as long as it is an antioxidant having a hindered phenol structure. By using such an antioxidant, the effect of suppressing a decrease in the molecular weight of the polyester resin (I) in a heat-resistant environment is greatly increased.

The content of the antioxidant (VI) is based on 100 parts by mass of the polyester resin (I).
Preferably it is 0.01-10 mass parts, More preferably, it is 0.03-8 mass parts, More preferably, it is 0.05-5 mass parts.
If the content is too small, adhesive residue tends to be generated on the adherend, and if the content is too large, the physical properties of the adhesive tend to decrease.

[Other ingredients]
The polyester-based pressure-sensitive adhesive composition of the present invention is not limited to the effects of the present invention, and conventionally known additives such as softeners, ultraviolet absorbers, stabilizers, antistatic agents, tackifiers, etc., inorganic or You may contain additives, such as organic fillers, powders, such as a metal powder and a pigment, and a particulate form.
In addition to the above additives, a small amount of impurities and the like contained in the raw materials for producing the constituent components of the pressure-sensitive adhesive may be used.

<Polyester adhesive>
The polyester-based pressure-sensitive adhesive of the present invention is obtained by crosslinking the above-described polyester-based pressure-sensitive adhesive composition of the present invention with a crosslinking agent (III). Such a crosslinking reaction with the crosslinking agent (III) can usually be performed by heating the pressure-sensitive adhesive composition at 20 ° C. or higher and 120 ° C. or lower.

The polyester-based pressure-sensitive adhesive of the present invention preferably contains substantially no acidic group. Specifically, the acid value is preferably 10 mgKOH / g or less, more preferably 1 mgKOH / g or less, Preferably it is 0.1 mgKOH / g or less.
In addition, the acid value of a polyester-type adhesive can be calculated | required by the method similar to the acid value of polyester-type resin (I).

<Adhesive sheet>
The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer containing the polyester-based pressure-sensitive adhesive of the present invention.
Moreover, it is preferable that the adhesive sheet of this invention has a base material and an adhesive layer is provided in the at least single side | surface side of a base material.

Furthermore, the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer containing the polyester-based pressure-sensitive adhesive of the present invention and has no substrate from the viewpoint of excellent transparency and high pressure-sensitive adhesive strength with respect to the thickness to be formed. It is preferable to use a base-less type pressure-sensitive adhesive sheet.
The pressure-sensitive adhesive sheet of the present invention is particularly suitable as a pressure-sensitive adhesive sheet for optical members used for bonding optical members.

  The pressure-sensitive adhesive sheet of the present invention can be produced according to a known method for producing a pressure-sensitive adhesive sheet. For example, a polyester resin (I), a hydrolysis inhibitor (II) and a crosslinking agent (III) are formed on a substrate. The pressure-sensitive adhesive sheet of the present invention having a pressure-sensitive adhesive layer made of the polyester pressure-sensitive adhesive of the present invention on a substrate is obtained by coating, drying, and curing the polyester pressure-sensitive adhesive composition contained as necessary.

Moreover, a base material-less type adhesive sheet can be manufactured by forming an adhesive layer in a release sheet and bonding a release sheet on the opposite adhesive layer surface.
At the time of use, the obtained pressure-sensitive adhesive sheet or substrate-less type pressure-sensitive adhesive sheet peels the release sheet from the pressure-sensitive adhesive layer, and bonds the pressure-sensitive adhesive layer and the adherend.

Examples of the base material include polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate / isophthalate copolymer; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; polyvinyl fluoride, polyfluoride, and the like. Polyfluorinated ethylene resins such as vinylidene fluoride and polyfluorinated ethylene; polyamides such as nylon 6 and nylon 6,6; polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol Copolymers, vinyl polymers such as polyvinyl alcohol and vinylon; cellulose resins such as cellulose triacetate and cellophane; polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polyethylene Acrylic resin such as butyl acrylate; Synthetic resin sheet made of synthetic resin such as polystyrene, polycarbonate, polyarylate, polyimide; Metal foil such as aluminum, copper, iron, etc .; Paper such as fine paper, glassine paper; Glass fiber, natural Examples thereof include woven fabrics and nonwoven fabrics made of fibers and synthetic fibers.
These base materials can be used as a single layer body or a multilayer body in which two or more kinds are laminated.

  Among these, a synthetic resin sheet made of polyethylene terephthalate or polyimide is preferable, and a polyethylene terephthalate sheet is particularly preferable in terms of excellent adhesion to the pressure-sensitive adhesive. Furthermore, the polyethylene terephthalate sheet having the metal thin film layer has excellent adhesion between the base material and the adhesive, and can stably maintain the base material without corroding the metal thin film layer. This is preferable in that the effect of the pressure-sensitive adhesive sheet of the present invention having the polyester pressure-sensitive adhesive layer of the present invention can be remarkably exhibited.

  In the pressure-sensitive adhesive sheet of the present invention, the ITO (Indium Tin Oxide) electrode film has a pressure-sensitive adhesive layer on the PET side of the film formed on a PET (polyethylene terephthalate) substrate, and the pressure-sensitive adhesive layer is interposed therebetween. It is most preferable to form an optical laminate in which a PET substrate and a PC (polycarbonate) film are laminated and an acrylic film is laminated (layer structure: ITO electrode film / PET substrate / adhesive layer / PC). Film / acrylic film).

  As the release sheet, for example, various synthetic resin sheets exemplified for the base material, paper, cloth, non-woven fabric and the like can be used, for example, silicon release sheet, olefin Examples of the release sheet include fluorine-based release sheets, fluorine-based release sheets, long-chain alkyl-based release sheets, and alkyd-based release sheets, and it is preferable to use silicon-based release sheets.

  As thickness of a base material, it is preferable that it is 1-1000 micrometers, More preferably, it is 2-500 micrometers, More preferably, it is 3-300 micrometers.

  Examples of the method for applying the pressure-sensitive adhesive composition include a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, and a spray coater.

As conditions for the curing treatment, the temperature is usually room temperature to 70 ° C., preferably 30 to 50 ° C., and the time is usually 1 to 30 days, preferably 3 to 15 days.
Specifically, for example, the treatment may be performed at 23 ° C. for 1 day to 20 days, preferably at 23 ° C. for 3 to 10 days, at 40 ° C. for 1 to 7 days, and the like.

  As drying conditions, the drying temperature is preferably 60 to 140 ° C., more preferably 80 to 120 ° C., and the drying time is preferably 1 to 30 minutes, more preferably 2 to 5 minutes.

It is preferable that the thickness after drying of the adhesive layer of the adhesive sheet of this invention is 5-200 micrometers, More preferably, it is 10-100 micrometers.
If the thickness of the pressure-sensitive adhesive layer is too thin, the adhesive strength tends to decrease. If the thickness is too thick, it is difficult to apply uniformly, and problems such as bubbles entering the coating film tend to occur. is there.

  In addition, the thickness of the said adhesive layer is calculated | required by subtracting the measured value of the thickness of structural members other than an adhesive layer from the measured value of the thickness of the whole adhesive sheet using "ID-C112B" by Mitutoyo Corporation. Value.

The gel fraction of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is preferably 50% or more from the viewpoint of durability and pressure-sensitive adhesive force, more preferably 55 to 90%, and still more preferably 60 to 85%.
If the gel fraction is too low, the cohesive force tends to decrease and the durability tends to decrease. If the gel fraction is too high, the cohesive force tends to decrease and the adhesive force tends to decrease.

In addition, the said gel fraction becomes a standard of a crosslinking degree, for example, is computed with the following method.
That is, a pressure-sensitive adhesive sheet (not provided with a separator) in which a pressure-sensitive adhesive layer is formed on a polymer sheet (such as a polyethylene terephthalate film) as a base material is wrapped in a 200-mesh stainless steel wire mesh, and is added to toluene. It is immersed at 23 ° C. for 24 hours, and the mass percentage of the insoluble adhesive component remaining in the wire mesh is defined as the gel fraction. However, the mass of the substrate is subtracted.

  Furthermore, the pressure-sensitive adhesive sheet of the present invention may be protected by providing a release sheet outside the pressure-sensitive adhesive layer as necessary. Further, in the pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is formed on one side of the base material, the pressure-sensitive adhesive layer is applied to the surface of the base material opposite to the pressure-sensitive adhesive layer by using a release treatment surface. It is also possible to protect.

<Optical member with adhesive layer>
The optical member with the pressure-sensitive adhesive layer of the present invention has a pressure-sensitive adhesive layer containing the polyester-based pressure-sensitive adhesive of the present invention and an optical member, and the pressure-sensitive adhesive layer containing the polyester-based pressure-sensitive adhesive of the present invention is disposed on the optical member. Can be obtained by laminating and forming.

  Optical members include, for example, transparent electrode films such as ITO electrode films and organic conductive films such as polythiophene, polarizing plates, retardation plates, elliptical polarizing plates, optical compensation films, brightness enhancement films, electromagnetic wave shielding films, near infrared absorption Examples thereof include a film and an AR (anti-reflection) film.

Among these, a transparent electrode film is preferable, and an ITO electrode film is more preferable from the viewpoint that the effects of the present invention can be exhibited remarkably and high adhesive strength can be obtained.
The ITO electrode film is often formed as a thin film on a substrate such as glass or PET (polyethylene terephthalate).

In the optical member with the pressure-sensitive adhesive layer of the present invention, it is preferable to further provide a release sheet on the surface opposite to the optical member surface of the pressure-sensitive adhesive layer. Then, the pressure-sensitive adhesive layer and the adherend are bonded together.
As such a release sheet, a silicon-based release sheet is preferably used.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In the following examples, “part” means “part by mass”.

[Production of polyester resin]
Based on the molar ratio in Table 1 below, the following polyester resins (I-1) to (I-6) and (I′-1) to (I′-3) were produced.

(Production of polyester resin (I-1))
In a reaction vessel equipped with a thermometer, stirrer, rectifying column, nitrogen inlet tube and vacuum apparatus, 219.4 parts (1.3 mol) of isophthalic acid and 218.5 parts of sebacic acid as polyvalent carboxylic acid component (A) Parts (1.1 mol), 225 parts (2.2 mol) of neopentyl glycol as polyol component (B), 108.2 parts (1.2 mol) of 1,4-butanediol, 24 of 1,6-hexanediol 7 parts (0.2 mol) and 4.2 parts (0.03 mol) of trimethylolpropane, and 0.05 parts of tetrabutyl titanate as a catalyst were added, and the temperature was gradually raised to an internal temperature of 250 ° C. over 4 hours. The esterification reaction was performed.

Thereafter, the internal temperature was raised to 260 ° C., 0.05 part of tetrabutyl titanate was added as a catalyst, the pressure was reduced to 1.33 hPa, and a polymerization reaction was performed for 3 hours to produce a polyester resin (I-1).
The number average molecular weight of the obtained polyester resin (I-1) was 22,000, and the glass transition temperature was −18.0 ° C.

(Production of polyester resin (I-2))
In a reaction vessel equipped with a thermometer, a stirrer, a rectifying column, a nitrogen introducing tube and a vacuum apparatus, 240.6 parts (1.4 mol) of isophthalic acid as a polyvalent carboxylic acid component (A) and 195.3 sebacic acid Parts (1.0 mol), 226.3 parts (2.2 mol) of neopentyl glycol as polyol component (B), 108.8 parts (1.2 mol) of 1,4-butanediol, 1,6-hexane 24.8 parts (0.2 mol) of diol, 4.2 parts (0.03 mol) of trimethylolpropane, and 0.05 parts of tetrabutyl titanate as a catalyst were added, and the temperature was gradually raised to an internal temperature of 250 ° C. The esterification reaction was performed over time.

Thereafter, the internal temperature was raised to 260 ° C., 0.05 part of tetrabutyl titanate was charged as a catalyst, the pressure was reduced to 1.33 hPa, and a polymerization reaction was carried out over 3 hours to produce a polyester resin (I-2).
The number average molecular weight of the obtained polyester resin (I-2) was 22,000, and the glass transition temperature was -11.0 ° C.

(Production of polyester resin (I-3))
In a reaction vessel equipped with a thermometer, stirrer, rectifying column, nitrogen inlet tube and vacuum apparatus, 262.1 parts (1.6 mol) of isophthalic acid and 171.8 sebacic acid as polyvalent carboxylic acid component (A) Part (0.8 mol), 227.5 parts (2.2 mol) of neopentyl glycol as polyol component (B), 109.4 parts (1.2 mol) of 1,4-butanediol, 1,6-hexane 25 parts (0.2 mol) of diol, 4.2 parts (0.03 mol) of trimethylolpropane, and 0.05 part of tetrabutyl titanate as a catalyst were added, and the temperature was gradually raised to an internal temperature of 250 ° C. over 4 hours. The esterification reaction was performed.

Thereafter, the internal temperature was raised to 260 ° C., 0.05 part of tetrabutyl titanate was charged as a catalyst, the pressure was reduced to 1.33 hPa, and the polymerization reaction was carried out over 3 hours to produce a polyester resin (I-3).
The number average molecular weight of the obtained polyester resin (I-3) was 23,000, and the glass transition temperature was −6.3 ° C.

(Production of polyester resin (I-4))
In a reaction vessel equipped with a thermometer, a stirrer, a rectifying column, a nitrogen introduction tube and a vacuum apparatus, 283.8 parts (1.7 mol) of isophthalic acid and 148.1 of sebacic acid as the polyvalent carboxylic acid component (A) Parts (0.7 mol), 228.8 parts (2.2 mol) of neopentyl glycol as polyol component (B), 110 parts (1.2 mol) of 1,4-butanediol, 25 of 1,6-hexanediol .1 part (0.2 mole) and 4.3 parts (0.03 mole) of trimethylolpropane and 0.05 part of tetrabutyl titanate as a catalyst were added, and the temperature was gradually raised to an internal temperature of 250 ° C. over 4 hours. The esterification reaction was performed.

Thereafter, the internal temperature was raised to 260 ° C., 0.05 part of tetrabutyl titanate was charged as a catalyst, the pressure was reduced to 1.33 hPa, and a polymerization reaction was performed for 3 hours to produce a polyester resin (I-4).
The number average molecular weight of the obtained polyester resin (I-4) was 22,000, and the glass transition temperature was 1.6 ° C.

(Production of polyester resin (I-5))
In a reaction vessel equipped with a thermometer, a stirrer, a rectifying column, a nitrogen introduction tube, and a vacuum apparatus, 328 parts (2.0 mol) of isophthalic acid and 99.8 parts of sebacic acid as a polyvalent carboxylic acid component (A) ( 0.5 mol), 231.3 parts (2.2 mol) of neopentyl glycol, 111.2 parts (1.2 mol) of 1,4-butanediol as polyol component (B), 25 of 1,6-hexanediol .4 parts (0.2 mol) and 4.3 parts (0.03 mol) of trimethylolpropane and 0.05 parts of tetrabutyl titanate as a catalyst were added, and the temperature was gradually raised to an internal temperature of 250.degree. C. over 4 hours. The esterification reaction was performed.

Thereafter, the internal temperature was raised to 260 ° C., 0.05 part of tetrabutyl titanate was added as a catalyst, the pressure was reduced to 1.33 hPa, and a polymerization reaction was performed for 3 hours to produce a polyester resin (I-5).
The number average molecular weight of the obtained polyester resin (I-5) was 23,000, and the glass transition temperature was 13.5 ° C.

(Production of polyester resin (I-6))
In a reaction vessel equipped with a thermometer, stirrer, rectifying column, nitrogen inlet tube and vacuum apparatus, 182.5 parts (1.1 mol) of isophthalic acid as polyvalent carboxylic acid component (A), 101.4 terephthalic acid Parts (0.61 mol) and 148.1 parts (0.73 mol) of sebacic acid, 228.8 parts (2.2 mol) of neopentyl glycol as the polyol component (B), 1,1.0-butanediol 111.0 Parts (1.2 mol), 1,6-hexanediol 25.1 parts (0.2 mol), trimethylolpropane 4.3 parts (0.03 mol), and tetrabutyl titanate 0.05 parts as a catalyst were charged. The temperature was gradually raised to an internal temperature of 250 ° C., and the esterification reaction was carried out over 4 hours.

Thereafter, the internal temperature was raised to 260 ° C., 0.05 part of tetrabutyl titanate was added as a catalyst, the pressure was reduced to 1.33 hPa, the polymerization reaction was carried out over 3 hours, and a polyester resin (I-6) was produced.
The number average molecular weight of the obtained polyester resin (I-6) was 16,000, and the glass transition temperature was 2.1 ° C.

(Production of polyester resin (I′-1))
In a reaction vessel equipped with a thermometer, a stirrer, a rectifying column, a nitrogen introducing tube and a vacuum apparatus, 76.9 parts (0.5 mol) of isophthalic acid and 374.3 sebacic acid as the polyvalent carboxylic acid component (A) Parts (1.9 mol), 216.8 parts (2.1 mol) of neopentyl glycol as polyol component (B), 104.2 parts (1.2 mol) of 1,4-butanediol, 1,6-hexane 23.8 parts (0.2 mol) of diol, 4 parts (0.03 mol) of trimethylolpropane, and 0.05 part of tetrabutyl titanate as a catalyst were added, and the temperature was gradually raised to an internal temperature of 250 ° C. over 4 hours. The esterification reaction was performed.

Thereafter, the internal temperature was raised to 260 ° C., 0.05 part of tetrabutyl titanate was added as a catalyst, the pressure was reduced to 1.33 hPa, and a polymerization reaction was performed for 3 hours to produce a polyester resin (I′-1).
The number average molecular weight of the obtained polyester resin (I′-1) was 25,000, and the glass transition temperature was −48.5 ° C.

(Production of polyester resin (I'-2))
In a reaction vessel equipped with a thermometer, a stirrer, a rectifying column, a nitrogen introducing tube and a vacuum apparatus, 76.6 parts (0.5 mol) of isophthalic acid as a polyvalent carboxylic acid component (A), 186.5 sebacic acid Parts (0.9 mol), 173.6 parts (0.9 mol) azelaic acid, 14.3 parts (0.2 mol) ethylene glycol as polyol component (B), 349 parts (2.4 mol) cyclohexanedimethanol ), 0.04 part of germanium dioxide was charged as a catalyst, the temperature was gradually raised to an internal temperature of 250 ° C., and an esterification reaction was carried out over 4 hours.

Thereafter, the internal temperature was raised to 270 ° C., the pressure was reduced to 1.33 hPa, and a polycondensation reaction was performed over 3 hours to produce a polyester resin (I′-2).
The number average molecular weight of the obtained polyester resin (I′-2) was 30,000, and the glass transition temperature was −25.6 ° C.

(Production of polyester resin (I'-3))
In a reaction vessel equipped with a thermometer, a stirrer, a rectifying column, a nitrogen introduction tube and a vacuum apparatus, 120.3 parts (0.7 mol) of terephthalic acid as polyvalent carboxylic acid component (A), 120.3 of isophthalic acid Parts (0.7 mol) and 195.3 parts (1.0 mol) of sebacic acid, 226.3 parts (2.2 mol) of neopentyl glycol as the polyol component (B), 108.8 of 1,4-butanediol Parts (1.2 mol), 1,6-hexanediol 24.8 parts (0.2 mol), trimethylolpropane 4.2 parts (0.03 mol), and tetrabutyl titanate 0.05 parts as a catalyst were charged. The temperature was gradually raised to an internal temperature of 250 ° C., and the esterification reaction was carried out over 4 hours.

Thereafter, the internal temperature was raised to 260 ° C., 0.05 part of tetrabutyl titanate was added as a catalyst, the pressure was reduced to 1.33 hPa, and a polymerization reaction was performed for 3 hours to produce a polyester resin (I′-3).
The number average molecular weight 22,000 of the obtained polyester resin (I′-3) had a glass transition temperature of −10.4 ° C.

[Production of polyester pressure-sensitive adhesive composition]
Example 1
The polyester resin (I-1) obtained above is diluted with ethyl acetate to a solid content concentration of 55% by mass, and a hydrolysis inhibitor is added to 100 parts (solid content) of this polyester resin (I-1) solution. (Nisshinbo Chemical Co., Ltd .; trade name “Carbodilite V-07”) 1 part (solid content) and trimethylolpropane / tolylene diisocyanate adduct as a crosslinking agent (manufactured by Tosoh Corporation; product name “Coronate L55E”) 3 A polyester-based pressure-sensitive adhesive composition was obtained by blending parts (solid content), stirring and mixing.

(Example 2)
In Example 1, the polyester-based pressure-sensitive adhesive composition was the same as Example 1 except that the polyester-based resin (I-1) was changed to the polyester-based resin (I-2) and the amount of the crosslinking agent was changed to 4 parts. Got.

(Example 3)
In Example 1, the polyester-based pressure-sensitive adhesive composition was the same as Example 1 except that the polyester-based resin (I-1) was changed to the polyester-based resin (I-3) and the blending amount of the crosslinking agent was changed to 4 parts. Got.

Example 4
In Example 1, the polyester-based pressure-sensitive adhesive composition was the same as Example 1 except that the polyester-based resin (I-1) was changed to the polyester-based resin (I-4) and the blending amount of the crosslinking agent was changed to 4 parts. Got.

(Example 5)
In Example 1, the polyester-based pressure-sensitive adhesive composition was the same as Example 1 except that the polyester-based resin (I-1) was changed to the polyester-based resin (I-5) and the amount of the crosslinking agent was changed to 4 parts. Got.

(Example 6)
The polyester resin (I-6) obtained above is diluted with ethyl acetate to a solid concentration of 55% by mass, and a hydrolysis inhibitor is added to 100 parts (solid content) of this polyester resin (I-6) solution. (Nisshinbo Chemical Co., Ltd .; trade name “Carbodilite V-09GB”) 0.7 parts (solid content) and trimethylolpropane / tolylene diisocyanate adduct as a crosslinking agent (manufactured by Tosoh Corporation; product name “Coronate L55E”) ) 5.0 parts (solid content), zirconium-based compound diluted to 1% solid content concentration with acetylacetone, which is a catalyst inhibitor as a urethanization catalyst (Matsumoto Fine Chemical Co., Ltd .; product name “Orgatechs ZC-150”) 0.01 part (solid content ratio), hindered phenol-based antioxidant (made by BASF Corp .; product name “Ir” as an antioxidant) anox1010 ") were blended 0.1 part (solid content ratio), stirred by mixing to obtain a polyester-based pressure-sensitive adhesive composition.

(Comparative Example 1)
In Example 1, the polyester-type adhesive composition was obtained like Example 1 except having changed the polyester-type resin (I-1) into the polyester-type resin (I'-1).

(Comparative Example 2)
In Example 1, the polyester-type adhesive composition was obtained like Example 1 except having changed the polyester-type resin (I-1) into the polyester-type resin (I'-2).

(Comparative Example 3)
In Example 1, the polyester-based pressure-sensitive adhesive composition was the same as in Example 1 except that the polyester-based resin (I-1) was changed to the polyester-based resin (I′-3) and the blending amount of the crosslinking agent was changed to 4 parts. I got a thing.

[Manufacture of adhesive film]
Each polyester-based pressure-sensitive adhesive composition obtained above was applied on a PET (polyethylene terephthalate) separator having a thickness of 38 μm using an applicator and dried at 100 ° C. for 4 minutes. A 50 μm pressure-sensitive adhesive sheet was obtained.

  Next, the surface of the obtained pressure-sensitive adhesive composition layer was covered with a PET separator having a thickness of 38 μm different from that of the separator, and an aging treatment was performed at 40 ° C. for 4 days to obtain a pressure-sensitive adhesive film with a double-sided separator.

[Adhesive sheet evaluation]
(Adhesive strength under high temperature)
The separator on one side was peeled off from the pressure-sensitive adhesive layer of each of the double-sided pressure-sensitive adhesive films obtained above, and the pressure-sensitive adhesive layer was transferred to a PET film (100 μm) to prepare a pressure-sensitive adhesive sheet for evaluation.

  The separator on the other side is peeled off from the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet obtained as described above, and the pressure-sensitive adhesive layer is bonded to a polycarbonate plate (“STELLA” manufactured by Mitsubishi Plastics, Inc.). For 20 minutes under the conditions of 0.5 MPa and 50 ° C. using a pressure depressurization apparatus (“YK-350S type” manufactured by Kurihara Seisakusho), and then a tensile tester with a thermostat (“Auto” manufactured by Shimadzu Corporation) Using graph AGS-H 500N "), a 180 degree peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min at 85 ° C. The results are shown in Table 2.

(Blister resistance)
The other separator was peeled off from the pressure-sensitive adhesive layer of the evaluation pressure-sensitive adhesive sheet obtained above, and the pressure-sensitive adhesive layer was bonded to a polycarbonate plate (“STELLA” manufactured by Mitsubishi Plastics, Inc.). A test piece having a configuration of “PC board / polyester-based pressure-sensitive adhesive layer / PET film” was produced by pressure bonding at 20 ° C. for 20 minutes.

  Thereafter, the test piece was subjected to a load for 24 hours in a constant temperature and humidity chamber of 85 ° C./85%, the appearance of the test piece after the load (whether foaming was present) was visually confirmed, and blister resistance was evaluated according to the following criteria. . The results are shown in Table 2.

(Double-circle): There was no foaming and there was no external appearance change.
◯: The area of the portion where foaming occurred relative to the area of the test piece was about ¼ or less.
(Triangle | delta): The area of the part which produced foam with respect to the area of a test piece exceeded about 1/4, and was about half or less.
X: The area of the part which foamed with respect to the area of a test piece exceeded about half.

  From the above results, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer using the pressure-sensitive adhesive composition of Examples 1 to 6 containing a polyester resin (I) having a glass transition temperature within a desired range and having a specific composition. It has excellent adhesive strength even at high temperatures, and even when the pressure-sensitive adhesive layer is exposed to high temperature and high humidity, it is found that foaming is small and the blister resistance is very excellent.

On the other hand, in Comparative Examples 1 and 2 using a polyester resin whose glass transition temperature is not within the desired range, it can be seen that the adhesive strength at high temperatures is low and the blister resistance is not satisfactory.
It can also be seen that Comparative Example 3 using a polyester resin that does not satisfy the specific composition although the glass transition temperature is within the desired range does not satisfy both the adhesive strength and the blister resistance.

Claims (9)

  It is obtained from a polyol component (B) containing a polyvalent carboxylic acid component (A) having an aromatic dicarboxylic acid (a1) content of 50 mol% or more and a diol compound (b1) having a hydrocarbon group in the side chain. Polyester resin (I) which is polyester resin (I), has a content ratio of isophthalic acid with respect to the whole aromatic dicarboxylic acid (a1) of 60 mol% or more, and has a glass transition temperature of -20 to + 30 ° C. A polyester-based pressure-sensitive adhesive composition comprising:   Furthermore, 0.01-10 mass parts of hydrolysis inhibitors (II) are contained with respect to 100 mass parts of said polyester-type resin (I), The polyester-type adhesive composition of Claim 1 characterized by the above-mentioned. .   The polyester pressure-sensitive adhesive composition according to claim 1 or 2, further comprising a crosslinking agent (III).   A polyester-based pressure-sensitive adhesive composition, wherein the polyester-based pressure-sensitive adhesive composition according to claim 3 is crosslinked with a crosslinking agent (III).   A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer containing the polyester-based pressure-sensitive adhesive according to claim 4.   The pressure-sensitive adhesive sheet according to claim 5, comprising a base material, wherein the pressure-sensitive adhesive layer is provided on at least one side of the base material.   The pressure-sensitive adhesive sheet according to claim 5, wherein the pressure-sensitive adhesive sheet is a substrate-less type having no substrate.   The pressure-sensitive adhesive sheet according to claim 5, wherein the pressure-sensitive adhesive sheet is used for bonding optical members.   An optical member with an adhesive layer, comprising an adhesive layer containing the polyester-based adhesive according to claim 4 and an optical member.