JP2006299252A - Pressure-sensitive adhesive composition and utilization thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive composition capable of providing an adhesive layer having excellent adhesiveness to a base material or an adherend, heat resistance, moist heat resistance and transparency; and to provide a laminate obtained by using the composition. <P>SOLUTION: The pressure-sensitive adhesive composition contains (1) a composite resin obtained by polymerizing (b) an α,β-unsaturated compound in the presence of (A) a urethane-modified polyester obtained by reacting (a1) a polyester polyol having 5,000-100,000 weight average molecular weight and a cyclic structure with (a2) a polyisocyanate compound, and having a functional group X, and (2) a compound having a functional group Y reactable with the functional group X. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition excellent in adhesion to various substrates and adherends, heat resistance, moist heat resistance and transparency, and in particular, a pressure-sensitive adhesive composition for optical members and the like It is related with the adhesion laminated body which uses this.

Due to the dramatic progress of electronics in recent years, various flat 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 the field. 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.
A polarizing film and a retardation film are laminated on a glass member for a liquid crystal cell constituting the LCD.
These display devices use an antireflection film for preventing reflection from an external light source, a protective film (protection film) for preventing scratches on the surface of the display device, and the like.
Furthermore, the FPD is not only used as a display device, but also provided with a touch panel function on the surface thereof, and may be used as an input device. A protective film, an antireflection film, an ITO vapor deposition resin film, and the like are also used for this touch panel.

Various films used in the display device are used by being attached to an adherend with a pressure-sensitive adhesive. Since it is used for a display device, the pressure-sensitive adhesive is first required to be excellent in transparency. Therefore, 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 protective films. Because of the characteristics of the materials that make up each layer, the polarizing film undergoes significant dimensional changes due to expansion and contraction due to heat and humidity.

Therefore, the acrylic pressure-sensitive adhesive for sticking the polarizing film to the glass member for a liquid crystal cell is required to suppress the dimensional change of the polarizing film itself.
By making the pressure-sensitive adhesive layer itself hard or increasing the adhesive strength, it is possible to suppress a relatively small dimensional change or a relatively short-term dimensional change.
However, with the recent increase in screen size of liquid crystal panels, the size of the polarizing film has also increased, and the amount of thermal deformation of the polarizing film has increased. When using a conventional pressure-sensitive adhesive, the stress at the time of sticking remaining in the adhesive layer is not sufficiently relaxed, so the adhesive layer cannot sufficiently follow the distortion of the polarizing film. When exposed to high temperature or high humidity, there is a problem that the polarizing film peels off from the glass substrate of the large liquid crystal cell, stress concentration occurs on the polarizing film, and light leakage occurs on the large liquid crystal panel.

  In addition, the polarizing film changes in dimensions while the liquid crystal panel is used over a long period of time, and the stress is accumulated in the adhesive layer. If the stress continues to accumulate in the adhesive layer, the distribution of the adhesive force between the polarizing film and the liquid crystal cell glass member becomes non-uniform. During long-term use, stress is concentrated especially on the periphery of the polarizing film, and as a result, the periphery of the liquid crystal element is brighter or darker than the center. appear.

In addition, after laminating a polarizing film on the glass surface for a liquid crystal cell to make a laminate, in the inspection process, peel off the polarizing film etc. from the glass cell surface for those involving air or dust in the laminating process. Then, a new polarizing film or the like is pasted again.
However, generally after lamination, the laminate is stored at a high temperature for a certain period of time to promote adhesion, and then inspected. During that time, the peel strength becomes too high and it is difficult to peel off the polarizing film, etc. After that, adhesive residue is generated, and the removability is insufficient.

  As described in detail, the pressure-sensitive adhesive used for laminating a polarizing film on a liquid crystal cell requires good optical properties (transparency), heat resistance and moist heat resistance, good stress relaxation, and removability. It is done. And the same performance is calculated | required also for the pressure sensitive adhesive for laminating | stacking the retardation film and the cover film of various displays.

Various pressure sensitive adhesives have been proposed for these various requirements.
For example, a pressure-sensitive adhesive composed of an acrylic resin whose main component is an alkyl ester of (meth) acrylic acid having 1 to 12 carbon atoms in the alkyl group, the pressure-sensitive adhesive having a weight average molecular weight of 100,000 or less There is known a pressure-sensitive adhesive made of an acrylic resin containing 15% by weight or less of a resin component and 10% by weight or more of a polymer component having a weight average molecular weight of 1 million or more (see, for example, Patent Document 1). .

  A copolymer having a weight average molecular weight of 500,000 to 2,000,000, which is obtained by copolymerizing an alkyl ester of (meth) acrylic acid, a functional group component, and a specific macromonomer having an α, β-unsaturated group. There is known a pressure-sensitive adhesive mainly composed of A (see, for example, Patent Document 2).

  Furthermore, 100 parts by weight of a high molecular weight (meth) acrylic copolymer having a weight average molecular weight of 1 million or more, and 20 to 200 parts by weight of a low molecular weight (meth) acrylic copolymer having a weight average molecular weight of 30,000 or less, A pressure sensitive adhesive for polarizing plates comprising 0.005 to 5 parts by weight of a polyfunctional compound is known (see, for example, Patent Document 3).

  Furthermore, a high molecular weight acrylic resin having a reactive functional group and a weight average molecular weight of 1 million to 2.5 million, and a low molecular weight acrylic having a glass transition point (Tg) of 0 ° C. to −80 ° C. and a weight average molecular weight of 30,000 to 100,000 A pressure-sensitive adhesive for polarizing films made of a polyfunctional compound having a functional group capable of forming a crosslinked structure with a resin is known (for example, see Patent Document 4).

  By using the pressure-sensitive adhesive, foaming of the adhesive layer and lifting off of the polarizing plate from the liquid crystal cell can be suppressed, but stress due to dimensional change of the polarizing plate cannot be absorbed or relaxed, and the periphery of the polarizing plate Since the stress is concentrated on the portion, the brightness of the peripheral portion and the central portion of the liquid crystal display device is different, and there is a problem that color unevenness and whitening occur on the surface of the liquid crystal display device.

In addition to the acrylic pressure-sensitive adhesive containing an acrylic resin and a crosslinking agent, there are also pressure-sensitive adhesives formed by using a polyester resin or a polyurethane resin in combination with an acrylic resin.
For example, a pressure-sensitive adhesive containing a mixture of a viscoelastic resin having a glass transition point (Tg) of −60 to −5 ° C. and an elastic resin such as a polyurethane resin having a glass transition point (Tg) of −5 ° C. or less is known. (For example, see Patent Document 5).

  Moreover, a pressure-sensitive adhesive containing 10 to 50 parts by weight of an amino group-containing polyurethane resin with respect to 100 parts by weight of an acrylic resin is known (see, for example, Patent Document 6).

  Furthermore, a pressure-sensitive adhesive containing a hydroxyl group-containing polyurethane resin mixed with an acrylic resin is known (for example, see Patent Document 7).

  Furthermore, a pressure-sensitive adhesive containing a polyester resin such as polycaprolactone mixed with an acrylic resin is known (for example, see Patent Document 8).

  It is generally considered that a pressure-sensitive adhesive obtained by mixing various resins can compensate for the shortcomings of each resin, improve the adhesion to the adherend, and improve various performances. However, the acrylic resin and the polyester resin or polyurethane resin are not compatible with each other, and if they are mixed only slightly, the transparency is not impaired so much, but if you try to mix a little more polyester resin or polyurethane resin. The pressure-sensitive adhesive itself is whitened or separated. The pressure-sensitive adhesive for sticking a polarizing film or the like to a glass for a liquid crystal cell is required to have extremely high transparency. And even if it tried to stick a polarizing film etc. to the glass for liquid crystal cells using such a pressure-sensitive-type adhesive agent, there existed a problem that phase separation and fluctuation | variation generate | occur | produced in a contact bonding layer.

On the other hand, a method for producing a pressure-sensitive adhesive obtained by polymerizing an acrylic resin containing an alkylene oxide group in polyester in order to improve low-temperature adhesion to a polyolefin-based adherend is known (for example, patents). Reference 9).
The pressure-sensitive adhesive by the production method described in Patent Document 9 is effective in improving the elastic modulus of the pressure-sensitive adhesive derived from polyester. However, the obtained resin is less flexible. It is also difficult to ensure transparency. Furthermore, since polyether such as alkylene oxide is an essential component, it is difficult to satisfy heat resistance and moist heat resistance. Therefore, it is not suitable for a pressure-sensitive adhesive for attaching an optical film such as a polarizing film or a retardation film.

In addition, a pressure-sensitive adhesive obtained by blending a polyisocyanate compound with a composite resin obtained by polymerizing an unsaturated monomer in the presence of a polyurethane resin is known (for example, see Patent Document 10). And it is described that it is preferable to use together polyester polyol and polyether polyol as a polyol which comprises a polyurethane resin.
The pressure-sensitive adhesive described in Patent Document 10 is suitable for general labels, sheets, tapes and the like. However, since polyether polyol is used as the polyol constituting the urethane resin, it is highly hydrophilic and easily deteriorates by heat at a relatively low temperature. Moreover, even if it uses polyester polyol together, since the polyester polyol is comparatively low molecular weight, it is difficult to suppress the thermal deterioration of polyether polyol. In a composite resin obtained from such a polyurethane resin, it is difficult to satisfy the heat resistance and heat-and-moisture resistance required for pressure-sensitive adhesives for attaching optical films such as polarizing films and retardation films. .
JP-A-1-66283 Japanese Unexamined Patent Publication No. Hei 8-209090 JP-A-10-279907 JP 2002-121521 A JP 2003-73646 A JP 2004-2827 A JP 2004-83648 A JP 2002-53835 A JP-A-5-320607 Japanese Unexamined Patent Publication No. 2000-328035

  An object of the present invention is to provide a pressure-sensitive adhesive composition capable of forming an adhesive layer excellent in adhesion to a substrate, adhesion to an adherend, heat resistance, moist heat resistance and transparency, and using the same. It is to provide a laminate.

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, the first invention is the presence of a urethane-modified polyester (A) obtained by reacting a polyester polyol (a1) having a cyclic structure having a weight average molecular weight of 5,000 to 100,000 with a polyisocyanate compound (a2). A composite resin (1) having a functional group X obtained by polymerizing an α, β-unsaturated compound (b) and a compound (2) having a functional group Y capable of reacting with the functional group X are contained. It is a pressure-sensitive adhesive composition.

In the second invention, the urethane-modified polyester (A) comprises a polyol component other than the polyether polyol in addition to the polyester polyol (a1) as a constituent component. The pressure-sensitive adhesive composition of the first invention It is.
In the third invention, the glass transition point of the urethane-modified polyester (A) is in the range of −50 to 50 ° C., and the weight average molecular weight is in the range of 10,000 to 500,000. Pressure-sensitive adhesive composition.

The fourth invention is characterized in that at least one of the urethane-modified polyester (A) or the α, β-unsaturated compound (b) has a hydroxyl group and / or a carboxyl group as the functional group X. The pressure-sensitive adhesive composition according to any one of the inventions.
In the fifth invention, the urethane-modified polyester (A) is 2 to 90% by weight in the total of 100% by weight of the urethane-modified polyester (A) and the α, β-unsaturated compound (b), and α, β-unsaturated. The pressure-sensitive adhesive composition according to any one of the first to fourth inventions, wherein the compound (b) is 10 to 98% by weight.

A sixth invention is the pressure-sensitive adhesive composition according to any one of the first to fifth inventions, wherein the composite resin (1) has a weight average molecular weight of 50,000 to 2,000,000.
7th invention contains 0.001-20 weight part of compounds (2) which have a functional group Y with respect to 100 weight part of composite resin (1), Any of 1-6 invention characterized by the above-mentioned. The pressure-sensitive adhesive composition described.

  An eighth invention is an adhesive laminate comprising an adhesive layer and an optical member formed from the pressure-sensitive adhesive composition according to any one of the first to seventh inventions.

  A ninth invention is a liquid crystal cell member in which a glass member for a liquid crystal cell, an adhesive layer formed from the pressure-sensitive adhesive composition according to any one of the first to seventh inventions, and an optical member are sequentially laminated.

  In a tenth aspect of the invention, a urethane-modified polyester (A) is obtained by reacting a polyester polyol (a1) having a cyclic structure having a weight average molecular weight of 5,000 to 100,000 with a polyisocyanate compound (a2). The α, β-unsaturated compound (b) is polymerized in the presence of the modified polyester (A) to obtain a composite resin (1) having a functional group X, and then the composite resin (1) and the functional group X And a compound (2) having a functional group Y capable of reacting with the pressure-sensitive adhesive composition.

  By using the pressure-sensitive adhesive composition of the present invention, foaming or peeling does not occur even under severer heat or wet heat conditions than in the past, particularly in optical member applications that require heat resistance and moist heat resistance. In addition, it is possible to provide an optical member that relaxes stress concentration caused by expansion and contraction of a polarizing plate and does not cause color unevenness or whitening in a liquid crystal element.

The matters necessary for carrying out the present invention are specifically described below.
The pressure-sensitive adhesive composition of the present invention comprises a composite resin (1) having a functional group X and a compound (2) having a functional group Y capable of reacting with the functional group X.
The composite resin (1) having a functional group X is an interpenetrating polymer in which a urethane-modified polyester (A) and a polymer formed from an α, β-unsaturated compound (b) are closely intertwined and molecular chains are entangled with each other. A structure (interpenetrated polymer network, IPN) is formed.

That is, first, in the first step, the polyester polyol (a1) having a cyclic structure and the polyisocyanate compound (a2) are reacted to obtain a urethane-modified polyester (A), and then the urethane-modified polyester (A) is α , Β-unsaturated compound (b) is swollen, and specifically, both are sufficiently mixed until transparent, and the α, β-unsaturated compound (b) is polymerized to obtain urethane-modified polyester (A) and A composite resin (1) having a functional group X having an IPN structure containing a polymer formed from an α, β-unsaturated compound (b) is obtained.
Next, in the second step, the composite resin (1) having the functional group X and the compound (2) having the functional group Y capable of reacting with the functional group X are mixed to obtain a pressure-sensitive adhesive composition.
In the third step, when the pressure-sensitive adhesive composition is applied to a sheet-like substrate and dried to obtain a pressure-sensitive adhesive sheet, the functional group X and the functional group Y in the pressure-sensitive adhesive are combined. By reacting, the composite resin (1) having an IPN structure is cured and crosslinked to form an adhesive layer.

That is, since the α, β-unsaturated compound (b) is mixed in the monomer unit with the urethane-modified polyester (A) and polymerized, the urethane-modified polyester (A) and the α, β-unsaturated compound ( A composite resin (1) having an IPN structure can be obtained from the polymer formed from b). A part of the polymer formed from the α, β-unsaturated compound (b) may be grafted and bonded to the urethane-modified polyester (A).
Unlike a simple mixture of urethane-modified polyester (A) and a polymer formed from α, β-unsaturated compound (b), IPN composite resin (1) is nanoscale and both are molecular units. Since they are intricately entangled with each other and bonded in some cases, the pressure-sensitive adhesive of the present invention and the adhesive layer formed from the pressure-sensitive adhesive are excellent in transparency.
In addition, since the functional group X is uniformly distributed throughout the composite resin (1) on a micro scale, when the glass is re-applied to the liquid crystal cell glass, there is no contamination such as adhesive residue or cloudiness on the glass. Even when the polarizing film attached to the glass for a liquid crystal cell using such a pressure-sensitive adhesive is exposed to more severe heat or wet heat conditions, the volume shrinkage of the polarizing film can be suppressed.

<Urethane modified polyester (A)>
The urethane-modified polyester (A) is obtained by reacting a polyester polyol (a1) having a cyclic structure with a polyisocyanate compound.
First, the polyester polyol (a1) having a cyclic structure will be described.
The polyester polyol (a1) having a cyclic structure is obtained by polymerizing a polyvalent carboxylic acid component and a polyol component according to a conventional method, and is amorphous from the viewpoint of heat resistance and heat and humidity resistance of the pressure-sensitive adhesive. Preferably there is.

As the polyvalent carboxylic acid component, aromatic, aliphatic or alicyclic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids can be used as appropriate.
Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, o-phthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1 , 2-bisphenoxyethane-p, p′-dicarboxylic acid, phenylindanedicarboxylic acid and the like, and ester-forming derivatives thereof.
Examples of the aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4 -Cyclohexanedicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3- Cyclohexene-1,2-dicarboxylic acid and the like, and ester-forming derivatives thereof can be used.
Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, 1,2 , 3,4-butanetetracarboxylic 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, polyvalent carboxylic acid such as ethylenetetracarboxylic acid, and alkali metal salts, alkaline earth metal salts, Monium salt etc. can be used

Moreover, what contains a sulfonic acid group and a sulfonate group can also be used as needed.
Examples of such include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfo-p-xylylene glycol, 2-sulfo-1, Examples thereof include 4-bis (hydroxyethoxy) benzene and alkali metal salts, alkaline earth metal salts and ammonium salts thereof.

  Examples of the polyol component constituting the polyester polyol (a1) having a cyclic structure include ethylene glycol, diethylene glycol, propylene glycol, 1,3-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, 2,4-dimethyl-2-ethylhexane-1 , 3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexane Methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4′-thiodiphenol, bisphenol A, 4, 4'-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 4 , 4′-isopropylidenebin diol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, polyamide diol, polyester amide diol, etc. it can.

The polyester polyol (a1) having a cyclic structure is composed of a polyvalent carboxylic acid component and a polyol component, and at least one of the polyvalent carboxylic acid component or the polyol component has a cyclic structure. is important. A part or all of the polyvalent carboxylic acid component may have a cyclic structure. Similarly, part or all of the polyol component may have a cyclic structure.
The cyclic structure referred to in the present invention means an aromatic ring structure such as a benzene ring or a naphthalene ring, or an alicyclic structure such as a cyclohexane ring. By introducing a polyester polyol having a cyclic structure, the heat resistance and heat-and-moisture resistance of the pressure-sensitive adhesive are improved.
In the present invention, if a polyol component having a branch in the side chain such as neopentyl glycol or a polyvalent carboxylic acid component having a cyclic structure in which the carboxyl group is in the ortho-position or meta-position is an essential component, an amorphous structure is easily obtained. Particularly preferred for maintaining the transparency of the pressure-sensitive adhesive.

The polyester polyol (a1) having a cyclic structure can be produced according to a conventionally known polyester production method.
For example, a polycarboxylic acid component such as terephthalic acid and isophthalic acid and a polyol component such as ethylene glycol are directly esterified (polycondensation) in the molten state, or a dialkyl ester of a dicarboxylic acid is used as the polyvalent carboxylic acid component. In the case of using a polyester, a transesterification reaction between a dialkyl ester of a dicarboxylic acid and a polyol component is carried out in a molten state, and in either case, the excess polyol component is then removed by heating under reduced pressure to produce a polyester polyol. Can do.
The direct esterification reaction or transesterification reaction can be carried out either batchwise or semi-continuously.

In obtaining the polyester polyol (a1), various catalysts can be used.
As the catalyst for polycondensation, compounds such as antimony, germanium, titanium and the like can be used. Specific examples of the ester exchange reaction catalyst include compounds such as magnesium, manganese, titanium, zinc, calcium, and cobalt.
The addition amount of these catalysts may be arbitrary as long as the heat resistance and transparency of the formed polyester polyol are not impaired and the reactivity between the formed polyester polyol and the polyisocyanate compound is not impaired.
For example, in the case of direct esterification (polycondensation), the polycondensation catalyst is 0.0005 to 0.2 mol%, preferably in terms of metal atoms in the polycondensation catalyst, based on the polyvalent carboxylic acid component, It is desirable to use in an amount of 0.001 to 0.1 mol%.

Further, when a polyester polyol is obtained using a direct esterification reaction or transesterification reaction in a molten state, a stabilizer such as a phosphorus compound may be added.
Specific examples of the phosphorus compound include phosphoric triesters such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, triphenyl phosphite, and trisdodecyl phosphite. Phosphorous esters such as trisnonylphenyl phosphite, phosphoric acid esters such as methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate and phosphorous compounds such as phosphoric acid and polyphosphoric acid Can be mentioned.

A polyester polyol obtained by utilizing a direct esterification reaction or transesterification reaction in a molten state is usually melt-extruded and formed into a pellet or a sheet.
In the present invention, the polyester once molded may be further subjected to solid phase polycondensation in a non-molten state at a temperature lower than the melting point. For example, the pelletized polyester obtained above is heated at a temperature of 160 ° C. to less than the melting point, preferably 170 to 220 ° C. for 8 to 40 hours, more preferably 15 to 30 hours, and the pressure is usually 700 to 10 Torr, preferably Can be subjected to a solid-phase polycondensation reaction under an atmosphere of an inert gas such as nitrogen gas, argon gas, carbon dioxide gas under conditions of normal pressure to 100 Torr. Of these inert gases, nitrogen gas is preferred.

The weight average molecular weight (Mw) of the polyester polyol (a1) having a cyclic structure thus obtained is important to be in the range of 5,000 to 100,000, and in the range of 8,000 to 50,000. It is preferable that it exists in. If the Mw is less than 5,000, the cohesive force of the urethane-modified polyester cannot be expressed, and the heat resistance and heat-and-moisture resistance are reduced. On the other hand, when Mw exceeds 100,000, the compatibility between the urethane-modified polyester and a polymer of an α, β-unsaturated compound (b) described later is lowered, and the transparency of the composite resin is impaired.
The weight average molecular weight (Mw) is a value in terms of polystyrene measured by gel permeation chromatograph (GPC, solvent: tetrahydrofuran).

The polyester polyol (a1) having a cyclic structure must have a hydroxyl group capable of reacting with the polyisocyanate compound (a2) described later, and the hydroxyl value is preferably in the range of 2 to 300 (KOHmg / g), It is more preferable that it is 3-100 (KOHmg / g).
If the hydroxyl value is less than 2, it is difficult to obtain a urethane-modified polyester (A) that satisfies the flexibility. On the other hand, when the hydroxyl value exceeds 300, hydroxyl groups that do not participate in the reaction with the polyisocyanate compound (a2) are likely to remain in the urethane-modified polyester, and the heat-and-moisture resistance of the pressure-sensitive adhesive decreases.

The acid value of the polyester polyol (a1) having a cyclic structure is preferably in the range of 0.1 to 30 (KOHmg / g), more preferably 1 to 10 (KOHmg / g).
Since the polyester polyol having an acid value of less than 0.1 has an excessively large weight average molecular weight, compatibility with a polymer of an α, β-unsaturated compound (b) described later is lowered. On the other hand, since the polyester polyol having an acid value of more than 30 has a weight average molecular weight that is too small, it adversely affects the heat resistance of the pressure-sensitive adhesive.

Moreover, the glass transition point (Tg) of the polyester polyol (a1) having a cyclic structure is preferably −70 ° C. to 60 ° C., and more preferably −20 to 20 ° C. When the temperature is less than -70 ° C, the elasticity of the urethane-modified polyester (A) is lowered, and its own cohesive force tends to be lowered. On the other hand, when the temperature exceeds 60 ° C., the adhesion between the adhesive layer and the adherend is lowered, and the floating is likely to occur.
The glass transition point (Tg) is a value measured with a differential scanning calorimeter (DSC, heating rate 10 ° C./min).

When obtaining the urethane-modified polyester (A), in addition to the polyester polyol (a1), if necessary, other polyols can be used in combination.
Other polyols include compounds having three or more hydroxyl groups such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, methylglucoside;
A polyamide polyol, a polyesteramide polyol, a polycarbonate polyol, and a urethane polyol having a hydroxyl group at the end obtained by reacting them with the following polyisocyanate compound (a2) of less than an equivalent molar equivalent;
One or more of these can be used.
From the viewpoint of heat resistance and heat and humidity resistance, those containing many ether bonds such as polyether polyol are not preferred. More preferred is polycarbonate polyol, and specific examples include Kuraray Polyol C series from Kuraray Co., Ltd.

The urethane-modified polyester (A) is obtained by reacting the polyester polyol (a1) having the above cyclic structure and, if necessary, another polyol with the polyisocyanate compound (a2).
A conventionally well-known thing can be used as a polyisocyanate compound (a2).
For example, aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate and the like can be mentioned.

  Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-triisocyanate. Range isocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 " -Triphenylmethane triisocyanate etc. can be mentioned.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate. 2,4,4-trimethylhexamethylene diisocyanate and the like.

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

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

  In addition, a trimethylolpropane adduct of the above polyisocyanate, a trimer having an isocyanurate ring, etc. 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.

  As these polyisocyanate compounds (a2), 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate; IPDI), xylylene diisocyanate From the viewpoint of weather resistance, it is particularly preferable to use a non-yellowing or hard yellowing polyisocyanate compound such as 4,4′-methylenebis (cyclohexyl isocyanate) (hydrogenated MDI).

  In the reaction of the polyester polyol (a1) having a cyclic structure and other polyols used as necessary with the polyisocyanate compound (a2), a known catalyst can be used as necessary. For example, a tertiary amine compound, an organometallic compound and the like can be mentioned, and they may be used alone or in combination.

  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 and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate, naphthene Zirconium-based compounds such as zirconium acid are listed.
Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

The urethane-modified polyester (A) can be produced according to a known polyurethane production method from the polyester polyol (a1) having the above cyclic structure and, if necessary, another polyol and the polyisocyanate compound (a2), In particular, it is roughly divided into the following two methods.
1) a polyester polyol (a1) having a cyclic structure, another polyol as necessary, a polyisocyanate compound (a2), and a compound having a functional group capable of reacting with an isocyanate group and an ionic functional group as necessary, And / or a method in which a solution consisting of a solvent and / or a catalyst is charged into the reaction vessel in its entirety.
2) Reaction container containing polyester polyol (a1) having a cyclic structure, another polyol as necessary, and a compound having a functional group capable of reacting with an isocyanate group and an ionic functional group, and / or a solvent, if necessary And adding a catalyst as needed after adding the polyisocyanate compound (a2) dropwise.
When the reaction is precisely controlled, the method 2) is preferred. The reaction temperature during urethanization is preferably 120 ° C. or lower. More preferably, it is 50-110 degreeC. When the temperature is higher than 120 ° C., it becomes difficult to control the reaction rate, and it becomes difficult to obtain a urethane-modified polyester having a preferable weight average molecular weight. The urethane modification reaction is preferably performed at 50 to 110 ° C. for 1 to 20 hours in the presence of a catalyst.
Examples of the compound having a functional group capable of reacting with an isocyanate group such as a hydroxyl group or a methylol hydroxyl group and an ionic functional group such as a carboxyl group, which are used as necessary, include dimethylolpropionic acid and 2,2-dimethylol. Examples include anionic functional group-containing polyols such as acetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, and dihydroxypropionic acid. When such an anionic functional group-containing polyol is used, an anionic functional group such as a carboxylic acid can be held as a side chain.

The polyester polyol (a1) having a cyclic structure is preferably 10 to 99% by weight and more preferably 15 to 80% by weight in 100% by weight of all the components constituting the urethane-modified polyester (A). Of the components constituting the urethane-modified polyester (A), the component other than the polyester polyol (a1) having a cyclic structure is other than the polyester polyol used as necessary in addition to the polyisocyanate compound (a2). Other polyols and compounds having a functional group capable of reacting with an isocyanate group and an ionic functional group.
If the polyester polyol (a1) having a cyclic structure is less than 10% by weight, that is, if the other component exceeds 90% by weight, the rubber elasticity of the composite resin (1) described later becomes too large, and the pressure sensitive type for polarizing film is used. When used as an adhesive, it is difficult to suppress the shrinkage of the polarizing film. On the other hand, when the polyester polyol (a1) having a cyclic structure is more than 99% by weight, that is, when the other components are less than 1% by weight, the energy elasticity of the composite resin (1) described later is too high, and the composite resin (1) becomes rigid, and it tends to float and foam under severe conditions of heat and wet heat.

The weight average molecular weight (Mw) of the urethane-modified polyester (A) used in the present invention is preferably 10,000 to 500,000, more preferably 15,000 to 400,000, and still more preferably 20,000. ~ 300,000.
When Mw is less than 10,000, it is difficult to express its own cohesive force, and when it is larger than 500,000, it is a phase with a polymer of an α, β-unsaturated compound (b) described later. Solubility falls and transparency of composite resin (1) tends to be impaired.
Moreover, it is preferable that the glass transition point (Tg) of urethane-modified polyester (A) is 50 degrees C or less, Preferably it is -50 degreeC-50 degreeC. When the temperature is lower than −50 ° C., the elasticity of the composite resin (1) is lowered and the cohesive force tends to be lowered. When it exceeds 50 degreeC, adhesiveness with a to-be-adhered body will fall, and floating will occur easily.
The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatograph (GPC, solvent: tetrahydrofuran), and the glass transition point (Tg) is a differential scanning calorimeter (DSC, heating rate 10). (C / min).

  It is important that the urethane-modified polyester (A) used in the present invention has a functional group X involved in the reaction with the compound (2) having a functional group Y described later. Examples of the functional group X include a hydroxyl group, a carboxyl group, an amino group, an amide group, a maleimide group, a nitrile group, an epoxy group, an alkoxysilyl group, and an allyl group. Among these, a hydroxyl group and a carboxyl group are preferable.

  The urethane-modified polyester (A) has various additives such as an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, a pigment, and a dye as long as the effects of the present invention are not impaired. Further, a filler, an antistatic agent, a nucleating agent and the like may be blended.

<Α, β-unsaturated compound (b)>
The α, β-unsaturated compound (b) used in the present invention is a compound having a radical polymerizable double bond in the molecule, and may be an α, β-unsaturated carboxylic acid ester or an alkenyl group-containing compound. The α, β-unsaturated carboxylic acid ester is, for example, methyl (meth) acrylate [methyl acrylate and methyl methacrylate are collectively referred to as “methyl (meth) acrylate”. . The same applies hereinafter. ], (Meth) acrylic acid ethyl, (meth) acrylic acid isopropyl, (meth) acrylic acid propyl, (meth) acrylic acid n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid t-butyl, (meta ) N-amyl acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Alkyl (meth) acrylates such as dodecyl acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;

  For example, (meth) acrylic acid cyclic esters such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobonyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate;

  For example, allyl (meth) acrylate, methallyl (meth) acrylate, 1-methylallyl (meth) acrylate, 2-methylallyl (meth) acrylate, 1-butenyl (meth) acrylate, (meth) acrylate 2- Butenyl, 3-butenyl (meth) acrylate, 1,3-methyl-3-butenyl (meth) acrylate, 2-chloroallyl (meth) acrylate, 3-chloroallyl (meth) acrylate, (meth) acrylic acid o -Allylphenyl, 2- (allyloxy) ethyl (meth) acrylate, allyl lactyl (meth) acrylate, citronellyl (meth) acrylate, geranyl (meth) acrylate, rosinyl (meth) acrylate, cinnamyl (meth) acrylate , (Meth) acrylic acid esters containing unsaturated groups such as vinyl (meth) acrylate;

  For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic acid 2-perfluorode Ruechiru, (meth) (meth) acrylic acid fluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

  For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- Benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- (2- (meth) acryloyloxyethoxy)]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- (2- (meth) acryloyloxyethoxy)]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2- (meth) acryloyloxyethoxy) )] -S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2- (meth) acryloyloxyethoxy)] -S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- (2- (meth) acryloyloxyethoxy)]-S-triazine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2- Hydro -4- (2- (2-methyl) prop-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- ( 2- (meth) acryloyloxyethoxy)]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- (2- (meth) acryloyloxyethoxy)] -S-triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- (2- (meth) acryloyloxyethoxy)] -triazine-based (meth ) Acrylic esters;

  For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy- 3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, etc. Benzotriazole (meth) acrylate;

  For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy (meth) acrylate (Meth) acrylic acid esters containing a hydroxyl group or an alkoxy group such as butyl, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate;

  For example, as commercial products, Phosmer M, Phosmer CL, Phosmer PE, Phosmer MH (manufactured by Unichemical Co., Ltd.), light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.), JAMP-514 (manufactured by Johoku Chemical Industry Co., Ltd.), Phosphoric acid group-containing (meth) acrylic acid esters such as KAYAMER PM-2 and KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.);

  For example, sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-sulfobutyl (meth) acrylate, (meth) 4-sulfobutyl acrylate, 2-sulfobutyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, sulfooctyl (meth) acrylate, sulfodecyl (meth) acrylate, sulfolauryl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters containing a sulfonyl group such as sulfostearyl acrylate;

  For example, (meth) acrylic acid glycidyl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid tetrahydrofurfuryl, etc. Heterocycle-containing (meth) acrylic acid esters;

  For example, N-methylaminoethyl (meth) acrylate, N-tributylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, etc. Amino group-containing (meth) acrylic acid esters;

  For example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, etc. Alkoxysilyl group-containing (meth) acrylic acid esters;

  For example, (meth) acrylic acid esters such as an ethylene oxide adduct of (meth) acrylic acid;

For example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Multifunctional (meth) acrylic acid esters such as 1,1,1-trishydroxymethylethane diacrylic acid, 1,1,1-trishydroxymethylethane triacrylic acid, 1,1,1-trishydroxymethylpropane triacrylic acid Kind;
And the like.

  Examples of the alkenyl group-containing compound include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1-butylstyrene, chlorostyrene, styrenesulfonic acid and sodium thereof. Aromatic vinyl monomers such as salts;

  For example, fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride;

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

  For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane trivinyl ether, etc. Di- or trivinyl ether monomers of

  For example, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-o-propylene carbonate Monovinyl ether monomers such as dodecyl vinyl ether, diethylene glycol monovinyl ether and octadecyl vinyl ether;

  For example, nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile;

  For example, (meth) acrylamide, diacetone (meth) acrylamide, N-methylol acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-methoxymethyl (Meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N- (n-, iso-) butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N, Amide group-containing vinyl monomers such as N-dimethyl (meth) acrylamide, N- (n-, iso-) butoxyethyl (meth) acrylamide, (meth) acrylamide-tert-butylsulfonic acid;

  For example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, vinyl crotonic acid, vinyl oleate, vinyl linolenate;

  For example, unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid, and their monoalkyl esters or diesters;

  For example, unsaturated carboxylic acid anhydrides such as itaconic anhydride and maleic anhydride;

  For example, diallyl esters of unsaturated dibasic acids such as diallyl maleate, diallyl itaconic acid;

  Other examples include monomers such as vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  In obtaining the composite resin (1) used in the present invention, other compounds having an α, β-unsaturated double bond other than these can be used as necessary, and examples of such compounds are as follows. Are maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

  For example, alkenes such as ethylene, propylene, butene;

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

  As described above, the α, β-unsaturated compound (b) used in the present invention is appropriately selected from α, β-unsaturated compounds to be used for polymerization, whereby a hydroxyl group, a carboxyl group, an amino group, It may have a functional group X such as an amide group, a maleimide group, a nitrile group, an epoxy group, an alkoxysilyl group, or an allyl group. In consideration of a crosslinking reaction with the compound (2) described later, it preferably has a hydroxyl group or a carboxyl group.

The α, β-unsaturated compound (b) is a component constituting the composite resin (1) described later together with the urethane-modified polyester (A) after polymerization. Therefore, a polymer having a glass transition point (Tg) of −60 to −30 ° C. can be formed so that the composite resin (1) can exhibit a good balance of adhesive properties (particularly, both tack and cohesive force). It is preferable to select the type of the α, β-unsaturated compound (b) as described above, and the α, β-unsaturated compound so that a polymer having a glass transition point (Tg) of −55 to −30 ° C. can be formed. It is more preferable to select the type of (b).
Even if the α, β-unsaturated compound (b) capable of forming the polymer (B) having a glass transition point of less than −60 ° C. is selected and polymerized in the presence of the urethane-modified polyester (A), the urethane-modified polyester The compatibility between (A) and a polymer comprising an α, β-unsaturated compound is inferior, the transparency of the pressure-sensitive adhesive and the adhesive layer is lowered, and the adhesive force is too high. There is a possibility that the pressure-sensitive adhesive composition may remain on the adherend surface and cause adherend contamination.
On the other hand, if an α, β-unsaturated compound (b) capable of forming a polymer having a glass transition point exceeding −30 ° C. is selected, sufficient adhesive strength may not be obtained.

Therefore, as the α, β-unsaturated compound (b), 2-ethylhexyl acrylate, n-butyl acrylate, octyl acrylate, which can form a homopolymer having a glass transition point (Tg) of −50 ° C. or lower, Α, β-unsaturated compound (b) 100 weight of acrylic acid ester or methacrylic acid ester of alkyl side chain such as nonyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, lauryl methacrylate, stearyl methacrylate, etc. % Is preferably 20 to 80% by weight.
The remaining 80 to 20% by weight can form a homopolymer having a glass transition point (Tg) in the range of −30 to 100 ° C. in order to control cohesion and improve compatibility with the urethane-modified polyester (A). , Alkenyl group-containing compounds and α, β-unsaturated carboxylic acid esters, such as hydroxyl group, carboxyl group, amino group, amide group, maleimide group, nitrile group, epoxy group, alkoxysilyl group, allyl group, etc. Those having the following are preferred.

<Composite resin having functional group X (1)>
The composite resin (1) in the present invention has a functional group X and is obtained by polymerizing the α, β-unsaturated compound (b) in the presence of the urethane-modified polyester (A). The functional group X can be introduced by the urethane-modified polyester (A) and / or the α, β-unsaturated compound (b) as described above.

In the presence of the urethane-modified polyester (A), the composite resin (1) having the functional group X is polymerized in an amount of 0.001 to 5 parts by weight with respect to 100 parts by weight of the α, β-unsaturated compound (b), for example. It is synthesized by a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization using an initiator. 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].

  Benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxy Organics such as 2-ethylhexanoate, t-butylperoxyneodecanoate, t-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.

In the composite resin (1) having such a functional group X, the polymer formed from the urethane-modified polyester (A) and the α, β-unsaturated compound (b) is 2/98 to 90/10 (weight). %) Is preferable in terms of adhesion to the adherend, and more preferably 5/95 to 80/20 (% by weight).
If the amount of the urethane-modified polyester (A) is too small, the heat resistance and heat-and-moisture resistance may decrease. Conversely, if the amount of the polymer of the α, β-unsaturated compound (b) is too small, the coating film may be whitened or covered. Adhesiveness to the body may be significantly reduced.

  The weight average molecular weight (Mw) of the composite resin (1) having the functional group X is preferably 50,000 to 2,000,000 from the viewpoint of adhesiveness, and 200,000 to 1,500,000. The range of is more preferable. If Mw exceeds 2,000,000, the fluidity of the composite resin (1) becomes poor, making it difficult to produce an adhesive laminate, and if it is less than 50,000, cohesive failure of the adhesive layer is likely to occur. Absent.

<Compound (2) having functional group Y>
The pressure-sensitive adhesive composition of the present invention contains a composite resin (1) having a functional group X and a compound (2) having a functional group Y capable of reacting with the functional group X.
Examples of the functional group X in the composite resin (1) include a hydroxyl group, a carboxyl group, an amino group, an amide group, a maleimide group, a nitrile group, an epoxy group, an alkoxysilyl group, and an allyl group as described above. A carboxyl group is preferred.
The functional group Y in the compound (2) is a functional group capable of reacting with the functional group X. As the compound (2), a polyisocyanate compound, an epoxy compound, an amine compound, an aziridine compound, a carbodiimide compound, an oxazoline compound, a melamine Examples thereof include compounds and metal chelate compounds.
The
When the functional group X is a carboxyl group, examples of the functional group Y include an isocyanate group, an epoxy group, an amino group, an aziridyl group, and an oxazoline group.
When the functional group X is a hydroxyl group, examples of the functional group Y include an isocyanate group and an N-methylol group.
In particular, polyisocyanate compounds are widely used because they have excellent adhesion to the adherend of the pressure-sensitive adhesive composition after the crosslinking reaction and adhesion to the coating layer (base material).

  For example, as a polyisocyanate compound, the thing similar to the polyisocyanate compound (a2) which can be used when obtaining urethane-modified polyester (A) can be illustrated.

  Examples of the epoxy compound include bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol. Diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) And cyclohexane.

As an example of the amine compound, any polyamine having two or more primary amino groups can be used without particular limitation. From the viewpoint of excellent curing speed, a primary amino group that is not directly bonded to an aromatic ring is used. An aliphatic polyamine (which may contain an aromatic ring in its skeleton) which is a polyamine having two or more is preferable.
Aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene branched carbon at both ends of the molecule. Polypropylene glycol having an amino group bonded thereto (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, propylene Diamine, Butylenediamine, Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine, Pentaethylenehexamine, Hexamethylenediamine, Trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2-diamidine Propane, 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)] and 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 of norbornane skeleton Emissions (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 preferable.

  Ketimine, which is a reaction product of these polyamines and ketones, is also included in the amine compound. 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 and ethylene Examples include those obtained from Jeffamine EDR148, Jeffamine D230, Jeffamine D400, which is a diamine having a glycol skeleton or propylene skeleton, or Jeffamine T403, which is a triamine having a propylene skeleton. It is.

  Examples of aziridine compounds include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), bisiso Phthaloyl-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-aziridinyl) butyrate], Trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate], 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 and the like.

  The carbodiimide compound is a compound having two or more carbodiimide groups (—N═C═N—) in the molecule, and known polycarbodiimides 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 decarboxylation condensation reaction of the following diisocyanates.
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 kind of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate or a mixture thereof can be used.

  Examples of the carbodiimidization catalyst include 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.

  Examples of such high molecular weight polycarbodiimides include the Carbodilite series of Nisshinbo Industries, Ltd. Of these, Carbodilite V-01, 03, 05, 07, 09 is preferable because of its excellent compatibility with organic solvents.

  Further, the oxazoline compound as the compound (2) is a compound having two or more oxazoline groups in the molecule. 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'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-p-phenylene Bis (4,4′-dimethyl-2-oxazoline), 2,2′-p-phenylenebis (4-methyl-2-oxazoline), 2,2′-p-phenylenebis ( -Phenyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylene Bis (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 ' -Bis (4-ethyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline) and the like can be mentioned. Alternatively, vinyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline and other monomers copolymerizable with this vinyl monomer And a copolymer thereof.

  The melamine compound is a compound having a triazine ring in the molecule, and examples thereof include melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, vinylguanamine, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine and the like. These low-condensates, alkyl etherified formaldehyde resins and aminoplast resins may also be used.

  Examples of metal chelate compounds include coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium and acetylacetone or ethyl acetoacetate. Is mentioned.

<Pressure-sensitive adhesive composition>
The pressure-sensitive adhesive composition of the present invention preferably contains 0.001 to 20 parts by weight of the compound (2) having the functional group Y with respect to 100 parts by weight of the composite resin (1) having the functional group X. More preferably, the content is 0.01 to 10 parts by weight. If the amount of compound (2) added exceeds 20 parts by weight, the adhesiveness tends to decrease, and if it is less than 0.001 parts by weight, the heat resistance and moist heat resistance tend to decrease.
By the reaction of the functional groups X and Y, the composite resin (1) having an IPN structure is three-dimensionally cross-linked to ensure adhesion with various adherends, and heat resistance and heat and humidity resistance under severer conditions than before. Can be improved.

The pressure-sensitive adhesive composition of the present invention is suitable as a pressure-sensitive adhesive composition for optical members, and preferably contains an organic solvent.
Further, in the pressure-sensitive adhesive composition of the present invention, various resins, silane coupling agents, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, as long as the effects of the present invention are not impaired. You may mix | blend a weather stabilizer, an adhesion imparting agent, a plasticizer, a filler, an anti-aging agent, and the like.

Using the pressure-sensitive adhesive composition of the present invention, a laminated product (hereinafter referred to as “adhesive sheet”) composed of an adhesive layer and a sheet-like substrate can be obtained.
For example, an adhesive sheet can be obtained by applying a pressure-sensitive adhesive to various sheet-like substrates, drying and curing.
In coating, an appropriate liquid medium, for example, ethyl acetate, toluene, isopropyl alcohol, and other organic solvents and water can be further added to adjust the viscosity, or the pressure-sensitive adhesive composition can be adjusted. The viscosity can also be lowered by heating.

Examples of the sheet-like base material include cellophane, various plastic sheets, rubber, cloth, rubber cloth, resin-impregnated cloth, glass plate, metal plate, wood and the like in a flat shape. Moreover, various base materials can also be used independently, and the thing in the multilayer state formed by laminating | stacking a several thing can also be used. Further, the surface can be peeled off.
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.

After applying the pressure-sensitive adhesive composition to the sheet-like substrate 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, heating, etc. If the liquid medium is removed or the pressure-sensitive adhesive composition does not contain a liquid medium to be volatilized, the adhesive layer in the molten state is cooled and solidified, and the An adhesive layer can be formed.
The thickness of the adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 1 μm to 100 μm. If the thickness is 0.1 μm or less, sufficient adhesive strength may not be obtained, and even 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 sheet-like substrate 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 pressure-sensitive adhesive composition, the film thickness, and the selected solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.

<Adhesive laminate><Liquid crystal cell member>
Next, the adhesive laminate and the liquid crystal cell member of the present invention will be described.
The adhesive laminate of the present invention has various optical properties such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film, so-called sheet (also referred to as a film as described above) in an optical member, The adhesive layer formed from the pressure-sensitive adhesive composition of the present invention is laminated. On the other surface of the adhesive layer, a sheet-like base material subjected to a release treatment can be laminated.
The adhesive laminate of the present invention is
(A) The pressure-sensitive adhesive composition is applied to the release-treated surface of the release-treated sheet-like substrate, dried, and a sheet-like optical member is laminated on the surface of the adhesive layer,
(A) It can be obtained by applying a pressure-sensitive adhesive composition to a sheet-like optical member, drying it, and laminating the release-treated surface of the release-treated sheet-like substrate on the surface of the adhesive layer. .
The curing reaction between the composite resin (1) having the functional group X and the compound (2) having the functional group Y is carried out when the pressure-sensitive adhesive composition is dried and on the surface of the adhesive layer by a sheet-like optical member or a release treatment. When the laminated sheet-like base material is laminated and after lamination.

  The sheet-like base material subjected to the release treatment covering the surface of the adhesive layer was peeled off from the adhesive laminate thus obtained, and the adhesive layer was adhered to the glass member for a liquid crystal cell, whereby a sheet-like optical member / A liquid crystal cell member having a constitution of adhesive layer / liquid crystal cell glass member can be obtained.

The pressure sensitive adhesive composition of the present invention has a shear storage modulus at 120 ° C. of 1 × 10 ^{5 to} 5 × 10 ⁶ dyn / cm ² , preferably 5 × 10 ⁵ to 2 × 10 ⁶ dyn / cm. ^Two adhesive layers can be formed. The shear storage elastic modulus can be measured using a viscoelastic spectrometer “RDS-II” manufactured by Rheometric Scientific F.E.
When the shear storage modulus at 120 ° C. of the adhesive layer is smaller than 1 × 10 ⁵ dyn / cm ² , the adhesive layer softens when exposed to high temperatures after being adhered to the glass member for a liquid crystal cell. As a result, foaming, swelling and peeling are likely to occur. On the other hand, when the shear storage modulus at 120 ° C. of the adhesive layer is larger than 5 × 10 ⁶ dyn / cm ² , the heat resistance is sufficiently high, but the adhesive layer is hard at room temperature, and the adhesive laminate is a liquid crystal cell. When adhering to the glass member for an adhesive, the adhesive layer does not sufficiently adhere to the surface of the glass member for a liquid crystal cell, and as a result, the adhesive force is reduced.
That is, the pressure-sensitive adhesive composition of the present invention can form an adhesive layer having a shear storage elastic modulus at 120 ° C. of 1 × 10 ^{5 to} 5 × 10 ⁶ dyn / cm ^2. Floating peel after leaving a laminate of a film and a glass plate at 120 ° C. for 1000 hours (heat resistance), floating peel after leaving at 80 ° C. and 90% relative humidity for 1000 hours (moisture and heat resistance), Since light leakage when light is transmitted through the laminate after being left at 80 ° C. and 90% relative humidity for 1000 hours is suppressed, it is suitable as a pressure-sensitive adhesive composition for optical members.

  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.

(Synthesis Example 1)
Isophthalic acid: 83 parts (25 mol%), sebacic acid: 50 parts (12.5 mol%), adipic acid: 37 parts (12.5 mol%), 1,6-hexanediol: 30 parts (12.5 mol%), Neopentyl glycol: 52 parts (25 mol%), ethylene glycol: 16 parts (12.5 mol%), and tributyl phosphate 0.025 part were charged in a reactor and stirred at 160 ° C. for 3 hours under a nitrogen atmosphere at normal pressure. Reacted. Next, the reaction was performed at a heating temperature of 260 ° C. for 3 hours. The water produced by this reaction is always distilled out of the reaction system, polyester having Mw = 20,000, Tg = −10 ° C., hydroxyl value = 10 (KOHmg / g), acid value = 5 (KOHmg / g) or less. A polyol (a1-1) was obtained.
Mw, Tg, hydroxyl value, acid value, etc. were determined according to the method described later.

(Synthesis Example 2)
After obtaining polyester polyol (a1-1) in the same manner as in Synthesis Example 1, the reactor temperature was then cooled to 120 ° C., and Kuraray polyol C-1090 (bifunctional polycarbonate diol, Mw = 2,000, hydroxyl group) (Valence = 112, manufactured by Kuraray Co., Ltd.) 6 parts and isophorone diisocyanate (manufactured by Huls Japan Co., Ltd.) 10 parts were added, the temperature in the reactor was increased to 180 ° C. over 3 hours, and the reaction was continued for 2 hours.
After completion of the reaction, the reaction product was cooled and solidified, and a urethane-modified polyester (A1) having Mw = 45,000, Tg = 0 ° C., hydroxyl value = 5 (KOHmg / g), acid value = 3 (KOHmg / g) or less was obtained. Obtained.

(Synthesis Example 3)
Mw = 15000, Tg = 0 ° C., hydroxyl value = 5 (KOHmg / g), acid value = 5 (KOHmg), except that the composition of the polyester polyol was changed as shown in Table 1. / G) The following polyester polyol (a1-2) was obtained.
Then, using polyester polyol (a1-2), Mw = 60,000, Tg = 10 ° C., hydroxyl value = 2 (KOHmg / g), acid value = 3 (KOHmg / g) in the same manner as in Synthesis Example 2. The following urethane-modified polyester (A2) was obtained.

(Synthesis Example 4)
Mw = 15,000, Tg = 10 ° C., hydroxyl value = 5 (KOHmg / g), acid value = 5, except that the composition of the polyester polyol was changed as shown in Table 1. The following polyester polyol (a1-3) was obtained (KOHmg / g).
Then, using polyester polyol (a1-3), Mw = 50,000, Tg = 20 ° C., hydroxyl value = 2 (KOHmg / g), acid value = 3 (KOHmg / g) in the same manner as in Synthesis Example 2. The following urethane-modified polyester (A3) was obtained.

(Synthesis Example 5)
Polyester having an aromatic ring with Mw = 28,000, Tg = −18 ° C., hydroxyl value = 4 (KOHmg / g), acid value = 2 (KOHmg / g) or less instead of polyester polyol (a1-1) Mw = 80,000, Tg = −10 ° C., hydroxyl value = 2 (KOHmg / g), acid except that a polyol (“Byron BX1001”, manufactured by Toyobo Co., Ltd.) was used. A urethane-modified polyester (A4) having a value of 2 (KOH mg / g) or less was obtained.

(Synthesis Example 6)
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 15.3 parts of isophoronediamine (IPDA) and 15.3 parts of ethyl acetate, and 25.9 of 4-hydroxybutyl acrylate. Parts (a ratio of 2 mol of 4-hydroxybutyl acrylate to 1 mol of IPDA) was added dropwise at room temperature. After completion of dropping, the reaction is performed at 70 ° C. for 2 hours, and two first amino groups in IPDA are reacted with acryloyl group, two second amino groups and two hydroxyl groups derived from 4-hydroxybutyl acrylate. The chain extender was obtained and diluted by adding 12.1 g of ethyl acetate to obtain a chain extender solution having a nonvolatile content of 60%.

Separately, “AOE polyester AL-1013” having an aromatic ring with Mw = 6,000, Tg = 10 ° C., hydroxyl value = 60 (KOHmg / g), acid value = 6 (KOHmg / g) or less in the reactor. (Polyester polyol, nonvolatile content concentration: 70%, manufactured by Daicel Chemical Industries, Ltd.) 55.2 parts, “Kuraray polyol C-2090” [bifunctional polycarbonate diol, Mw = 4,000, hydroxyl value = 56 (KOH mg / g) Kuraray Co., Ltd.] 12.9 parts, isophorone diisocyanate (Huls Japan Co., Ltd.) 8.6 parts, ethyl acetate 22.5 parts, dibutyltin dilaurate 0.005 part as a catalyst, and gradually raised to 80 ° C The reaction was carried out for 2 hours to obtain a urethane-modified polyester having an isocyanate group with Mw = 150,000.
Then, after cooling to 40 ° C., 20.5 parts of ethyl acetate and 0.3 part of acetylacetone were added, 10 parts of the above chain extender solution having a nonvolatile content of 60% dissolved in ethyl acetate was added dropwise over 1 hour, Further, after aging for 1 hour, 0.13 part of 2-amino-2-methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.) was added, and the remaining isocyanate group was reacted with a hydroxyl group. Mw = 150,000, Tg = 20 A solution having a non-volatile content of 50% of urethane-modified polyester (A5) having a temperature of ℃, hydroxyl value = 10 (KOH mg / g) and acid value = 3 (KOH mg / g) or less was obtained.

(Synthesis Example 7)
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, sebacic acid: 40.4 parts (50 mol%), 3-methylpentanediol: 24.6 parts (50 mol%) And 0.025 part of dibutyltin oxide were added, stirred under an inert gas stream, heated to 220 ° C., held for 8 hours while distilling off the generated water, and subjected to a condensation reaction, Mw = 15,000 , Tg = −68 ° C., hydroxyl value = 1 (KOH mg / g), acid value = 5 (KOH mg / g) or less polyester polyol (a1-4) was obtained.

(Synthesis Example 8)
The raw material composition of the polyester was changed to phthalic anhydride: 35.6 parts (50 mol%), 1,3-butanediol: 22.7 parts (50 mol%), and the catalyst was changed to 0.033 parts of dibutyltin oxide. In the same manner as in Synthesis Example 7, a polyester polyol (a1-5) having Mw = 11,000, Tg = 28 ° C., hydroxyl value = 5 (KOH mg / g), acid value = 5 (KOH mg / g) or less is obtained. It was.

(Synthesis Example 9)
In a reaction vessel, 39.1 parts of ethyl acetate, Kuraray polyol “C-2090” [bifunctional polycarbonate diol, Mw = 4,000, hydroxyl value = 56 (KOH mg / g), manufactured by Kuraray Co., Ltd.] 12.9 parts, “Sun Nix PP-1000 "(bifunctional polyether diol, Mw = 1,000, hydroxyl value = 112 (KOHmg / g), manufactured by Sanyo Chemical Co., Ltd.) 38.6 parts, isophorone diisocyanate (manufactured by Huls Japan KK) 8. 6 parts, 21.0 parts of ethyl acetate and 0.005 part of dibutyltin dilaurate as a catalyst were added, and the reaction was carried out for 10 hours while controlling the temperature in the reactor at 80 ° C.
After completion of the reaction, the product was cooled and solidified, and the solid content of urethane-modified polyether having Mw = 120,000, Tg = 20 ° C., hydroxyl value = 10 (KOHmg / g), acid value = 2 (KOHmg / g) or less. A 50% solution was obtained.

(Synthesis Example 10)
Instead of polyester polyol (a1-1), an aromatic ring having Mw = 10,000, Tg = −20 ° C., hydroxyl value = 19 (KOHmg / g), acid value = 0.5 (KOHmg / g) or less is used. Mw = 50,000, Tg = 0 ° C. in the same manner as in Synthesis Example 2 except that the polyester polyol not contained (“Kuraray polyol P-6010”, manufactured by Kuraray Co., Ltd.) was used as the polyester polyol (a1-6). A urethane-modified polyester (A6) having a hydroxyl value of 5 (KOH mg / g) and an acid value of 3 (KOH mg / g) or less was obtained.

(Synthesis Example 11)
The same raw materials as in Synthesis Example 1 were charged into a reactor, and reacted under stirring at 160 ° C. for 3 hours at normal pressure in a nitrogen atmosphere. Next, the reaction was carried out at a heating temperature of 200 ° C. for 1 hour. Water produced by this reaction is always distilled out of the reaction system, and polyester having Mw = 4,000, Tg = −12 ° C., hydroxyl value = 10 (KOHmg / g), acid value = 5 (KOHmg / g) or less. A polyol (a1-7) was obtained.
Next, after obtaining polyester polyol (a1-7), the temperature of the reactor was cooled to 120 ° C. in the same manner as in Synthesis Example 2, and “Kuraray polyol C-1090” [bifunctional polycarbonate diol, Mw = 20. , 000, hydroxyl value = 112 (KOHmg / g), manufactured by Kuraray Co., Ltd.] 6 parts, 10 parts of isophorone diisocyanate (manufactured by Huls Japan Co., Ltd.) was added, and the temperature in the reactor was increased to 180 ° C over 3 hours. The reaction was continued for another 2 hours.
After completion of the reaction, the product was cooled and solidified, and urethane-modified polyester (A7) having Mw = 15,000, Tg = 0 ° C., hydroxyl value = 5 (KOHmg / g), acid value = 3 (KOHmg / g) or less was obtained. Obtained.

(Synthesis Example 12)
The same raw materials as in Synthesis Example 1 were charged into a reactor, and reacted under stirring at 160 ° C. for 3 hours at normal pressure in a nitrogen atmosphere. Subsequently, the temperature was raised to 260 ° C. and reacted for 8 hours. During this time, water produced by the reaction is always distilled out of the reaction system, and Mw = 120,000, Tg = −8 ° C., hydroxyl value = 8 (KOHmg / g), acid value = 5 (KOHmg / g) or less. A polyester polyol (a1-8) was obtained.
Next, after obtaining the polyester polyol (a1-8), the temperature of the reactor was cooled to 120 ° C. in the same manner as in Synthesis Example 2, and “Kuraray polyol C-1090” [bifunctional polycarbonate diol, Mw = 2. , 000, hydroxyl value = 112 (KOHmg / g), manufactured by Kuraray Co., Ltd.] 6 parts, 10 parts of isophorone diisocyanate (manufactured by Huls Japan Co., Ltd.) was added, and the temperature in the reactor was increased to 180 ° C over 3 hours. The reaction was continued for another 2 hours.
After completion of the reaction, the product was cooled and solidified, and urethane-modified polyester (A8) having Mw = 580,000, Tg = 0 ° C., hydroxyl value = 4 (KOHmg / g), acid value = 3 (KOHmg / g) or less was obtained. Obtained.

(Synthesis Example 32)
After obtaining the polyester polyol (a1-1) in the same manner as in Synthesis Example 1, the reactor temperature was then cooled to 120 ° C., and the polyester amide “TPAE-617” [bifunctional polyester amide diol, Mw = 3000, Hydroxyl value = 16 (KOHmg / g), manufactured by Fuji Kasei Kogyo Co., Ltd.] 6 parts, isophorone diisocyanate (manufactured by Huls Japan Co., Ltd.) 10 parts was added, and the temperature in the reactor was raised to 180 ° C. over 3 hours. For another 2 hours.
After completion of the reaction, the product was cooled and solidified, and urethane-modified polyester (A9) having Mw = 55,000, Tg = 10 ° C., hydroxyl value = 5 (KOHmg / g), acid value = 3 (KOHmg / g) or less was obtained. Obtained.

(Synthesis Example 13)
The urethane-modified polyester (A1) produced in Synthesis Example 2 and the following α, β- were added to the polymerization tank and the dropping device of the polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube. The unsaturated compound (b) was charged at the following ratio, respectively.

[Polymerization tank]
Urethane-modified polyester (A1) 50 parts benzyl methacrylate 30 parts 2-ethylhexyl acrylate 15 parts methyl acrylate 4 parts 2-hydroxyethyl acrylate 1 part ethyl acetate 25 parts 2,2'-azobisbutyronitrile 0.05 Part [Drip device]
2-ethylhexyl acrylate 45 parts methyl acrylate 4 parts 2-hydroxyethyl acrylate 1 part ethyl acetate 39 parts 2,2'-azobisbutyronitrile 0.05 part

  After the air in the polymerization tank was replaced with nitrogen gas, the reaction was started at reflux temperature in a nitrogen atmosphere with stirring. When the polymerization rate reached about 70%, the dropping of the mixture of the α, β-unsaturated compound (b), the polymerization initiator and ethyl acetate was started from the dropping device. After completion of the dropwise addition, the mixture was further aged with stirring for 8 hours, and then 536 parts of toluene was added and cooled to room temperature to obtain a transparent solution containing the composite resin (1) -1.

(Synthesis Examples 14-16, 33)
Synthetic examples except that the urethane-modified polyesters (A2) to (A4) and (A9) obtained in Synthesis Examples 3 to 5 and 32 were used in place of the urethane-modified polyester (A1) used in Synthesis Example 13. The reaction was carried out in the same manner as in Example 13 to obtain a transparent liquid containing composite resins (1) -2 to (1) -4 and (1) -16.

(Synthesis Example 17)
The solution of the urethane-modified polyester (A5) prepared in Synthesis Example 6 and the following α, β-unsaturated compound (b) were charged in the polymerization tank and the dropping device at the following ratios, respectively. To obtain a transparent liquid containing the composite resin (1) -5.
[Polymerization tank]
100 parts of urethane-modified polyester (A5) solution (nonvolatile content: 50 parts)
Benzyl methacrylate 30 parts 2-ethylhexyl acrylate 15 parts Methyl acrylate 4 parts 2-hydroxyethyl acrylate 1 part 2,2'-azobisbutyronitrile 0.05 part [Drip device]
2-ethylhexyl acrylate 45 parts methyl acrylate 4 parts 2-hydroxyethyl acrylate 1 part ethyl acetate 14 parts 2,2'-azobisbutyronitrile 0.05 part

(Synthesis Example 18)
In the same manner as in Synthesis Example 13, the urethane-modified polyester (A1) and the following α, β-unsaturated compound (b) are charged in the polymerization tank and the dropping device at the following ratios, respectively, otherwise the same as in Synthesis Example 13. To obtain a transparent liquid containing the composite resin (1) -6.
[Polymerization tank]
Urethane-modified polyester (A1) 50 parts Phenoxyethyl acrylate 30 parts Butyl acrylate 13 parts Methyl methacrylate 5 parts 2-Hydroxypropyl methacrylate 1 part Acrylic acid 1 part Methyl acetate 25 parts t-Butylperoxy-2-ethylhexa Noate 0.05 parts [Drip device]
Butyl acrylate 38 parts Phenoxyethyl acrylate 10 parts 2-Hydroxypropyl methacrylate 1 part Acrylic acid 1 part Methyl acetate 39 parts t-Butylperoxy-2-ethylhexanoate 0.05 parts

(Synthesis Example 19)
The composition of the α, β-unsaturated compound (b) of Synthesis Example 13 was changed as shown in Table 2, and the polymerization tank and the dropping layer were respectively changed.
[Polymerization tank]
Urethane-modified polyester (A1) prepared in Synthesis Example 2 50 parts 2-acryloyloxyethyl acrylate-phthalic acid 30 parts vinyl acetate 4 parts 2-ethylhexyl acrylate 20 parts butyl acrylate 10 parts acrylic acid 1 part ethyl acetate 25 Part 2,2'-Azobisbutyronitrile 0.05 part [Drip device]
2-ethylhexyl acrylate 20 parts butyl acrylate 10 parts acrylic acid 1 part ethyl acetate 39 parts 2,2'-azobisbutyronitrile 0.05 parts, and the reaction is carried out in the same manner as in Synthesis Example 13, A transparent solution containing the composite resin (1) -7 was obtained.

(Synthesis Example 20)
Of α, β-unsaturated compound (b) comprising 46.5 parts of 2-ethylhexyl acrylate, 40 parts of butyl acrylate, 10 parts of vinyl acetate, 3 parts of acrylic acid and 0.5 part of 2-hydroxyethyl acrylate 40 parts of 100 parts of the mixture, 20 parts of urethane-modified polyester (A1) obtained in Synthesis Example 2 and 100 parts of ethyl acetate were equipped with a stirrer, thermometer, inert gas introduction tube, cooler, and dropping funnel. A four-necked flask was charged.

  The mixture was stirred under a nitrogen stream, and at 80 ° C., 0.2 part of “Niper BMT-K40” (an organic peroxide manufactured by NOF Corporation) was added as a polymerization initiator to start polymerization, and 15 minutes after the start of polymerization. The remaining 60 parts of the mixture of α, β-unsaturated compound (b) was continuously added dropwise over 2 hours, and after completion of the addition, 80 parts of toluene and a polymerization initiator “NIPER BMT-K40” (same as above) 0.1 part was added, and it was made to react at 85 degreeC for 3 hours, and the transparent solution containing composite resin (1) -8 was obtained.

(Synthesis Examples 21-23)
Instead of the urethane-modified polyester (A1) used in Synthesis Example 20, the polyester polyols (a1-1), (a1-4), and (a1-5) obtained in Synthesis Examples 1, 7, and 8 were used, respectively. Otherwise, the reaction was carried out in the same manner as in Synthesis Example 20 to obtain a liquid containing composite resins (1) -9 to (1) -11. All the solutions had a loss of transparency.

(Synthesis Example 24)
The composite resin (1) was reacted in the same manner as in Synthesis Example 17 except that the urethane-modified polyether (A5) solution used in Synthesis Example 17 was used instead of the urethane-modified polyether solution obtained in Synthesis Example 9. A clear liquid containing -12.

(Synthesis Examples 25 to 27)
Instead of the urethane-modified polyester (A1) used in Synthesis Example 13, the reaction was performed in the same manner as in Synthesis Example 13 except that the urethane-modified polyesters (A6) to (A8) obtained in Synthesis Examples 10 to 12 were used. A liquid containing composite resins (1) -13 to (1) -15 was obtained.

(Synthesis Example 28) .. <Polymer (B) of α, β-unsaturated compound (b)>
As in Synthesis Example 13, except that the urethane-modified polyester (A1) was not used and 58 parts of ethyl acetate and 303 parts of toluene for dilution were changed to α, Mw = 400,000, A solution of β-unsaturated compound polymer (B1) was obtained. Table 3 shows the solid content and the like.

(Synthesis Example 29)
A solution of α, β-unsaturated compound polymer (B2) having Mw = 320,000 was obtained in the same manner as in Synthesis Example 20 except that the urethane-modified polyester (A1) was not used. Table 3 shows the solid content and the like.

(Synthesis Example 30)
99 parts of n-butyl acrylate, 1 part of acrylic acid, 100 parts of ethyl acetate and 0.2 part of 2,2′-azobisisobutyronitrile were placed in a reaction vessel, and the air in the reaction vessel was replaced with nitrogen gas. Thereafter, the reaction vessel was heated to 60 ° C. and reacted for 6 hours in a nitrogen atmosphere with stirring, and further heated to 70 ° C. and reacted for 2 hours. Thereafter, a solution prepared by dissolving 0.4 part of 2,2′-azobisisobutyronitrile in 20 parts of ethyl acetate was added dropwise over 1 hour, and the reaction was further continued for 2 hours. After the reaction, the solution was diluted with toluene to obtain a solution of a high molecular weight α, β-unsaturated compound polymer (B3) having Mw = 1,400,000. Table 3 shows the solid content and the like.

(Synthesis Example 31)
99.5 parts of n-butyl acrylate, 0.5 part of acrylic acid, 350 parts of toluene and 0.5 part of 2,2′-azobisisobutyronitrile are placed in a reaction vessel, and the air in the reaction vessel is nitrogen gas. The reaction vessel was heated to 90 ° C. and reacted for 6 hours in a nitrogen atmosphere with stirring. Thereafter, a solution in which 1.0 part of 2,2′-azobisisobutyronitrile was dissolved in 30 parts of ethyl acetate was added dropwise over 1 hour, and the mixture was further reacted for 2 hours. After the reaction, it was diluted with toluene to obtain a solution of a low molecular weight α, β-unsaturated compound polymer (B4) having Mw = 50,000. Table 3 shows the solid content and the like.

  About each resin composition obtained from the synthesis examples 1-31, Mw, a hydroxyl value, an acid value, Tg, etc. were calculated | required according to the following method, and the result was shown to Tables 1-3.

<< Solution appearance >>
The appearance of each composite resin and each α, β-unsaturated compound polymer solution was visually evaluated.

<Measurement of non-volatile content>
About 1 g of urethane-modified polyester, urethane-modified polyether, composite resin, α, β-unsaturated compound polymer or their solution obtained from each synthesis example is weighed in a metal container and dried in a 150 ° C. oven for 20 minutes. Then, the residue was weighed and the remaining rate was calculated to obtain a non-volatile content concentration (solid content).

<< Measurement of solution viscosity >>
Each solution of urethane-modified polyester, urethane-modified polyether, composite resin and α, β-unsaturated compound polymer was measured at 23 ° C. using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). 3 or No. The measurement was performed under conditions of 4 rotors, 12 rpm, and 1 minute rotation.

<< Measurement of weight average molecular weight (Mw) >>
Mw was measured using Showa Denko GPC (Gel Permeation Chromatography) “Shodex GPC System-21”. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

<< Measurement of glass transition point (Tg) >>
The measurement was performed by connecting a “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) to a robot DSC (differential scanning calorimeter) “RDC220” (manufactured by Seiko Instruments Inc.). About 10 mg of a sample was weighed in an aluminum pan, set in a DSC apparatus (reference: aluminum pan of the same type without a sample), heated at a temperature of 300 ° C. for 5 minutes, and then rapidly cooled using liquid nitrogen. The sample was heated at 10 ° C./min, and the glass transition point (Tg) was measured from the DSC chart.

Example 1
As a compound (2), 0.02 part of XDI / TMP (trimethylopepropane adduct of xylylene diisocyanate) with respect to 100 parts by weight of the solution of the composite resin (1) -1 obtained in Synthesis Example 13 Was added and stirred well to obtain a pressure-sensitive adhesive composition of the present invention.
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 an adhesive layer.
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 protective films (hereinafter referred to as “TAC film”) is bonded to the adhesive layer, and a release film / adhesive layer A laminate of / TAC film / PVA / TAC film was obtained.
Next, the obtained laminate was aged (dark reaction) for 1 week under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, and the reaction of the adhesive layer was advanced to obtain an adhesive laminate (polarizing plate).

(Comparative Example 1)
A polarizing plate was obtained in the same manner as in Example 1 except that the solution of the α, β-unsaturated compound polymer (B1) was used instead of the solution of the composite resin (1) -1.

(Comparative Examples 2 to 4)
Synthesis example using polyester polyols (a1-1), (a1-4) and (a1-5) instead of urethane-modified polyester instead of the solution of composite resin (1) -1 used in Example 1 A polarizing plate was obtained in the same manner as in Example 1 except that the solutions of composite resins (1) -9 to (1) -11 obtained in 21 to 23 were used.
At this time, in Comparative Examples 3 and 4 using the composite resins (1) -10 and (1) -11, respectively, the coating property was not good, for example, uneven stripes appeared on the coated surface.

(Comparative Example 5)
A polarizing plate was obtained in the same manner as in Example 1 except that instead of the composite resin (1) -1 used in Example 1, a solution of the composite resin (1) -12 containing urethane-modified polyether was used. Got.

(Comparative Examples 6-8)
Instead of using the composite resin (1) -1 solution used in Example 1, each of the composite resin (1) -13 to (1) -15 solutions obtained in Synthesis Examples 25 to 27 was used. In the same manner as in Example 1, a polarizing plate was obtained.
At this time, in Comparative Example 8 using the composite resin (1) -15, the coating property was not particularly good, such as unevenness appearing on the coated surface.

(Examples 2-5, 12)
Except having used each solution of composite resin (1) -2-(1) -5, (1) -16 instead of the solution of composite resin (1) -1, it carried out similarly to Example 1. A polarizing plate was obtained.

(Examples 6 to 8)
It is the same as that of Example 1 except having used each solution of composite resin (1) -6-(1) -8 obtained by the synthesis examples 18-20 instead of the solution of composite resin (1) -1. Thus, a polarizing plate was obtained. The composite resin (1) -8 solution was diluted with toluene to a solid content concentration of 20%.

(Examples 9 to 11)
Instead of the solution of the composite resin (1) -1, as a compound (2) with respect to 100 parts by weight of a 20% solid content solution of the composite resin (1) -6 obtained in Synthesis Example 18, TDI in Example 9 was used. / TMP (trimethylopropanepropane adduct of tolylene diisocyanate) 0.02 part, in Example 10, TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) 0.02 In Example 11, 0.02 part of TAT (tris-2,4,6- (1-aziridinyl) -1,3,5-triazine) was added in each case, and the mixture was stirred well and pressure-sensitive adhesive composition A polarizing plate was obtained in the same manner as in Example 1.

(Comparative Examples 9, 13, and 17)
Example 9 except that instead of the solution of the composite resin (1) -6, a solution obtained by diluting a solution of the α, β-unsaturated compound polymer (B2) with toluene to a solid content concentration of 20% was used. Polarizing plates were obtained in the same manner as in Nos. 10 and 11, respectively.
(Comparative Example 9 corresponds to Example 9, Comparative Example 13 corresponds to Example 10, and Comparative Example 17 corresponds to Example 11.)

(Comparative Examples 10-12, 14-16, 18-20)
Instead of the urethane-modified polyester, polyester polyols (a1-1), (a1-4), and (a1-5) were used instead of the solution of the composite resin (1) -6 used in Examples 9, 10, and 11. Examples 9 and 10 except that the solutions of the composite resins (1) -9 to (1) -11 obtained in Synthesis Examples 21 to 23 were each diluted with toluene to a solid content concentration of 20%. , 11, respectively, to obtain polarizing plates.
(Comparative Examples 10-12 correspond to Example 9, Comparative Examples 14-16 correspond to Example 10, and Comparative Examples 18-20 correspond to Example 11, respectively.)
At this time, in Comparative Examples 11, 12, 15, 16, 19, and 20 using the composite resins (1) -10 and (1) -11, the coating property was not good, for example, uneven stripes appeared on the coated surface.

(Comparative Example 21)
Instead of the solution of composite resin (1) -1 used in Example 1, an α, β-unsaturated compound polymer (B3) solution and an α, β-unsaturated compound polymer (B4) solution A polarizing plate was obtained in the same manner as in Example 1 except that the solution mixed at a ratio of 80/20 was used.

  The blending ratios in the examples and comparative examples are shown in Table 4.

<< Measurement of shear storage modulus (G ') >>
The pressure-sensitive adhesive compositions obtained in the examples and comparative examples were coated on a release film, dried in an oven at 150 ° C., and an adhesive layer having a thickness of about 0.3 mm was provided. The layers were laminated and laminated repeatedly, and the thickness of the adhesive layer was about 2 mm. This was punched out into a disk shape having a diameter of 8 mm with a punch, and used as a sample for measuring the shear storage modulus. Using a viscoelastic spectrometer “RDS-II” manufactured by Rheometric Scientific F.E., the frequency was 1 Hz, the shear strain was 0.1π radians, and the temperature was 120 ° C. The results are shown in Table 4. The unit of the shear storage modulus (G ′) is dyne / cm ² (= 0.1 Pa).

  About the polarizing plate obtained by the Example and the comparative example, the heat resistance performance, the heat-and-moisture resistance performance, the optical characteristic, and the removability were evaluated with the following method. The results are shown in Table 5.

<< Evaluation methods for heat resistance, heat and humidity resistance, and optical characteristics
Cut the polarizing plate into a size of 150 mm x 80 mm, peel off the release film, and paste it on both sides of a 1.1 mm thick float glass plate using a laminator so that the axial direction of the absorption axis of the polarizing plate is orthogonal. I wore it. 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 adhere the adhesive layer to the glass plate. Further, the floating peel after leaving the laminate of the polarizing plate and the glass plate at 120 ° C. for 1000 hours (heat resistance), the floating peel after leaving at 80 ° C. and a relative humidity of 90% for 1000 hours (moisture and heat resistance), and Light leakage (white spots) when light was transmitted through the laminate of the polarizing plate and the glass plate after being left at 80 ° C. and 90% relative humidity for 1000 hours was visually observed and evaluated in four stages.
A: “Floating peels and white spots are not recognized at all”
○: “Slightly floating peeling / whitening is observed, but there is no practical problem”
△: “There are many floating peelings and white spots, and there are practical problems”
×: “There are floating floats and white spots on the whole surface, which is not practical”
Means each.

<< Evaluation Method of Optical Properties (Haze) >>
After the pressure-sensitive adhesive composition was applied to a release-treated polyester film and dried to provide an adhesive layer having a thickness of 25 μm, the release-treated polyester film was further bonded to the adhesive layer. The adhesive layer sandwiched between the release-treated polyester films was aged at a temperature of 23 ° C. and a relative humidity of 50% for 1 week, then the release-treated polyester film was removed, the appearance of the adhesive layer alone was visually judged, NDH-300A ”(manufactured by Nippon Denshoku Industries Co., Ltd.).

<Evaluation method of removability (reworkability)>
Cut the bonded polarizing plate into a size of 25 mm x 150 mm, peel off the release film, attach it to a 1.1 mm thick float glass using a laminator, and hold it in an autoclave at 50 ° C and 5 atm for 20 minutes The adhesive layer was adhered to the glass plate. After leaving this test piece for 1 week at 23 ° C. and 50% relative humidity, a 180 ° peel test was performed in which the test piece was peeled off at a speed of 300 mm / min in the direction of 180 °. Cloudiness) was visually observed and evaluated in three stages.
○: “No problem in practical use”
Δ: “Slightly cloudy is recognized and there is a practical problem”
X: “Transfer of the adhesive layer is recognized over the entire surface, and is not practical”
Means each.

The pressure-sensitive adhesive composition of the present invention has an IPN-structured viscoelasticity that combines the properties of strong energy elasticity observed in polyester resins, flexible rubber elasticity recognized in polyurethane resins, and viscosity recognized in acrylic resins. Since it is a resin, transparency, weather resistance, water resistance, and hydrolysis resistance can be selected by arbitrarily selecting the type of each monomer component and α, β-unsaturated compound (b) constituting the urethane-modified polyester (A). , Chemical resistance, heat resistance, and heat and humidity resistance, and can exhibit the characteristics of being extremely stretched (good in bending workability) and tough.
Therefore, in addition to being suitable as a pressure-sensitive adhesive composition for optical members, paints, elastic wall materials, coating waterproofing materials, flooring materials, tackifiers, adhesives, adhesives for laminated structures, sealing agents, molding materials, Coating agent for surface modification, binder (magnetic recording medium, ink binder, casting binder, fired brick binder, graft material, microcapsule, glass fiber sizing, etc.), urethane foam (hard, semi-rigid, soft), urethane RIM, UV・ EB cured resin, high solid paint, thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent, artificial marble resin, imparting impact resistance for artificial marble Agent, ink resin, film (laminate adhesive, protective film, etc.), laminated glass resin, reactive dilution , Various molding materials, elastic fiber, artificial leather, as a raw material for synthetic leather, can also very effectively used as various resin additives and a raw material thereof or the like.

Claims (10)

In the presence of the urethane-modified polyester (A) obtained by reacting a polyester polyol (a1) having a cyclic structure with a weight average molecular weight of 5,000 to 100,000 and a polyisocyanate compound (a2), α, β- A pressure-sensitive adhesive composition comprising a composite resin (1) having a functional group X obtained by polymerizing a saturated compound (b) and a compound (2) having a functional group Y capable of reacting with the functional group X. The pressure-sensitive adhesive composition according to claim 1, wherein the urethane-modified polyester (A) contains a polyol component other than the polyether polyol in addition to the polyester polyol (a1). The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the urethane-modified polyester (A) has a glass transition point in the range of -50 to 50 ° C and a weight average molecular weight in the range of 10,000 to 500,000. . The pressure-sensitive type according to any one of claims 1 to 3, wherein at least one of the urethane-modified polyester (A) or the α, β-unsaturated compound (b) has a hydroxyl group and / or a carboxyl group as the functional group X. Adhesive composition. In a total of 100% by weight of the urethane-modified polyester (A) and the α, β-unsaturated compound (b), the urethane-modified polyester (A) is 2 to 90% by weight and the α, β-unsaturated compound (b) is 10%. The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive composition is -98 wt%. The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the composite resin (1) has a weight average molecular weight of 50,000 to 2,000,000. The pressure-sensitive adhesive composition according to any one of claims 1 to 6, comprising 0.001 to 20 parts by weight of the compound (2) having a functional group Y with respect to 100 parts by weight of the composite resin (1). object. An adhesive laminate comprising an adhesive layer formed from the pressure-sensitive adhesive composition according to claim 1 and an optical member. A liquid crystal cell member comprising a glass member for a liquid crystal cell, an adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 7, and an optical member. A polyester polyol (a1) having a cyclic structure with a weight average molecular weight of 5,000 to 100,000 is reacted with a polyisocyanate compound (a2) to obtain a urethane-modified polyester (A), and the urethane-modified polyester (A) In the presence, the α, β-unsaturated compound (b) is polymerized to obtain a composite resin (1) having a functional group X, and then the functional group capable of reacting with the composite resin (1) and the functional group X A method for producing a pressure-sensitive adhesive composition, wherein the compound (2) having Y is mixed.