JP2009280776A - Pressure-sensitive adhesive composition and pressure-sensitive adhesive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive optical film which is for sticking to a glass member for a liquid crystal cell, and excellent in stable releasability of the release sheet, in removability from the glass member for the liquid crystal cell, and in durability after sticking. <P>SOLUTION: The pressure-sensitive adhesive composition includes: a polymer [P] having a carboxyl group or a hydroxyl group and exhibiting a glass transition temperature of (-80) to 10°C; a reaction product (F) being the reaction product (F) of a silane compound (f2) having an isocyanate group and an alkoxysilyl group with a polyol (f1) and comprising a hydroxyl group and an alkoxysilyl group; and a reactive compound (G) capable of reacting with at least one of the carboxyl group or the hydroxyl group in the polymer [P]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention is excellent in adhesiveness, heat resistance, moist heat resistance and transparency with an optical film, and can be suitably used as a pressure sensitive adhesive composition for laminating an optical film on a liquid crystal cell member. Related to things. Specifically, the present invention relates to a pressure-sensitive adhesive composition mainly composed of a copolymer obtained by polymerizing an α, β-unsaturated compound, or mainly composed of a polyester-based resin.
Furthermore, this invention relates to the pressure sensitive adhesive film which uses a pressure sensitive adhesive composition.

Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal display (LCD), plasma display (PDP), rear projection display (RPJ), EL display, light emitting diode display, etc. It has come to be used as a display device in various fields. For example, these FPDs are not only used indoors, including personal computer displays and liquid crystal televisions, but are also used in vehicles such as car navigation displays.
For such display devices, various films such as an antireflection film for preventing reflection from an external light source and a protective film (protection film) for preventing scratches on the surface of the display device are usually used. For example, in a liquid crystal cell member constituting an LCD, a polarizing film or a retardation film is laminated.
Further, the FPD is not only used as a display device, but may be used as an input device by providing a touch panel function on the surface thereof. A protective film, an antireflection film, an ITO vapor deposition resin film, or the like is also used for the touch panel.
Such a film is attached to an adherend with a pressure-sensitive adhesive and used in a display device. Since the pressure-sensitive adhesive used for the display device is required to have excellent transparency, a pressure-sensitive adhesive mainly composed of an acrylic resin is generally used.

  By the way, among the various films described above, the polarizing film has a three-layer structure in which both surfaces of a polyvinyl alcohol-based polarizer are sandwiched between triacetyl cellulose-based or cycloolefin-based protective films. For this reason, in a polarizing film, the remarkable dimensional change by expansion / contraction accompanying the change of temperature or humidity arises according to the characteristic of the material which comprises each layer.

In addition, in the inspection process of a laminate with a polarizing film attached to the glass surface for a liquid crystal cell, the polarizing film etc. is peeled off and a new polarizing film is attached to the one that has air or dust trapped during lamination. Will be fixed. This re-pasting is also called “rework”.
However, since the laminated body is generally inspected after being stored at a high temperature for a certain period of time in order to improve adhesion, not only does the peel strength increase during that time, but it becomes difficult to peel off the polarizing film, etc. The glass member as the adherend is contaminated, such as adhesive residue and cloudiness, after re-peelability is reduced and peeled off.

  In addition, since the dimensional change due to the shrinkage of the polyvinyl alcohol film is severe under high temperature or high temperature and high humidity conditions, the laminate composed of the optical film / adhesive layer / adhered body is not subjected to high temperature or high temperature and high humidity conditions. When the dimensions of the polarizing film are changed, bubbles are generated at the interface between the adhesive layer and the adherend (foaming phenomenon), and the optical film is lifted from the adherend and peeled off (floating / peeling phenomenon). By adjusting the molecular weight of the main component of the pressure-sensitive adhesive composition and the degree of crosslinking of the pressure-sensitive adhesive composition, and increasing the adhesive strength, it resists the dimensional change of the polarizing film and foams even in harsh environments. Attempts have been made to prevent floating and peeling.

  However, simply trying to resist the dimensional change of the optical film simply by increasing the adhesive force, the stress distribution due to the dimensional change of the polarizing film that occurs under high temperature or high temperature and high humidity conditions becomes non-uniform, and the stress becomes optical. It concentrates on the four corners and the peripheral edge of the film. As a result, in the display device using the polarizing film, there is a problem that light leaks from the peripheral end portion of the display device, that is, so-called white spots occur.

  As described above, the pressure-sensitive adhesive for laminating a polarizing film on a glass member for a liquid crystal cell has good optical properties (transparency), heat resistance and moist heat resistance, good stress relaxation properties, and removability. Etc. are required. Similar performance is also required for pressure-sensitive adhesives for laminating retardation films and cover films for various displays.

Conventionally, various pressure-sensitive adhesives have been proposed for such various requirements.
For example, a pressure-sensitive adhesive composition obtained by blending a propenoic acid-based pressure-sensitive adhesive containing a propenoic acid-based resin and a crosslinking agent with a polyether polyol is known (see Patent Document 1).

However, when the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive composition described in Patent Document 6 is attached to an adherend and exposed to a high temperature or high temperature and high humidity for a long time, Extremely small bubbles are generated in a streak-like state at the peripheral edge of the optical film. This phenomenon is called a “crack” because very small bubbles that appear as streaks look like a kind of crack.
In addition, about 10 bubbles of 10 μm or less, which cannot be confirmed unless using an electron microscope, are generated in the center part per 10 m ² .
Further, in a display device of 20 inches or more, the luminance of the light source must be set high from the viewpoint of easy viewing. In the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive composition described in Patent Document 1, white spots were not regarded as a problem in a display device of less than 20 inches. However, there has also been a problem that white spots are conspicuous in a display device using a high-intensity light source used at 20 inches or more.

As pressure-sensitive adhesive compositions for forming pressure-sensitive adhesive optical films, propenoic acid-based pressure-sensitive adhesives containing a propenoic acid-based resin, a crosslinking agent, and various silane coupling agents are disclosed in various documents.
However, even if a relatively low molecular weight silane coupling agent such as 3-glycidoxypropyltrimethoxysilane or 3-aminopropyltrimethoxysilane is contained, the demand for rework becomes more severe, which is more severe. The request has become unsatisfactory. In addition, there has been a problem that cracks and foaming are likely to occur when exposed to an adherend for a long period of time under high temperature or high temperature and high humidity conditions.

Patent Documents 2 to 6 disclose pressure-sensitive adhesive compositions using various silane coupling agents having a relatively large molecular weight.
For example, Patent Document 2 contains a propenoic acid copolymer having a carboxyl group and a hydroxyl group in the molecule, a polyisocyanate compound, and a mercapto group or alicyclic epoxy group-containing silane coupling agent as essential components. A pressure sensitive adhesive composition for a polarizing film is disclosed.

  Moreover, for example, a pressure-sensitive adhesive composition is known, which is characterized by blending a silicate oligomer obtained by condensing a curing agent and a silane compound in a propenoic acid resin (see Patent Documents 3 to 5). .

  Further, for example, it comprises a propenoic acid resin and a polymer type silane coupling agent having a functional group for an inorganic substance and a functional group for an organic substance, and the main chain is formed of a siloxane skeleton. There is known a pressure-sensitive adhesive composition for liquid crystal elements, which contains 0.001 to 4 parts by weight of the polymer type silane coupling agent with respect to parts (see Patent Document 6). .

  The pressure-sensitive adhesive film using the pressure-sensitive adhesive composition containing various silane coupling agents having a relatively large molecular weight described in Patent Documents 2 to 6 is attached to an adherend, Even when exposed to a high temperature or high temperature and high humidity for a long period of time, cracks in the vicinity of the peripheral edge and microbubbles in the center did not occur, and no white spots were seen in a display device of less than 20 inches.

However, the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive composition containing various silane coupling agents having a relatively large molecular weight is liable to deteriorate the peelability from the peelable sheet as described in detail below. There was a problem.
The pressure-sensitive adhesive optical film is formed by applying a pressure-sensitive adhesive composition to the release-treated surface of a release-treated sheet-like substrate (hereinafter referred to as a peelable sheet), and drying the optical film. It can be obtained by laminating on the surface, or coating and drying the pressure-sensitive adhesive composition on the optical film, and laminating the release-treated surface of the peelable sheet on the surface of the pressure-sensitive adhesive layer. However, the pressure-sensitive adhesive optical film is not always attached to an adherend, that is, a liquid crystal cell member immediately after production. The obtained pressure-sensitive adhesive optical film is often used after being stored for a certain period. In such a case, when the peelable sheet is peeled off and the exposed pressure-sensitive adhesive layer is to be attached to a liquid crystal cell member such as glass, the peelable sheet is not peeled off or peeled off. There was a problem that the pressure-sensitive adhesive layer remained on the sheet.

Furthermore, the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive composition containing various silane coupling agents having a relatively large molecular weight also has a problem that the adhesive force to the adherend tends to decrease.
That is, when the pressure-sensitive adhesive optical film is stored for a certain period after manufacturing and then adhered to a liquid crystal cell member such as glass, the adhesive strength is significantly greater than when a pressure-sensitive adhesive optical film immediately after manufacturing is adhered. Will drop, causing floating and peeling. Moreover, even if it is a pressure sensitive adhesive optical film immediately after manufacture, with the passage of time after sticking to liquid crystal cell members, such as glass, an adhesive force will fall significantly and a float and peeling will arise. Since the decrease in the adhesive strength to the adherend becomes more apparent as the adhesion area increases, a pressure-sensitive adhesive optical film using a pressure-sensitive adhesive composition containing various silane coupling agents having a relatively large molecular weight is used. It was difficult to use for a display device of 20 inches or more.

Furthermore, in recent years, in addition to propenoic acid pressure-sensitive adhesives, application of polyester resins to pressure-sensitive adhesives has been studied.
For example, a sensitivity obtained by blending various curing agents with a polyester resin having a glass transition temperature (Tg) of −60 to 0 ° C. formed from dimer acid and a glycol component having an alkyl group in a side chain of 30 mol% or more. A pressure-type adhesive is known (see, for example, Patent Document 7).

Also known is a pressure-sensitive adhesive comprising a repeating unit in which an ester of a glycol having a methyl group in the side chain and a carboxylic acid is linked with a polyisocyanate, and comprising an aliphatic polyester having a Tg of -40 ° C or lower. (For example, see Patent Document 8).
The pressure-sensitive adhesive disclosed in Patent Document 7 is intended for biodegradability and is an aliphatic polyester pressure-sensitive adhesive, so that it is easy to obtain tack and a relatively flexible pressure-sensitive adhesive layer is obtained. However, the heat resistance is insufficient. For example, when it is used as a pressure-sensitive adhesive for laminating a polarizing film on a glass member for a liquid crystal cell, it floats or peels off when placed for a long time under high temperature or high temperature and high humidity after sticking.

  Also, polycondensation of a dicarboxylic acid component containing an aromatic dicarboxylic acid, a diol component containing a glycol having a hydrocarbon group in the side chain, a trihydric or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid. A polyester resin in which a structural portion derived from a trihydric or higher polyhydric alcohol and / or trihydric or higher polycarboxylic acid is contained in an amount of 0.1 to 5 mol% in the polyester resin. A pressure-sensitive adhesive characterized by containing a resin is known (for example, see Patent Document 9).

  And 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 characterized by containing a polyester resin having a number average molecular weight of 5000 or more is known (see, for example, Patent Document 10).

Patent Documents 9 and 10 disclose that a polyester resin is a main ingredient and that the reaction between a hydroxyl group and / or a carboxyl group in a polyester resin and a crosslinking agent is used to increase the cohesive strength of the pressure-sensitive adhesive layer. ing.
The hydroxyl group and / or carboxyl group responsible for the reaction with the crosslinking agent is considered to be introduced using a polyfunctional alcohol or a polyfunctional carboxylic acid component. In order to increase the cohesive force of the pressure-sensitive adhesive layer, it is considered necessary to increase these functional groups in the polyester resin.

From conventional propenoic acid pressure-sensitive adhesives using various silane coupling agents and polyester resin pressure-sensitive adhesives, it is possible to re-release the peelable sheet from the adherend, which is said to be called “reworkability”. It was not possible to obtain a pressure-sensitive adhesive optical film that satisfactorily satisfied the peelability and the high durability after sticking.
JP-A-6-128539 JP-A-8-199130 JP-A-8-209090 Japanese Patent No. 8-209103 JP 7-331206 A JP 2004-224873 A Japanese Patent Laid-Open No. 04-328186 Japanese Patent Laid-Open No. 11-021340 JP 2007-099879 A JP 2007-045914 A

  The present invention is a pressure-sensitive adhesive optical film for adhering to a glass member for a liquid crystal cell, having excellent peel stability of the peelable sheet, excellent removability from the glass member for a liquid crystal cell, and after sticking An object of the present invention is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive optical film having excellent durability (heat resistance, heat and humidity resistance).

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, in the first invention, the polymer [P] having at least one of a carboxyl group or a hydroxyl group and having a glass transition temperature of −80 to 10 ° C., a silane compound (f2) having an isocyanate group and an alkoxysilyl group, a polyol ( a reaction product (F) with f1), which is a reaction product (F) containing a hydroxyl group and an alkoxysilyl group, and a reactive compound capable of reacting with at least one of a carboxyl group or a hydroxyl group in the polymer [P] (G) and a pressure-sensitive adhesive composition.

  In the second invention, the reaction product (F) comprises a silane compound (f2) having an isocyanate group and an alkoxysilyl group and a polyol (f1) (f1) :( f2) = 3 to 9: 7. It is related with the pressure-sensitive-type adhesive composition as described in the said invention which is made to react by -1 (mol ratio).

  Moreover, 3rd invention is the number average molecular weight (Mn) of a polyol (f1) of 100-50,000, The hydroxyl value is 5-1,000 (mgKOH / g), In any one of the said invention. The present invention relates to a pressure-sensitive adhesive composition.

  Moreover, 4th invention is related with the pressure sensitive adhesive composition in any one of the said invention whose hydroxyl value of reaction product (F) is 3-200 (mgKOH / g).

  In addition, the fifth invention is any one of the above inventions, wherein the polymer [P] is a copolymer [PA] or a polyester resin [PD] obtained by copolymerizing an α, β-unsaturated compound. The pressure-sensitive adhesive composition of the present invention.

Further, the sixth invention is such that the copolymer [PA] has at least one of an α, β-unsaturated compound having a carboxyl group or an α, β-unsaturated compound having a hydroxyl group, and other than the above two. a copolymer with an α, β-unsaturated compound,
The α, β-unsaturated compound having a carboxyl group is propenoic acid or 2-methylpropenoic acid,
The α, β-unsaturated compound having a hydroxyl group is a propenoic acid derivative having a hydroxyl group or a 2-methylpropenoic acid derivative having a hydroxyl group,
The other α, β-unsaturated compound is a propenoic acid derivative having neither a carboxyl group nor a hydroxyl group, and a 2-methylpropenoic acid derivative having neither a carboxyl group nor a hydroxyl group. It relates to the pressure sensitive adhesive composition described in the invention.

  The seventh invention is a total of 100% by weight of an α, β-unsaturated compound having a carboxyl group, an α, β-unsaturated compound having a hydroxyl group and other α, β-unsaturated compounds other than the above two. Among them, the total of the α, β-unsaturated compound having a carboxyl group and the α, β-unsaturated compound having a hydroxyl group is 0.01 to 20% by weight, and the pressure-sensitive formula according to the sixth invention The present invention relates to an adhesive composition.

  The eighth invention is the pressure-sensitive adhesive according to the fifth invention, wherein the polyester resin [PD] is a condensation type polyester resin [PD1] or an addition type polyester resin [PD2]. The agent composition.

In the ninth invention, the condensation-type polyester resin [PD1]
A dibasic acid component (A) having no hydroxyl group;
A diol (B) having no carboxyl group;
A trihydric or higher polyhydric alcohol (c1), a trihydric or higher polyhydric carboxylic acid (c2), a compound having two cyclic ether groups in the molecule (c3), two hydroxyl groups and one carboxyl group in one molecule At least one component for introducing a side chain functional group selected from the group consisting of dioxycarboxylic acid (c4) having the above and oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule ( The pressure-sensitive adhesive composition according to the eighth invention, which is a condensation-type polyester resin [PD1-1] obtained by reacting C).

  In the tenth invention, the condensed polyester resin [PD1] is obtained by further ring-opening addition of a cyclic ester compound (E) to the side chain functional group in the condensed polyester resin [PD1-1]. The polyester resin [PD1-2] having a ring-opening portion of the cyclic ester compound (E) as a side chain and a hydroxyl group at the terminal of the ring-opening portion. The present invention relates to a pressure-sensitive adhesive composition.

  An eleventh invention is a pressure-sensitive adhesive optical film comprising an optical film and a pressure-sensitive adhesive layer located on at least one surface of the optical film, wherein the pressure-sensitive adhesive layer is the first to tenth inventions. It is formed from the pressure-sensitive adhesive composition in any one of these, It is related with the pressure-sensitive adhesive optical film characterized by the above-mentioned.

  According to the present invention, a pressure-sensitive adhesive optical film for adhering to a glass member for a liquid crystal cell, excellent in peeling stability from the peelable sheet, excellent in removability from the glass member for liquid crystal cell, and sticking It has become possible to provide a pressure-sensitive adhesive composition that can form a pressure-sensitive adhesive optical film having excellent durability (heat resistance and heat and humidity resistance).

First, a general description of the pressure-sensitive adhesive and the pressure-sensitive adhesive sheet will be given.
The pressure sensitive adhesive is used to form a pressure sensitive adhesive sheet.
The basic laminated structure of the pressure-sensitive adhesive sheet is as follows: sheet-like substrate / pressure-sensitive adhesive layer / single-sided pressure-sensitive adhesive sheet such as peelable sheet, or peelable sheet / pressure-sensitive adhesive layer / sheet-like substrate / It is a double-sided pressure-sensitive adhesive sheet such as a pressure-sensitive adhesive layer / peelable sheet. At the time of use, the peelable sheet is peeled off, and the pressure-sensitive adhesive layer is attached to the adherend. The pressure-sensitive adhesive is not only a pressure-sensitive adhesive layer that has a tack at the moment when the pressure-sensitive adhesive layer touches the adherend but also an adhesive other than the pressure-sensitive adhesive (hereinafter simply referred to as a pressure-sensitive adhesive). Unlike adhesives), it is necessary to have a cohesive force for maintaining the sticking state while having a tack and appropriate hardness without being completely solidified even during sticking. The cohesive force greatly depends on the molecular weight.

The polymer [P] used in the pressure-sensitive adhesive of the present invention has a glass transition temperature of −80 to 10 ° C. and has at least one of a carboxyl group and a hydroxyl group. A carboxyl group or a hydroxyl group is located in a side chain position, and these functional groups react with a reactive compound (G) described later to form a pressure-sensitive adhesive layer.
As the polymer [P], an α, β-unsaturated compound, that is, a copolymer [PA] obtained by copolymerizing a compound having a polymerizable α, β-unsaturated double bond in the molecule, polyester, Resin [PD] and other various resins are mentioned, and a copolymer [PA] of an α, β-unsaturated compound and a polyester resin [PD] are preferable. Examples of the polyester resin [PD] include condensation-type polyester resin [PD1] and addition-type polyester resin [PD2].

<Copolymer of α, β-unsaturated compound [PA]>
For the formation of the copolymer [PA] of α, β-unsaturated compounds, propenoic acid, 2-methylpropenoic acid, propenoic acid derivatives and 2-methyl are used as compounds having an α, β-unsaturated double bond. It is preferable to use at least one compound selected from propenoic acid derivatives as an essential component, and it is also preferable to use an alkenyl group-containing compound.

  Examples of the propenoic acid derivative or 2-methylpropenoic acid derivative include, for example, methyl (2-methyl) propenoate [combination of methyl propenoate and methyl 2-methylpropenoate is referred to as “methyl (2-methyl) propenoate”. To do. The same applies hereinafter. ], (2-methyl) propenoic acid ethyl, (2-methyl) propenoic acid 1-propyl, (2-methyl) propenoic acid 2-propyl, (2-methyl) propenoic acid n-butyl, (2-methyl) propene Sec-butyl acid, iso-butyl (2-methyl) propenoate, tert-butyl (2-methyl) propenoate, n-amyl (2-methyl) propenoate, iso-amyl (2-methyl) propenoate, 2-methyl) propenoic acid n-hexyl, (2-methyl) propenoic acid 2-ethylhexyl, (2-methyl) propenoic acid n-octyl, (2-methyl) propenoic acid iso-octyl, (2-methyl) propenoic acid n-nonyl, iso-nonyl (2-methyl) propenoate, decyl (2-methyl) propenoate, dodecyl (2-methyl) propenoate, (2-methyl) propyl Pensan octadecyl, (2-methyl) propenoic acid lauryl, (2-methyl) (2-methyl) such as propenoic acid stearyl propenoic acid alkyl esters;

  For example, cyclohexyl (2-methyl) propenoate, benzyl (2-methyl) propenoate, iso-bonyl (2-methyl) propenoate, phenyl (2-methyl) propenoate, 2-phenoxy (2-methyl) propenoate (2-methyl) propenoic acid cyclic esters such as ethyl, (2-methyl) propenoic acid 2-oxo-1,2-phenylethyl, (2-methyl) propenoic acid 2-oxo-1,2-diphenylethyl;

  For example, allyl (2-methyl) propenoate, 1-methylallyl (2-methyl) propenoate, 2-methylallyl (2-methyl) propenoate, 1-butenyl (2-methyl) propenoate, (2-methyl) propene 2-butenyl acid, 3-butenyl (2-methyl) propenoate, 1,3-methyl-3-butenyl (2-methyl) propenoate, 2-chloroallyl (2-methyl) propenoate, (2-methyl) propene Acid 3-chloroallyl, (2-methyl) propenoic acid-o-allylphenyl, (2-methyl) propenoic acid 2- (allyloxy) ethyl, (2-methyl) propenoic acid allyl lactyl, (2-methyl) propenoic acid citronellyl, Geranyl (2-methyl) propenoate, rosinyl (2-methyl) propenoate, cinnamyl (2-methyl) propenoate, (2-methyl) ) Containing more unsaturated groups vinyl propenoic acid (2-methyl) propenoic acid esters;

  For example, (2-methyl) propenoic acid perfluoromethyl, (2-methyl) propenoic acid perfluoroethyl, (2-methyl) propenoic acid perfluoropropyl, (2-methyl) propenoic acid perfluorobutyl, (2-methyl) ) Perfluorooctyl propenoate, trifluoromethyl methyl (2-methyl) propenoate, 2-trifluoromethyl ethyl (2-methyl) propenoate, diperfluoromethyl methyl (2-methyl) propenoate, (2-methyl) ) 2-perfluoroethylethyl acrylate, (2-methyl) propenoic acid 2-perfluoromethyl-2-perfluoroethylmethyl, (2-methyl) propenoic acid triperfluoromethylmethyl, (2-methyl) propenoic acid 2-perfluoroethyl-2-perfluorobutylethyl, (2-methyl) (2-methyl) propenoic acid perfluoroalkyl esters such as 2-perfluorohexylethyl lopenate, 2-perfluorodecylethyl (2-methyl) propenoate, 2-perfluorohexadecylethyl (2-methyl) propenoate Kind;

  For example, 2-hydroxyethyl (2-methyl) propenoate, 1-hydroxypropyl (2-methyl) propenoate, 2-hydroxypropyl (2-methyl) propenoate, 2-methoxyethyl (2-methyl) propenoate, Hydroxyl or alkoxysilyl group-containing (2-methyl) propenoic acid such as 2-ethoxyethyl (2-methyl) propenoate, 2-hydroxybutyl (2-methyl) propenoate, 4-hydroxybutyl (2-methyl) propenoate Esters;

  For example, N-methylaminoethyl (2-methyl) propenoate, N-tributylaminoethyl (2-methyl) propenoate, N, N-dimethylaminoethyl (2-methyl) propenoate, (2-methyl) propenoic acid Amino group-containing (2-methyl) propenoates such as N, N-diethylaminoethyl;

  For example, glycidyl (2-methyl) propenoate, (2-methyl) propenoate (3,4-epoxycyclohexyl) methyl, (2-methyl) propenoate (3-methyl-3-oxetanyl) methyl, (2-methyl) ) Heterocycle-containing (2-methyl) propenoates such as tetrahydrofurfuryl propenoate;

  For example, 3- (2-methylpropane-2-enoyloxypropyl) trimethoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) triethoxysilane, 3- (2-methylpropan-2- Enoyloxypropyl) triisopropoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) methyldimethoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) methyldiethoxysilane, 3 -(2-methyl) propenoic acid esters containing alkoxysilyl groups such as (propane-2-enoyloxypropyl) trimethoxysilane;

  For example, 2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(2-methyl) Propane-2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5 '-(2-methyl) propan-2-enoyloxypropylphenyl) -2H-benzo Triazole, 2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-3′-tert) -Butyl-5 '-(2-methyl) propane-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl) Benzotriazole-based (2-methyl) propenoic acid derivatives such as ru-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole;

  For example, 2-hydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxydiphenylmethanone, 2-hydroxy-4- {2-((2-methyl) propane-2-enoyloxy} butoxydiphenyl Methanone, 2,2′-dihydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxydiphenylmethanone, 2-hydroxy-4- {2- (2-methyl) propan-2-enoyloxy } Diphenylmethanone-based (2-methyl) propenoic acid derivatives such as ethoxy-4 ′-(2-hydroxyethoxy) diphenylmethanone;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methylphenyl) ) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [ 2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2- (2-Methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2- (2- Methyl) propane-2-enoyloxyethoxy )]-S-triazine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S -Triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)] -S-triazine, 2 , 4-Bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2, 4- Bis (2,4-diethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine-based (2-methyl) ) Propenoic acid derivatives;

  For example, alkylene oxide-containing (2-methyl) propenoic acid derivatives such as ethylene oxide adduct of (2-methyl) propenoic acid;

  For example, ethylene glycol di (2-methyl) propenoate, triethylene glycol di (2-methyl) propenoate, tetraethylene glycol di (2-methyl) propenoate, trimethylolpropane tri (2-methyl) propenoate, tri (2-methyl) propenoic acid pentaerythritol, di (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, tri (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, tri ( And polyfunctional (2-methyl) propenoic acid esters such as 2-methyl) propenoic acid 1,1,1-trishydroxymethylpropane.

  Examples of the alkenyl group-containing compound include ethenylbenzene, α-isopropenylbenzene, β-isopropenylbenzene, 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethenylbenzene, 1-butylethenyl. Aromatic vinyl monomers such as tenenylbenzene, 1-chloro-4-isopropenylbenzene, ethenylbenzenesulfonic acid and its sodium and potassium salts;

  For example, fluorine-containing vinyl monomers such as perfluoroethene, perfluoropropene, perfluoro (propyl vinyl ether), ethenidene fluoride;

  For example, vinyl monomers containing trialkyloxysilyl groups such as vinyltrimethoxysilane and vinyltriethoxysilane;

  For example, cis-butenedioic acid diallyl, 2-methylidene succinate diallyl, (E) -but-2-enoic acid vinyl, (Z) -octadeca-9-enoic acid vinyl, (9Z, 12Z, 15Z) -octadeca-9 Vinyl ester monomers containing further unsaturated bonds such as vinyl 12,12,15-trienoate;

  For example, nitrile group-containing vinyl monomers such as 2-propenenitrile and 2-methyl-2-propenenitrile;

  For example, amide group-containing vinyl monomers such as propenamide and 2-methylpropenamide;

  For example, vinyl esters such as vinyl ethanoate, vinyl propanoate, vinyl pivalate, vinyl benzenecarboxylate, vinyl 3-phenyl-2-propenoate;

  For example, unsaturated carboxylic acids such as 2-carboxyethyl propenoate, 2-methylidene succinic acid, cis-butenedioic acid, trans-butenedioic acid, penta-2-enedioic acid, and 2-methylfumaric acid;

  For example, unsaturated carboxylic acid anhydrides such as 2,5-dihydrofuran-2,5-dione;

  For example, monoalkyl esters and dialkyl esters of the above unsaturated carboxylic acids;

  Examples include chloroethylene, 1,1-dichloroethylene, allyl chloride, and allyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  In addition, in obtaining the copolymer [PA] used in the present invention, other compounds having an α, β-unsaturated double bond can be used as necessary. Examples include maleimide derivatives such as, for example, maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

  For example, alkenes such as ethene, propene, 1-butene, 2-butene, 2-methylpropene;

  Examples thereof include dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like.

The copolymer [PA] used in the present invention is appropriately selected from α, β-unsaturated compounds to be polymerized, so that a hydroxyl group, a carboxyl group, an amino group, an amide group, a maleimide group, and a nitrile group are included in the structure. And various functional groups such as an epoxy group, an alkoxysilyl group, and an allyl group. In consideration of crosslinking reactivity with the reactive compound (G) described later, it preferably has at least one of a carboxyl group and a hydroxyl group.
The carboxyl group is preferably introduced into the copolymer [PA] using propenoic acid or 2-methylpropenoic acid at the time of copolymerization.
Moreover, it is preferable that the hydroxyl group is introduced into the copolymer [PA] by using a propenoic acid derivative having a hydroxyl group or a 2-methylpropenoic acid derivative having a hydroxyl group during the copolymerization.

A compound having a carboxyl group or a hydroxyl group capable of reacting with the reactive compound (G) when the total of various α, β-unsaturated compounds used as a raw material for the copolymer [PA] is 100% by weight. It is preferable that the total use amount of the compound to be included is 0.01 to 20% by weight. If it is less than 0.01% by weight, a sufficient cross-linked structure cannot be obtained. Therefore, the cohesive strength of the pressure-sensitive adhesive layer is low, and the stability and durability during repeated use are inferior.
On the other hand, if it exceeds 20% by weight, the cohesive force of the pressure-sensitive adhesive layer becomes too high, and as a result, the glass and the pressure-sensitive adhesive layer are easily peeled off, which is not preferable. In particular, when placed in an environment where the temperature and humidity vary, the glass and the pressure-sensitive adhesive layer are more easily peeled off.

The above-mentioned copolymer [PA] forms a copolymer having a glass transition point (Tg) of −80 to 10 ° C. so that a well-balanced adhesive property (particularly, both tack and cohesive force) can be exhibited. It is preferable to select an α, β-unsaturated compound so that it can be formed, and an α, β-unsaturated compound is selected so that a copolymer having a glass transition point (Tg) of −60 to 0 ° C. can be formed. More preferably.
When the glass transition point of the copolymer is less than −80 ° C., the cohesive force of the pressure-sensitive adhesive layer obtained by using the copolymer is lowered, and the peeling off tends to occur. On the other hand, when the glass transition point exceeds 0 ° C., a pressure-sensitive adhesive layer having sufficient tack cannot be obtained.

If the Tg of the homopolymer that can be formed from each monomer that is a constituent component of the copolymer [PA] is known, the copolymer [PA] can be formed based on the Tg of each homopolymer and the constituent ratio of each monomer. Tg can be obtained theoretically.
By the way, in the case of a pressure-sensitive adhesive composition, a small amount of the reactive compound (G) as a curing agent is generally blended with the copolymer [PA] as a main component. Since the pressure-sensitive adhesive layer formed from such a pressure-sensitive adhesive composition has a loose cross-linked state (in other words, sparse), unlike a cured coating film that is densely cross-linked, the Tg of the pressure-sensitive adhesive layer Is approximately equal to the Tg of the copolymer [PA] before crosslinking. Accordingly, if the types and amounts of various α, β-unsaturated compounds are selected so that the Tg of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is 10 ° C. or less, preferably 0 ° C. or less. Good.

As the α, β-unsaturated compound, 2-ethylhexyl propenoate, n-butyl propenoate, n-octyl propenoate, isopropenoate which can form a homopolymer having a glass transition point (Tg) of −50 ° C. or less. -Octyl, iso-octyl propenoate, n-nonyl propenoate, iso-nonyl propenoate, n-decyl pepropenoate, lauryl propenoate, stearyl propenoate, decyl 2-methylpropenoate, lauryl 2-methylpropenoate, 2 -It is preferable to contain 20 to 80% by weight of a propenoic acid ester of alkyl side chain such as stearyl methylpropenoate or 2-methylpropenoic acid ester in a total of 100% by weight of the α, β-unsaturated compound.
Other compounds used for copolymerization with the above α, β-unsaturated compound include homopolymers having a glass transition point (Tg) in the range of −10 to 100 ° C. in order to control cohesion and improve heat resistance. An alkenyl group-containing compound or an α, β-unsaturated carboxylic acid ester, such as hydroxyl group, carboxyl group, amino group, amide group, maleimide group, nitrile group, epoxy group, alkoxysilyl group, allyl group, etc. Those having a functional group of Furthermore, a carboxyl group or a hydroxyl group is more preferable as the functional group in order to form a homogeneous cross-linked structure that does not clearly represent the density distribution with the reactive compound (G). When the reactivity of the functional group in the copolymer [PA] that reacts with the reactive compound (G) to form a crosslinked structure is slow, it takes a long time to complete the formation of the crosslinked structure. However, since it is not allowed for such a long time industrially, a uniform cross-linked state cannot be exhibited, and the pressure-sensitive adhesive layer has a sparse part and a dense part. The pressure-sensitive adhesive layer with such a coarse and dense distribution has a low cohesive force. Therefore, if the pressure-sensitive adhesive optical film is attached to an adherend and exposed to a harsh environment at high temperature or high humidity, it will be crosslinked. Since stress concentrates on the low density portion and foaming, floating and peeling are likely to occur, it is not preferable. Therefore, the functional group in the copolymer [PA] is preferably a highly reactive carboxyl group or hydroxyl group.

  The copolymer [PA] in the present invention is a block polymerization using 0.001 to 5 parts by weight of a polymerization initiator with respect to a total of 100 parts by weight of various α, β-unsaturated compounds as described above. It is synthesized by a method such as solution polymerization, emulsion polymerization or suspension polymerization. Preferably, it is synthesized by solution polymerization.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) An azo compound such as propane].

  Also, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy Organic such as 2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide A peroxide is mentioned.

  In the synthesis, mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, and chain transfer agents such as α-methylstyrene dimer and limonene may be used.

  The weight average molecular weight (Mw) of the copolymer [PA] is preferably 50,000 to 2,000,000 from the viewpoint of adhesiveness, and more preferably in the range of 200,000 to 1,500,000. preferable. When the Mw exceeds 2,000,000, the fluidity of the copolymer becomes poor, so that the coating property of the pressure-sensitive adhesive composition deteriorates, and the pressure-sensitive adhesive layer itself is produced on the peelable sheet. It becomes difficult. On the other hand, when Mw is less than 50,000, the pressure-sensitive adhesive optical layer is liable to cohesive failure after the pressure-sensitive adhesive optical film is attached to a liquid crystal cell member such as glass, such being undesirable.

<Polyester resin [PD]>
Next, the polyester resin [PD] suitably used as the polymer [P] in the present invention will be described. The polyester resin [PD] can be obtained by various methods, and examples thereof include condensation-type polyester resin [PD1] and addition-type polyester resin [PD2].

<Condensation type polyester resin [PD1]>
The condensed polyester resin [PD1] is preferably a condensed polyester resin [PD1-1] having a hydroxyl group or a carboxyl group in the side chain. The condensed polyester resin [PD1-1] is, for example, as follows. Can be obtained.
When reacting the dibasic acid component (A) having no hydroxyl group and the diol (B) having no carboxyl group to obtain a polyester resin, a trihydric or higher polyhydric alcohol (c1), a trivalent or higher polyhydric alcohol Polycarboxylic acid (c2), compound (c3) having two cyclic ether groups in the molecule, dioxycarboxylic acid (c4) having two hydroxyl groups and one or more carboxyl groups in one molecule, and one molecule By using at least one side chain functional group-introducing component (C) selected from the group consisting of oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups, a condensed polyester resin [PD1] A hydroxyl group or a carboxyl group can be introduced into the side chain.

Examples of the dibasic acid component (A) having no hydroxyl group used in the present invention include known dicarboxylic acids and acid anhydrides thereof, and dicarboxylic acids and acid anhydrides and monoalcohols such as methanol and ethanol. Examples include esterified products.
For example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, etc. Aliphatic dicarboxylic acids;

  For example, o-phthalic acid, isophthalic acid, terephthalic acid, 2,5-dimethylterephthalic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane Aromatic dicarboxylic acids such as -4,4'-dicarboxylic acid and phenylindanedicarboxylic acid;

For example, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid,
Alicyclic dicarboxylic anhydrides such as hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride;

  For example, succinic anhydride, methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl succinic anhydride Glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, maleic anhydride, 2-methyl maleic anhydride 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic anhydride, 2,3-dichloromaleic anhydride, phenyl Maleic anhydride, 2,3-diphenyl maleic anhydride, none Itaconic acid, citraconic anhydride, phthalic anhydride, 4-methylphthalic anhydride, dimer acid, 1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride Acid, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, chlorendic anhydride, het anhydride, biphenyldicarboxylic anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride Methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, B hexene dicarboxylic acid anhydride, trimellitic anhydride, 1,8-naphthalene dicarboxylic acid anhydride, acid anhydrides such as octahydro-1,3-dioxo-4,5-isobenzofurandione carboxylic acid anhydrides.

  High molecular weight dicarboxylic acids obtained by ring-opening addition of high molecular weight polyols such as polyester polyols, polyether polyols, polyurethane polyols and polycarbonate polyols with the above acid anhydrides are also included in the dicarboxylic acids.

  These dicarboxylic acids, their acid anhydrides, or esterified compounds thereof may be used alone or in combination of two or more.

  The dibasic acid component (A) having no hydroxyl group preferably includes a dibasic acid component (a1) having an aromatic ring and / or an alicyclic structure, and the condensed polyester resin [PD1] The structure derived from the dibasic acid component (a1) is preferably contained in an amount of 5 to 50 mol%, and the inclusion of 10 to 35 mol% is a condensed polyester type excellent in adhesiveness, heat resistance, moist heat resistance and transparency. Since resin [PD1] is obtained, it is the most preferable. When the structure derived from the dibasic acid component (a1) is less than 5 mol% or more than 50 mol%, the adhesion property balance of the polyester resin to be obtained (especially compatibility between tack and cohesive force) should be ensured. In addition, since the heat resistance and heat-and-moisture resistance are reduced, it is difficult to obtain the target resin.

  Examples of the diol (B) having no carboxyl group include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, 2-methyl-1,3-propanediol, and 2-methyl-2-ethyl-1. , 3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-methyl-1,3-propanediol, 2 -Butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, , 3,5-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 3,3 -Dimethylol heptane, polyoxyethylene glycol (addition mole number 10 or less), polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, 3-butyl-3-ethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, Aliphatic or alicyclic diols such as cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol;

  For example, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 1,2-indanediol, , 3-naphthalenediol, 1,5-naphthalenediol, 1,7-naphthalenediol, 9,9′-bis (4-hydroxyphenyl) fluorene, 9,9′-bis (3-methyl-4-hydroxyphenyl) Fluorene, bisphenols such as bisphenol A and bisphenol F, ethylene oxide, propylene By adding an alkylene oxide such as Kisaido and aromatic diols such as bisphenols comprising.

  These diols (B) may be used alone or in combination of two or more. Polyamide obtained by reacting a dibasic acid component with a relatively low molecular weight diol component, a polyester diol, a dibasic acid component and a diamine component, and a relatively low molecular weight diol component. Polycarbonate diol, diol obtained by reacting polyether diol, relatively low molecular weight diol component with carbonate ester or phosgene, obtained by ring-opening addition polymerization of diol, cyclic ether or dehydration condensation reaction of relatively low molecular weight diol component A polyurethane diol or the like obtained by reacting a component with a diisocyanate compound can also be used as the diol (B).

The side chain functional group introduction component (C) used in the present invention will be described.
As the side chain functional group-introducing component (C), a trihydric or higher polyhydric alcohol (c1), a trivalent or higher polyvalent carboxylic acid (c2), a compound having two cyclic ether groups in the molecule (c3) Dioxycarboxylic acid (c4) having two hydroxyl groups and one or more carboxyl groups in one molecule and oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule are preferably used. be able to.

  Examples of the trihydric or higher polyhydric alcohol (c1) used in the present invention include glycerin, trimethylolethane, trimethylolpropane, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpentane. 1,1,1-trimethylolhexane, 1,1,1-trimethylolheptane, 1,1,1-trimethyloloctane, 1,1,1-trimethylolnonane, 1,1,1-trimethyloldecane 1,1,1-trimethylol undecane, 1,1,1-trimethylol dodecane, 1,1,1-trimethylol tridecane, 1,1,1-trimethylol tetradecane, 1,1,1-trimethylol Pentadecane, 1,1,1-trimethylol hexadecane, 1,1,1-trimethylol heptadecane, 1,1,1-trimethyl Ruokutadekan, trimethylol linear alkanes 1,1,1-trimethylol nano-decane, etc.,

  1,1,1-trimethylol-sec-butane, 1,1,1-trimethylol-tert-pentane, 1,1,1-trimethylol-tert-nonane, 1,1,1-trimethylol-tert- Tridecane, 1,1,1-trimethylol-tert-heptadecane, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1 -Trimethylol branched alkanes such as trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1,1,1-trimethylolisoheptadecane,

  Trimethylol butene, trimethylol heptene, trimethylol pentene, trimethylol hexene, trimethylol heptene, trimethylol octene, trimethylol decene, trimethylol dodecene, trimethylol tridecene, trimethylol pentadecene, trimethylol hexadecene, tri Trihydric alcohols such as metrolheptadecene, trimethyloloctadecene, 3-methylpentane-1,3,5-triol, 1,2,6-hexanetriol;

  Pentaerythritol, dipentaerythritol, tripentaerythritol, diglycerin, triglycerin, polyglycerol, ditrimethylolethane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, inositol, tetrakishydroxymethylphosphonium chloride, sorbitan, Examples include tetravalent or higher alcohols such as sorbitol, mannitol, saccharose, and cellulose.

  These trivalent or higher valent alcohols (c1) can be used alone or in combination at any desired ratio. The trihydric or higher polyhydric alcohol (c1) reacts with the dibasic acid component (A) having no hydroxyl group as the hydroxyl component in the same manner as the diol (B) having no carboxyl group, so that only the main chain end is reacted. Instead, a hydroxyl group is introduced into the side chain.

Examples of the trivalent or higher polyvalent carboxylic acid (c2) used in the present invention include trimellitic acid, pyromellitic acid, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, and 1,2. , 3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, cyclopentanetetracarboxylic acid, 2,3,6, 7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, ethylene glycol bistrimellitate carboxylic acid, 9,9-bis (3,4-dicarboxyphenyl) fluorene diacid, 2,2 ′ , 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid, 3,3 ′, 4,4′-bi Trifunctional or more polycarboxylic acids and anhydrides thereof, such as E sulfonic tetracarboxylic acid and further esterification products such as monoalcohol anhydride with methanol or ethanol.
These trivalent or higher polyvalent carboxylic acids (c2) can be used singly or in combination in any quantity ratio. The trivalent or higher polyvalent carboxylic acid (c2) reacts with the diol (B) not having a carboxyl group as a carboxyl group component in the same manner as the dibasic acid component (A) having no hydroxyl group, A carboxyl group is introduced not only at the terminal but also in the side chain.

  Examples of the compound (c3) having two cyclic ether groups in the molecule used in the present invention include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether. , Propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Diglycidyl ester of glycerin diglycidyl ether, diglycidyl amine, butadiene dioxide, dimer acid Aliphatic diglycidyl compound of;

  2,6-diglycidylphenyl ether, phthalic acid diglycidyl ester, trimellitic acid diglycidyl ester, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, 2,2-bis (4-hydroxyphenyl) ) Propanediglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, 1,1-bis (4-hydroxyphenyl) ethanediglycidyl ether, 3,3 ′, 5,5′-tetramethyl-4,4 '-Dihydroxybiphenyl diglycidyl ether, 2,2-bis (4- (β-hydroxypropoxy) phenyl) propane diglycidyl ether, resorcinol diglycidyl ether, bisphenoxyethanol fluorangeglycidyl Ether, aromatic diglycidyl compounds such as bis aryl diglycidyl ether;

  Cyclohexanedimethanol diglycidyl ether, dicyclopentadiene dioxide, 3,4-glycidylcyclohexylmethyl-3,4-glycidylcyclohexanecarboxylate, 3,4-glycidyl-6-methylcyclohexylmethyl-3,4-glycidyl-6 Methylcyclohexanecarboxylate, vinylcyclohexene dioxide, dicyclodienol epoxide glycidyl ether, tetrahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl) ) Alicyclic diglycidyl compounds such as propanediglycidyl ether;

  In addition, bisphenol A high molecular weight glycidyl resin, bisphenol F high molecular weight glycidyl resin, or high molecular weight diglycidyl resin such as phenoxy resin obtained by reacting the diglycidyl compound may be used.

  Examples of the compound having an oxetanyl group used in the present invention include carbonate bisoxetane, adipate bisoxetane, xylylene bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylate bisoxetane, and bis (3-ethyl-3-oxetanylmethyl). Examples include ether, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di {1-ethyl- (3-oxetanyl)} methyl ether, and the like.

  The compound (c3) having two cyclic ether groups in the molecule can be used either alone or in combination at an arbitrary quantitative ratio. When the dibasic acid component (A) and the diol (B) undergo a polycondensation reaction, the cyclic ether group of the compound (c3) having two cyclic ether groups in the molecule undergoes a ring-opening addition reaction to form a side chain. Secondary hydroxyl groups are introduced. Since the secondary hydroxyl group of the side chain has a low activity of the esterification reaction, a three-dimensional reaction is unlikely to occur during the esterification reaction. As a result, the obtained condensation type polyester resin [PD1-1] is difficult to partially agglomerate, has high uniformity, exhibits good fluidity, and further contains a reactive compound (G) described later, after curing. A pressure-sensitive adhesive having a relatively long pot life that can form a pressure-sensitive adhesive layer rich in cohesive force can be obtained. In addition, when using compound (c3) which has two cyclic ether groups in a molecule | numerator, since the ring-opening addition reaction of a cyclic ether group is utilized, the obtained condensation type polyester-type resin [PD1-1] is called an addition type. You can also. Further, the end of the ring-opening portion, which is obtained by ring-opening addition of a cyclic ester compound (E) described later to a part of the introduced side chain by the compound (c3) having two cyclic ether groups in the molecule. It can also be said that the polyester resin [PD1-2] having a hydroxyl group is a kind of the polyester resin [PD2] described later.

  Examples of the dioxycarboxylic acid (c4) having two hydroxyl groups and one or more carboxyl groups in one molecule used in the present invention include dihydroxyfumaric acid, dihydroxymaleic acid, and 2,2-bis (hydroxymethyl). ) Ethanoic acid (also known as dimethylolacetic acid), 2,3-dihydroxypropanoic acid (also known as glyceric acid), 2,2-bis (hydroxymethyl) propanoic acid (also known as 2,2-dimethylolpropionic acid), 3, 3-bis (hydroxymethyl) propanoic acid (also known as 3,3-dimethylolpropionic acid), 2,3-dihydroxy-2-methylpropanoic acid, 2,2-bis (hydroxymethyl) butanoic acid (also known as dimethylolbutyric acid) ), 2,2-dihydroxybutanoic acid, 2,3-dihydroxybutanoic acid, 2,4-dihydroxybutanoic acid (also known as -Deoxytetronic acid), 3,4-dihydroxybutanoic acid, 2,4-dihydroxy-3,3-dimethylbutanoic acid, 2,3-dihydroxy-2-methylbutanoic acid, 2,3-dihydroxy-2-ethylbutanoic acid, 2,3-dihydroxy-2-isopropylbutanoic acid, 2,3-dihydroxy-2-butylbutanoic acid, (R) -2,4-dihydroxy-3,3-dimethylbutanoic acid (also known as bantoic acid), 2,3 -Dihydroxybutanedioic acid (also known as tartaric acid), 2,2-bis (hydroxymethyl) pentanoic acid (also known as dimethylolvaleric acid), 3,5-dihydroxy-3-methylpentanoic acid (also known as mevalonic acid), 2, 2-bis (hydroxymethyl) hexanoic acid (also known as dimethylol caproic acid), 2,2-bis (hydroxymethyl) heptanoic acid (also known as, Methylol enanthate), 3,5-dihydroxyheptanoic acid, 2,2-bis (hydroxymethyl) octanoic acid (also known as dimethylolcaprylic acid), 2,2-bis (hydroxymethyl) nonanoic acid (also known as dimethylolberal) Gonic acid), 2,2-bis (hydroxymethyl) decanoic acid (also known as dimethylol capric acid), 2,2-bis (hydroxymethyl) dodecanoic acid (also known as dimethylol lauric acid), 2,2-bis ( Hydroxymethyl) tetradecanoic acid (also known as dimethylol myristic acid), 2,2-bis (hydroxymethyl) pentadecanoic acid, 2,2-bis (hydroxymethyl) hexadecanoic acid (also known as dimethylol palmitic acid), 2,2- Bis (hydroxymethyl) heptadecanoic acid (also known as dimethylol margaric acid), 2,2-bis ( Hydroxymethyl) octadecanoic acid (also known as dimethylol stearic acid), dimethylol oleic acid, dimethylol linoleic acid, dimethylol linolenic acid, dimethylol aracodonic acid, dimethylol docosahexaenoic acid, dimethylol eicosapentaenoic acid, etc. Dioxycarboxylic acids;

  For example, 2,3-dihydroxybenzoic acid (also known as o-pyrocatechuic acid), 2,4-dihydroxybenzoic acid (also known as β-resorcinic acid), 2,5-dihydroxybenzoic acid (also known as gentisic acid), 2, 6-dihydroxybenzoic acid (also known as γ-resorcinic acid), 3,4-dihydroxybenzoic acid (also known as protocatechuic acid), 3,5-dihydroxybenzoic acid (also known as α-resorcinic acid), 2,6-dihydroxy- 4-methylbenzoic acid, 2,4-dihydroxy-6-dimethylbenzoic acid (also known as o-orceric acid), 3,5-dihydroxy-4-methylbenzoic acid, 2,4-dihydroxy-3,6-dimethylbenzoic acid Acid, 2,3-dihydroxy-4-methoxybenzoic acid, 3,4-dihydroxy-5-methoxybenzoic acid, 2,4-dihydroxymethylbenzoic acid, 3, -Dihydroxymethylbenzoic acid, 4-bromo-3,5-dihydroxybenzoic acid, 5-bromo-2,4-dihydroxybenzoic acid, 3-chloro-2,6-dihydroxybenzoic acid, 5-chloro-2,4- Dihydroxybenzoic acid, hydroxy (4-hydroxy-3-methoxyphenyl) acetic acid (also known as vanylmandelic acid), D, L-3,4-dihydroxymandelic acid, 2,5-dihydroxyphenylacetic acid (also known as homogentisic acid), 3 , 4-Dihydroxyphenylacetic acid (also known as homoprotocatechuic acid), 3,4- (methylenedioxy) phenylacetic acid, 3- (3,4-dihydroxyphenyl) propanoic acid (also known as hydrocaffeic acid), 3- (2, 4-dihydroxyphenyl) acrylic acid (also known as umbelic acid), 3- (3,4-dihydroxyphenyl) a Lauric acid (also known as caffeic acid), 4,4′-bis (p-hydroxyphenyl) pentanoic acid, 3- (3,4-methylenedioxyphenyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, 2,4-dihydroxycinnamic acid, 2,5-dihydroxy cinnamic acid, cinnamyl-3,4-dihydroxy-α-cyanocinnamic acid, 2-bromo-4,5-methylenedioxycinnamic acid, 3,4-methylenedioxy Cinnamic acid, 4,5-methylenedioxy-2-nitrocinnamic acid, 2,6-dihydroxyisonicotinic acid, DL-3,4-dihydroxymandelic acid, 1,4-dihydroxy-2-naphthalenecarboxylic acid, 3, 5-dihydroxy-2-naphthalenecarboxylic acid, 3,7-dihydroxy-2-naphthalenecarboxylic acid, 4,8-dihydroxyquinoline-2-carboxylic acid , Xanthurenic acid) 3- (3,4-dihydroxyphenyl) propionic acid, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,6-dihydroxypyridine-4-carboxylic acid (also known as citrazic acid), 2,4 -Dihydroxythiazole-5-acetic acid, 2- (1-thienyl) ethyl-3,4-dihydroxybenzylidenecyanoacetic acid, 6-estradiol dipropionate, 2,5-dihydroxy-1,4-benzenediacetic acid, (2R , 3R) -2,3-dihydroxy-3- (phenylcarbamoyl) propionic acid and the like, and aromatic ring- or heterocycle-containing dioxycarboxylic acids. In addition, when it has an aromatic ring, what does not directly bond two hydroxyl groups to an aromatic ring is preferable.

  The publicly known dioxycarboxylic acid (c4) used in the present invention can be used alone or in combination at any arbitrary ratio.

Since the dioxycarboxylic acid (c4) has two hydroxyl groups, it is polycondensed with the dibasic acid component (A) as an OH component in the same manner as the diol (B) having no carboxyl group, and used in the present invention. The condensed polyester-based resin [PD1-1] is produced. And the carboxyl group derived from dioxycarboxylic acid (c4) becomes the carboxyl group of the side chain of the condensation-type polyester resin [PD1].
It is preferable that the two hydroxyl groups in the dioxycarboxylic acid (c4) are both primary in that they are rich in activity during the esterification reaction. On the other hand, when the dioxycarboxylic acid (c4) functions as a COOH component during the esterification reaction, it easily reacts three-dimensionally during the reaction, easily causes gelation, or does not gel, and is a condensed polyester resin [ Even if PD1-1] is obtained, it tends to partially aggregate. Therefore, in the esterification reaction, the carboxyl group in the dioxycarboxylic acid (c4) is secondary or so that the dioxycarboxylic acid (c4) functions exclusively as an OH component and not as a COOH component. It is preferable that it is tertiary. Since the activity of the esterification reaction is low, the dioxycarboxylic acid (c4) can have one or more secondary or tertiary carboxyl groups in one molecule.

  Examples of the oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule used in the present invention include dihydroxyfumaric acid, dihydroxymaleic acid, 2-hydroxy-2-methylsuccinic acid (also known as , Citramalic acid), 2-hydroxypropane diacid (also known as tartronic acid), 2,2-dihydroxypropane diacid, 2-hydroxypentanedioic acid (also known as 2-hydroxyglutaric acid), 2,3,4-tri Hydroxypentanedioic acid, 2-hydroxybutanedioic acid (also known as malic acid), 2,2-dihydroxybutanedioic acid, 2,3-dihydroxybutanedioic acid (also known as tartaric acid), 3- [2,3-dihydroxy- 3- (pentyloxycarbonyl) propanoyloxy] -2-hydroxybutanedioic acid, 2,3-dihydroxyheptane (Also known as 2,3-dihydroxypimelic acid), 2,4-dihydroxyhexanedioic acid (also known as 2,4-dihydroxyadipic acid), 2,5-dihydroxyoctanedioic acid (also known as 2,5-dihydroxysuberine) Acid), 2,6-dihydroxynonanedioic acid (also known as 2,6-dihydroxyrepargylic acid), 2,7-dihydroxydecanedioic acid (also known as 2,7-dihydroxysebacic acid), 2-hydroxycyclohexane-1 Aliphatic or alicyclic oxydicarboxylic acids such as 1,4-dicarboxylic acid and 3-hydroxycyclohexane-1,4-dicarboxylic acid;

  For example, 4-hydroxyphthalic acid, 3,6-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, 4-hydroxypyridine-2,6-dicarboxylic acid, 3- Hydroxy-4-oxo-4H-pyran-2,6-dicarboxylic acid (also known as meconic acid), 1-hydroxy-2,3-naphthalenedicarboxylic acid, 2-hydroxy-1,8-naphthalenedicarboxylic acid, 3-hydroxy -2,5-pyridinedicarboxylic acid, (1α, 2β, 4aα, 4bβ, 10β) -2,4a, 7-trihydroxy-1-methyl-8-methylenediva-3-ene-1,10-dicarboxylic acid 1, Aromatic or hetero ring-containing oxydicarboxylic acids such as 4a-lactone (also known as gibberellic acid) are exemplified.

The well-known oxydicarboxylic acid (c5) used for this invention can be used individually or in combination of 2 or more types, respectively.
Since the oxydicarboxylic acid (c5) has two carboxyl groups, it is polycondensed with the diol (B) as a COOH component in the same manner as the dibasic acid component (A) having no hydroxyl group, and used in the present invention. Condensed polyester resin [PD1-1] is produced. And the hydroxyl group derived from oxydicarboxylic acid (c5) turns into a hydroxyl group of the side chain of condensation type polyester-type resin [PD1-1].
It is preferable that the two carboxyl groups in the oxydicarboxylic acid (c5) are both primary in terms of rich activity during the esterification reaction. On the other hand, when the oxydicarboxylic acid (c5) functions as an OH component during the esterification reaction, it tends to react three-dimensionally during the reaction, and is easily gelled, or it is not gelled, and the condensed polyester resin [PD1 -1] may be partially aggregated easily. Therefore, in the esterification reaction, the hydroxyl group in the oxydicarboxylic acid (C) is secondary or tertiary so that the oxydicarboxylic acid (c5) functions exclusively as a COOH component and not as an OH component. Preferably there is. Since the activity of the esterification reaction is low, the oxydicarboxylic acid (c5) can have one or more secondary or tertiary hydroxyl groups in one molecule.
In the case of the oxydicarboxylic acid (c5) having an aromatic ring, OH directly bonded to the aromatic ring is preferable in that the activity of the esterification reaction is low, but the reaction activity with the reactive compound (E) is also low. Accordingly, the hydroxyl group of the oxydicarboxylic acid (c5) is preferably a secondary or tertiary hydroxyl group that is not directly connected to the aromatic ring.

  The condensed polyester resin [PD1-1] used in the present invention preferably contains 0.1 to 10 mol% of the structure derived from the side chain functional group introduction component (C). That is, the amount of hydroxyl group and / or carboxyl group introduced into the side chain depends on the structure derived from the side chain functional group introduction component (C). The hydroxyl group and / or carboxyl group introduced into the side chain crosslinks with the reactive compound (E) described later to form a pressure-sensitive adhesive layer, and contributes to the improvement of cohesive strength, adhesiveness, heat resistance, and heat and humidity resistance. . However, if there are too many hydroxyl groups and / or carboxyl groups introduced by the side chain functional group-introducing component (C), the pot life will be shortened, while if too little, the cohesive force and adhesion of the pressure-sensitive adhesive layer formed will be reduced. , Heat resistance and moist heat resistance are reduced. Therefore, from the balance between the pot life as the pressure-sensitive adhesive and the performance of the pressure-sensitive adhesive layer, the structure derived from the side chain functional group introduction component (C) is 0 in the condensed polyester resin [PD1-1]. It is preferable that it is 1-10 mol%.

  Condensed polyester having a hydroxyl group or a carboxyl group in the side chain by the reaction of the dibasic acid component (A) having no hydroxyl group, the diol (B) having no carboxyl group and the component for introducing a side chain functional group (C) When forming the resin [PD1-1], the reaction proceeds even without a catalyst, but a catalyst can be used as appropriate in order to allow the reaction to proceed more smoothly. Catalysts used include ammonia, amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal hydroxides, alkaline earth metal hydroxides, Lewis acids, tin, lead, titanium, iron, zinc, zirconium. , Organometallic compounds containing cobalt, metal halides, and the like.

  Examples of amines include triethylamine, pyridine, aniline, morpholine, N-methylmorpholine, pyrrolidine, piperidine, N-methylpiperidine, cyclohexylamine, n-butylamine, dimethyloxazoline, imidazole, N-methylimidazole, N, N- Examples thereof include dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethylisopropanolamine, N-methyldiethanolamine and the like.

  Examples of the quaternary ammonium salts include tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium fluoride trihydrate, tetramethylammonium hexafluorophosphate, tetramethylammonium hydrogen phthalate, tetramethylammonium hydroxide pentahydrate. , Tetramethylammonium hydroxide, tetramethylammonium iodide, tetramethylammonium nitrate, tetramethylammonium perchlorate, tetramethylammonium tetrafluoroborate, tetramethylammonium tribromide, phenyltrimethylammonium bromide, tetraethylammonium bromide, tetraethylammonium chloride Tetraethylammonium fluoride trihydrate, tetraethylammonium hydroxide, tetraethylammonium iodide, tetraethylammonium perchlorate, tetraethylammonium tetrafluoroborate, tetraethylammonium-p-toluenesulfonate, tetrapropylammonium bromide, tetrapropylammonium chloride, tetra Propylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium perchlorate, tetra-n-propylammonium hydrogensulfate, tetra-n-propylammonium pearlate (VII), tetrabutylammonium bromide, tetrabutylammonium trichloride bromide, Trabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium hydroxide, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogensulfate, tetrabutylammonium nitrate, tetrabutylammonium tetrahydroborate, tetrabutylammonium tetrafluoroborate, Tetrabutylammonium cyanotrihydroborate, tetrabutylammonium difluorotriphenylstannate, tetrabutylammonium fluoride trihydrate, tetrabutylammonium tetrathiophenate (IV), tetrabutylammonium fluoride hydrate, tetra-n-butyl Ammonium dihydrogen trifluoride, Tetra-n-butylammonium trifluoromethanesulfonate, tributylammonium bis (2,3-dimercapto-2-butenedinyllate-S, S ′) nicolate, tetra-n-heptylammonium bromide, tetra-n-heptylammonium chloride, Tetra-n-heptylammonium iodide, tetra-n-hexylammonium benzoate, tetra-n-hexylammonium bromide, tetra-n-hexylammonium chloride, tetra-n-hexylammonium iodide, tetra-n-hexylammonium perchlorate , Tetraoctyl ammonium bromide, tetraoctadecyl ammonium bromide and the like.

Quaternary phosphonium salts include, for example, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium tetrafluoroborate, Tetrabutylphosphonium hexafluorophosphate, tetrabutylphosphonium tetraphenylborate, tetrabutylphosphonium benzotriazolate, tetrabutylphosphonium bis (1,2-benzenedithiolate) nicolate (III), tetrabutylphosphonium bis (4-methyl-1) , 2-Benzenedithiolate) Nicolate (III), Tetrabutylphospho Umubisu (4,5-mercapto-1,3-dithiol-2 thionating -S ^4, S ⁵⁾ Nikoreto (III) and the like.

Examples of the alkali metal or alkaline earth metal hydroxide include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide;
Alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide;
Can be mentioned.

  Examples of the organic tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, Examples thereof include tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

  Examples of organic zirconium compounds include zirconium acetate, zirconium benzoate, zirconium naphthenate, and the like.

  Examples of the organic titanium compounds include dibutyltitanium dichloride, tetrabutyltitanate, tetrabutoxytitanate, tetraethyltitanate, tetraisopropyltitanate, butoxytitanium trichloride, and the like.

  Examples of the organic lead compounds include lead acetate, lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.

  Examples of organic iron compounds include iron 2-ethylhexanoate and iron acetylacetonate.

  Examples of the organic cobalt compounds include cobalt acetate, cobalt benzoate, and cobalt 2-ethylhexanoate.

  Examples of the organic zinc compounds include zinc acetate, zinc oxalate, zinc naphthenate, and zinc 2-ethylhexanoate.

  Examples of metal halides include stannous chloride, stannous bromide, stannous iodide, and the like.

  Furthermore, Lewis acids such as boron trifluoride, manganese acetate, germanium oxide, antimony trioxide, aluminum trichloride, zinc chloride, and titanium chloride are exemplified, but not limited thereto. A catalyst may use only 1 type or may use 2 or more types together. The catalyst is used in an amount of 10 parts by weight or less with respect to 100 parts by weight of all reaction components. The range of 0.0001 to 1 part by weight is more preferable. When the amount exceeding 10 parts by weight is used, there arises a disadvantage that the product is colored or a catalyst that has not been deactivated remains and acts as a negative catalyst, causing a decomposition reaction.

The condensation type polyester resin [PD1-1] used in the present invention can be produced by a conventionally known polyester reaction method. For example, it can be obtained by the following method.
(1) One-step reaction: the dibasic acid component (A), the diol (B), and the side chain functional group introduction component (C) are 160 to 260 ° C, preferably 180 to 250 ° C, more preferably 200 to 250. Direct esterification reaction at 0 ° C. After cooling, an organic solvent can be added as appropriate to prepare a pressure-sensitive adhesive composition.
(2) Two-stage reaction: a dibasic acid component (A), a diol (B), and a side chain functional group-introducing component (C) are subjected to dehydration reaction or transesterification at 160 to 260 ° C., preferably 180 to 250 ° C. The reaction is performed, and then the excess diol component is removed by heating to 180 to 280 ° C., preferably 200 to 260 ° C. under a reduced pressure of 5 Torr or less to obtain a polyester resin. After cooling, an organic solvent can be added as appropriate to prepare a pressure-sensitive adhesive composition.
The component (C) for introducing a side chain functional group may be charged into the reaction vessel from the beginning together with the dibasic acid component (A) and the diol (B), or the dibasic acid component (A) and The reaction may be conducted after the dehydration reaction or transesterification reaction of the diol (B).
Incidentally, when the polymerization temperature is less than the above lower limit, the reaction does not proceed sufficiently. On the other hand, if the polymerization temperature exceeds the upper limit, side reactions such as decomposition may occur or coloring may be easily caused. Moreover, reaction time can be normally made into about 1 to 60 hours.

  In the present invention, the cyclic ester compound (E) is further subjected to ring-opening addition to the side chain hydroxyl group or carboxyl group introduced using the side chain functional group introduction component (C), and the cyclic ester compound (E) A pressure-sensitive adhesive composition can also be obtained by using a polyester resin [PD1-2] having a ring-opening portion as a side chain and a hydroxyl group at the end of the ring-opening portion. When the cyclic ester compound (E) is subjected to ring-opening addition, the side chain functional group of the condensed polyester resin [PD1-1] is preferably a hydroxyl group in terms of reactivity. That is, it is preferable to further utilize the side chain hydroxyl group introduced by (c1), (c3) or (c5) in the side chain functional group introduction component (C).

  For example, the polyester resin can be obtained by reacting the condensed polyester resin [PD1-1] obtained by the method (1) or (2) and the cyclic ester compound (E) in a total amount. By reacting [PD1-1] while adding the cyclic ester compound (E), or by reacting while adding the polyester resin [PD1-1] to the cyclic ester compound (E), the polyester resin ( D2) can be obtained. Alternatively, the cyclic ester compound (E) may be added and reacted during the reaction of the polyester resin [PD1-1]. The polyester resin [PD1-1] is preferably used in a solution state. For example, the ring-opening addition reaction is preferably performed at 20 to 220 ° C, more preferably 60 to 180 ° C. An ester bond can be introduced into the side chain of the polyester resin [PD1-1] by ring opening of the cyclic ester compound (E). Further, the cyclic ester compound (E) can be further subjected to ring-opening addition to the added hydroxyl group at the end of the ring-opening portion, and the side chain can be lengthened to have a high molecular weight. By introducing an ester bond into the side chain, an improvement in adhesive properties (particularly tack) is expected. The obtained polyester resin [PD1-2] can be adjusted for non-volatile content by appropriately adding an organic solvent after cooling.

As the cyclic ester compound (E) used in the present invention, a cyclic ester (e1) of hydroxycarboxylic acid can be preferably used.
The cyclic ester (e1) of hydroxycarboxylic acid used in the present invention is not particularly limited, and intramolecular or intermolecular condensates of aliphatic, alicyclic, aromatic and heterocyclic hydroxycarboxylic acids can be used. .

  Examples of the aliphatic hydroxycarboxylic acid include glycolic acid, lactic acid, hydroacrylic acid, α-oxybutyric acid, α-hydroxyisobutyric acid, hydroxyvaleric acid, α-hydroxycaproic acid, δ-hydroxycaproic acid, glyceric acid, and tartron. Acid, malic acid, citric acid, caprylic acid, lauric acid, ricinoleic acid, α-hydroxytriacontanoic acid, α-hydroxytetratriacontanoic acid, α-hydroxyhexatriacontanoic acid, α-hydroxyoctatriacontanoic acid, α -Hydroxytetraacontanic acid, hydroxypiparic acid, hydroxypropionic acid, 6-hydroxypentanoic acid, α-hydroxyheptanoic acid, 10-hydroxystearic acid, 12-hydroxystearic acid, 10-hydroxydecanoic acid, 12-hydroxydodecane acid, -Hydroxymistilic acid, 16-hydroxyhexadecanoic acid, 15-hydroxypentadecanoic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxytetraeicosanoic acid, α-hydroxyhexaicosanoic acid, α- Examples include hydroxyoctaeicosanoic acid, α-hydroxytriacontanoic acid, β-hydroxymyristic acid, dimethylolpropionic acid, 3,5-di-tert-butylsalicylic acid and the like.

  Alicyclic, aromatic and heterocyclic hydroxycarboxylic acids include, for example, salicylic acid, 2-oxybenzoic acid, 3-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 4-hydroxy-3-phenylbenzoic acid, 4-hydroxy-3-methoxybenzoic acid, 4-hydroxy-3,5-dimethoxybenzoic acid, 4′-hydroxy-4-carboxybiphenyl, 6-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, Examples include 5-hydroxy-1-naphthoic acid.

  The hydroxycarboxylic acid can be used as long as it has a carboxylic acid and a hydroxyl group in one molecule of the organic compound, and is not necessarily limited to those exemplified above.

  The cyclic ester (e1) of a hydroxycarboxylic acid used in the present invention is obtained by intramolecular or intermolecular condensation reaction between a hydroxyl group in the hydroxycarboxylic acid and the carboxylic acid in the hydroxycarboxylic acid. That is, it includes cyclic monomers, dimers, or multimers of trimers or more of hydroxycarboxylic acids produced by intramolecular or intermolecular condensation reactions of hydroxycarboxylic acids.

  Among the cyclic esters (e1) of the hydroxycarboxylic acid used in the present invention, lactones can be used as the cyclic monomer, and there is no particular limitation. For example, β-butyrolactone, β-propiolactone, γ-butyrolactone Γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, ε-caprolactone glycolide, pivalolactone, 7-heptanolide, 8-octonolide, 11-undecanolide, 12-dodecanolide, 15-pentadecanolide, 16-hexadodecanolide, α-methyl-β-propiolactone, β-methyl-α-propiolactone, α, α -Dimethyl-β-propiolactone and the like.

  Examples of the cyclic dimer in the cyclic ester (e1) of hydroxycarboxylic acid used in the present invention include lactide by lactic acid, glycolide by glycolic acid, and the like.

  The cyclic ester (e1) of hydroxycarboxylic acid used in the present invention is not limited in the size of the ring, but in order to efficiently perform a ring-opening addition reaction with a hydroxyl group contained in the polyester resin [PD1-1], Cyclic monomer lactones having 6 to 18 carbon atoms in the ring are preferred, and ε-caprolactone is more preferred.

  The cyclic ester (e1) of the hydroxycarboxylic acid used in the present invention may be subjected to ring-opening addition in the form of one molecule to the polyester resin [PD1-1] having a side chain hydroxyl group, or the cyclic ester (e1) As an embodiment of a polymer formed by ring-opening polymerization of a plurality of molecules, it may be added to the polyester resin (D1).

<Additional polyester resin [PD2]>
Next, among the polyester resins [PD], an addition type polyester resin [PD2] in which a main chain is formed by an addition reaction will be described. The addition-type polyester resin [PD2] has an addition-type polyester main chain (I) and a plurality of side chains branched from the polyester main chain (I).

  The addition type polyester main chain (I) is a compound having a structure derived from a dibasic acid component and two cyclic ether groups by a ring-opening reaction between the dibasic acid component and a compound having two cyclic ether groups. The derived structure is alternately and repeatedly bonded via an ester bond.

The plurality of side chains have a first side chain (II) having a functional group selected from the group consisting of a hydroxyl group and a carboxyl group, and a second side chain (II ′) having no hydroxyl group.
At least one of the plurality of side chains contains a ring-opening structural unit of the cyclic ester compound, and the second side chain (II ′) has a structure in which a hydroxyl group is sealed with a sealing compound.

As the dibasic acid component used for forming the addition type polyester main chain (I), the dibasic acid component (A) having no hydroxyl group exemplified in the case of the condensed polyester [PD1] is the same. Can be illustrated.
Further, the dibasic acid component (A) having no hydroxyl group and the diol (B) having no carboxyl group, which are exemplified in the case of the condensed polyester [PD1], are reacted under an acid-excess condition. Those having a carboxyl group at both ends of the condensation type polyester can also be used as a dibasic acid component for forming the addition type polyester main chain (I).

The compound having two cyclic ether groups used for forming the addition type polyester main chain (I) is one of the side chain functional group introduction components (C) in the case of the condensed type polyester [PD1-1]. The compound (c3) which has two cyclic ether groups in the molecule | numerator illustrated as can be illustrated similarly.
When the dibasic acid component used for forming the addition type polyester main chain (I) has a carboxyl group at both ends of the condensed polyester, the dibasic acid component and the cyclic ether group are The addition type polyester main chain (I) obtained by the reaction with two compounds can also be referred to as a condensation type.

At least one of the plurality of side chains of the addition-type polyester resin [PD2] contains a ring-opening structural unit of the cyclic ester compound.
When forming an addition-type polyester main chain (I) by a ring-opening reaction between a dibasic acid component and a compound having two cyclic ether groups, a part of a secondary hydroxyl group generated and a cyclic ester compound By reacting, it is possible to form a directly-bonded hydroxyl group side chain remaining in the main chain (I) and a side chain containing a ring-opening structural unit of the cyclic ester compound. Sealing part of the hydroxyl group directly bonded to the main chain (I) and part of the hydroxyl group at the end of the side chain containing the ring-opening structural unit of the cyclic ester compound with the sealing compound (H) You can also.

  Alternatively, when the addition type polyester main chain (I) is formed, all the secondary hydroxyl groups produced are reacted with the cyclic ester compound to form a side chain containing a ring-opening structural unit of the cyclic ester compound, A part of the hydroxyl group at the end of the side chain containing the ring-opening structural unit of the cyclic ester compound can also be sealed with the sealing compound (H).

  Alternatively, when the addition-type polyester main chain (I) is formed, a part of the resulting secondary hydroxyl group is sealed with a sealing compound, and then the remaining hydroxyl group is reacted with a cyclic ester compound, thereby deriving from the sealing compound. And a side chain containing a ring-opening structural unit of the cyclic ester compound can also be formed.

  The addition-type polyester resin [PD2] is a ring-opening structural unit of a cyclic ester compound after forming a polyester main chain (I) by a ring-opening reaction between a dibasic acid component and a compound having two cyclic ether groups. It is also possible to form a side chain containing benzene, or to seal a part of the generated hydroxyl group with the sealing compound (H). Alternatively, while forming the polyester main chain (I), a side chain containing a ring-opening structural unit of the cyclic ester compound is formed, or a part of the generated hydroxyl group is sealed with the sealing compound (H). You can also

  As the cyclic ester compound for forming the side chain of the addition type polyester resin [PD2], a cyclic ester compound exemplified when the side chain functional group of the condensation type polyester resin [PD-1] is further modified ( E) can be exemplified as well.

  Of the addition-type polyester resin [PD2] in the present invention, the polyester resin having a hydroxyl group can further use a sealing compound (H) for controlling the reactivity with the reactive compound (G) described later. . The sealing compound (H) also has a role of finally adjusting the hydroxyl group of the polyester resin [PD2]. The sealing compound (H) is preferably, for example, any one of a silylating agent (h1), an acid anhydride (h2), or an isocyanate compound (h3), and a plurality of functional groups having no monofunctional or crosslinking action. Is more preferable. The sealing compound (h) may be used alone or in combination of two or more.

  Examples of the silylating agent (h1) used in the present invention include hydrosilanes, alkoxysilanes, chlorosilanes, silanols, silylamines, and cyclic compounds thereof.

  Examples of hydrosilanes include trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, trihexylsilane, diethylmethylsilane, butyldimethylsilane, dimethylphenylsilane, triphenylsilane, methylphenylvinylsilane, pentamethyldisiloxane, allyl Dimethylsilane, tris (trimethylsiloxy) silane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, Examples thereof include hydrosilanes having a monofunctional Si—H group such as 1,3,5,7,9-octaphenylcyclotetrasiloxane.

  Examples of alkoxysilanes include methoxytrimethylsilane, methoxytriethylsilane, methoxydimethylvinylsilane, dimethylethoxyethynylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, allyloxytrimethylsilane, ethoxydimethylvinylsilane, trimethylpropoxysilane, and trimethylisopropoxysilane. 1-methylpropoxytrimethylsilane, butoxytrimethylsilane, isobutoxytrimethylsilane, t-butoxytrimethylsilane, hexyloxytrimethylsilane, 3-aminopropyldimethylethoxysilane, tetrahydrofurfuryloxytrimethylsilane, phenoxytrimethylsilane, cyclohexyloxytrimethylsilane 1-cyclohexenyloxytrimethyl Alkoxysilanes having monofunctional alkoxy groups such as lan, dimethylethoxyphenylsilane, benzyloxytrimethylsilane, methoxytripropylsilane, benzyldimethylethoxysilane, 2-ethylhexyloxytrimethylsilane, octyloxytrimethylsilane, dodecyloxytrimethylsilane Kind.

  Examples of chlorosilanes include trimethylchlorosilane, dimethylvinylchlorosilane, allyldimethylchlorosilane, dimethylpropylchlorosilane, dimethylisopropylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, dimethylphenylchlorosilane, methylphenylvinylchlorosilane, benzyldimethylchlorosilane, and tripropyl. Examples include chlorosilanes having a monofunctional chlorosilyl group such as chlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, diphenylmethylchlorosilane, diphenylvinylchlorosilane, triphenylchlorosilane, trihexylchlorosilane, dimethyloctadecylchlorosilane, and tribenzylchlorosilane.

  Examples of silanols include silanol compounds having a monofunctional silanol group such as trimethylsilanol, triethylsilanol, and triphenylsilanol.

  Examples of silylamines include trimethylsilyldimethylamine, trimethylsilyldiethylamine, dimethylaminotrimethylsilane, allylaminotrimethylsilane, N-methyl-N-trimethylsilylacetamide, anilinotrimethylsilane, 1-trimethylsilylpyrrole, 1-trimethylsilylpyrrolidone, 1- Silylamines having a monofunctional silylamino group such as trimethylsilylimidazole and 1-trimethylsilyl-1,2,4-triazole; 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, 1,3-divinyl Silylamines having a bifunctional silylamino group such as -1,1,3,3-tetramethyldisilazane, N, N′-bis (trimethylsilyl) -N-phenylurea; 5,5 hexamethylcyclotrisilazane, silylamines and the like can be mentioned bearing trifunctional or more cyclic silylamino group such as 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane.

  Examples of the acid anhydride (h2) used in the present invention include dibasic acid (for example, used for forming the polyester main chain (I) of the above-mentioned condensation type polyester resin [PD1] and addition type polyester [PD2]). The acid anhydrides of dicarboxylic acids exemplified as A) are preferred.

  Among the isocyanate compounds (h3) used in the present invention, examples of the monofunctional isocyanate compound include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, and phenyl. Isocyanate, benzyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R) -(+)-Α-methylbenzyl isocyanate (S)-(−)-α-methylbenzyl isocyanate, (R)-(−)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S) — (-)-1-phenylethyl isocyanate, p-toluenesulfonyl isocyanate, etc. are mentioned.

Such a condensation-type polyester resin [PD1] and an addition-type polyester resin [PD2] have a glass transition point (Tg) so that they can exhibit well-balanced adhesive properties (particularly, both tack and cohesive force). Is selected from the dibasic acid component (A) having no hydroxyl group, the diol (B) having no carboxyl group, the component for introducing a side chain functional group (C), etc. It is preferable to select a dibasic acid-based component (A), a cyclic ether compound, a cyclic ester compound (E), etc. that do not have a glass transition point, so that the glass transition point (Tg) is −60 to −10 ° C. More preferably, the components are selected.
When the glass transition temperature of the condensation-type polyester resin [PD1] is less than −80 ° C., the cohesive force of the pressure-sensitive adhesive layer obtained by using the polyester resin is lowered, and the floating is likely to occur. On the other hand, when the glass transition temperature exceeds 0 ° C., the pressure-sensitive adhesive layer becomes too hard and does not exhibit sufficient tack, or the adhesive strength is weak when plastics or a glass plate and a plastic film are laminated. In addition, the solubility in a solvent decreases, and the viscosity of the pressure-sensitive adhesive increases, which makes it difficult to handle at the time of coating.
The glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).

  The weight average molecular weight (Mw) of the polyester resin [PD] in the present invention is preferably in the range of 2,000 to 1,000,000 from the viewpoint of adhesiveness, and in the range of 8,000 to 500,000. More preferably. When such a polyester resin is used, a pressure-sensitive adhesive having excellent adhesion and wettability can be obtained. If the Mw is less than 2,000, the cohesive force as the pressure-sensitive adhesive layer becomes difficult to develop, and the heat resistance and heat and humidity resistance are reduced. On the other hand, if Mw exceeds 1,000,000, the fluidity of the pressure-sensitive adhesive becomes poor even when diluted with a solvent, and the coating property is reduced when producing a pressure-sensitive adhesive sheet. Absent.

  The hydroxyl value or acid value of the polyester resin [PD] in the present invention is 0.1 by the side chain functional group introduction component (C), the cyclic ester compound (E), the sealing compound (H) and the like. It is preferably controlled in the range of ˜50 mg KOH / g, more preferably in the range of 0.5 to 30 mg KOH / g. When both the hydroxyl value and the acid value are lower than 0.1 mgKOH / g, the reactivity with the reactive compound (G) described later is inferior and the cohesive force becomes insufficient. Not only is it difficult to peel off the laminate obtained by use, for example, a glass member for a liquid crystal cell, but adhesive peeling may occur after peeling, resulting in insufficient removability. Further, when both the hydroxyl value and the acid value are higher than 50 mgKOH / g, the pot life is shortened, and workability at the time of coating and bonding is remarkably lowered, which is not preferable.

  In addition, the refractive index of the material used for optical members, such as a film for optical members mentioned later and glass, is a thing of about 1.50-1.58. The polyester resin [PD] can have a refractive index of 1.50 to 1.58 by controlling its composition.

<Reaction product containing hydroxyl group and alkoxysilyl group (F)>
The pressure-sensitive adhesive composition of the present invention is a reaction product (F) having a hydroxyl group and an alkoxy group, obtained by reacting a silane compound (f1) having an isocyanate group and an alkoxy group with a polyol (f2). It is important to contain.
As the silane compound (f1) having an isocyanate group and an alkoxysilyl group, those having one isocyanate group are preferable.
As the polyol (f2), a diol having two hydroxyl groups is preferable.

The reaction between the polyol (f2) and the silane compound (f1) will be described.
The hydroxyl group of the polyol (f2) and the isocyanate group of the silane compound (f1) react to generate a urethane bond, or the hydroxyl group of the polyol (f2) and the alkoxysilyl group of the silane compound (f1) react to generate an ether bond. I think that.
By the way, under basic conditions, hydroxyl groups react preferentially with isocyanate groups. Since the silane compound (f1) contains an isocyanate group, it is in a basic state, and the hydrolysis reaction of the alkoxysilyl group is suppressed by simply mixing and heating the polyol (f2) and the silane compound (f1). Therefore, the hydroxyl group and the isocyanate group react preferentially. Unless there is a catalytic acid compound such as a protonic acid or Lewis acid that causes the hydrolysis reaction of the alkoxysilyl group, the polyol (f2) and the silane compound (f1) are bonded via a urethane bond. A reaction product (F) containing as a main component a compound (F1) having a hydroxyl group derived from the polyol (f2) and an alkoxysilyl group derived from the silane compound (f1), which are linked, can be obtained.
The reaction product (F) may contain an unreacted polyol (f2) and an unreacted silane compound (f1) in addition to the compound (F1).

  The hydroxyl group in the reaction product (F) is derived from the polyol (f2). The hydroxyl group is oriented near the interface with the peelable sheet and near the interface with the glass for liquid crystal cells rather than inside the pressure-sensitive adhesive layer, reducing the interface free energy, improving the peel stability of the peelable sheet However, it is considered that reworkability is improved.

When the copolymer [PA] or the polyester resin [PD] has a hydroxyl group, the alkoxysilyl group in the reaction product (F) reacts with the hydroxyl group, and the copolymer [PA] or the polyester resin [PD] side. The reaction product (F) is in a pendant state at the chain position. On the other hand, when the copolymer [PA] or the polyester-based resin [PD] has a carboxyl group, a pseudo-affinity state close to bonding even if the alkoxysilyl group in the reaction product (F) does not react with the carboxyl group. It is considered that the reaction product (F) is in a pendant state at the side chain position of the copolymer [PA] or the polyester resin [PD].
Since the reaction product (F) contains a siloxane bond, it is generally considered that the reaction product (F) has a high affinity with the peelable sheet. However, in the case of the present invention, the reaction product (F) is in a pendant state at the side chain position of [PA] or polyester resin [PD], so that the affinity between the pressure-sensitive adhesive layer and the peelable sheet is increased. As a result, it seems that the peel stability of the peelable sheet was improved.
Furthermore, since the reaction product (F) is bonded to the copolymer [PA] or the polyester resin [PD], the pressure-sensitive adhesive optical film is attached to the liquid crystal cell member, and is then subjected to a harsh environment. Even if exposed for a long period of time, foaming, floating / peeling, cracks and the like do not occur.

  The urethane bond has a remarkable effect on improving the durability after the pressure-sensitive adhesive optical film is attached to the liquid crystal cell member.

The silane compound (f1) and the polyol (f2) are preferably reacted in the range of (f1) :( f2) = 7 to 1: 3 to 9 (mol ratio), and 6 to 3: 4 to 7 (mol). Ratio). Since the reaction product (F) preferably contains a compound (F1) having a hydroxyl group and an alkoxysilyl group as a main component, a silane compound having one isocyanate group and a diol are added in an amount of 6 to 5: 4 to 5 ( It is particularly preferable to carry out the reaction in the range of (mol ratio).
When the polyol (f2) is less than 3 (mol ratio), the part derived from the polyol (f2) in the reaction product (F) decreases and the part derived from the silane compound (f1) increases. As the portion derived from the silane compound (f1) increases, the number of siloxane bonds contained in the pressure-sensitive adhesive layer increases. As a result, the affinity between the pressure-sensitive adhesive layer and the peelable sheet is increased, so that the peelable sheet is difficult to peel off or the pressure-sensitive adhesive layer is easily transferred to the peelable sheet side. Further, after the pressure-sensitive adhesive optical film is attached to an adherend such as glass for liquid crystal cells, the portion derived from the silane compound (f1) in the pressure-sensitive adhesive layer becomes a glass interface for liquid crystal cells with the passage of time. Since there is a possibility of orientation in the vicinity and there is a concern that the adhesive force is reduced, it is not preferable.
On the other hand, when the polyol (f2) is more than 9 (mol ratio), the content of the portion derived from the silane compound (f1) is reduced, and the reaction site with the copolymer [PA] or the polyester resin [PD] or The alkoxysilyl group which is an affinity site is reduced. As a result, the reaction product (F) -derived component that does not bind to the copolymer [PA] or the polyester-based resin [PD] is often contained in the pressure-sensitive adhesive layer. If a pressure-sensitive adhesive optical film is applied and then exposed to a harsh environment for a long period of time, foaming and cracking are likely to occur, such being undesirable.

As described above, under basic conditions, 1 mol of the isocyanate group in the silane compound (f1) reacts with 1 mol of the hydroxyl group in the polyol (f2).
Therefore, when the silane compound (f1) is excessive, the free silane compound (f1) remains in the reaction product (F). Since the free silane compound (f1) has an isocyanate group, the isocyanate group reacts with a hydroxyl group or a carboxyl group of the copolymer [PA] or the polyester resin [PD], so that the copolymer [PA] or the polyester resin [ The silane compound (f1) can be pendant to the side chain position of PD]. Further, when the copolymer [PA] or the polyester resin [PD] and the reaction product (F) are mixed, the alkoxysilyl group of the silane compound (f1) contained in the reaction product (F) is hydrolyzed, Reacting with a hydroxyl group or a carboxyl group in the copolymer [PA] or the polyester resin [PD] to pendant the silane compound (f1) at the side chain position of the copolymer [PA] or the polyester resin [PD]. You can also.

On the other hand, when the polyol (f2) is excessive, free polyol (f2) remains in the reaction product (F). However, since the copolymer [PA] and the polyester resin [PD] function acidic with respect to the reaction product (F) regardless of the presence or absence of a carboxyl group, the copolymer [PA] or polyester When the system resin [PD] and the reaction product (F) are mixed, hydrolysis of the alkoxysilyl group of the compound (F1) contained in the reaction product (F) is promoted. The alkoxysilyl group of the compound (F1) is hydrolyzed and reacted with a hydroxyl group or a carboxyl group in the copolymer [PA] or the polyester resin [PD], and the copolymer [PA] or the polyester resin [PD]. The compound (F1) is pendant at the side chain position. Since the compound (F1) has a relatively low molecular weight as compared with the copolymer [PA] and the polyester resin [PD], free alkoxy contained in the reaction product (F) is further added to the remaining alkoxysilyl group. The polyol (f2) reacts.
When the polyol (f2) is excessive, the structure derived from the polyol (f2) starts from the siloxane bond derived from the silane compound (f1) in the pressure-sensitive adhesive layer. PD] is located at the side chain position, and the siloxane bond derived from the silane compound (f1) is not easily localized in the vicinity of the liquid crystal cell glass interface.

The silane compound (f1) having an isocyanate group and an alkoxysilyl group, which is one of the raw materials of the reaction product (F) used in the present invention, has one or more isocyanate groups and alkoxysilyl groups. is there. Silane coupling agents having a molecular weight of 50 to 1,000 and partially condensed oligomers thereof are preferred, and the molecular weight is more preferably 100 to 800, most preferably 200 to 600.
When such a silane compound (f1) is used, a pressure-sensitive adhesive having excellent adhesion, wettability, and removability can be obtained. When the molecular weight is less than 50, when the glass for liquid crystal cells and the optical film are laminated, the adhesion is improved, but the removability such as reworkability is not improved, which is not preferable.
On the other hand, if the molecular weight exceeds 1,000, since the molecular weight of the silane compound (f1) is high, the affinity between the pressure-sensitive adhesive layer and the peelable sheet increases during storage, and the peelability of the peelable sheet deteriorates. Not good

  Examples of the silane compound (f1) having an isocyanate group and an alkoxysilyl group include 2-isocyanatoethyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 4-isocyanatobutyltrimethoxysilane, and 6-isocyanatohexyltrimethoxysilane. 8-isocyanatooctyltriethoxysilane, 2-isocyanatoethyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 4-isocyanatobutyltriethoxysilane, 6-isocyanatohexyltriethoxysilane, 8-isocyanateoctyltriethoxysilane, 2 -Isocyanatoethyldimethoxymethylsilane, 3-isocyanatopropyldimethoxymethylsilane, 4-isocyanatobutyldimethoxy Methyl silane, 2-isocyanatoethyldiethoxymethylsilane, 3-isocyanatepropyldiethoxymethylsilane, 4-isocyanatobutyldiethoxymethylsilane, 2-isocyanateethyldimethoxyethylsilane, 3-isocyanatepropyldimethoxyethylsilane, 4-isocyanatebutyldimethoxy Ethylsilane, 2-isocyanatoethyldiethoxyethylsilane, 3-isocyanatopropyldiethoxyethylsilane, 4-isocyanatobutyldiethoxyethylsilane, dimethylethoxy-2-isocyanatomethylsilane, dimethylethoxy-2-isocyanatoethylsilane, dimethylethoxy Silane coupling agents such as -3-isocyanatopropylsilane and at least one of these partially condensed It may be mentioned an oligomer having isocyanate groups and an alkoxysilyl group of the above.

  In the present invention, the silane compound (f1) having an isocyanate group and an alkoxysilyl group can be used singly or in combination of two or more, or can be used in combination with other silane coupling agents. it can.

The polyol (f2) which is another raw material of the reaction product (F) used in the present invention is a known low molecular weight polyol such as an aliphatic, alicyclic or aromatic polyol having a molecular weight of 100 to 5,000. (F2-1) is preferably used, and a high molecular weight polyol having a repeating unit having a polymerization degree of 2 or more is also preferably used. For example, polyester polyols (f2-2), polyamide polyols (f2-3), polyether polyols (f2-4) or polycarbonate polyols (f2-5) having a number average molecular weight (Mn) of 200 to 50,000 Can be preferably used.
The polyester polyols (f2-2) can be obtained by a condensation reaction of low molecular weight polyols and polycarboxylic acids.
The polyamide polyols (f2-3) can be obtained by a condensation reaction of a low molecular weight polyol, a polycarboxylic acid and a polyamine.
The polyol (f2) is particularly preferably a diol having two hydroxyl groups.

Among the polyols (f2), examples of the low molecular weight polyol (f2-1) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, 3-methyl-1,5-pentanediol, and 2,4. -Diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3 -Propanediol, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (added mole number 10 or less), polyoxypropylene glycol (added mole number 10 or less), propanediol, 1,3- Butanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentylglycol, octanediol, butylethylpentanediol, 2- Aliphatic or alicyclic diols such as ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, spiroglycol, dimer diol;
For example, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4,4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4′-isopropylidenephenol, bisphenol A, bisphenol F, etc. Aromatic diols such as bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols;

  For example, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpentane, 1,1,1-trimethylolhexane, 1,1,1-trimethylolheptane, 1,1,1-trimethylol Octane, 1,1,1-trimethylol nonane, 1,1,1-trimethylol decane, 1,1,1-trimethylol undecane, 1,1,1-trimethylol dodecane, 1,1,1-trimethylol Tridecane, 1,1,1-trimethyloltetradecane, 1,1,1-trimethylolpentadecane, 1,1,1-trimethylolhexadecane, 1,1,1-trimethylolheptadecane, 1,1,1- Trimethylol octadecane, 1,1,1-trimethylol nanodecane, 1,1,1-trimethylol-sec-butane, 1,1,1-trimethyl Roll-tert-pentane, 1,1,1-trimethylol-tert-nonane, 1,1,1-trimethylol-tert-tridecane, 1,1,1-trimethylol-tert-heptadecane, 1,1,1 -Trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1-trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3 -Trimethylol branched alkanes such as ethyl-hexane, 1,1,1-trimethylolisoheptadecane, trimethylol butene, trimethylol heptene, trimethylol pentene, trimethylol hexene, trimethylol heptene, trimethylol octene, Trimethylol decene, trimethylol dodecene, trimethylol tridece , Trifunctional polyols trimethylolpropane penta-decene, trimethylol hexa decene, trimethinecyanine trawl hepta-decene, trimethylol octadecene, 1,2,6-butane triol, 1,2,4-butane triol, glycerin and the like;

  Furthermore, tetrafunctional or higher functional polyols such as pentaerythritol, dipentaerythritol, sorbitol and the like can be exemplified.

  These low molecular weight polyols (f2-1) may be used alone or in combination of two or more. Further, these low molecular weight polyols (f2-1) are preferably used as a part of a component of a polymerizable polyol having a repeating unit having a polymerization degree of 2 or more described later.

  Among the polyols (f2), polyester polyols (f2-2), which is a kind of high molecular weight polyol, are generally used in the above polycondensation reaction of low molecular weight polyols (f2-1) and known polycarboxylic acids. can get. Examples of known polycarboxylic acids used to obtain polyester polyols (f2-2) include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, and chloromalein. Aliphatic dicarboxylic acids such as acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride and the like;

  For example, o-phthalic acid, isophthalic acid, terephthalic acid, 2,5-dimethylterephthalic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane Aromatic dicarboxylic acids such as -4,4'-dicarboxylic acid, phenylindanedicarboxylic acid and phthalic anhydride, and anhydrides thereof;

  Examples thereof include alicyclic dicarboxylic acids such as dimer acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid and tetrahydrophthalic acid, and anhydrides thereof.

  Furthermore, for example, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, 1,2,3,4-butanetetra Carboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, cyclopentanetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol bistrimellitic carboxylic acid, 2,2 ′, 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, Examples thereof include trifunctional or higher polycarboxylic acids such as ethylene tetracarboxylic acid and anhydrides thereof.

  These polycarboxylic acids may be used alone or in combination of two or more.

  As the polyester polyol (b2-2) used as the polyol (f2), a commercially available product can be used. Specifically, Byron GK640 (Mn = 18,000, Tg = 79 ° C., hydroxyl value = 5, acid value) <4, linear type), Byron GK880 (Mn = 18,000, Tg = 84 ° C., hydroxyl value = 5, acid value <4, linear type), Byron 300 (Mn = 23,000, Tg = 7 ° C., hydroxyl group) Value = 5, acid value <2, linear type), Byron 500 (Mn = 23,000, Tg = 4 ° C., hydroxyl value = 5, acid value <2, linear type), Byron 560 (Mn = 19000, Tg = 7 ° C., hydroxyl value = 8, acid value <2, branched type) [above, manufactured by Toyobo Co., Ltd.];

  UE-3690 (Mn = 14,000, Tg = 91 ° C., hydroxyl value = 8, acid value = 1) [above, manufactured by Unitika Ltd.];

  P510 (Mn = 500, hydroxyl value = 336, acid value <0.5, linear liquid type), P1010 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), P2010 ( Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), P4010 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), P5010 ( Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type), P6010 (Mn = 6,000, hydroxyl value = 19, acid value <0.5, linear liquid type), P1050 ( Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), P2050 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), P3050 ( Mn = 3,000, hydroxyl value = 3 , Acid value <0.5, linear liquid type), P4050 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), P6050 (Mn = 6,000, hydroxyl value = 19). Acid value <0.5, linear liquid type), P520 (Mn = 500, hydroxyl value = 224, acid value <0.5, linear liquid type), P1020 (Mn = 1,000, hydroxyl value = 112, acid) Value <0.5, linear liquid type), P2020 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), P530 (Mn = 500, hydroxyl value = 224, acid value < 0.5, linear liquid type), P1030 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), P2030 (Mn = 2,000, hydroxyl value = 56, acid value < 0.5, linear liquid type), N2010 Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), N4010 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), PNOA4014 ( Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), P1011 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), P2011 ( Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), P4011 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), F510 ( Mn = 500, hydroxyl value = 336, acid value <0.5, linear liquid type), F1010 (Mn = 1,000, hydroxyl value = 168, acid value <0.5, linear liquid type), F2010 (Mn = 2,000, hydroxyl value = 84, acid Value <0.5, linear liquid type), F3010 (Mn = 3,000, hydroxyl value = 56, acid value <0.5, linear liquid type) [above, manufactured by Kuraray Co., Ltd.];

  Kyowapol 2000BA (Mn = 2,000, hydroxyl value = 58, acid value <0.5, linear liquid type), Kyowapol 5000PA (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear) Liquid type) [above, manufactured by Kyowa Hakko Chemical Co., Ltd.];

  URIC SE-3506 (Mn = 3,500, hydroxyl value = 32, acid value <0.5, melting point = 67 ° C., linear wax type), URIC SE-2606 (Mn = 2,600, hydroxyl value = 43, acid) Value <0.5, melting point = 65 ° C., linear wax type), URIC H-62 (Mn = 430, hydroxyl value = 260, acid value <0.5, linear liquid type), URIC H-368 (Mn = 430) , Hydroxyl value = 570, acid value <0.5, linear liquid type), URIC H-5001 (Mn = 2500, hydroxyl value = 45, acid value <0.5, linear liquid type), URIC Y-202 (Mn = 980, hydroxyl value = 115, acid value <0.5, linear liquid type), URIC Y-406 (Mn = 680, hydroxyl value = 165, acid value <0.5, linear liquid type), [above, Ito Oil Refinery];

  PLACCEL 205 (Mn = 530, hydroxyl value = 280, acid value <0.5, linear liquid type), PLAXEL L205AL (Mn = 500, hydroxyl value = 211, acid value <0.5, linear liquid type), PLACEL 208 (Mn = 830, hydroxyl value = 135, acid value <0.5, linear liquid type), ip), Plaxel 210 (Mn = 1,000, hydroxyl value = 110, acid value <0.5, linear liquid type) Plaxel 212 (Mn = 1,250, hydroxyl value = 90, acid value <0.5, linear liquid type), Plaxel 220 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear wax) Type), Plaxel 230 (Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear wax type), Plaxel 240 (Mn = 4,000, hydroxyl value = 28, acid value <0) 5, the linear wax type) [manufactured by Daicel Chemical Industries];

  Tereite 2031 (Mn = 200, hydroxyl value = 300, acid value <2.5, linear liquid type), tereto 2541 (Mn = 240, hydroxyl value = 238, acid value <1, linear liquid type), tereite 3522 (Mn = 235, hydroxyl value = 236, acid value <1, linear liquid type) [above, manufactured by Mihama Corporation];

  FSK-700 (Mn = 700, hydroxyl value = 150, acid value <1.5, linear liquid type), FSK-1200 (Mn = 700, hydroxyl value = 90, acid value <1.5, linear liquid type), FSK-2000 (Mn = 2,000, hydroxyl value = 56, acid value <1.5, linear liquid type) [above, manufactured by Kawasaki Chemical Industry Co., Ltd.];

  Polylite OD-X-286 (Mn = 980, hydroxyl value = 112, acid value <0.5, linear waxy type), polylite OD-X-102 (Mn = 2,000, hydroxyl value = 562, acid value < 0.5, linear waxy type), polylite OD-X-2330 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear waxy type), polylite OD-X-668 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear wax type), polylite OD-X-2108 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear wax shape) Type), polylite OD-X-2044 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), polylite OD-X-688 (Mn = 2,000, hydroxyl value = 56). , Acid value <0.5, linear waxy type), polylite OD-X-2068 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear waxy type), polylite OD-X-2420 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), polylite OD-X-2560 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear) Liquid type), polylite OD-X-640 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear wax type) [above, manufactured by DIC Corporation];

Sanester 5620 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type) [Sanyo Chemical Industries, Ltd.];
Pine Crystal KE-615-3 (Mn = 1,900, hydroxyl value = 59, acid value <0.5, linear liquid type), Pine Crystal D-6011 (Mn = 950, hydroxyl value = 118, acid value <0) .5, linear liquid type) [above, manufactured by Arakawa Chemical Industries Ltd.];
Etc.

  In addition, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, 8-octonolide, 11-undecanolide, 12-dodecanolide, 15-pentadecanolide, 16-hexadecanolide, α-methyl- Polyester polyols obtained by ring-opening polymerization of lactones such as β-propiolactone, α, α-dimethyl-β-propiolactone polyvalerolactone, and β-methyl-γ-valerolactone can also be used. .

  Among the polyols (f2), polyamide polyols (f2-3) which are a kind of high molecular weight polyols are generally obtained by polycondensation reaction of the above-mentioned low molecular weight polyols (f2-1) with known polyamines. It is done. As the known polyamines used for obtaining the polyamide polyols (f2-3), any polyamine having two or more primary amino groups can be used without particular limitation.

For example, aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene branches at both molecular ends. Polypropylene glycol having an amino group bonded to carbon (propylene skeleton diamine, such as “Jeffamine D230” and “Jephamine D400” manufactured by Sun Techno Chemical Co., Ltd.), propylene skeleton triamine, such as “Jephamine T403”, ethylenediamine , Propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2 Diaminopropane, iminobispropylamine, methyl _{iminobispropylamine, H 2 N (CH 2 CH} 2 O) 2 (CH 2) 2 NH 2 [Sun Techno Chemical Co., Ltd. "Jeffamine EDR148" (diamines of ethylene glycol skeleton)] Polyether skeleton diamine with methylene group bonded to amine nitrogen such as 1,5-diamino-2-methylpentane ("MPMD" manufactured by DuPont Japan), metaxylylenediamine (MXDA), polyamidoamine (Sanwa) “X2000” manufactured by Chemical Co., Ltd.), isophoronediamine, 1,3-bisaminomethylcyclohexane (“1,3BAC” manufactured by Mitsubishi Gas Chemical Company), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethyl Hexamethylenediamine, 1-cyclohexylamino-3-aminopro Down, 3-aminomethyl-3,3,5-trimethyl - cyclohexylamine, can be exemplified norbornane skeleton dimethylene amines (manufactured by Mitsui Chemicals, Inc. "NBDA") and the like.

In addition, ketimine, which is a reaction product of these polyamines and ketones, is also included in the polyamines, from the viewpoint of adjusting polymerization stability and reactivity,
Obtained from acetophenone or propiophenone and 1,3-bisaminomethylcyclohexane;
Obtained from acetophenone or propiophenone and norbornane skeleton dimethyleneamine (NBDA);
Obtained from acetophenone or propiophenone and metaxylylenediamine;
Those obtained from acetophenone or propiophenone and Jeffamine EDR148, Jeffamine D230, Jeffamine D400, etc., which are diamines of ethylene glycol skeleton or propylene skeleton, or Jeffamine T403, which is a propylene skeleton triamine;
Etc.

  These polyamines may be used alone or in combination of two or more.

  Commercially available products may be used as the polyamide polyols (f2-3), specifically, TPAE617 (Mn = 7,000, Tg = 90 ° C., hydroxyl value = 16, acid value = 1, linear type). [Fuji Kasei Kogyo Co., Ltd.] and the like.

Among the polyols (f2), as polyether polyols (f2-4) which are a kind of high molecular weight polyol, for example,
1) Ring-opening addition polymerization reaction of a known cyclic ether such as alkylene oxide;
Or
2) Dehydration condensation reaction of the diol described in the above low molecular weight polyol (b-1-1);
Can be obtained.
Specific examples of the cyclic ether used in the case of 1) above include three-membered ring ethers such as ethylene oxide, propylene oxide, isobutylene oxide, epichlorohydrin, glycidol, and styrene oxide;
4-membered ring ethers such as oxetane, dimethyloxetane, 3,3-bischloromethyloxetane;
5-membered ring ethers such as tetrahydrofuran;
Cyclic formal such as trioxane, tetraoxane, dioxalane, 1,3-dioxane, 1,4-dioxane, butylene glycol formal;
Etc.

  These polyethers may be used alone or in combination of two or more.

  As the polyether polyols (f2-4), commercially available products can also be used. Specifically, EXENOL 420 (Mn = 400, hydroxyl value = 280, acid value <0.05, linear liquid type), EXENOL 720 (Mn = 700, hydroxyl value = 160, acid value <0.05, linear liquid type), EXENOL 1020 (Mn = 1,000, hydroxyl value = 112, acid value <0.05, linear liquid type), EXENOL 2020 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear liquid type), EXENOL 3020 (Mn = 3,200, hydroxyl value = 35, acid value <0.05, linear liquid type) EXENOL 3021 (Mn = 3,300, hydroxyl value = 34, acid value <0.05, linear liquid type) [above, manufactured by Asahi Glass Urethane Co., Ltd.];

  Lupranol 2046 (Mn = 3,600, hydroxyl value = 30, acid value <0.05, linear liquid type), Lupranol VP9207 (Mn = 3,600, hydroxyl value = 30, acid value <0.05, linear liquid type) ), Lupranol 4100 (Mn = 4,500, hydroxyl value = 25, acid value <0.05, linear liquid type), Lupranol 4200 (Mn = 3,600, hydroxyl value = 27, acid value <0.05, linear) Liquid type) [above, manufactured by BASF AG];

Softanol DE30 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear liquid type) [manufactured by Catalyst Science Inc.];
NGE-04 (Mn = 300, hydroxyl value = 370, acid value <0.05, linear liquid type) [above, manufactured by Catalyst Science Co., Ltd.];

  ADEKA polyether P-400 (Mn = 400, hydroxyl value = 260, acid value <0.05, linear liquid type), ADEKA polyether P-1000 (Mn = 1,000, hydroxyl value = 112, acid value <0) .05, linear liquid type), ADEKA polyether P-2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear liquid type), ADEKA polyether BPX21 (Mn = 400, hydroxyl value = 280, acid value <0.05, linear liquid type), ADEKA polyether BPX-11 (Mn = 360, hydroxyl value = 310, acid value <0.05, linear liquid type), ADEKA polyether BPX-33 (Mn = 580, hydroxyl value = 200, acid value <0.05, linear liquid type) [above, manufactured by Adeka Company];

  PEG200 (Mn = 200, hydroxyl value = 561, acid value <0.05, linear liquid type), PEG400 (Mn = 400, hydroxyl value = 281, acid value <0.05, linear liquid type), PEG1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.05, linear liquid type), PEG2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear waxy type), PEG4000S (Mn = 4,000, hydroxyl value = 34, acid value <0.05, linear flake type), PEG 6000S (Mn = 6,000, hydroxyl value = 13, acid value <0.05, linear flake type), PEG 10000 (Mn = 11,000, hydroxyl value = 10, acid value <0.05, linear liquid type), PEG 20000 (Mn = 20,000, hydroxyl value = 5.6, acid) <0.05, linear liquid type), PP200 (Mn = 200, hydroxyl value = 561, acid value <0.05, linear liquid type), PP400 (Mn = 400, hydroxyl value = 281, acid value <0.05) , Linear liquid type), PP1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.05, linear liquid type), PP2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.05). , Linear liquid type), PP4000 (Mn = 4,100, hydroxyl value = 34, acid value <0.05, linear liquid type), TP400 (Mn = 400, hydroxyl value = 281, acid value <0.05, linear Liquid type), TP700 (Mn = 700, hydroxyl value = 160, acid value <0.05, linear liquid type), GP250 (Mn = 250, hydroxyl value = 448, acid value <0.05, linear liquid type) GP400 (Mn = 400, hydroxyl value = 281, acid value <0.05, linear liquid type), GP1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.05, linear liquid type), GP3000 (Mn = 3,000, hydroxyl value = 37, acid value <0.05, linear liquid type), GP4000 (Mn = 4,000, hydroxyl value = 28, acid value <0.05, linear liquid type), GP5000 (Mn = 5,000, hydroxyl value = 22, acid value <0.05, linear liquid type), TL6000 (Mn = 6,100, hydroxyl value = 13, acid value <0.05, linear liquid type), GEP2800 (Mn = 2,600, hydroxyl value = 43, acid value <0.05, linear liquid type), LB65 (Mn = 340, hydroxyl value = 329, acid value <0.05, linear liquid type), LB285 (M n = 1,200, hydroxyl value = 93, acid value <0.05, linear liquid type), LB385 (Mn = 1,500, hydroxyl value = 74, acid value <0.05, linear liquid type), LB625 ( Mn = 1,870, hydroxyl value = 60, acid value <0.05, linear liquid type), LB1145 (Mn = 1,980, hydroxyl value = 56, acid value <0.05, linear liquid type), LB1715 ( Mn = 2,400, hydroxyl value = 47, acid value <0.05, linear liquid type), LB3000 (Mn = 2,800, hydroxyl value = 40, acid value <0.05, linear liquid type), LB300X ( Mn = 1,200, hydroxyl value = 93, acid value <0.05, linear liquid type), LB650X (Mn = 1,870, hydroxyl value = 57, acid value <0.05, linear liquid type), LB1800X ( Mn = 2,40 , Hydroxyl value = 46, acid value <0.05, linear liquid type), LB400XY (Mn = 1,500, hydroxyl value = 74, acid value <0.05, linear liquid type), 50HB-55 (Mn = 240) , Hydroxyl value = 467, acid value <0.05, linear liquid type), 50HB-100 (Mn = 540, hydroxyl value = 329, acid value <0.05, linear liquid type), 50HB-260 (Mn = 880) , Hydroxyl value = 127, acid value <0.05, linear liquid type), 50HB-400 (Mn = 1,340, hydroxyl value = 82, acid value <0.05, linear liquid type), 50HB-660 (Mn) = 1,800, hydroxyl value = 62, acid value <0.05, linear liquid type), 50HB-2000 (Mn = 2,300, hydroxyl value = 48, acid value <0.05, linear liquid type), 50HB -5100 Mn = 3,750, hydroxyl value = 29, acid value <0.05, linear liquid type), 75H-90000 (Mn = 15,000, hydroxyl value = 2, acid value <0.05, linear liquid type), BP-2P (Mn = 350, hydroxyl value = 321, acid value <0.05, linear liquid type), BP-5P (Mn = 530, hydroxyl value = 211, acid value <0.05, linear liquid type), BPE-20 (Mn = 330, hydroxyl value = 343, acid value <0.05, linear liquid type), BPE-40 (Mn = 400, hydroxyl value = 278, acid value <0.05, linear liquid type), BPE-60 (Mn = 490, hydroxyl value = 228, acid value <0.05, linear liquid type), BPE-100 (Mn = 1,300, hydroxyl value = 168, acid value <0.05, linear liquid type) ), BPE-180 (Mn = 1,0) 50, hydroxyl value = 109, acid value <0.05, linear liquid type) [above, manufactured by Sanyo Chemical Industries];

  HP-800E (Mn = 800, hydroxyl value = 137, acid value <0.05, linear liquid type), HP-1000 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type) ), HP-2000 (Mn = 2,000, hydroxyl value = 58, acid value <0.05, linear liquid type) [above, manufactured by Toagosei Co., Ltd.];

Pine Crystal KE-622 (Mn = 1,100, hydroxyl value = 98, acid value <0.5, linear liquid type), Pine Crystal D-6240 (Mn = 4,000, hydroxyl value = 27, acid value <0) .5, linear liquid type) [above, manufactured by Arakawa Chemical Industries Ltd.];
Etc.

Among the polyols (f2), as the polycarbonate polyols (f2-5) which is a kind of high molecular weight polyol, for example,
1) Reaction of the low molecular weight polyol (f2-1) with a carbonate ester;
Or
2) A reaction in which phosgene is allowed to act on the low molecular weight polyol (f2-1) in the presence of alkali;
Can be obtained.
Specific examples of the carbonic acid ester used in the case 1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

  As the polycarbonate polyol (f2-5), a commercially available product can be used. Specifically, oximer N112 (Mn = 1,000, Tg = 60 ° C., hydroxyl value = 112, acid value <0.5, linear type) [Manufactured by Perstorp];

  PCDL-T5651 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), PCDL-T5652 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear) Liquid type), PCDL-T4671 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), PCDL-T4672 (Mn = 2,000, hydroxyl value = 52, acid value <0). .05, linear liquid type) [above, manufactured by Asahi Kasei Chemicals Corporation];

  PMHC-1050 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), PMHC-2050 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear) Liquid type), C-1090 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), C-2090 (Mn = 2,000, hydroxyl value = 56, acid value <0). .5, linear liquid type), C-3090 (Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear liquid type), C-4090 (Mn = 4,000, hydroxyl value = 28, Acid value <0.5, linear liquid type), C-5090 (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type), C-1065N (Mn = 1,000, hydroxyl group) Value = 112, acid value <0.5, linear liquid type), C-2 65N (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), C-1015N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type) ), C-2015N (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type) [above, manufactured by Kuraray Co., Ltd.];

Oxymer M112 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), Oxymer M56 (Mn = 2,000, hydroxyl value = 562, acid value <0.5, linear liquid type) ), Oxymer D112 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type) [above, manufactured by Perstorp];
PLACCEL CD CD205 (Mn = 500, hydroxyl value = 224, acid value <0.5, linear liquid type), PLACCEL CD CD210 (Mn = 10,000, hydroxyl value = 112, acid value <0.5, linear liquid type) ), Plaxel CD CD220 (Mn = 20000, hydroxyl value = 56, acid value <0.5, linear liquid type) [above, manufactured by Daicel Chemical Industries];
Etc.

  In this invention, a polyol (f2) can be used individually or in combination of 2 or more types, respectively. That is, low molecular weight polyols (f2-1) can be used in combination, and low molecular weight polyols (f2-1) and high molecular weight polyols (f2-2) to (f2-5) can be used in combination. The high molecular weight polyols (f2-2) to (f2-5) can also be used in combination. Of these polyols (f2), it is most preferable to use a bifunctional diol because a pressure-sensitive adhesive excellent in adhesiveness, heat resistance, moist heat resistance and removability can be obtained.

In the present invention, the molecular weight of the polyol (f2) is not particularly limited as long as it can be used from a low molecular weight to a high molecular weight as described above and can be dissolved in the solvent to be used, but the number average molecular weight ( Mn) is preferably in the range of 100 to 50,000. More preferably, it is 200-30,000, Most preferably, it is 500-10,000. When such a polyol is used, a pressure-sensitive adhesive having excellent adhesion, wettability, and removability can be obtained. When the number average molecular weight (Mn) is less than 100, when the glass for liquid crystal cells and the optical film are laminated, the adhesive strength is not lowered and re-peelability such as reworkability becomes difficult, which is not preferable.
On the other hand, if Mn exceeds 50,000, the molecular weight of the polyol (f2) is high, so that the solubility in a solvent is reduced or the compatibility with the copolymer [PA] or the polyester resin [PD] is reduced. As a result, the pressure-sensitive adhesive layer is whitened and transparency is lowered. In addition, when exposed to a high temperature or a high temperature and high humidity for a long period of time, the foaming generated at the interface of the glass for liquid crystal cells becomes remarkably large, which is not preferable.

  The hydroxyl value of the polyol (f2) is preferably in the range of 5 to 1,000 mgKOH / g, more preferably in the range of 10 to 800 mgKOH / g. When the hydroxyl value exceeds 1,000 mgKOH / g, the heat and humidity resistance is lowered, which is not preferable. When the hydroxyl value is less than 5 mgKOH / g, the solubility of the polyol (f2) in the solvent decreases or the compatibility with the copolymer (A) decreases, and the pressure-sensitive adhesive layer is whitened. This is not preferable.

  In the present invention, the reaction product (F) is preferably used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the copolymer [PA] or the polyester resin [PD], and 1 to 10 parts by weight is used. More preferably. If the amount is less than 0.1 parts by weight, improvement in reworkability cannot be expected. If the amount is more than 20 parts by weight, the pressure-sensitive adhesive composition and the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition are transparent. This is not preferable because the properties are reduced.

<Reactive compound (G)>
It is important that the pressure-sensitive adhesive composition of the present invention contains a reactive compound (G) that can react with a side chain functional group in the copolymer [PA] or the polyester resin [PD]. . The reactive compound (G) used in the present invention has a functional group capable of reacting with the side chain hydroxyl group or side chain carboxyl group in the copolymer [PA] or the polyester resin [PD] in the molecule. A compound.
Examples of such compounds include polyisocyanate compounds, epoxy compounds, amine compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, melamine compounds, and metal chelate compounds. Among these, in order to act as a crosslinking agent, a compound having two or more functional groups capable of reacting with a hydroxyl group or a carboxyl group in the copolymer [PA] or the polyester resin [PD] is preferably used. It is done.

When the functional group in the copolymer [PA] or the polyester resin [PD] is a carboxyl group, examples of the functional group of the reactive compound (G) include an isocyanate group, an epoxy group, an amino group, an aziridyl group, and an oxazoline group. It is done. When the functional group in [PA] or the polyester resin [PD] is a hydroxyl group, the functional group of the reactive compound (G) includes an isocyanate group and an N-methylol group.
In particular, the polyisocyanate compound is preferably used because it is excellent in the adhesion of the resin composition after the crosslinking reaction and the adhesion to the coating layer.

  For example, examples of the polyisocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', Examples thereof include 4 "-triphenylmethane triisocyanate.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca. Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene. 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples thereof include methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

  Further, a trimethylolpropane adduct of the above polyisocyanate, a trimer having an isocyanurate ring, and the like can be used in combination. Polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and these polyisocyanate modified products can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a polyisocyanate.

  Among these polyisocyanate compounds, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate), xylylene diisocyanate, 4,4 ′ Use of a non-yellowing or hard yellowing polyisocyanate compound such as methylenebis (cyclohexyl isocyanate) (also known as hydrogenated MDI) is particularly preferred from the viewpoint of weather resistance, heat resistance, and heat and humidity resistance.

  When a polyisocyanate compound is used as the reactive compound (G), a known catalyst can be used as necessary to accelerate the reaction. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned, and it is possible to use a single compound or plural compounds.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like, and depending on the case, they can be used alone or in combination. .

Examples of organometallic compounds include tin compounds and non-tin compounds.
Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate , Triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, 2- Examples thereof include iron series such as iron ethylhexanoate and iron acetylacetonate, cobalt series such as cobalt benzoate and cobalt 2-ethylhexate, zinc series such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate. .
Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Among the reactive compounds (G), examples of epoxy compounds include bisphenol A-epichlorohydrin type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, and glycerin triglycidyl ether. 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N '-Diglycidylaminomethyl) cyclohexane and the like.

  Among the reactive compounds (G), examples of amine compounds are preferably polyamines having two or more primary amino groups, and primary amino groups not directly bonded to the aromatic ring from the viewpoint of excellent curing speed. An aliphatic polyamine (which may contain an aromatic ring in its skeleton), which is a polyamine having two or more of them is preferred.

Aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene branched carbons at both ends of the molecule. Polypropylene glycol having an amino group bonded thereto (propylene skeleton diamine, such as “Jefamine D230” and “Jephamine D400” manufactured by Sun Techno Chemical Co., Ltd., etc.), propylene skeleton triamine, such as “Jephamine T403”, ethylenediamine, Propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2-dia Nopuropan, iminobispropylamine, methyl _{iminobispropylamine, H 2 N (CH 2 CH} 2 O) 2 (CH 2) 2 NH 2 [ Sun Techno Chemical Co., Ltd. "Jeffamine EDR148" (ethylene glycol skeleton diamine)] or the like Polyether skeleton diamine, 1,5-diamino-2-methylpentane (“MPMD” manufactured by DuPont Japan), metaxylylenediamine (MXDA), polyamidoamine (Sanwa Chemical) "X2000"), isophoronediamine, 1,3-bisaminomethylcyclohexane ("1,3BAC" manufactured by Mitsubishi Gas Chemical Company), 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3 5-Trimethyl-cyclohexylamine, dimethylene with norbornane skeleton Mention may be made of the Min (manufactured by Mitsui Chemicals, Inc. "NBDA"), and the like.
Among these, since the curing rate is particularly high, 1,3-bisaminomethylcyclohexane, dimethyleneamine having a norbornane skeleton, metaxylylenediamine, H ₂ N (CH ₂ CH ₂ O) ₂ (CH ₂ ) ₂ NH ₂ (ethylene glycol skeleton diamine), propylene skeleton diamine, propylene skeleton triamine, and polyamidoamine (trade name: X2000) are useful.

  Ketimine, which is a reaction product of these polyamines and ketones, is also included in the amino compound, and from the viewpoints of stability, reactivity adjustment and overcoatability, acetophenone or propiophenone and 1,3-bisaminomethylcyclohexane Obtained from acetophenone or propiophenone and dimethyleneamine (NBDA) of norbornane skeleton; obtained from acetophenone or propiophenone and metaxylylenediamine; acetophenone or propiophenone; Also obtained from Jeffamine EDR148, Jeffamine D230, Jeffamine D400, etc., which are diamines having an ethylene glycol skeleton or propylene skeleton, or Jeffamine T403, which is a triamine having a propylene skeleton, etc. It is possible to use.

  Among the reactive compounds (G), examples of the aziridine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis ( 1-aziridinecarboxite), bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite) ), Trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3, 5-triazine, trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1-a Dilidinyl) butyrate], trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate], 2,2 ′ -Bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N'-ethyleneurea, 1,6 -Hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide, etc. Is mentioned.

  Of the reactive compounds (G), as the carbodiimide compound, a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and a known polycarbodiimide can be used.

Moreover, as a carbodiimide compound, the high molecular weight polycarbodiimide produced | generated by carrying out the decarboxylation condensation reaction of diisocyanate in presence of a carbodiimidization catalyst can also be used.
Examples of such compounds include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction.
As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 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, 4,4′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.

  As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.

  An example of such a high molecular weight polycarbodiimide is a carbodilite series manufactured by Nisshinbo Industries, Ltd. Of these, Carbodilite V-01, 03, 05, 07, 09 is preferable because of its excellent compatibility with organic solvents.

  Among the reactive compounds (G), as the oxazoline compound, a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2′-methylenebis (2-oxazoline), 2,2′- Ethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-propylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline) ), 2,2'-hexamethylene bis (2-oxazoline), 2,2'-octamethylene bis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'- p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-fe Renbis (4-phenyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'- m-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-phenylenebis-2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline) ), 2,2'-o-phenylenebis (4-methyl-2-oxazoline), 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline) and the like. Alternatively, vinyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline and other monomers that can be copolymerized with these vinyl monomers. It may be a copolymer with a monomer.

  Among the reactive compounds (G), the melamine compound is a compound having a triazine ring in the molecule, such as melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, vinylguanamine, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine and the like. Can be mentioned. These low-condensates, alkyl etherified formaldehyde resins and aminoplast resins may also be used.

  Among reactive compounds (G), examples of metal chelate compounds include aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, and other polyvalent metals such as acetylacetone and Examples thereof include compounds coordinated with ethyl acetoacetate.

  These reactive compounds (G) may be used alone or in combination.

The pressure-sensitive adhesive composition of the present invention contains 0.001 to 20 parts by weight of the reactive compound (G) with respect to 100 parts by weight of the copolymer [PA] or the polyester resin [PD]. Is preferable, and it is more preferable to contain 0.01-10 weight part. When the amount of the reactive compound (G) used exceeds 20 parts by weight, the adhesiveness of the resulting pressure-sensitive adhesive composition tends to decrease, while the amount of the reactive compound (G) used is 0.001 wt. If it is less than the part, since a sufficient cross-linked structure cannot be obtained, the cohesive force of the adhesive layer is lowered, and the heat resistance and the heat and humidity resistance tend to be lowered.
By the reaction of the hydroxyl group or carboxylic acid group in the copolymer [PA] or polyester resin [PD] with the functional group in the reactive compound (G), the adhesive layer is three-dimensionally crosslinked, Ensure adhesion. Then, the reaction product (F) contained in the pressure-sensitive adhesive composition reacts with the copolymer [PA] or the polyester resin [PD], and the copolymer [PA] or the polyester resin [PD]. ], The reaction product (F) is pendant at the side chain position of the liquid crystal cell and oriented in the vicinity of the glass interface for the liquid crystal cell, so that the heat resistance and heat and humidity resistance under severer conditions than before are also improved. Therefore, it can be preferably used for an optical member.

The pressure-sensitive adhesive composition of the present invention preferably contains an organic solvent.
Further, the pressure-sensitive adhesive composition of the present invention includes various resins, softeners, dyes, pigments, antioxidants, tackifiers, silane coupling agents, plastics, as long as the effects of the present invention are not impaired. You may mix | blend an agent, a filler, an anti-aging agent, etc.
For example, the organic solvent such as acetone, methyl acetate, ethyl acetate, cyclohexane, toluene, methyl ethyl ketone, isopropyl alcohol, and other hydrocarbon solvents and water are further added to adjust the viscosity of the pressure sensitive adhesive composition. Alternatively, the pressure-sensitive adhesive composition can be heated to lower the viscosity. However, when an isocyanate compound is used as the reactive compound (G), a solvent containing a hydroxyl group cannot be used.

The pressure-sensitive adhesive composition of the present invention is suitable as a pressure-sensitive adhesive composition for optical films. That is, it is preferably used for forming a pressure-sensitive adhesive optical film comprising an optical film and a pressure-sensitive adhesive layer located on at least one surface of the optical film.
The pressure-sensitive adhesive optical film of the present invention can be obtained as follows.
Apply and dry the pressure-sensitive adhesive composition on the release-treated surface of the peelable sheet, laminate the optical film on the surface of the pressure-sensitive adhesive layer, or apply and dry the pressure-sensitive adhesive composition on the optical film. Then, a pressure-sensitive adhesive optical film can be obtained by laminating the release-treated surface of the peelable sheet on the surface of the pressure-sensitive adhesive layer.
The reaction between the copolymer [PA] or the polyester resin [PD] and the reaction product (F), the crosslinking reaction between the copolymer [PA] or the polyester resin [PD] and the reactive compound (G) When the pressure-sensitive adhesive composition is dried and when a sheet-like optical film or a peelable sheet is laminated on the surface of the formed pressure-sensitive adhesive layer, it further proceeds after lamination.

  Examples of the peelable sheet include those obtained by subjecting the surface of a sheet-like substrate such as cellophane, various plastic sheets, and paper to a release treatment. Various sheet base materials can be used alone or in a multilayered state in which a plurality of base materials are laminated.

  Various plastic sheets are also referred to as various plastic films, such as polyvinyl alcohol films, triacetyl cellulose films, films of polyolefin resins such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer, polyethylene terephthalate and polybutylene terephthalate. Polyester resin film, Polycarbonate resin film, Polynorbornene resin film, Polyarylate resin film, Acrylic resin film, Polyphenylene sulfide resin film, Polystyrene resin film, Vinyl resin film Polyamide resin film, polyimide resin film, epoxy resin film and the like.

Examples of the optical film used in the present invention include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
The polarizing film, also called a polarizing plate, is sandwiched between two triacetylcellulose protective films (hereinafter referred to as “TAC film”) and two cycloolefin films on both sides of a polyvinyl alcohol (PVA) polarizer. It is a multilayer structure film.

After applying the pressure-sensitive adhesive composition to the peelable sheet or optical film by an appropriate method according to a conventional method, if the pressure-sensitive adhesive composition contains a liquid medium such as an organic solvent or water, heat it. When the liquid medium is removed by a method such as the above, or when the pressure-sensitive adhesive composition does not contain a liquid medium that should be volatilized, the resin layer in a molten state is cooled and solidified, and a peelable sheet or optical A pressure sensitive adhesive layer can be formed on the film.
The thickness of the pressure-sensitive adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 0.1 μm to 100 μm. If the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained, and if the thickness exceeds 200 μm, characteristics such as adhesive strength are often not improved further.

The method for applying the pressure-sensitive adhesive composition of the present invention to a peelable sheet or the like is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, Various coating methods such as a knife coater, a reverse coater, and a spin coater can be used.
There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although it depends on the cured form of the resin composition, the film thickness, and the selected solvent, heating with hot air of about 60 to 180 ° C. is usually sufficient.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

<Production of copolymer [PA]>
(Synthesis Example 1)
The following α and β-unsaturated compounds were charged at the following ratios in a polymerization tank and a dropping device of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, respectively.

[Polymerization tank]
N-butyl propenoate 29 parts methyl propenoate 20 parts propenoic acid 0.5 parts 4-hydroxybutyl propenoate 0.5 parts ethyl acetate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [drip apparatus ]
N-butyl propenoate 49 parts propenoic acid 0.5 part propenoic acid 4-hydroxybutyl 0.5 part ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

  After the air in the polymerization tank was replaced with nitrogen gas, the reaction was started at a reflux temperature in a nitrogen atmosphere while stirring. When the polymerization rate reached about 70%, the dropping of the mixture of the α, β-unsaturated compound, the polymerization initiator and the organic solvent was started from the dropping device. After completion of the dropwise addition, the mixture was further aged with stirring for 8 hours, and then 197 parts of toluene was added and cooled to room temperature. A transparent solution having a nonvolatile content of 30.1% containing a copolymer of α, β-unsaturated compound was obtained. Obtained. The Tg of the copolymer determined from DSC was −33 ° C.

(Synthesis Example 2)
The composition of the α, β-unsaturated compound used in Synthesis Example 1 was changed, and charged in the polymerization tank and the dropping device at the following ratios respectively. Otherwise, polymerization was performed in the same manner as in Synthesis Example 1, and α, β- A clear solution containing a copolymer of unsaturated compounds was obtained.
[Polymerization tank]
2-ethylhexyl propenoate 30 parts n-butyl propenoate 19 parts methyl 2-methylpropenoate 10 parts propenoic acid 1 part ethyl acetate 30 parts 2,2′-azobisisobutyronitrile 0.05 part [drip apparatus]
2-ethylhexyl propenoate 35 parts n-butyl propenoate 4 parts propenoic acid 1 part ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

(Synthesis Example 3)
The composition of the α, β-unsaturated compound used in Synthesis Example 1 was changed, and charged in the polymerization tank and the dropping device at the following ratios respectively. Otherwise, polymerization was performed in the same manner as in Synthesis Example 1, and α, β- A clear solution containing a copolymer of unsaturated compounds was obtained.
[Polymerization tank]
Lauryl 2-methylpropenoate 30 parts Ethyl propenoate 9 parts Vinyl ethanoate 10 parts 2-Hydroxyethyl propenoate 1 part Ethyl acetate 30 parts 2,2'-Azobisisobutyronitrile 0.05 part [Drip device]
Lauryl 2-methylpropenoate 45 parts Ethyl propenoate 4 parts 2-Hydroxyethyl propenoate 1 part Ethyl acetate 36 parts 2,2'-Azobisisobutyronitrile 0.05 part

(Synthesis Example 4)
In addition to the α, β-unsaturated compound, an ultraviolet absorber is further added, and charged in the polymerization tank and the dropping device in the following ratios respectively. A transparent liquid containing a copolymer of the compound was obtained.
[Polymerization tank]
N-butyl propenoate 29 parts methyl 2-methylpropenoate 10 parts methyl propenoate 10 parts 4-hydroxybutyl propenoate 0.5 parts ethyl acetate 30 parts 2,2′-azobisisobutyronitrile 0.05 part [ Dripping device]
N-butyl propenoate 50 parts 4-hydroxybutyl propenoate 0.5 parts ethyl acetate 36 parts 2,2′-azobisisobutyronitrile 0.05 part

(Synthesis Example 5)
The composition of the α, β-unsaturated compound used in Synthesis Example 1 was changed, and charged in the polymerization tank and the dropping device at the following ratios respectively. Otherwise, polymerization was performed in the same manner as in Synthesis Example 1, and α, β- A clear solution containing a copolymer of unsaturated compounds was obtained.
[Polymerization tank]
2-ethylhexyl propenoate 20 parts methyl propenoate 30 parts propenoic acid 1 part ethyl acetate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [drip apparatus]
2-ethylhexyl propenoate 47 parts propenoic acid 2 parts ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

(Synthesis Example 6)
The composition of the α, β-unsaturated compound used in Synthesis Example 1 was changed, and charged in the polymerization tank and the dropping device at the following ratios respectively. Otherwise, polymerization was performed in the same manner as in Synthesis Example 1, and α, β- A clear solution containing a copolymer of unsaturated compounds was obtained.
[Polymerization tank]
N-Butyl propenoate 30 parts Benzyl propenoate 20 parts 2-Methylpropenoate 2-hydroxyethyl 1 part Ethyl acetate 30 parts 2,2'-Azobisisobutyronitrile 0.05 part [Drip device]
N-Butyl propenoate 48 parts 2-Methylpropenoate 2-hydroxyethyl 1 part Ethyl acetate 36 parts 2,2'-Azobisisobutyronitrile 0.05 part

Table 1 summarizes the weight average molecular weight and the like of each copolymer [PA] obtained in Synthesis Examples 1 to 6.

<Manufacture of polyester resin [PD]>
(Synthesis Example 7)
A polymerization tank, a stirrer, a thermometer, a reflux condenser, a polymerization tank equipped with a nitrogen introduction tube, and a dropping apparatus, the following dibasic acid-based component (A) having no hydroxyl group, diol having no carboxyl group (B) and the side chain functional group-introducing component (C) were respectively charged at the following ratios.

[Polymerization tank]
Trimethylolpropane (c1) 2.5 parts Neopentyl glycol (B) 57 parts 1,4-butanediol (B) 30 parts 1,6-hexanediol (B) 26 parts Isophthalic acid (A) 116 parts Sebacic acid ( A) 61 copies

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. in a nitrogen atmosphere while stirring. After maintaining at 100 ° C. for 1 hour, dehydration reaction was performed by gradually raising the temperature to 180 to 240 ° C. over about 8 hours. Next, when the acid value became 15 or less, 0.1 part of tetrabutyl titanate was added as a catalyst, the pressure was gradually reduced, the reaction was carried out at 1 to 3 torr and 260 ° C. for 5 hours, the solution was gradually cooled, and toluene The reaction was terminated by dissolving in a solution / ethyl acetate mixed solution (weight ratio = 1/3).
This reaction solution is light yellow and transparent, has a nonvolatile content of 50.1% by weight, a viscosity of 4,700 mPa · s, an acid value of a polyester resin of 0.3 mgKOH / g, a hydroxyl value of 10.2 mgKOH / g, and a glass transition temperature of −30 ° C. The weight average molecular weight was 90,000.

(Synthesis Example 8)
Instead of trimethylolpropane (c1) used as the side chain functional group introduction component (C) in Synthesis Example 7, 3 parts of trimellitic anhydride (c2) was used, and the amount of sebacic acid (A) was 50. The reaction was the same as in Synthesis Example 1 except that the amount was changed to 5 parts, dissolved in a toluene / ethyl acetate mixed solution (weight ratio = 1/3), light yellow and transparent, nonvolatile content of 50.2 wt%, viscosity of 5, A solution of a polyester resin of 600 mPa · s was obtained. The polyester resin had an acid value of 5.5 mgKOH / g, a hydroxyl value of 1.5 mgKOH / g, a glass transition temperature of −30 ° C., and a weight average molecular weight of 105,000.

(Synthesis Example 9)
Synthesis example except that 13.4-parts of 1,4-butanediol diglycidyl ether (c3) was used instead of trimethylolpropane (c1) used as component (C) for side chain functional group introduction in Synthesis Example 7. 1 and dissolved in a toluene / ethyl acetate mixed solution (weight ratio = 1/3) to obtain a pale yellow transparent polyester resin solution having a nonvolatile content of 50.0% by weight and a viscosity of 4,500 mPa · s. Obtained. The polyester resin had an acid value of 0.5 mgKOH / g, a hydroxyl value of 11.7 mgKOH / g, a glass transition temperature of −40 ° C., and a weight average molecular weight of 85,000.

(Synthesis Example 10)
Except for using 8.1 parts of 2,2-bis (hydroxymethyl) butanoic acid (c4) instead of trimethylolpropane (c1) used as the component (C) for introducing a side chain functional group in Synthesis Example 7. It reacts in the same manner as in Synthesis Example 1 and dissolves in a toluene / ethyl acetate mixed solution (weight ratio = 1/3). A solution was obtained. The acid value of the polyester resin was 4.2 mgKOH / g, the hydroxyl value was 1.2 mgKOH / g, the glass transition temperature was −40 ° C., and the weight average molecular weight was 82,000.

(Synthesis Example 11)
Instead of trimethylolpropane (c1) used as the side chain functional group introduction component (C) in Synthesis Example 7, 6.7 parts of 2-hydroxybutanedioic acid (c5) was used, and further sebacic acid (A) The reaction was the same as in Synthesis Example 1 except that the amount was changed to 50.5 parts, dissolved in a toluene / ethyl acetate mixed solution (weight ratio = 1/3), light yellow and transparent with a nonvolatile content of 50.0% by weight. A polyester resin solution having a viscosity of 4,300 mPa · s was obtained. The polyester resin had an acid value of 0.3 mg KOH / g, a hydroxyl value of 10.5 mg KOH / g, a glass transition temperature of −40 ° C., and a weight average molecular weight of 80,000.

(Synthesis Example 12)
To 100 parts of the polyester resin [PD] solution obtained in Synthesis Example 9, 6 parts of ε-caprolactone (g1) as a cyclic ester compound (E) is added, and 0.1 part of tetrabutylammonium tetrahydroborate is further added as a catalyst. Then, after the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 100 ° C. in a nitrogen atmosphere with stirring and reacted for 10 hours. Next, after cooling, the resultant was dissolved in a toluene / ethyl acetate mixed solution (weight ratio = 1/3) to obtain a pale yellow transparent polyester resin solution having a nonvolatile content of 50.1 wt% and a viscosity of 4,600 mPa · s. The polyester resin had an acid value of 0.1 mgKOH / g, a hydroxyl value of 5.3 mgKOH / g, a glass transition temperature of −45 ° C., and a weight average molecular weight of 88,000.

(Synthesis Example 13)
6 parts of ε-caprolactone (g1) as a cyclic ester compound (E) was added to 100 parts of the polyester resin [PD] solution obtained in Synthesis Example 9 and reacted in the same manner as in Synthesis Example 6 to obtain a pale yellow transparent A polyester resin solution having a nonvolatile content of 50.1% by weight and a viscosity of 4,800 mPa · s was obtained. The polyester resin had an acid value of 0.1 mgKOH / g, a hydroxyl value of 4.8 mgKOH / g, a glass transition temperature of −45 ° C., and a weight average molecular weight of 95,000.

(Synthesis Example 14)
To 100 parts of the condensed polyester resin [PD1-1] solution obtained in Synthesis Example 10, 6 parts of ε-caprolactone (g1) as a cyclic ester compound (E) was added and reacted in the same manner as in Synthesis Example 6, A solution of polyester resin [PD1-2] having a pale yellow transparent and non-volatile content of 50.1% by weight and a viscosity of 4,600 mPa · s was obtained. The polyester resin had an acid value of 0.1 mgKOH / g, a hydroxyl value of 4.2 mgKOH / g, a glass transition temperature of −45 ° C., and a weight average molecular weight of 86,000.

(Synthesis Example 15)
A polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, a polymerization tank of a polymerization reactor equipped with a nitrogen introduction tube and a dropping device have polyester polyol, acid anhydrides, and two cyclic ether groups in the molecule. The compound (c3), the cyclic ester compound (e1), the catalyst and the organic solvent were charged in the following ratios.

[Polymerization tank]
Polyester diol * (B) 376 parts
* Kuraray polyol P4010 (Kuraray)
Succinic anhydride (A) 18 parts Toluene 76 parts Ethyl acetate 30 parts Tetrabutylammonium tetrahydroborate (catalyst) 0.5 part [Drip device]
Bisphenol A diglycidyl ether (c3) 34 parts ε-caprolactone (e1) 32 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 part Ethyl acetate 47 parts

  After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 100 ° C. in a nitrogen atmosphere while stirring, and the reaction was performed for 8 hours. The acid value was 25.1 mgKOH / g, the weight average molecular weight was 4,200, and the condensation type polyester was used. A dibasic acid component having carboxyl groups at both ends of the resin was obtained.

Subsequently, the said mixture was dripped at constant velocity over 1 hour from the dripping apparatus.
After completion of dropping, 1 part of tetrabutylammonium tetrahydroborate was added after 8 hours with stirring, and further aged for 8 hours. Thus, a polyester having a condensed and addition-type polyester main chain (I) and having a ring-opening portion of ε-caprolactone as a side chain was obtained.

Next, 39 parts of phenyl isocyanate was added dropwise at a constant rate over 1 hour in order to reduce excess hydroxyl groups. After completion of dropping, the mixture was aged for 6 hours with further stirring, and then a toluene / ethyl acetate mixed solution was added and cooled to room temperature to obtain a polyester resin solution.
This reaction solution is light yellow and transparent with a non-volatile content of 50.3% by weight and a viscosity of 12,000 mPa · s. The weight average molecular weight was 130,000.

(Synthesis Example 16)
In the polymerization tank of the polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction pipe,
A dibasic acid (A), a compound (c3) having two cyclic ether groups in the molecule, a cyclic ester compound (e1), a catalyst and an organic solvent were charged in the following ratios.

[Polymerization tank]
Adipic acid (A) 159 parts Isophthalic acid (A) 120 parts Bisphenol A diglycidyl ether (c3) 721 parts ε-caprolactone (e1) 871 parts Tetrabutylammonium tetrahydroborate (catalyst) 2 parts Ethyl acetate 200 parts Toluene 200 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. in a nitrogen atmosphere while stirring to initiate the reaction. Every 8 hours, 2.0 parts of this tetrabutylammonium tetrahydroborate (catalyst) was added twice in total, and a ripening reaction was carried out for a total of 24 hours. Further, 600 parts of ethyl acetate and 200 parts of benzyl isocyanate were added. Aged for hours. Then, 458 parts of ethyl acetate was added and cooled to room temperature to obtain a polyester resin solution.
This reaction solution is light yellow and transparent, has a non-volatile content of 50.2% by weight, a viscosity of 15,000 mPa · s, an acid value of the resin of 0.5 mgKOH / g, a hydroxyl value of 5.8 mgKOH / g, a glass transition temperature of −10 ° C. The weight average molecular weight was 150,000.

Table 2 summarizes the weight average molecular weight and the like of each polyester resin [PD] obtained in Synthesis Examples 7 to 16.

<Production of reaction product (F) having a hydroxyl group and an alkoxy group>
(Synthesis Example 17)
The following components were charged at the following ratios in a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, respectively.

[Polymerization tank]
1,8-octanediol (f2) 146 parts (1 mol)
(Hydroxyl value: 767 mgKOH / g)
Methyl ethyl ketone 100 parts [Drip device]
247 parts (1 mol) of 3-isocyanatopropyltriethoxysilane (f1)
96 parts of methyl ethyl ketone

  After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 60 ° C. in a nitrogen atmosphere while stirring. Next, the mixture of the silane compound (f1) and the solvent was dropped from the dropping device at a constant rate over 1 hour. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was continued under reflux for 3 hours. Thereafter, 197 g of methyl ethyl ketone was added and then cooled to 30 ° C. or lower to obtain a solution of the reaction product (F) having a nonvolatile content concentration of 50.1% and a hydroxyl value of 142 (mgKOH / g).

(Synthesis Example 18)
The following components were charged at the following ratios in a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, respectively.

[Polymerization tank]
Kuraray polyol N2010 (f2) 500 parts (0.25 mol)
(Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type)
180 parts of methyl ethyl ketone [drip device]
3-isocyanatopropyltriethoxysilane (f1)
62 parts (0.25 mol)
100 parts of methyl ethyl ketone

  After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 60 ° C. in a nitrogen atmosphere while stirring. Next, the mixture of the silane compound (f1) and the solvent was dropped from the dropping device at a constant rate over 1 hour. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was continued under reflux for 5 hours. Thereafter, 282 g of methyl ethyl ketone was added and then cooled to 30 ° C. or lower to obtain a solution of the reaction product (F) having a nonvolatile content concentration of 50.2% and a hydroxyl value of 25 (mgKOH / g).

(Synthesis Example 19)
The following components were charged at the following ratios in a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, respectively.

[Polymerization tank]
PLACCEL 240 (f2) 400 parts (0.1 mol)
((Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear wax type)
500 parts of methyl ethyl ketone [drip device]
3-isocyanatopropyltriethoxysilane (f1)
25 parts (0.1 mol)
500 parts of methyl ethyl ketone

  After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 60 ° C. in a nitrogen atmosphere while stirring. Next, the mixture of the silane compound (f1) and the solvent was dropped from the dropping device at a constant rate over 1 hour. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was continued under reflux for 5 hours. Thereafter, 700 g of methyl ethyl ketone was added and then cooled to 30 ° C. or lower to obtain a solution of a reaction product (F) having a nonvolatile content concentration of 20.2% and a hydroxyl value of 13 (mgKOH / g).

(Synthesis Example 20)
The following components were charged at the following ratios in a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, respectively.

[Polymerization tank]
TPAE617 (f2) 700 parts (0.1 mol)
(Mn = 7,000, Tg = 90 ° C., hydroxyl value = 16, acid value = 1, linear type)
1,500 parts of methyl ethyl ketone [drip device]
3-isocyanatopropyltriethoxysilane (f1)
25 parts (0.1 mol)
1,500 parts of methyl ethyl ketone

  After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 60 ° C. in a nitrogen atmosphere while stirring. Next, the mixture of the silane compound (f1) and the solvent was dropped from the dropping device at a constant rate over 1 hour. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was continued under reflux for 5 hours. Thereafter, 625 g of methyl ethyl ketone was added and then cooled to 30 ° C. or lower to obtain a solution of a reaction product (F) having a nonvolatile content concentration of 20.1% and a hydroxyl value of 8 (mgKOH / g).

(Synthesis Example 21)
The following components were charged at the following ratios in a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, respectively.

[Polymerization tank]
PP2000 (f2) 500 parts (0.25 mol)
(Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear liquid type)
180 parts of methyl ethyl ketone [drip device]
3-isocyanatopropyltriethoxysilane (f1)
62 parts (0.25 mol)
100 parts of methyl ethyl ketone

  After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 60 ° C. in a nitrogen atmosphere while stirring. Next, the mixture of the silane compound (f1) and the solvent was dropped from the dropping device at a constant rate over 1 hour. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was continued under reflux for 5 hours. Thereafter, 282 g of methyl ethyl ketone was added and then cooled to 30 ° C. or lower to obtain a solution of the reaction product (F) having a nonvolatile content concentration of 50.1% and a hydroxyl value of 25 (mgKOH / g).

(Synthesis Example 22)
The following components were charged at the following ratios in a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, respectively.

[Polymerization tank]
C2090 (f2) 500 parts (0.25 mol)
(Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type)
180 parts of methyl ethyl ketone [drip device]
3-isocyanatopropyltriethoxysilane (f1)
62 parts (0.25 mol)
100 parts of methyl ethyl ketone

  After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 60 ° C. in a nitrogen atmosphere while stirring. Next, the mixture of the silane compound (f1) and the solvent was dropped from the dropping device at a constant rate over 1 hour. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was continued under reflux for 5 hours. Thereafter, 282 g of methyl ethyl ketone was added and then cooled to 30 ° C. or lower to obtain a solution of the reaction product (F) having a nonvolatile content concentration of 50.0% and a hydroxyl value of 24 (mgKOH / g).

(Synthesis Example 23)
The following components were charged at the following ratios in a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, respectively.

[Polymerization tank]
PP2000 (f2) 500 parts (0.25 mol)
(Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear liquid type)
180 parts of methyl ethyl ketone [drip device]
3-isocyanatopropyltrimethoxysilane (f1)
51 parts (0.25 mol)
3-glycidoxypropyltrimethoxysilane 12 parts (0.05 mol)
100 parts of methyl ethyl ketone

  After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 60 ° C. in a nitrogen atmosphere while stirring. Next, a mixture of the silane compound (f1), 3-glycidoxypropyltrimethoxysilane and a solvent was dropped at a constant rate over 1 hour from the dropping device, and the temperature was raised to 80 ° C. after the dropping was completed. The reaction continued for hours. Thereafter, 282 g of methyl ethyl ketone was added, and then cooled to 30 ° C. or lower to obtain a solution of the reaction product (F) having a nonvolatile content concentration of 50.2% and a hydroxyl value of 20 (mgKOH / g).

(Synthesis Example 24)
The following components were charged at the following ratios in a polymerization tank of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a deaeration device, and a nitrogen introduction tube.

[Polymerization tank]
2-glycidoxypropyltrimethoxysilane 23.6 parts (0.1 mol)
Tetramethoxysilane 15.2 parts (0.1 mol)
Acetic acid (acid catalyst) 1 part Purified water 5 parts Methyl alcohol 5 parts Methyl ethyl ketone 17 parts

  After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 60 ° C. in a nitrogen atmosphere while stirring. The reaction was continued for 5 hours under reflux while distilling off the by-produced alcohol. Thereafter, 15 parts of methyl ethyl ketone was added, and then cooled to 30 ° C. or lower to obtain a silane oligomer solution having a nonvolatile content concentration of 50.1%, an average degree of polymerization of 6, and a hydroxyl value of 24 (mgKOH / g).

Table 3 summarizes the hydroxyl values and the like of the reaction products (F) obtained in Synthesis Examples 17 to 24.

  As shown in Tables 1-3, solution appearance, nonvolatile content, weight average molecular weight (Mw) of polyester resin, glass transition temperature (Tg), acid value (AV) and hydroxyl value (OHV) can be determined as follows, I evaluated it.

<Appearance of solution>
The appearance of the solution of the α, β-unsaturated copolymer [PA], the polyester resin [PD] and the reaction product (F) was visually evaluated.

<Measurement of nonvolatile content concentration (TS)>
About 1 g of each solution of α, β-unsaturated copolymer [PA], polyester resin [PD] and reaction product (F) is weighed in a metal container and dried in an oven at 150 ° C. for 20 minutes. The residue was weighed and the remaining rate was calculated to obtain a non-volatile content concentration (solid content concentration, unit:%).

<Measurement of viscosity (Vis) of solution>
The temperature of each solution of copolymer of [alpha], [beta] -unsaturated compound [PA] and polyester resin [PD] is maintained at 25 [deg.] C., using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), 12 rpm, Viscosity (unit: mPa · s) was measured under the condition of minute rotation.

<Measurement of weight average molecular weight (Mn, Mw)>
A copolymer [PA] of an α, β-unsaturated compound and a polyester resin [PD] are dissolved in tetrahydrofuran and subjected to liquid chromatography using GPC (gel permeation chromatograph) “HPC-8020” manufactured by Tosoh Corporation. Separation and quantification based on the difference in molecular size were performed by chromatography, and the number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were determined in terms of polystyrene.

<Measurement of glass transition temperature (Tg)>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.
The copolymer [PA] solution and polyester resin [PD] solution obtained in each synthesis example were applied to a release-treated polyester film, dried, and then dried (A) and polyester resin. About 10 mg of [PD] is scraped, put into an aluminum pan as a sample, weighed and set in a differential scanning calorimeter, and heated at a temperature of 100 ° C. for 5 minutes using the same type of aluminum pan without a sample as a reference. Rapid cooling to −120 ° C. was performed using liquid nitrogen. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the DSC chart obtained during the temperature elevation.

<Measurement of acid value (AV)>
Samples (copolymer [PA] solution: about 30% concentration about 1.5 g, polyester resin [PD] solution: about 50% concentration about 1 g) were accurately weighed in a stoppered Erlenmeyer flask, 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution was added and dissolved. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (unit: mg KOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Non-volatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<Measurement of hydroxyl value (OHV)>
Sample in a stoppered Erlenmeyer flask (copolymer [PA] solution: concentration about 30%, about 1.5 g, polyester resin [PD] solution: concentration about 50%, about 1 g, or reaction product (F)) About 1 g) is weighed accurately and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added and dissolved. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Nonvolatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

Example 1
To 100 parts by weight of the copolymer [PA] solution obtained in Synthesis Example 1, 15 parts by weight of toluene was added, and 1.2 parts by weight of the solution of the reaction product (F) prepared in Synthesis Example 17 was further added. In addition, as a reactive compound (G), 1.5 parts by weight of TDI / TMP (trimethyllopepropane adduct of tolylene diisocyanate) was added and stirred well to obtain a pressure-sensitive adhesive composition. .
This was coated on a release-treated polyester film (hereinafter referred to as “release film”) so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. .
After drying, one side of a polarizing film having a multilayer structure in which both sides of a polyvinyl alcohol (PVA) polarizer are sandwiched between triacetyl cellulose-based protective films (hereinafter referred to as “TAC film”) is bonded to the resin layer. A laminate having a structure of “/ pressure-sensitive adhesive layer / TAC film / PVA / TAC film” was obtained.
Next, the obtained laminate was aged (dark reaction) for 1 week under the condition of a temperature of 23 ° C. and a relative humidity of 50%, and the reaction of the pressure-sensitive adhesive layer was advanced to obtain a pressure-sensitive adhesive optical film.

(Comparative Example 1)
A pressure-sensitive adhesive optical film was prepared in the same manner as in Example 1 except that the reaction product (F) solution obtained in Synthesis Example 17 was not added to the copolymer [PA] solution obtained in Synthesis Example 1. Obtained.

(Comparative Example 2)
Instead of the reaction product (F) solution obtained in Synthesis Example 17 in the copolymer [PA] solution obtained in Synthesis Example 1, the polyol (f2-1) used in Synthesis Example 17, ie, 1 , 8-octanediol A pressure-sensitive adhesive optical film was produced in the same manner as in Example 1 except that 0.5 part by weight was added.

(Comparative Example 3)
Instead of the reaction product (F) solution obtained in Synthesis Example 17 in the copolymer [PA] solution obtained in Synthesis Example 1, the silane compound (f1) used in Synthesis Example 17, ie, 3-isocyanate. A pressure-sensitive adhesive optical film was produced in the same manner as in Example 1 except that 0.8 part by weight of propyltriethoxysilane was added.

(Comparative Example 4)
Instead of the reaction product (F) solution obtained in Synthesis Example 17, 0.8 part by weight of 3-glycidoxypropyltriethoxysilane was added to the copolymer [PA] solution obtained in Synthesis Example 1. A pressure-sensitive adhesive optical film was produced in the same manner as in Example 1 except that.

(Comparative Example 5)
In place of the reaction product (F) solution obtained in Synthesis Example 17 in the copolymer [PA] solution obtained in Synthesis Example 1, X41-1053 (epoxy group-containing, molecular weight: 1660, Shin-Etsu Chemical Co., Ltd.) A pressure-sensitive adhesive optical film was produced in the same manner as in Example 1 except that 0.8 part by weight of the product was added.

(Examples 2 to 6)
Instead of the reaction product (F) solution obtained in Synthesis Example 17 in the copolymer [PA] solution obtained in Synthesis Example 1, the reaction product (F) obtained in Synthesis Examples 18, 21, and 22 was used. ) 1.2 parts by weight (Examples 2, 5 and 6) of the solution and 3 parts by weight (Examples 3 and 4) of the reaction product (F) solution obtained in Synthesis Examples 19 and 20 were added. A pressure-sensitive adhesive optical film was produced in the same manner as Example 1 except for the above.

(Examples 7 to 9)
Instead of TDI / TMP as the reactive compound (G), the copolymer [PA] solution obtained in Synthesis Example 1 was replaced with HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]), TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) in Example 8, and V-05 (“carbodilite V, which is a carbodiimide compound) in Example 9. -05 ": manufactured by Nisshinbo Industries, Inc.) A pressure-sensitive adhesive optical film was produced in the same manner as in Example 1 except that 0.15 part of each was added.

(Example 10)
To the copolymer [PA] solution obtained in Synthesis Example 1, 1.2 parts by weight of the solution of the reaction product (F) obtained in Synthesis Example 17 and 15 parts of isopropyl alcohol (IPA) are added, and further reacted. As a functional compound (G), 0.15 part by weight of Al chelate (aluminum tris (acetylacetonate)) was added and stirred well to obtain a pressure-sensitive adhesive composition of the present invention. Using this, a pressure-sensitive adhesive optical film was produced in the same manner as in Example 1.

(Examples 11 and 12)
Instead of the copolymer [PA] solution obtained in Synthesis Example 1, the copolymer [PA] solution obtained in Synthesis Examples 2 and 5 was used in the same manner as in Example 1, A pressure-sensitive adhesive optical film was produced.

(Examples 13 to 15)
Instead of the copolymer [PA] solution obtained in Synthesis Example 1, the copolymer [PA] solution obtained in Synthesis Examples 3, 4, and 6 was used, respectively. Thus, a pressure-sensitive adhesive optical film was produced.

(Examples 16 to 21)
In contrast to the copolymer [PA] solution obtained in Synthesis Examples 3, 4, and 6 used in Examples 13 to 15, in Examples 16 to 18, XDI / TMP (xylylene range) was used as the reactive compound (G). In Examples 19 to 21, except that 1.5 parts of HMDI / burette (hexamethylene diisocyanate burette adduct) was added as the reactive compound (G) in Examples 19 to 21, respectively. Produced pressure-sensitive adhesive optical films in the same manner as in Examples 13-15.

The pot life and coating processability of the adhesive compositions obtained in Examples and Comparative Examples were evaluated according to the methods described below.
Moreover, about the polarizing plate (laminated body) obtained by the Example and the comparative example, the optical characteristic, the peelability of a peeling film, the rework property of an optical film, heat resistance, and heat-and-moisture resistance were evaluated by the method mentioned later. The results are shown in Table 4.

(Example 22)
2 parts by weight of the reaction product (F) solution obtained in Synthesis Example 17 and toluene with respect to 100 parts by weight of the solution (solid content: about 50%) of the polyester resin [PD1] obtained in Synthesis Example 7 25 parts is added, and 2.5 parts by weight of TDI / TMP (trimethylolpropane adduct body of tolylene diisocyanate) is further added as the reactive compound (G), and the mixture is well stirred, and the pressure-sensitive adhesive of the present invention. A composition was obtained. Using this pressure-sensitive adhesive composition, a pressure-sensitive adhesive optical film was produced in the same manner as in Example 1.

(Comparative Example 6)
A pressure-sensitive adhesive in the same manner as in Example 22 except that the reaction product (F) solution obtained in Synthesis Example 17 is not added to the condensed polyester resin [PD1] solution obtained in Synthesis Example 7. A composition and a pressure-sensitive adhesive optical film were prepared.

(Comparative Example 7)
Instead of the reaction product (F) solution used in Example 22, the polyol (f2-1) used in Synthesis Example 17, that is, 1 part by weight of 1,8-octanediol and 1 part by weight of methyl ethyl ketone were used. Except for this, a pressure-sensitive adhesive composition and a pressure-sensitive adhesive optical film were produced in the same manner as in Example 22.

(Comparative Example 8)
Instead of the reaction product (F) solution used in Example 22, 0.8 part by weight of the silane compound (f1) used in Synthesis Example 17, that is, 3-isocyanatopropyltriethoxysilane, and 1 part by weight of methyl ethyl ketone were added. A pressure-sensitive adhesive composition and a pressure-sensitive adhesive optical film were produced in the same manner as Example 22 except that it was used.

(Comparative Example 9)
Instead of the reaction product (F) solution used in Example 22, as a silane oligomer, 1 part by weight of X41-1056 (containing epoxy group, methyl group, [Shin-Etsu Chemical Co., Ltd.]) and 1 part by weight of methyl ethyl ketone were used. A pressure-sensitive adhesive composition and a pressure-sensitive adhesive optical film were produced in the same manner as in Example 22 except that the above was observed.

(Comparative Example 10)
Except for using 1 part by weight of MAC-2101 (containing an epoxy group, [manufactured by Nippon Unicar Co., Ltd.)] and 1 part by weight of methyl ethyl ketone as a silane oligomer instead of the reaction product (F) solution used in Example 22. In the same manner as in Example 22, a pressure-sensitive adhesive composition and a pressure-sensitive adhesive optical film were produced.

(Comparative Example 11)
In the same manner as in Example 22 except that 1 part by weight of the silane oligomer obtained in Synthesis Example 24 was used instead of the reaction product (F) solution used in Example 22, a pressure-sensitive adhesive composition, and A pressure-sensitive adhesive optical film was produced.

(Examples 23 to 28)
Instead of the reaction product (F) solution obtained in Synthesis Example 17 in the polyester resin [PD] solution obtained in Synthesis Example 7, the reaction product (F) obtained in Synthesis Examples 18, 21 to 23 was used. Except that 2 parts by weight of the solution (Examples 23 and 26 to 28) and 5 parts by weight of the reaction product (F) solution obtained in Synthesis Examples 19 and 20 (Examples 24 and 25) were added, respectively. In the same manner as in Example 22, a pressure-sensitive adhesive composition and a pressure-sensitive adhesive optical film were produced.

(Examples 29 to 30)
In the polyester resin [PD] solution obtained in Synthesis Example 7, as reactive compound (G), instead of TDI / TMP, in Example 29, instead of TDI / TMP, XDI / TMP (xylylene diisocyanate Trimethylolpropane adduct) and HMDI / burette (hexamethylene diisocyanate burette adduct) in Example 30 were added in the same manner as in Example 22 except that 2.5 parts of each were added. And a pressure-sensitive adhesive optical film.

(Examples 31-36)
Instead of the reaction product (F) solution obtained in Synthesis Example 17 in the polyester resin [PD] solution obtained in Synthesis Example 15, the reaction product (F) obtained in Synthesis Examples 18, 21 to 23 was used. Except that 2 parts by weight of the solution (Examples 31 and 34 to 36) and 5 parts by weight of the reaction product (F) solution obtained in Synthesis Examples 19 and 20 (Examples 32 and 33) were added, respectively. In the same manner as in Example 22, a pressure-sensitive adhesive optical film was produced.

(Examples 37 to 38)
In the polyester resin [PD] solution obtained in Synthesis Example 15, as a reactive compound (G), instead of TDI / TMP, in Example 37, XDI / TMP (xylylene diisocyanate) was used instead of TDI / TMP. Trimethylolpropane adduct) and HMDI / burette (hexamethylene diisocyanate burette adduct) in Example 38 were added in the same manner as in Example 22 except that 2.5 parts of each were added. And a pressure-sensitive adhesive optical film.

(Examples 39 to 47)
In the same manner as in Example 22, except that each polyester resin [PD] solution obtained in Synthesis Examples 8 to 16 was used instead of the polyester resin [PD] solution obtained in Synthesis Example 7, the pressure sensitive type was used. An adhesive composition and a pressure-sensitive adhesive optical film were prepared.

(Examples 48 to 50)
Instead of TDI / TMP as the reactive compound (G) in the polyester resin [PD] solution obtained in Synthesis Example 8, in Example 48, HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]), TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) in Example 49, and V-05 (carbodilite V which is a carbodiimide compound in Example 50). -05 ": manufactured by Nisshinbo Industries, Inc.) A pressure-sensitive adhesive composition and a pressure-sensitive adhesive optical film were produced in the same manner as in Example 22 except that 0.25 parts of each was added.

(Example 51)
2 parts by weight of the solution of the reaction product (F) obtained in Synthesis Example 17 and 25 parts of isopropyl alcohol (IPA) are added to the polyester resin [PD] solution obtained in Synthesis Example 8, and a reactive compound is further added. (G) Pressure sensitive adhesive composition and pressure sensitive adhesive as in Example 22 except that 0.25 parts by weight of Al chelate (aluminum tris (acetylacetonate)) was added and stirred well. An optical film was produced.

(Examples 52 to 55)
Instead of the polyester resin [PD] solution obtained in Example 8, the polyester resin [PD] solution obtained in Example 10 was used, and the reactive compound (G) was converted into HBAP, TGMXDA, V-05, respectively. A pressure-sensitive adhesive composition and a pressure-sensitive adhesive optical film were produced in the same manner as in Examples 48 to 51 except that Al chelate was used.

The pot life and coating processability of the adhesive compositions obtained in Examples and Comparative Examples were evaluated by the following methods.
Moreover, about the polarizing plate (laminated body) obtained by the Example and the comparative example, the refractive index of a coating film, an optical characteristic, tack (initial adhesiveness), the peelability of a peeling film, the rework property of an optical film, heat resistance, Wet heat resistance was evaluated by the following method. The results are shown in Tables 5 and 6.

<Evaluation method of pot life>
For the pressure-sensitive adhesive compositions obtained in each of the Examples and Comparative Examples, after adding the reactive compound (G), the viscosity at 25 ° C. was changed every 10 hours until 10 hours until the B type viscometer (manufactured by Tokyo Keiki Co., Ltd.). ) Was measured under the conditions of 12 rpm and 1 minute rotation, and the pot life was evaluated in three stages.
○: “No problem at all. The rate of increase in viscosity up to 8 hours is less than 2 times.”
Δ: “Slight increase in viscosity is observed and the rate of increase in viscosity up to 5 hours is less than 2 times.”
X: “A sudden increase in viscosity was observed and gelled in less than 5 hours.

<Coating process evaluation method>
The pressure-sensitive adhesive composition obtained in each Example and Comparative Example was applied to a release-treated polyester film with a comma coater at a speed of 2 m / min, dried in a 100 ° C. oven, and a thickness of 25 μm. A pressure-sensitive adhesive layer was formed, and a 50 μm thick polyester film was bonded to the surface of the pressure-sensitive adhesive layer to produce a pressure-sensitive adhesive sheet. The state of the coated surface was visually observed and evaluated in three stages.
○: “No problem at all”
Δ: “Slight repellency and foaming are recognized at the end of the coated surface, but there is no practical problem.”
×: “Repelling, foaming and streaking are recognized on the coated surface, and there are practical problems.”

<Evaluation method of refractive index of coating film>
The pressure-sensitive adhesive composition obtained in each Example and Comparative Example using a polyester resin [PD] was coated on a release film, dried in an oven at 120 ° C., and a pressure-sensitive type having a thickness of 25 μm. After providing the adhesive layer, the polyester film was laminated and laminated to prepare an adhesive sheet.
Then, the refractive index of the pressure-sensitive adhesive layer on the adhesive sheet was measured by irradiating sodium D-line in an atmosphere of 25 ° C. with an Abbe refractometer “DR-M2” manufactured by ATAGO.

<Evaluation method of optical characteristics>
The pressure-sensitive adhesive compositions obtained in each Example and Comparative Example were applied to the release-treated polyester film and dried in the same manner as described above to form a pressure-sensitive adhesive layer having a thickness of 25 μm. A pressure-sensitive adhesive sheet in which a release-treated polyester film was bonded to the surface of the pressure-sensitive adhesive layer was obtained. The pressure-sensitive adhesive sheet sandwiched between the release-treated polyester films was aged for one week under conditions of a temperature of 23 ° C. and a relative humidity of 50%. Then, both release-treated polyester films were removed, and the pressure-sensitive adhesive layer alone was removed. While visually judging the appearance, HAZE was measured by “NDH-300A” [manufactured by Nippon Denshoku Industries Co., Ltd.].
○: No problem in practical use. HAZE: less than 1.
(Triangle | delta): Cloudiness etc. are not recognized and it is 1 or more and less than 3.
X: Some cloudiness is recognized or HAZE: 3 or more. There are practical problems.

<Tack (initial adhesion) evaluation method>
The pressure-sensitive adhesive composition obtained in each Example and Comparative Example using the polyester resin [PD] was applied to a release film and dried in the same manner as described above to form a pressure-sensitive adhesive layer having a thickness of 25 μm. And a polyester film was bonded to the surface of the pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer sandwiched between the release film and the polyester film is aged for one week at a temperature of 23 ° C. and a relative humidity of 50%, then the release film is removed and the adhesive layer is removed using the J · Dow rolling ball method. The measurement was performed under the conditions of 23 ° C. and 65% RH.
○: “Sufficient tack appears. Ball value: # 8 or more.”
Δ: “Tack is weak, but there is no practical problem. Ball value: # 3 to # 8.”
X: “There is almost no tack and poor initial adhesion. Ball value: less than # 3.”

<Releasability of release film>
Using the pressure-sensitive adhesive compositions obtained in each Example and Comparative Example, a laminate having a configuration of “release film / pressure-sensitive adhesive layer / TAC film / PVA / TAC film” was obtained.
Next, the obtained laminate was aged at a temperature of 23 ° C. and a relative humidity of 50% for 1 week, and then the release film covering one surface of the pressure-sensitive adhesive layer was peeled off, and the peelability at that time (JIS K6301). In accordance with the peel strength and transferability of the adhesive to the release film).
Separately, the obtained laminate was aged for 3 weeks at a temperature of 23 ° C. and a relative humidity of 50%, and then the release film was peeled off in the same manner, and the peelability at that time was evaluated.
○: “The peel strength after 3 weeks is less than 1.2 times that after aging for 1 week, and there is no transfer of the adhesive to the release film, and there is no problem in practical use.”
Δ: “The peel strength after 3 weeks is 1.2 times or more and less than 1.5 times after aging for 1 week, there is no transfer of the adhesive to the release film, and there is no practical problem.”
X: “The peel strength after 3 weeks is 1.5 times or more after aging for 1 week, or the transfer of the adhesive to the release film is observed.

<Evaluation method of removability (reworkability) of optical film>
The pressure-sensitive adhesive optical film obtained in each Example and Comparative Example was cut into a size of 25 mm × 150 mm, the release film was peeled off, and was attached to a float glass plate with a thickness of 1.1 mm using a laminator, 50 ° C. And kept in an autoclave at 5 atm for 20 minutes to obtain a laminate of a polarizing plate and a glass plate.
The laminate was allowed to stand at 23 ° C. and 50% relative humidity for 1 week, and then peeled off at a speed of 300 mm / min in the direction of 180 °. The haze on the glass surface after peeling was visually observed and evaluated in three stages.
○: “No cloudiness, no problem in practical use”
Δ: “Slightly cloudy, but practically no problem”
X: “Transfer of the adhesive layer is recognized over the entire surface and is not practical”.

<Method for evaluating heat resistance and heat and humidity resistance>
The pressure-sensitive adhesive optical film obtained in each example and comparative example was cut into a size of 150 mm × 80 mm, the release film was peeled off, and the absorption of each polarizing plate on both surfaces of a 1.1 mm thick float glass plate The laminator was used to stick the axes so that they were orthogonal. Subsequently, the glass plate on which the polarizing plate was attached was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to obtain a laminate of the polarizing plate and the glass plate.

  Floating peeling and displacement after leaving the laminates obtained in each Example and Comparative Example at 80 ° C. for 1000 hours and 100 ° C. for 1000 hours, and light leakage when light is transmitted through the laminates (White spots) were visually observed to evaluate heat resistance.

  In addition, the laminate obtained in each of the examples and comparative examples was left to stand at 60 ° C. and a relative humidity of 90% for 1000 hours, and at 80 ° C. and a relative humidity of 90% for 1000 hours. Light leakage (white spots) when light was transmitted through the laminate was visually observed to evaluate moisture and heat resistance.

The “displacement” is the displacement of the attaching position observed around the polarizing plate attached to the glass due to the contraction of the polarizing plate.
The heat resistance and moist heat resistance were evaluated based on the following four criteria.

A: “No floating peeling, no whitening, no displacement, and no problem in practical use”
○: “No floating peeling or whitening is observed, the displacement is less than 0.2 mm, and there is no practical problem.”
Δ: “Slightly floating peeling or whitening is observed, but the deviation is less than 02 to 0.5 mm, and there is no practical problem”
X: “There are floating floats and white spots on the entire surface, which is not practical”.

As described above, it can be seen that the pressure-sensitive adhesive composition of the present invention is excellent in coating processability, heat resistance, heat and humidity resistance, optical properties, peelability of the release film, and reworkability of the optical film.
On the other hand, in Comparative Examples 1 and 6 that do not contain the reaction product (F), it can be seen that the reworkability is poor. Moreover, it has the isocyanate group and the alkyl alkoxy group which are the other raw materials of the reaction products (F), and the comparative examples 2 and 7 which contain the polyol (f2) which is not the reaction product (F) but the raw material. In Comparative Examples 3 and 8 containing a silane compound (f1), foaming or peeling off occurs after being stuck to a glass plate for a long time under further severe high temperature or high temperature and high humidity. Inferior to sex.
Furthermore, in the case of Comparative Example 4 using 3-glycidoxypropyltriethoxysilane instead of the reaction product (F), the adhesion to the glass plate is improved, but foaming or the like occurs under more severe conditions. It becomes easy to do.
Moreover, Comparative Examples 5 and 9 to 11 using a silane oligomer instead of the reaction product (F) are rich in high durability after being attached to a glass plate, but on the other hand, the peelability of the peelable film is remarkable. bad.

Claims (11)

Reaction product (Polymer [P] having a glass transition temperature of −80 to 10 ° C. having at least one of a carboxyl group and a hydroxyl group, a silane compound (f2) having an isocyanate group and an alkoxysilyl group, and a polyol (f1) ( F), including a reaction product (F) containing a hydroxyl group and an alkoxysilyl group, and a reactive compound (G) capable of reacting with at least one of a carboxyl group or a hydroxyl group in the polymer [P]. A pressure-sensitive adhesive composition. The reaction product (F) reacts the silane compound (f2) having an isocyanate group and an alkoxysilyl group with the polyol (f1) at (f1) :( f2) = 3 to 9: 7 to 1 (mol ratio). The pressure-sensitive adhesive composition according to claim 1, wherein The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the polyol (f1) has a number average molecular weight (Mn) of 100 to 50,000 and a hydroxyl value of 5 to 1,000 (mgKOH / g). object. The pressure sensitive adhesive composition according to any one of claims 1 to 3, wherein the hydroxyl value of the reaction product (F) is 3 to 200 (mgKOH / g). The pressure-sensitive type according to any one of claims 1 to 4, wherein the polymer [P] is a copolymer [PA] or a polyester resin [PD] obtained by copolymerizing an α, β-unsaturated compound. Adhesive composition. Copolymer [PA] is an α, β-unsaturated compound having a carboxyl group or an α, β-unsaturated compound having a hydroxyl group, and another α, β-unsaturated compound other than the above two A copolymer of
The α, β-unsaturated compound having a carboxyl group is propenoic acid or 2-methylpropenoic acid,
The α, β-unsaturated compound having a hydroxyl group is a propenoic acid derivative having a hydroxyl group or a 2-methylpropenoic acid derivative having a hydroxyl group,
The other α, β-unsaturated compound is a propenoic acid derivative having neither a carboxyl group nor a hydroxyl group, and a 2-methylpropenoic acid derivative having neither a carboxyl group nor a hydroxyl group. 5. The pressure-sensitive adhesive composition according to 5. Α, β-unsaturated compound having a carboxyl group, α, β-unsaturated compound having a hydroxyl group, and α, β-unsaturated compound other than the two mentioned above in a total of 100% by weight, The pressure-sensitive adhesive composition according to claim 6, wherein the total of the β-unsaturated compound and the α, β-unsaturated compound having a hydroxyl group is 0.01 to 20% by weight. 6. The pressure sensitive adhesive composition according to claim 5, wherein the polyester resin [PD] is a condensation type polyester resin [PD1] or an addition type polyester resin [PD2]. Condensed polyester resin [PD1]
A dibasic acid component (A) having no hydroxyl group;
A diol (B) having no carboxyl group;
A trihydric or higher polyhydric alcohol (c1), a trihydric or higher polyhydric carboxylic acid (c2), a compound having two cyclic ether groups in the molecule (c3), two hydroxyl groups and one carboxyl group in one molecule At least one side-chain functional group-introducing component selected from the group consisting of dioxycarboxylic acid (c4) having the above and oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule ( The pressure-sensitive adhesive composition according to claim 8, which is a condensation-type polyester resin [PD1-1] obtained by reacting with C). The above-mentioned cyclic ester compound (E), wherein the condensed polyester resin [PD1] is obtained by ring-opening addition of a cyclic ester compound (E) to the side chain functional group in the condensed polyester resin [PD1-1]. The pressure-sensitive adhesive composition according to claim 9, which is a polyester resin [PD1-2] having a ring-opening portion as a side chain and a hydroxyl group at the terminal of the ring-opening portion. 11. A pressure-sensitive adhesive optical film comprising an optical film and a pressure-sensitive adhesive layer located on at least one surface of the optical film, wherein the pressure-sensitive adhesive layer is a pressure-sensitive adhesive according to claim 1. A pressure-sensitive adhesive optical film formed from a composition.