JPWO2008069298A1 - Adhesive composition, method for producing the same, and laminate using the adhesive composition - Google Patents

Abstract

Provided is an adhesive composition that can form an adhesive layer excellent in initial adhesiveness, adhesion, heat resistance, moist heat resistance and transparency and can be used as a pressure-sensitive adhesive. The adhesive composition contains a polyester resin containing a total of 5 to 80% by weight of a side chain having a hydroxyl group or a carboxyl group and a side chain having no hydroxyl group and a crosslinking agent. The polyester resin has a hydroxyl value of 50 mgKOH / g or less when using a crosslinking agent that reacts with a hydroxyl group, and a hydroxyl value of 100 mgKOH / g or less and an acid value of 50 mgKOH / g or less when a crosslinking agent that reacts with carboxyl is used. And 1) ring-opening addition polymerization of a dibasic acid and a compound having two cyclic ether groups to form a polyester main chain having a hydroxyl group, and 2) ring-opening addition of a cyclic ester compound to the hydroxyl group to form a side chain. 3) It is manufactured through each step of sealing a hydroxyl group with a sealing compound.

Description

  The present invention relates to an adhesive composition mainly composed of a polyester resin, a method for producing the same, and a laminate produced using the same, and in particular, adhesion to various adherends, heat resistance, moisture and heat resistance, and transparency. The present invention relates to an adhesive composition that is excellent and can be suitably used as a pressure-sensitive adhesive in the lamination of optical members, a production method thereof, and a laminate using an adhesive composition that is used in the production of various optical devices and the like.

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

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

    In recent years, from the viewpoint of effectively using light, suppression of interface reflection due to a difference in refractive index between an optical member and an adherend has been demanded. If the difference in refractive index at the interface between the two layers is large, the incident angle causing total reflection is reduced and the effective utilization of light is reduced. Therefore, in the bonding process of the optical member, the refractive index of the optical member and the adherend It has been found advantageous to form the adhesive layer using a pressure sensitive adhesive having a refractive index intermediate to that of the refractive index.

    However, the refractive index of the adhesive layer using the conventional acrylic resin is around 1.46, whereas the refractive index of the material forming the optical member is, for example, around 1.52 for glass, methacrylic resin Is around 1.51, polycarbonate resin is around 1.54, and polyethylene terephthalate (PET) resin is around 1.60, so the difference in refractive index between them is large. Further, for example, when an optical member made of glass and an optical member made of methacrylic resin, polycarbonate resin, or PET resin are bonded, an intermediate refractive index cannot be obtained.

Therefore, in order to attach a polarizing film to a glass member for a liquid crystal cell using an acrylic pressure-sensitive adhesive, the dimensional change of the polarizing film itself is suppressed and the refractive index of the adhesive layer is further increased. Is required.
The dimensional change can be made relatively small, or the dimensional change can be suppressed for a relatively short period of time by hardening the pressure-sensitive adhesive layer itself or increasing the adhesive strength. The refractive index can be increased to some extent by using an aromatic ring-containing monomer, or using an aromatic compound, a compound containing a sulfur atom, or an inorganic compound.

    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. For this reason, when the conventional pressure sensitive adhesive is used, the stress at the time of sticking remaining in the adhesive layer is not sufficiently relaxed, and the adhesive layer cannot sufficiently follow the distortion of the polarizing film. Therefore, as a result of exposure of the large liquid crystal panel to high temperature or high humidity, the polarizing film peels off from the glass substrate of the liquid crystal cell, causing the discoloration or transparency of the polarizing film, and stress concentration occurs in the polarizing film. This causes problems such as light leakage or volatile gas generation.

    In addition, the polarizing film undergoes dimensional changes 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 glass member for a liquid crystal cell becomes non-uniform. During long-term use, the stress is particularly concentrated on the peripheral portion of the polarizing film. As a result, the peripheral portion of the liquid crystal element becomes brighter or darker than the center, and uneven color and white spots occur on the surface of the liquid crystal element. .

In addition, in the inspection process of a laminate with a polarizing film attached to the glass surface for a liquid crystal cell, the polarizing film etc. is peeled off and a new polarizing film etc. is attached to those that have air or dust trapped during lamination. Will be fixed.
However, since the laminated body is generally inspected after being stored at a high temperature for a certain period of time in order to improve adhesion, not only does the peel strength increase during that time, but it becomes difficult to peel off the polarizing film and the like. , The re-peelability is lowered and adhesive residue is generated after peeling.

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

Conventionally, various pressure-sensitive adhesives have been proposed for such various requirements. For example, inventions relating to a pressure-sensitive adhesive containing an acrylic resin and a crosslinking agent are disclosed in the following documents 1 to 4.
Specifically, according to the following Document 1, a pressure-sensitive adhesive comprising an acrylic resin whose main component is an alkyl ester of (meth) acrylic acid having 1 to 12 carbon atoms in the alkyl group, A pressure-sensitive adhesive comprising an acrylic resin containing 15% by weight or less of a resin component having a weight average molecular weight of 100,000 or less and 10% by weight or more of a polymer component having a weight average molecular weight of 1 million or more is known. It has been.

  Further, the following document 2 describes that 100 parts by weight of a high molecular weight (meth) acrylic copolymer having a weight average molecular weight of 1 million or more and 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 20 to 200 parts by weight and 0.005 to 5 parts by weight of a polyfunctional compound is described.

  Furthermore, in the following document 3, a high molecular weight acrylic resin having a weight average molecular weight of 1,000,000 to 2,500,000 containing a reactive functional group, and a weight average molecular weight of 30,000 to -80 ° C. having a glass transition temperature (Tg) of 0 ° C. to −80 ° C. A pressure-sensitive adhesive for polarizing films comprising 100,000 low molecular weight acrylic resins and a polyfunctional compound having a functional group capable of forming a crosslinked structure with them has been proposed.

Furthermore, according to the following Document 4, an acrylic copolymer having an aromatic ring-containing monomer as a copolymerization component and the copolymerization ratio of the aromatic ring-containing monomer component being 40 to 90% by weight of the total monomer components. A pressure-sensitive adhesive having a controlled refractive index is known.
Reference 5 below describes a pressure-sensitive adhesive in which the refractive index is controlled by adding 10 to 60% by weight of a tackifier resin to 40 to 90% by weight of an acrylic pressure-sensitive adhesive.

  By using the acrylic resin as described above as a pressure-sensitive adhesive, foaming of the adhesive layer and lifting off of the polarizing plate from the liquid crystal cell can be suppressed. However, the stress due to the dimensional change of the polarizing plate cannot be absorbed and relaxed, and the stress concentrates on the peripheral part of the polarizing plate, so the brightness of the peripheral part and the central part of the liquid crystal display device is different, and the surface of the liquid crystal display device The problem of uneven color and white spots on the surface cannot be solved. Furthermore, in order to adjust the refractive index of the adhesive layer, it is necessary to copolymerize or mix a large amount of an aromatic component with this acrylic resin, so that the transparency of the adhesive is reduced or initial adhesion ( Due to the lowering of the tack, a slight float may occur or it may be easily peeled off. In addition, when stored for a certain period of time at high temperature or high humidity, there is a problem that coloring or a balance between adhesive physical properties and refractive index is impaired and image contrast and visibility in a liquid crystal display device are lowered.

In addition to the acrylic pressure-sensitive adhesive containing an acrylic resin and a crosslinking agent, some pressure-sensitive adhesives use an acrylic resin and a polyester resin or a polyurethane resin in combination.
For example, according to Document 6 below, a viscoelastic resin having a glass transition temperature (Tg) of −60 to −5 ° C. and an elastic resin such as a polyurethane resin having a glass transition temperature (Tg) of −5 ° C. or lower are mixed. There are known pressure-sensitive adhesives.

  Reference 7 below describes a pressure-sensitive adhesive containing 100 parts by weight of an acrylic resin and 10 to 50 parts by weight of an amino group-containing polyurethane resin.

  Furthermore, in the following document 8, a pressure-sensitive adhesive containing an acrylic resin and a hydroxyl group-containing polyurethane resin is disclosed.

  Further, the following document 9 proposes a pressure-sensitive adhesive containing an acrylic resin and a polyester resin such as polycaprolactone.

  The pressure-sensitive adhesive obtained by mixing multiple types of resins in this way improves various performances such as increasing the refractive index by increasing the adhesion to the adherend by compensating each other's disadvantages. It is generally considered possible. However, in practice, the acrylic resin and the polyester resin or polyurethane resin are poorly compatible, and if the amount of the polyester resin or polyurethane resin is mixed with the acrylic resin, the transparency is greatly impaired. However, when a large amount of polyester resin or polyurethane resin is mixed, the pressure-sensitive adhesive itself is whitened or separated. Since pressure sensitive adhesives for attaching polarizing films etc. to glass for liquid crystal cells require extremely high transparency, polarizing films using pressure sensitive adhesives having poor compatibility as described above are used. Etc., even if it is attached to glass for liquid crystal cells, there is a problem that phase separation and fluctuation occur in the adhesive layer.

  On the other hand, the following document 10 is composed of a copolyester resin of dimer acid and a glycol component having an alkyl group at 30 mol% or more in the side chain, and has a glass transition temperature (Tg) in the range of −60 to 0 ° C. A pressure sensitive adhesive is disclosed.

  In addition, the following document 11 includes a diol component essential for polycarbonate diol, and a dicarboxylic acid component essential for dicarboxylic acid having a molecular skeleton of an aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms. Describes pressure sensitive adhesives containing polyesters with a weight average molecular weight of 10,000 or more.

  The following document 12 discloses a pressure-sensitive adhesive characterized by containing a biodegradable polyester having a polylactone structure in the main chain and having a weight average molecular weight of 10,000 or more.

  Moreover, according to the following literature 13, the pressure sensitive adhesive which consists of aliphatic polyester whose Tg is -40 degrees C or less where the unit which connected the ester of glycol and carboxylic acid which has a methyl group in a side chain with polyisocyanate is repeated. It has been known.

  It is generally considered that pressure-sensitive adhesives using these polyester resins can improve the disadvantages of acrylic resins, particularly heat resistance or moist heat resistance. However, in practice, the functions necessary as a pressure-sensitive adhesive are impaired, for example, the initial adhesiveness (tack) is too low or there is no cohesive force. Moreover, since these have insufficient compatibility, when applied to an optical film such as a polarizing film or a retardation film, phase separation, fluctuation, and protrusion occur in the pressure-sensitive adhesive layer. At the same time, starting from these, not only causes phenomena such as foaming and misalignment, but also the peel strength after sticking increases excessively, and it is difficult to peel off the polarizing film and the like, and adhesive residue is generated after peeling. Moreover, since re-peelability is insufficient, it is not suitable for a pressure-sensitive adhesive for attaching an optical film such as a polarizing film or a retardation film.

  On the other hand, with respect to the polyester-based resin composition, for example, there are the following documents 14 to 16, and the document 14 describes a modified polyester resin composition having a structure in which a lactone is ring-opened and added to the side chain of a linear polyester resin. Are listed.

  Document 15 discloses a method for producing a hydroxyl group-containing polyester resin, characterized by ring-opening addition of a lactone to a secondary hydroxyl group of a compound produced by a polyaddition reaction between a diglycidyl compound and a dicarboxylic acid compound.

  Reference 16 describes a process for producing a lactone graft copolymer, which comprises ring-opening addition polymerization of a lactone monomer to a hydroxyl group produced by reacting a carboxylic acid compound with a glycidyl group in a polymer. ing.

  Furthermore, according to the following document 17, the reaction product of a glycidyl compound having at least two or more glycidyl groups in the molecule and a polybasic carboxylic acid is reacted with the polybasic carboxylic acid or its anhydride. Resin compositions containing polycarboxylic acid resins are known.

  Document 18 below describes an unsaturated group-containing resin obtained by reacting a reaction product of an epoxy resin with an unsaturated group-containing carboxylic acid or an anhydride thereof with a polybasic carboxylic acid or an anhydride thereof.

  Moreover, in the following literature 19, the adhesive resin composition containing the polyester resin which has a glass transition temperature (Tg) in the range of 45-80 degreeC, a glycidyl resin, and block free isocyanate is disclosed.

  Further, according to the following Document 20, a resin composition for an adhesive mainly comprising a resin obtained by reacting a hydroxyl group and / or carboxyl group at the molecular end, a glycidyl resin and a diisocyanate compound is known. Yes.

Since these polyester resins have excellent adhesion to a wide range of adherends and durability such as chemical resistance, they are various as binder resins for coatings and hot melt adhesives. Used in various fields. However, they generally have high melting temperature and melt viscosity of resin, are difficult to dissolve in low-boiling solvents, and have a short pot life when mixed with a crosslinking agent. Sexually inferior. In addition, since the glass transition temperature (Tg) of the resin is high and the initial adhesiveness (tack) is poor, if a polyester resin dissolved or dissolved in a solvent is applied to the adherend and cooled, the wetness to the adherend is caused. There are problems such as lack of adhesion. Furthermore, since the peel strength after sticking becomes too high and the re-peelability is insufficient, it is not suitable for a pressure-sensitive adhesive.
Document 1: Japanese Patent Laid-Open No. 01-066283 Document 2: Japanese Patent Laid-Open No. 10-279907 Document 3: Japanese Patent Laid-Open No. 2002-121521 Document 4: Japanese Patent Laid-Open No. 2003-013029 Document 5: Japanese Patent Laid-Open No. 2002-014225 Document 6: Japanese Patent Application Laid-Open No. 2003-073646 Document 7: Japanese Patent Application Laid-Open No. 2004-002827 Document 8: Japanese Patent Application Laid-Open No. 2004-083648 Document 9: Japanese Patent Application Laid-Open No. 2002-053835 Document 10: Japanese Patent Application Laid-Open No. 04-328186 Document 11: Japanese Patent Application Laid-Open No. 09-263549 Document 12: Japanese Patent Application Laid-Open No. 11-154552 Document 13: Japanese Patent Application Laid-Open No. 11-021340 Document 14: Japanese Patent Application Laid-Open No. 06-025395 Document 15: Japanese Patent Application Laid-Open No. 08-165337 Document 16: Japanese Patent Laid-Open No. 09-077785 Document 17: Japanese Patent Laid-Open No. 200 Japanese Patent Laid-Open No. 3-107694 Document 18: Japanese Patent Laid-Open No. 2005-352472 Document 19: Japanese Patent Laid-Open No. 08-199147 Document 20: Japanese Patent Laid-Open No. 09-208654

  An object of the present invention is to form an adhesive layer excellent in initial adhesiveness (tack), adhesion to an adherend (that is, a substrate), heat resistance, moist heat resistance and transparency, and suitable as a pressure sensitive adhesive. It is providing the laminated body using the adhesive composition which can be used for, its manufacturing method, and an adhesive composition.

    According to one aspect of the present invention, the adhesive composition is a polyester resin (D) having a polyester main chain (I) and a plurality of side chains branched from the polyester main chain (I), The plurality of side chains have a first side chain (II) having a functional group selected from the group consisting of a hydroxyl group and a carboxyl group, and a second side chain (II ′) having no hydroxyl group, and the polyester resin The polyester resin (D) in which the proportion of the plurality of side chains in the molecule of (D) is 5 to 80% in terms of an average value by weight ratio; a crosslinking agent that can crosslink the polyester resin (D) ( E), and when the crosslinking agent (E) is capable of reacting with a hydroxyl group, the hydroxyl value of the polyester resin (D) is 50 mgKOH / g or less, Crosslinking agent (E) When possible reactions, the hydroxyl value of the polyester resin (D) is 100 mg KOH / g or less, an acid value of at most 50 mg KOH / g.

According to one aspect of the present invention, the laminate includes an optical member and a layer of the adhesive composition that is laminated on the optical member.
Furthermore, the liquid crystal cell member may be a laminate in which an optical member, a layer of the adhesive composition, and a glass member for a liquid crystal cell are laminated.

    According to one aspect of the present invention, a method for producing an adhesive composition includes a polyester main chain (I), a first side chain (II) branched from the polyester main chain (I), and a second side chain (II '), The first side chain (II) has a functional group selected from the group consisting of a hydroxyl group and a carboxyl group, and the second side chain (II') has the sealing compound ( c) a preparation step for preparing a polyester resin (D) having a structure in which a hydroxyl group is sealed by: a dibasic acid (a-1) and a compound (a-2) having two cyclic ether groups Formation reaction of a polyester main chain having a plurality of hydroxyl groups by ring-opening addition polymerization; Side chain formation reaction by ring-opening addition of a cyclic ester compound (b) to a hydroxyl group of the polyester main chain; and hydroxyl group by a sealing compound (c) The above preparation step for performing the sealing reaction is included.

  In the said manufacturing method, it is also possible to perform the said side chain formation reaction before the said sealing reaction, or to perform the said sealing reaction before the said side chain formation reaction.

  In order to use a curable resin as a pressure-sensitive adhesive, the cured resin forms a layer with a shape-retaining force (that is, appropriate hardness) that does not collapse when pressed, and the surface of the resin layer is sticky. It is necessary to have affinity for the adherend so that force (tack) can be expressed. In this regard, the main chain of polyester is more compatible with adherends such as glass substrates, wettability, and adhesiveness due to the polarity of ester groups (particularly carbonyl bonds) than the main chain of acrylic polymers. It can be said that polyester is basically useful as an adhesive material since the durability and shape retention of the formed resin layer are increased due to the rigidity of the carbonyl bond. Further, by changing the acid component and / or alcohol component of the raw material as necessary, it is possible to further impart polarizability, hydrophilicity or lipophilicity, flexibility or rigidity, hardness, durability, etc. to the polyester molecule. Conceivable. When pressure sensitive adhesives are used to construct precision instrument products such as optical components, it is also necessary to have as little impact as possible on the product due to heat and humidity. It is desirable to provide resin properties with excellent adaptability so that changes that occur in the resin layer after bonding can be followed while appropriately suppressing changes in the adherend. In order to realize these, it is effective to apply a polyester having a molecular structure in which a large number of side chains branch from the polyester main chain as the main component of the curable resin of the pressure-sensitive adhesive. The side chain of the curable resin molecule cures the resin by reacting with a crosslinking agent blended in the resin to form a crosslink, but the cured resin is cured to exhibit tack as a pressure sensitive adhesive. Since it is important that the resin has an appropriate hardness without losing flexibility, the crosslinking is limited to a part of the side chain. Side chains that are not cross-linked moderately bind each other by affinity with the main chain or side chain of a neighboring polyester molecule, and absorb and relax strain to some extent while restricting relative movement between molecules. That is, the non-crosslinked side chain has a function of acting on the cured resin layer elastically against an external pressure acting on the cured resin layer to enhance shape retention. Accordingly, it can be said that the polyester molecule preferably has a large number of side chains having a certain length of flexibility. However, in such a state where side chains can be closely arranged in parallel, there is a possibility that crystallization may occur due to the orientation of the side chains, so that the molecular structure has an appropriate interval between the side chains. Is preferred.

Polyesters with side chains that cause moderate binding between molecules as described above are produced by introducing branched side chains into functional groups by performing an addition reaction on the polyester molecules with functional groups bound to the polyester main chain. it can. Specifically, for example, a polyester (C) having a secondary hydroxyl group as a branching functional group is prepared, for example, by ring-opening addition polymerization of a dicarboxylic acid (a-1) and a bicyclic ether compound (a-2). The branched side chain in which the ring-opening structure is bonded to the polyester main chain through an ester bond is formed by ring-opening addition of a cyclic ester such as an acid anhydride or lactone. The side chain of the addition-type polyester produced | generated by such a ring-opening addition reaction has a carboxyl group or a hydroxyl group at the terminal, and can react with a crosslinking agent by this functional group. The side chain with an ester bond increases not only the binding between polyester molecules but also the affinity with the adherend by enhancing the affinity with the adherend by means of a carbonyl bond, and the tack to the adherend is also improved. To express. Therefore, such a side chain is advantageous as a side chain branched from the polyester main chain at an appropriate interval as described above, and is extremely advantageous. In particular, in the side chain formation by the ring-opening addition of the cyclic ester (b), a highly flexible side chain is formed, and when the ring-opening addition is multiplexed, the ester group is repeated in the ring-opening structural unit of the cyclic ester. Side chains are constituted by polyester chains intervening. This is preferable in terms of increasing the affinity of the side chain to the adherend and the affinity between adjacent molecules, and the side chain can be easily involved in the adjacent molecule due to the extension of the side chain. In order for the side chain to act effectively, it is preferable that the main chain is a saturated bond having a length corresponding to a straight-chain hydrocarbon group having about 4 or more carbon atoms and having flexibility. Ring-opening addition of cyclic esters (particularly lactones) is suitable as a method for forming branched side chains. For this reason, in the present invention, the curing that constitutes the adhesive composition so that the cured resin layer can suitably exhibit the shape retention and tack that are basic characteristics as a pressure-sensitive adhesive. An addition type polyester resin (D) having a side chain branched from the polyester main chain is used as the main component of the conductive resin. The side chain branched from the polyester main chain is a side chain having a ring-opening structural unit of the cyclic ester (b) and using the sealing agent (c).
The proportion (side chain content) of the side chain in the molecule of the polyester resin (D) is an approximate value from the weight of the raw materials used (dicarboxylic acid, bicyclic ether compound, cyclic ester and sealing compound). [= 100% × (weight of cyclic ester (b) + weight of sealing compound (c)) / total weight of raw material]. By setting this side chain content to an average value by weight ratio of 5 to 80%, preferably 7 to 70%, more preferably 10 to 60%, side chains can be contained at a suitable ratio and cured. The obtained resin acts elastically against external pressure and the like, has high shape retention, and exhibits a good function as a pressure sensitive adhesive.

  The ratio between the side chain that crosslinks and the side chain that does not crosslink (or the degree of crosslinking) can be adjusted by the ratio of the crosslinking agent blended in the polyester resin. Focusing on the fact that there is a relationship with the decrease in performance as an adhesive, it was found that the properties as a pressure-sensitive adhesive can be improved by improving the side chain of the polyester resin. Specifically, when the side chain has a hydroxyl group as a functional group, if the amount of hydroxyl groups remaining without crosslinking or hydroxyl groups remaining in the polyester main chain without forming side chains is large, the moisture resistance of the cured resin is increased. Considering this, since the heat resistance is lowered, in the present invention, the hydroxyl group bonded to the side chain and / or the polyester main chain is sealed with the sealing compound (c) so that the hydroxyl value becomes a predetermined amount or less. (D) is made into the main component of curable resin, a crosslinking agent (E) is mix | blended with this curable resin, and an adhesive composition is comprised. When the hydroxyl group bonded to the polyester main chain is sealed, a side chain having no hydroxyl group derived from the structure of the sealing compound (c) is formed.

  The sealing compound (c) is not limited to a compound in which a group having no functional group is bonded by sealing with a hydroxyl group, but may be a compound in which a group having a functional group other than a hydroxyl group is bonded by sealing. If the generated functional group can be used for crosslinking, the adhesive composition can be constituted in combination with a crosslinking agent that reacts with the functional group. That is, the type of the crosslinking agent (E) can be appropriately changed depending on the functional group contained in the polyester resin (D). Examples of the sealing compound (c) include a silylating agent, an acid anhydride, and an isocyanate compound, and the acid anhydride and the isocyanate compound are compounds having no hydroxyl group. When an acid anhydride is used as the sealing compound (c), a carboxyl group is generated instead of sealing the hydroxyl group, and this can be used for crosslinking.

  The hydroxyl value of the polyester resin (D) that is acceptable for improving the heat and moisture resistance of the cured resin is distinguished in two ways depending on the crosslinking agent (E) that is blended in the adhesive composition. In the case where the cross-linking agent to be blended reacts with a hydroxyl group, if the hydroxyl value of the polyester resin (D) is about 50 mgKOH / g or less, the reduction in wet heat resistance is suppressed. When a hydroxyl group and a carboxyl group coexist as functional groups of the polyester resin (D) and the compounded crosslinking agent (E) reacts with the carboxyl group, the hydroxyl value of the polyester resin (D) is about 100 mgKOH / g or less. Become. The reason for this is not clear, but the crosslinking agent for the carboxyl group has the property of coordinating or associating the hydroxyl group, and the action of the hydroxyl group and the outside is suppressed by the influence of the crosslinking agent, allowing up to about 100 mgKOH / g It is thought that it is done.

  By the sealing as described above, the side chain branched from the polyester main chain of the polyester resin (D) has a side chain that is crosslinked and a side chain that is not crosslinked and has no hydroxyl group (sealed). To do. That is, the polyester resin (D) of the present invention includes a side chain (first side chain) having a crosslinkable functional group and a side chain (second side chain) having no hydroxyl group (sealed). A polyester molecule in which a plurality of side chains are branched from the polyester main chain, and 15% or more of the total number of side chains contains a ring-opening structure of a cyclic ester with an ester bond (carbonyl bond), and is 30% or more. It is preferable. Depending on the form of sealing, each of the first and second side chains may or may not contain a cyclic ester ring-opening structure. If hydroxyl groups directly bonded to the polyester main chain remain, the polyester molecules are likely to aggregate in a lump due to the association of the hydroxyl groups, which makes it difficult to apply the adhesive composition. Therefore, in the present invention, an appropriate preparation method so that substantially all of the hydroxyl groups directly bonded to the raw material polyester main chain react with the cyclic ester (b) or the sealing compound (c), so that the residual hydroxyl groups are minimized. Is adopted. Based on this, the total number of side chains is equal to the number of secondary hydroxyl groups of the main chain polyester, and the number of secondary hydroxyl groups of the main chain polyester is the number of cyclic ether groups of the raw material and the secondary hydroxyl groups of the cyclic ether. Equal to the sum of the numbers. Therefore, in determining the ratio of the number of side chains containing the ring-opening structure of the cyclic ester, it can be estimated based on the number of secondary hydroxyl groups of the main chain polyester.

Below, the sealing form of a polyester resin (D) is demonstrated.
The molecular structure of the polyester resin (D) can be broadly classified into the following forms depending on the sealing form of the hydroxyl group. In the first form, side chains (first side chains) are formed by ring-opening addition to substantially all of the hydroxyl groups bonded to the polyester main chain, and at least a part of the formed side chains is sealed. Polyester resin (D1) converted to the second side chain by sealing the hydroxyl group with the compound (c), the second form is a part of the hydroxyl group bonded to the polyester main chain sealed with the sealing compound (c) Thus, the second side chain is formed, and the remaining hydroxyl group is a polyester resin (D2) in which a side chain (first side chain) is formed by ring-opening addition. The polyester resin (D2) of the second form further becomes a polyester resin (D3) of the third form having two types of second side chains by sealing a part of the hydroxyl groups of the first side chain. The 3rd form is useful at the point which enables correction of the amount of hydroxyl groups of polyester resin (D2) of the 2nd form. When an acid anhydride is used as the sealing compound (c), it is possible to seal all terminal hydroxyl groups of the side chain formed by ring-opening addition of a cyclic ester and use the carboxyl group for crosslinking. is there. However, if there are many functional groups capable of reacting with the cross-linking agent, the pot life of the adhesive composition is shortened due to the progress of the cross-linking reaction, and coating processability is reduced. Sealing is performed so that the hydroxyl group remains in the range of 50 mg KOH / g or less, and a crosslinking agent that reacts with the hydroxyl group is combined, or a compound that blocks the carboxyl group is further acted to reduce the acid value. Use a crosslinking agent for the carboxyl group. In order for the pot life and coating processability of the adhesive composition to be good and the crosslinking agent to act effectively, when the crosslinking agent reacts with a hydroxyl group, the hydroxyl value of the polyester resin (D) is 0.1. When the crosslinking agent reacts with a carboxyl group, the acid value is preferably about 0.1 to 50 mg KOH / g, and more preferable ranges are about 0.5 to 30 mg KOH / g, respectively. In any of the above-mentioned sealing forms, the reaction conditions and the mixing ratio of the raw materials are adjusted so that the acid value and the hydroxyl value of the polyester resin become appropriate values according to the type of the crosslinking agent to be blended. That is, when the crosslinking agent (E) is reactive with a hydroxyl group, the crosslinking agent (E) is reactive with a carboxyl group so that the hydroxyl value of the polyester resin (D) is 50 mgKOH / g or less. In this case, the sealing compound (c) and its use amount are appropriately adjusted so that the hydroxyl value of the polyester resin (D) is 100 mgKOH / g or less and the acid value is 50 mgKOH / g or less.

  The adjustment method of a polyester resin (D) is suitably selected according to a sealing form. In any of the first to third embodiments, the polyester resin (D) is produced by three reactions including a polyester main chain forming reaction, a side chain forming reaction, and a hydroxyl group sealing reaction.

  Specifically, the polyester main chain formation reaction is a polyaddition reaction between a dicarboxylic acid (a-1) and a bicyclic ether compound (a-2). Dicarboxylic acid (a-1) is a dibasic acid compound having two carboxyl groups (hereinafter sometimes referred to as dibasic acid (a-1)), and bicyclic ether (a-2) is a cyclic ether. A compound having two groups, both of which are bifunctional compounds. Trifunctional or higher polyfunctional compounds can be used, but bifunctional compounds are easy to control in terms of molecular design. As the ring opening of the cyclic ether group and the addition of the carboxyl group proceed, the polymer main chain (I) is extended by polymerization, and a hydroxyl group directly connected to the polyester main chain (I) is generated. Increases to form a polyester main chain having a plurality of hydroxyl groups.

  The side chain formation reaction is a ring-opening addition of the cyclic ester (b) to the hydroxyl group of the polyester main chain, and an addition type polyester in which the side chain branches from the polyester main chain (I) is generated. As the first side chain (II) having a crosslinkable functional group, it has at least one ring-opening structural unit of the cyclic ester (b) bonded to the chain (I) via an ester bond and a terminal hydroxyl group. Can work. Since this ring-opening addition has higher reactivity when the ratio of the cyclic ester (b) to the hydroxyl group is higher, a production method with good side chain formation efficiency is provided by devising the preparation process.

  The hydroxyl group sealing reaction is an addition reaction of the sealing compound (c) to the hydroxyl group of the side chain formed by ring-opening addition of the cyclic ester (b) or the hydroxyl group of the polyester main chain. A side chain having a structure sealed with the stopper compound (c), that is, a second side chain (II ′) having no hydroxyl group is formed. When the sealing compound (c) is an acid anhydride, a side chain having a carboxyl group at the terminal is formed, and this side chain can also be used as the first side chain (II). Since the hydroxyl group of the side chain is more reactive than the hydroxyl group of the polyester main chain, in the second and third embodiments including the sealing of the hydroxyl group directly bonded to the polyester main chain, the hydroxyl group is blocked before the side chain addition reaction. It is preferable that a stop reaction is performed. In the first embodiment, a small amount of the cyclic ester (b) is reacted so that the hydroxyl group directly bonded to the polyester main chain remains, and the side chain hydroxyl group formed by the ring-opening addition of the cyclic ester (b) If an excessive amount of the sealing compound (c) is reacted, the residual hydroxyl group directly bonded to the polyester main chain can also be sealed with the sealing compound (c).

  Below, the detail of the preparation method of the polyester resin (D) in each of the 1st-3rd sealing form is demonstrated.

  In the first sealing form, a side chain is formed by the cyclic ester (b) on substantially all of the hydroxyl groups directly bonded to the polyester main chain, and a part of the side chain is sealed by the sealing compound (c). It is preferable. Such an addition-type polyester resin (D1) can be obtained by three kinds of manufacturing methods as described below: a three-stage type, a pseudo two-stage type, and a two-stage type.

The three-stage production method is a method for obtaining an addition-type polyester resin (D1) stepwise by the following three steps (1) to (3).
Step (1): Dibasic acid (a-1) and dicyclic ether compound, ie, compound (a-2) having two cyclic ether groups, are subjected to ring-opening addition polymerization to form dibasic acid (a-1) and dibasic acid (a-1). Polyester (B) having a polyester main chain (I) in which structural units derived from the cyclic ether compound (a-2) are alternately and repeatedly connected via ester bonds, and a plurality of hydroxyl groups directly connected to the polyester main chain (I) (B ).
Step (2): A side chain composed of a ring-opening structural unit of the cyclic ester (b) is obtained by ring-opening addition reaction of the cyclic ester (b) with the hydroxyl group directly bonded to the polyester main chain (I) of the polyester ( A step of obtaining an addition-type polyester precursor (C1) by forming II).
Step (3): A part of the terminal hydroxyl group of the side chain (II) of the addition-type polyester precursor (C1) is reacted with the sealing compound (c) to form a side chain having no hydroxyl group (sealed) ( A step of reducing the hydroxyl value of the polyester resin (D1) by forming II ′).

  This three-stage production method is advantageous in adjusting the reaction conditions because changes in the degree of polymerization and the hydroxyl value can be confirmed by measurements before and after steps (2) and (3). However, since the hydroxyl group to which the cyclic ester (b) is added in the step (2) is present in the polyester in a dense state in the polyester produced as a result of the step (1), hydrogen bonding occurs, and the step (1) The resulting polyester becomes very viscous and agglomerates, hindering the efficiency of the addition reaction in step (2). In this respect, the pseudo two-stage type and the two-stage type manufacturing method described later are more advantageous.

The pseudo two-stage manufacturing method is a method of obtaining an addition-type polyester resin (D1) step by step through the following three steps (4) to (6).
Step (4): Opening the dibasic acid (a-1) and the bicyclic ether compound (a-2) in an amount corresponding to a part of the polyester main chain (I), for example, about 50 to 70% (weight conversion) In this process, a polyester having an acid value of about 5 gKOH / g is obtained by cycloaddition polymerization. In this polyester, each structural unit derived from a dibasic acid (a-1) and a bicyclic ether compound (a-2) has an ester bond. It is the same as the polyester of the step (1) in that it has a polyester main chain (I ′) alternately and repeatedly connected via a plurality of hydroxyl groups directly connected to the polyester main chain (I ′).
Step (5): The cyclic ester (b) is added to the polyester main chain (I ′), and the cyclic ester (b) is added to the hydroxyl group of the polyester main chain (I ′) to form the side chain (II). In addition, the polyester main chain (I ′) is extended by addition polymerization of the remaining dibasic acid (a-1) and bicyclic ether compound (a-2) to complete the formation of the main chain, thereby adding type polyester. A step of obtaining a precursor (C1).
Step (6): A part of the terminal hydroxyl group of the side chain (II) of the addition type polyester precursor (C1) is reacted with the sealing compound (c) to form a side chain having no hydroxyl group (sealed) ( A step of obtaining a polyester resin (D1) having II ′).

  The steps (4) and (5) may be a series of work steps. In this pseudo two-stage production method, the formation of the polyester main chain in the step (4) is in progress, and the ratio of the cyclic ester (b) to the amount of hydroxyl groups in the polyester main chain (I ′) is high in the step (5). Therefore, the reaction efficiency of the ring-opening addition of the cyclic ester (b) is improved and the side chain is easily formed. Therefore, the unreacted hydroxyl group remaining in the polyester main chain of the addition-type polyester precursor (C1) is easier to reduce in the pseudo two-stage type than in the three-stage type of the previous operation. However, on the other hand, since the hydroxyl group of the polyester main chain (I ′) produced in the step (5) also contributes to the formation of hydrogen bonds, it is unlikely to have a high viscosity as compared with the case of the three-stage type. However, the two-stage type described later is more preferable.

The two-stage production method is a method for obtaining an addition-type polyester resin (D1) stepwise by two steps of the following steps (7) to (8).
Step (7): The dibasic acid (a-1), the bicyclic ether compound (a-2), and the cyclic ester (b) are reacted at the same time to allow polyaddition and ring-opening addition to proceed in parallel. The polyester main chain (I) in which the structural units derived from the acid (a-1) and the bicyclic ether compound (a-2) are alternately and repeatedly connected via an ester bond, and the ester bond on the polyester main chain (I) The side chain (II) comprised by the ring-opening structural unit of the cyclic ester (b) couple | bonded through this is formed in parallel, and the addition type polyester precursor (C1) is obtained.
Step (8): A part of the terminal hydroxyl group of the side chain (II) of the addition-type polyester precursor (C1) is reacted with the sealing compound (c) to form a side chain having no hydroxyl group (sealed) ( A step of obtaining a polyester resin (D1) having II ′).

  In this two-stage production method, the addition of the side chain proceeds simultaneously with the formation of the polyester main chain in step (7), and the ratio of the cyclic ester (b) to the amount of hydroxyl groups in the polyester main chain becomes extremely high. The reaction efficiency of the ring-opening addition of the ester (b) is further improved. Therefore, the unreacted hydroxyl groups remaining in the polyester main chain of the addition-type polyester precursor (C1) are more easily reduced in the two-stage type than in the pseudo-stage type of the previous operation. Further, since the association and agglomeration of the polyester molecules due to the hydroxyl group directly bonded to the polyester main chain does not substantially occur, the reaction system can be easily made uniform and the reaction efficiency is very good.

  That is, the difference between the above three production methods is that when the precursor addition type polyester (C1) having the polyester main chain (I) and the side chain (II) is obtained, the formation of the side chain (II) is started. The degree of formation of the polyester main chain (I) is either completed, in the middle of formation, or not formed, and the reaction efficiency in the ring-opening addition of the cyclic ester (b) is different.

Next, the manufacturing method of addition type polyester resin (D2) in a 2nd sealing form is demonstrated.
In the addition type polyester resin (D2) of the second sealing form, a part of the hydroxyl group directly bonded to the polyester main chain (I) is sealed with the sealing compound (c) and has no hydroxyl group (sealed). ) The second side chain (II ′) is formed, and the first side chain (II) containing the ring-opening structural unit of the cyclic ester (b) is added to the remaining hydroxyl group. The second side chain (II ′) does not contain the ring-opening structural unit of the cyclic ester (b). In the production of the addition-type polyester resin (D2), before the ring-opening addition of the cyclic ester (b), the hydroxyl group directly bonded to the polyester main chain is reacted with the sealing compound (c). The reason why the sealing reaction is performed first is that the residual hydroxyl group after the side chain formed by the cyclic ester (b) is easily inhibited by the side chain and can remain after the sealing reaction.

  The production method of the addition type polyester resin (D2) in the second sealing form is the same as in the first sealing form in that the polyester at the start of the formation of the second side chain (II ′) by the sealing compound (c) It can be obtained by three different production methods depending on the degree of formation of the main chain.

The three-stage production method is a method of obtaining an addition-type polyester resin (D2) stepwise by the following three steps (9) to (11).
Step (9): From the polyaddition of dibasic acid (a-1) and bicyclic ether compound (a-2), each derived from dibasic acid (a-1) and bicyclic ether compound (a-2) A step of obtaining a polyester (B) having a polyester main chain (I) in which structural units are alternately and repeatedly connected through ester bonds and a plurality of hydroxyl groups directly connected to the polyester main chain (I).
Step (10): The sealing compound (c) is reacted with a part of the hydroxyl group directly bonded to the polyester main chain (I) to form a hydroxyl group-free (sealed) second side chain (II ′). And reducing the number of hydroxyl groups to obtain an addition-type polyester precursor (C2).
Step (11): The cyclic ester (b) is reacted with the residual hydroxyl group of the addition-type polyester precursor (C2) in which the second side chain (II ′) is formed, and the ring-opening structural unit of the cyclic ester (b) and The process of obtaining addition type polyester resin (D2) by forming the 1st side chain (II) containing a terminal hydroxyl group.

  In the case of the second sealing form, in step (10), a part of the hydroxyl group directly bonded to the main chain (I) is reacted with the sealing compound (c) to reduce the hydroxyl group, and in step (11) The rate at which one side chain is formed is controlled by the degree of sealing in step (10).

The pseudo two-stage manufacturing method is a method of obtaining an addition type polyester resin (D2) stepwise by the following three steps (12) to (14).
Step (12): Opening the dibasic acid (a-1) and the bicyclic ether compound (a-2) in an amount corresponding to a part of the polyester main chain (I), for example, about 50 to 70% (weight conversion) In this process, a polyester having an acid value of about 5 gKOH / g is obtained by cycloaddition polymerization. In this polyester, each structural unit derived from a dibasic acid (a-1) and a bicyclic ether compound (a-2) has an ester bond. It is the same as the polyester of the step (9) in that it has a polyester main chain (I ′) alternately and repeatedly connected via a plurality of hydroxyl groups directly connected to the polyester main chain (I ′).
Step (13): The sealing compound (c) is added to the polyester main chain (I ′), and the sealing compound (c) is reacted with the hydroxyl group of the polyester main chain (I ′) to form the second side chain (II ') And the polyester main chain (I') is extended by polyaddition of the remaining dibasic acid (a-1) and bicyclic ether compound (a-2) to complete the formation of the main chain. A step of obtaining an addition-type polyester precursor (C2).
Step (14): The cyclic ester (b) is subjected to ring-opening addition to the residual hydroxyl group of the addition-type polyester precursor (C2), and the first side chain (II) containing the ring-opening structural unit and terminal hydroxyl group of the cyclic ester (b) (II) ) To obtain a polyester resin (D2).

  The steps (12) and (13) can be a series of work steps. The pseudo two-stage production method is a three-stage production method in which the amount of hydroxyl groups in the polyester main chain (I ′) in the step (13) is determined by the previous operation because the formation of the polyester main chain in the step (12) is in progress. Therefore, the reaction with the sealing compound (c) is less likely to be inhibited by the agglomeration of the polyester due to the association of the hydroxyl group directly bonded to the polyester main chain, and the cyclic ester (C2) with respect to the addition-type polyester precursor (C2) The reaction efficiency of b) ring-opening addition is also relatively good.

The two-stage production method is a method for obtaining an addition-type polyester resin (D2) stepwise by the following two steps (15) to (16).
Step (15): The dibasic acid (a-1), the bicyclic ether compound (a-2), and the sealing compound (c ′) are reacted at the same time to allow the polyaddition and the sealing reaction to proceed in parallel. Directly connected to the polyester main chain (I) and the polyester main chain (I) in which the structural units derived from the dibasic acid (a-1) and the bicyclic ether compound (a-2) are alternately and repeatedly connected via ester bonds And a second side chain (II) having a structure in which a hydroxyl group to be sealed is sealed with a sealing compound (c ′) to form an addition type polyester precursor (C2).
Step (16): The cyclic ester (b) is subjected to ring-opening addition to the residual hydroxyl group of the addition-type polyester precursor (C2), and the first side chain containing the ring-opening structural unit and terminal hydroxyl group of the cyclic ester (b) ( II) and a step of obtaining a polyester resin (D2) having the second side chain (II ′) having no (sealed) hydroxyl group.

  In this two-stage production method, the sealing of the hydroxyl group proceeds simultaneously with the formation of the polyester main chain in the step (15), and the association and agglomeration of the polyester molecules due to the hydroxyl group directly bonded to the polyester main chain does not occur. Therefore, it is easy to make the reaction system uniform and very easy to react. Therefore, the reaction efficiency of the two-stage type is better than the pseudo-stage type of the previous operation.

The difference between the above three production methods is that when the precursor addition type polyester (C2) having the polyester main chain (I) and the side chain (II ′) is obtained, the formation of the side chain (II ′) is started. The degree of formation of the polyester main chain (I) is either complete, in the middle of formation, or not formed. In this case, in order to prevent the extension of the side chain (II ′) by the sealing compound (c ′) from being superior to the extension of the polyester main chain (I), the sealing compound (c ′) is a monofunctional compound. Need to be.
Since the reduction in the uniformity of the reaction system due to the agglomeration of the reaction intermediate has a large influence on the reaction efficiency, the pseudo two-stage type and two-stage type production methods are preferred in this regard. On the other hand, a three-stage manufacturing method is suitable for examining the material characteristics and reaction states of the produced polyester resin (D). Therefore, what is necessary is just to select the manufacturing method of a polyester resin (D) suitably from the above-mentioned manufacturing method as needed.

Next, the manufacturing method of the addition type polyester resin (D3) of the 3rd sealing form is demonstrated.
The addition type polyester resin (D3) in the third sealing form is obtained by further reacting the addition type polyester resin (D2) in the second sealing form with the sealing compound (c) to obtain the addition type polyester resin (D2). It is obtained through a step (17) of sealing a part of the hydroxyl group at the terminal of the first side chain (II) containing the ring-opening structural unit of the cyclic ester (b) therein. That is, the manufacturing method according to the third sealing form includes any of the three-stage type, pseudo two-stage type, or two-stage type of the manufacturing method according to the second sealing form, and the above-described step (17). .
Such an addition-type polyester resin (D3) has a polyester main chain (I) in which structural units derived from dibasic acid (a-1) and bicyclic ether compound (a-2) are alternately and repeatedly bonded via ester bonds. ), The first side chain (II) having a ring-opening structural unit and a terminal hydroxyl group of the cyclic ester (b), and the side in which the hydroxyl group directly bonded to the polyester main chain (I) is sealed with the sealing compound (c) The chain and the terminal hydroxyl group of the first side chain (II) have two types of second side chains (II ′) of the side chain sealed with the sealing compound (c).

  In the second and third sealing forms, the side chain branched from the polyester main chain, that is, about 15% or more of the number of hydroxyl groups that the polyester main chain may have is the ring-opening structural unit of the cyclic ester (b). The addition-type polyester resin is preferably prepared so as to contain, more preferably 30% or more of the total number of hydroxyl groups in the side chain contains a ring-opening structural unit, so that the property derived from the cyclic ester (b) is effective. Demonstrated and preferred.

  In the said 1st-3rd sealing form, when an acid anhydride is used as a sealing compound (c), it seals by combining the compound which carries out a crosslinking reaction with respect to a carboxyl group as a crosslinking agent (E). The formed second side chain (II ′) also functions as the first side chain (I) having a functional group, and may be completely sealed in terms of hydroxyl value. However, in this case, it is necessary to regulate the acid value of the resin to a predetermined value or less in order to prevent a decrease in pot life and coating processability due to an increase in the crosslinking speed, and the amount of acid anhydride used is limited. For this reason, it copes by using sealing compound (c) other than an acid anhydride together.

Each raw material used for the manufacturing method of addition type polyester resin (D1), (D2), (D3) is demonstrated below.
As the dibasic acid (a-1) used for forming the polyester main chain (I), a known dicarboxylic acid compound (a-1-1) having a relatively low molecular weight (for example, a molecular weight of about 90 to 500) is used as it is. These include various dicarboxylic acids, anhydrides and derivatives thereof as described below, and any of aliphatic compounds, aromatic compounds and alicyclic compounds may be used.

  Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, Examples include glutaric acid, itaconic acid, succinic anhydride, maleic anhydride and the like, and these aliphatic dicarboxylic acids and anhydrides thereof can be used. Derivatives of succinic anhydride (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl anhydride Succinic acid, etc.), glutaric anhydride derivatives (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc. ), Maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecyl Maleic anhydride, 2,3-dichloromaleic anhydride, phenyl maleic anhydride Phosphate, also anhydride derivatives such as 2,3-diphenyl maleic anhydride, etc.) can be utilized.

    Examples of the aromatic dicarboxylic acid include o-phthalic acid, isophthalic acid, terephthalic acid, 2,5-dimethylterephthalic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Acid, norbornene dicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, phenylindanedicarboxylic acid, phthalic anhydride, 4-methylphthalic anhydride, and the like, and these aromatic dicarboxylic acids and anhydrides thereof can be used. . Hexahydrophthalic anhydride derivatives ((3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), tetrahydrophthalic anhydride derivatives (1,2,3,6-tetrahydrophthalic anhydride, 3 -Methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) The phthalic anhydride derivative can also be used.

  Examples of the alicyclic dicarboxylic acid include dimer acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid and the like, and these alicyclic dicarboxylic acids and anhydrides thereof are used. it can.

  Further, chlorendic anhydride, anhydrous head acid, biphenyldicarboxylic anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3 , 6-tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, octahydro- Examples include 1,3-dioxo-4,5-isobenzofurandicarboxylic anhydride.

  These low molecular weight dicarboxylic acid compounds (a-1-1) can be used alone or in combination of two or more as dibasic acid (a-1).

In the present invention, a dicarboxylic acid compound having a higher molecular weight than the low molecular weight dicarboxylic acid compound (a-1-1) can be used as the dibasic acid (a-1). Things.
For example, an average of about 2 per molecule obtained by reacting the low molecular weight dicarboxylic acid compound (a-1-1) with a polyol component (a-1-α) described below under an excess of carboxylic acid. High molecular weight dicarboxylic acid having a carboxyl group (a-1-2); a tri- or higher functional polycarboxylic acid compound (a-1-β) and a polyol component (a-1-α) described below under conditions of excess carboxylic acid A high-molecular-weight dicarboxylic acid (a-1-3) having an average of about 2 carboxyl groups per molecule obtained by reaction under the above; and the low-molecular-weight dicarboxylic acid compound (a-1-1) described later. Polyamide dicarboxylic acid (a-1-4) obtained by reacting polyamines (a-1-γ) with carboxylic acid in excess can be used as dibasic acid (a-1).

  The polyol component (a-1-α) used for the preparation of the high molecular weight dicarboxylic acid (a-1-2, a-1-3) includes a relatively low molecular weight diol having a number average molecular weight of about 50 to 500. (A-1-α-1) and relatively high molecular weight polyols (a-1-α-2) having a number average molecular weight of 500 to 50,000.

  Examples of relatively low molecular weight diols (a-1-α-1) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, and 3-methyl-1,5-pentanediol. 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, poly Oxyethylene glycol (addition mole number 10 or less), polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Hexanediol, 1,9-nonanediol, neopentyl glycol, octa Aliphatic or alicyclic diols such as diol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol; 1 , 3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, addition-type bisphenol obtained by adding alkylene oxide to bisphenol, etc. Aromatic diols Etc. Examples of the raw material bisphenol of addition-type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.

  The above relatively low molecular weight diols may be used alone or in combination of two or more.

  Examples of the relatively high molecular weight polyols (a-1-α-2) include high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. High molecular weight polycarbonate polyols are obtained by the reaction of relatively low molecular weight diols with carbonates or phosgene.

  Examples of commercially available high molecular weight polyester polyols include Byron GK640 manufactured by Toyobo Co., Ltd. [number average molecular weight (hereinafter also referred to as “Mn”) = 18,000, glass transition temperature (hereinafter also referred to as “Tg”). Described) = 79 ° C., hydroxyl value = 5, acid value <4, linear type], Byron GK880 (Mn = 18,000, Tg = 84 ° C., hydroxyl value = 5, acid value <4, linear type), Byron 300 (Mn = 23,000, Tg = 7 ° C., hydroxyl value = 5, acid value <2, linear type), Byron 500 (Mn = 23,000, Tg = 4 ° C., hydroxyl value = 5, acid value <2) , Linear type), Byron 560 (Mn = 19000, Tg = 7 ° C., hydroxyl value = 8, acid value <2, branched type) and Byron 630 (Mn = 20,000, Tg = 75 ° C., hydroxyl group) Value = 5, acid value UE-3600 (Mn = 20,000, Tg = 75 ° C., hydroxyl value = 4, acid value = 1), UE-3690 (Mn = 14,000, Tg = 91 ° C.) manufactured by Kuraray Co., Ltd. , Hydroxyl value = 8, acid value = 1) [manufactured by Unitika Ltd.], P1010 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), P2010 (Mn = 2, 000, hydroxyl value = 56, acid value <0.5, linear liquid type), P4010 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), P5010 (Mn = 5, 000, hydroxyl value = 22, acid value <0.5, linear liquid type), P6010 (Mn = 6,000, hydroxyl value = 19, acid value <0.5, linear liquid type), P4050 (Mn = 4, 000, hydroxyl value = 28, acid value <0.5, linear liquid Y), P6010 (Mn = 6,000, hydroxyl value = 19, acid value <0.5, linear liquid type), N4010 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid) Type), PNOA4014 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), P2011 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type) Type) and P4011 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type); Kyowapol 2000BA (Mn = 2,000, hydroxyl value = 58) manufactured by Kyowa Hakko Chemical Co., Ltd. , Acid value <0.5, linear liquid type), and Kyowapol 5000PA (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type).

  As a commercial product of the high molecular weight polyamide polyol, TPAE617 (Mn = 15,000, Tg = 90 ° C., hydroxyl value = 16, acid value = 1, linear type) manufactured by Fuji Kasei Kogyo Co., Ltd. can be used.

  Commercially available products of the above high molecular weight polycarbonate polyol include, for example, Oxomer N112 (Mn = 1,000, Tg = 60 ° C., hydroxyl value = 112, acid value <0.5, linear type) manufactured by Perstorp; Asahi Kasei Chemicals Corporation PCDL-T5651 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), PCDL-T5652 (Mn = 2,000, hydroxyl value = 56, acid value <0.05) , Linear liquid type), PCDL-T4671 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), and PCDL-T4672 (Mn = 2,000, hydroxyl value = 52, Acid value <0.05, linear liquid type); PMHC-1050 manufactured by Kuraray Co., Ltd. (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid tie) ), PMHC-2050 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), C-1090 (Mn = 1,000, hydroxyl value = 112, acid value <0.5). , Linear liquid type), C-2090 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), C-3090 (Mn = 3,000, hydroxyl value = 37, acid value). <0.5, linear liquid type), C-4090 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), C-5090 (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type), C-1065N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), C-2065N (Mn = 2,000) , Hydroxyl value = 56, acid value <0.5, linear liquid type), C-1 15N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type) and C-2015N (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear) Liquid type).

  Examples of commercially available high molecular weight polyurethane polyols include Byron UR1350 (Mn = 30,000, Tg = 3 ° C., hydroxyl value = 46, acid value <1, linear type) manufactured by Toyobo Co., Ltd., Byron UR1400 (Mn = 40,000, Tg = 83 ° C, hydroxyl value = 2, acid value <1, linear type), Byron UR3210 (Mn = 40,000, Tg = -3 ° C, hydroxyl value = 3, acid value <1, linear) Type), Byron UR5537 (Mn = 20,000, Tg = 34 ° C., hydroxyl value = 17, acid value <1, linear type), and Byron UR9500 (Mn = 25,000, Tg = 15 ° C., hydroxyl value = 5, acid value <1, linear type); Takelac E158 (hydroxyl value = 20, acid value <3), Takelac E551T (hydroxyl value = 30, acid) manufactured by Mitsui Chemicals Polyurethanes <3), and, Takelac A2789 (hydroxyl value = 10, acid number <2), and the like.

  In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly (β-methyl-γ-valerolactone) diol, polyvalerolactone diol, and the like are also used for the high molecular weight polyol (a-1- Included in high molecular weight diols that can be used as α-2).

  In the present invention, the high molecular weight polyols (a-1-α-2) can be used alone or in combination of two or more. Moreover, it can also use together with the said low molecular weight polyol. Among these polyols, when a bifunctional diol is used, a pressure-sensitive adhesive having excellent adhesiveness, heat resistance, moist heat resistance and transparency can be obtained, and thus a bifunctional diol is most preferable.

  The molecular weight of the high molecular weight polyols (a-1-α-2) is not particularly limited as long as it can be dissolved in the solvent used, but the number average molecular weight (Mn) is in the range of 500 to 50,000. Polyol (a-1-3b) is preferred. When such a high molecular weight polyol (a-1-3b) is used, a pressure-sensitive adhesive having excellent adhesion and wettability can be obtained. More preferably 1,000 to 30,000, most preferably 1,000 to 10,000 are used. When the number average molecular weight (Mn) of the high molecular weight polyol (a-1-α-2) is smaller than 500, the resulting addition type polyester resins (D1) to (D3) become excessively hard, and the adhesive composition When the pressure-sensitive adhesive sheet is formed by preparing the above, initial adhesiveness (tack) is hardly expressed. Moreover, when the plastics or a glass plate and a plastic film are laminated | stacked using the pressure sensitive adhesive composition containing addition type polyester resin (D1)-(D3) which is too hard, adhesive strength will become weak and such lamination | stacking will be carried out. It becomes easier to peel off when the body is kept under high temperature and high humidity for a long time. On the other hand, when Mn of the high molecular weight polyols (a-1-α-2) exceeds 50,000, the solubility of the addition type polyester resins (D1) to (D3) in the solvent is reduced, and the pressure sensitive type Since the viscosity of the adhesive increases, handling during coating becomes difficult, which is not preferable.

  The glass transition temperature (Tg) of the high molecular weight polyols (a-1-α-2) is not particularly limited, but is preferably −70 to 80 ° C., more preferably −50 to 20 ° C. When the glass transition temperature is less than -70 ° C, the adhesiveness and cohesive force of the adhesive composition may be insufficient, and cohesive failure may occur after lamination, resulting in peeling. On the other hand, when the temperature exceeds 80 ° C., the coating film becomes too hard and the initial adhesiveness (tack) may not be exhibited or the coating processability may be affected. The glass transition temperature of the high molecular weight polyols (a-1-α-2) can be adjusted by appropriately selecting the types of polycarboxylic acid, polyamine and low molecular weight polyol which are the raw materials. Moreover, it can also adjust to a suitable glass transition temperature using 2 or more types of polyol from which glass transition temperature differs.

  The hydroxyl value of the high molecular weight polyols (a-1-α-2) is preferably in the range of 5 to 200 mgKOH / g, more preferably in the range of 10 to 100 mgKOH / g. When the hydroxyl value exceeds 200 mgKOH / g, the addition type polyester resins (D1) to (D3) become too hard, and the initial adhesiveness (tack) may be difficult to be exhibited. When the hydroxyl value is less than 5 mg KOH / g, the solubility of the addition-type polyester resins (D1) to (D3) in the solvent is decreased, and the viscosity of the prepared adhesive composition is increased. This makes it difficult to handle and hinders workability.

  Next, trifunctional or higher polycarboxylic acids (a-1-β) used to react with the high molecular weight polyols (a-1-α) to obtain high molecular weight dicarboxylic acids (a-1-3) Will be described.

  The trifunctional or higher polycarboxylic acid (a-1-β) preferably has an anhydride ring, and the trifunctional or higher polycarboxylic acid (a-1-β) having one anhydride ring may be And trimellitic anhydride. Examples of the tri- or higher functional polycarboxylic acid (a-1-β) having two or more anhydride rings include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2, 3,5-tricarboxycyclopentylacetic acid dianhydride, 2,3,5,6-tetracarboxycyclohexane dianhydride, 2,3,5,6-tetracarboxynorbornane dianhydride, 3,5,6-tricarboxy Norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene- , 2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic anhydride, 1,2,4 5-Benzenetetracarboxylic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic Acid dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3,3 '-Biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracar Acid dianhydride, naphthalene-1,8: 4,5-tetracarboxylic dianhydride, 4,4 '-(hexafluoropropylidene) diphthalic anhydride, 3,3', 4,4'-biphenyl Ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1, 2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) Diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic acid Water, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m- Phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 9 , 9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene anhydride, ethylene glycol bis (anhydrotrimellitate), 3,4-dicarboxy-1,2,3,4-tetrahydro- 1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride Product, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, methyl nadic anhydride, allyl Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, allylmethyl Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, etc. Can be mentioned.

    The low molecular weight dicarboxylic acids (a-1-1) and the polycarboxylic acids (a-1-β) are each used alone or in combination of two or more for reaction with the polyol (a-1-α). be able to. Low molecular weight dicarboxylic acids (a-1-1) or polycarboxylic acids (a-1-β) used in the reaction with polyols (a-1-3) Use of an anhydride is preferable because a pressure-sensitive adhesive excellent in adhesiveness, heat resistance, moist heat resistance and transparency can be obtained.

In the present invention, the low molecular weight dicarboxylic acid (a-1) is used as the dibasic acid (a-1) for forming the polyester main chain (I), rather than using the low molecular weight dicarboxylic acid (a-1-1) as it is. -1) or a relatively high molecular weight dicarboxylic acid (a-1-2, obtained by previously reacting a tri- or higher functional polycarboxylic acid (a-1-β) with the polyol component (a-1-α) in advance. a-1-3) is preferably used.
When the polyester main chain (I) is formed using the high molecular weight dicarboxylic acid (a-1-2, a-1-3) as the dibasic acid (a-1), the low molecular weight dicarboxylic acid (a-1- Since the distance between the ester bonds in the polyester main chain (I) generated by polyaddition is longer than when the 1) is used as it is and an appropriate space is generated between the secondary hydroxyl groups, The agglomeration is suppressed, and at the same time, the hydroxyl value of the addition type polyester resins (D1) and (D2) can be easily reduced. When a pressure-sensitive adhesive composition is prepared using such addition-type polyester resins (D1) and (D2), it is possible to maintain a balance of adhesive properties (particularly, compatibility between tack and cohesive force). Become. Therefore, it is preferable to form the polyester main chain (I) using a high molecular weight dicarboxylic acid (a-1-2, a-1-3) as the dibasic acid (a-1).

Polyamide dicarboxylic acid (a-1-4), which can be used as dibasic acid (a-1), is a combination of low molecular weight dicarboxylic acid (a-1-1) and polyamine (a-1-γ). The product is condensed under the above conditions and has two carboxyl groups at the ends and is linked by an amide bond.
The polyamine (a-1-γ) used for the preparation of the polyamide dicarboxylic acid can be used without particular limitation as long as it is a polyamine having two or more primary amino groups.

For example, aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene branches at both molecular ends. Polypropylene glycol with an amino group bonded to carbon (propylene skeleton diamine, products “Jephamine D230” and “Jephamine D400” manufactured by Sun Techno Chemical Co., Ltd.), propylene skeleton triamine, product “Jeffamine T403” manufactured by Sun Techno Chemical Co., Ltd. Etc., ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethyl Perazine, 1,2-diaminopropane, iminobispropylamine, methyl _{iminobispropylamine, H 2 N (CH 2 CH} 2 O) 2 (CH 2) 2 NH 2 [diamine San Techno Chemical Co. ethylene glycol skeleton " Such as Jeffermine EDR148 "], a polyether diamine with a methylene group bonded to an amine nitrogen, 1,5-diamino-2-methylpentane (" MPMD "manufactured by DuPont Japan), metaxylylenediamine (DuPont Japan) “MXDA”), polyamidoamine (“X2000” manufactured by Sanwa Chemical Co., Ltd.), isophoronediamine, 1,3-bisaminomethylcyclohexane (“1,3BAC” manufactured by Mitsubishi Gas Chemical), 1-cyclohexylamino-3 -Aminopropane, 3-aminomethyl-3,3,5-trimethyl-silane Russia hexylamine, can be mentioned dimethylene amine of norbornane skeleton (manufactured by Mitsui Chemicals, Inc. "NBDA"), and the like.

In addition, ketimine, which is a reaction product of the above polyamine and ketone, can also be used as a polyamine (a-1-γ) for the preparation of polyamide dicarboxylic acid, and is preferable from the viewpoint of adjustment of polymerization stability and reactivity. A reaction product of acetophenone or propiophenone and 1,3-bisaminomethylcyclohexane; A reaction product of acetophenone or propiophenone and dimethyleneamine (NBDA) of norbornane skeleton; Acetophenone or propiophenone and metaxylylenediamine Reaction product of: acetophenone or propiophenone and Jeffamine EDR148, Jeffamine D230 and Jeffamine D400, which are diamines having an ethylene glycol skeleton or a propylene skeleton, or Jeffamine T403, which is a triamine having a propylene skeleton And the like.
Each of the above polyamines may be used alone or in combination of two or more.

  In the present invention, the dibasic acid (a-1) used for forming the polyester main chain (I) having a hydroxyl group at the side chain position is the above low molecular weight dicarboxylic acid (a-1-1), high molecular weight dicarboxylic acid. One or more of acids (a-1-2, a-1-3) and polyamide dicarboxylic acids (a-1-4) can be appropriately selected and used.

  Next, the bicyclic ether compound (a-2) for forming the polyester main chain (I), that is, a compound having two cyclic ether groups in the molecule will be described. The bicyclic ether compound (a-2) undergoes a polyaddition reaction with the dibasic acid (a-1) to produce an ester bond and a secondary hydroxyl group. The structural units derived from the dibasic acid (a-1) and the bicyclic ether compound (a-2) are alternately and repeatedly bonded via ester bonds to form the polyester main chain (I). The secondary hydroxyl group is directly connected to the polyester main chain (I) and is involved in the formation of branched side chains.

  As the bicyclic ether compound (a-2) used in the present invention, a compound containing a known glycidyl group and / or oxetanyl group can be preferably used. The compound having a glycidyl group, that is, the glycidyl compound may be an aliphatic compound, an aromatic compound, or an alicyclic compound, or may be a high molecular weight resin.

  Examples of the aliphatic diglycidyl compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and tripropylene. Glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, diglycidylamine, butadiene dioxide, dimer acid And diglycidyl ether.

  Examples of the aromatic diglycidyl ether compound include 2,6-diglycidyl phenyl ether, phthalic acid diglycidyl ester, trimellitic acid diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether. 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, 1,1-bis (4-hydroxyphenyl) ethanediglycidyl ether, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl diglycidyl ether, 2,2-bis (4- (β-hydroxypropoxy) phenyl) propane diglycidyl ether, resorcinol diglycidyl ether , Biphenyl-4,4'-diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, 1,6-dihydroxynaphthalenediglycidyl ether, 2,7-dihydroxynaphthalenediglycidyl ether, bisphenol full orange glycidyl ether, bisphenoxyethanol Examples thereof include full orange glycidyl ether.

  Examples of the alicyclic diglycidyl ether compound include cyclohexanedimethanol diglycidyl ether, dicyclopentadiene dioxide, 3,4-glycidylcyclohexylmethyl-3,4-glycidylcyclohexanecarboxylate, 3,4-glycidyl-6- Methylcyclohexylmethyl-3,4-glycidyl-6-methylcyclohexanecarboxylate, vinylcyclohexene dioxide, dicyclodienol epoxide glycidyl ether, tetrahydrophthalic acid diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl Ether, 2,2-bis (4-hydroxycyclohexyl) propanediglycidyl ether, bis- (3,4-epoxycyclohexyl) adipate Etc. The.

  Examples of the high molecular weight diglycidyl resin include bisphenol A type high molecular weight glycidyl resin, bisphenol F type high molecular weight glycidyl resin, and phenoxy resin obtained by reacting the above diglycidyl compound. Bisphenol resin-based (A-type, F-type, etc.) diglycidyl compounds have secondary hydroxyl groups, and these secondary hydroxyl groups have a cyclic ether group (glycidyl group) and a dibasic acid (a-1) carboxyl group. Like the secondary hydroxyl group generated by polyaddition, it acts as a starting point for forming a side chain.

Examples of the compound having an oxetanyl group include carbonate bisoxetane, adipate bisoxetane, xylylene bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, bis (3-ethyl-3-oxetanylmethyl) ether, 1,4- Bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di {1-ethyl- (3-oxetanyl)} methyl ether, and the like.
The said bicyclic ether compound (a-2) can be used individually or in combination of 2 or more types.

Next, the cyclic ester (b) used in the present invention will be described.
The cyclic ester (b) undergoes a ring-opening addition reaction with a secondary hydroxyl group directly bonded to the side chain of the polyester main chain (I) to form a side chain of the addition type polyester resin (D1, D2, D3). This side chain is bonded to the polyester main chain (I) via an ester bond, and contains a ring-opening structural unit of the cyclic ester (b) and a terminal hydroxyl group. The terminal hydroxyl group of the side chain reacts with a cross-linking agent (E) described later, whereby the polyester resin (D) is cured and a pressure-sensitive adhesive layer can be formed. By adjusting the amount of the cyclic ester (b) to be reacted with the secondary hydroxyl group of the polyester main chain (I), the amount of the side chain introduced in the ring-opening ester structure can be controlled, and the amount of the side chain introduced can be controlled. It is possible to ensure a balance of adhesive properties (particularly, both tack and cohesive force) as the pressure-sensitive adhesive of the adhesive composition containing the addition type polyester resins (D1) to (D3).

  As described above, the addition-type polyester resins (D1 to D3) can be obtained by a three-stage, pseudo-two-stage or two-stage manufacturing method, and the ring-opening addition or sealing compound of the cyclic ester (b). The progress of the formation reaction (polyaddition reaction) of the polyester main chain (I) at the start of addition of (c) is different. Polyesters that have completed the polyaddition reaction have a large number of hydroxyl groups, so the viscosity is high, there is a possibility of association between hydroxyl groups and side reactions, and uniform mixing with the cyclic ester (b) and the sealing compound (c) is inhibited. As a result, the reaction efficiency tends to decrease, and the addition reaction of the cyclic ester (b) and the sealing compound (c) is suppressed. Therefore, the smaller the amount of hydroxyl groups at the start of the reaction with the cyclic ester (b) or the sealing compound (c), the better the reaction efficiency, the more stable the reaction, the higher the homogeneity of the product, and the variation. Decrease. Therefore, in the two-stage production method in which the formation of the polyester main chain (I) and the formation of the side chains (II, II ′) proceed substantially simultaneously in parallel, the hydroxyl group generated by the polyaddition reaction is cyclic. Since it is successively consumed in the addition reaction of the ester (b) or the sealing compound (c) and is always maintained in a small amount, it is preferable to the three-stage production method.

The cyclic ester (b) used for the formation of the side chain in the present invention is an ester in which a hydroxyl structure of a hydroxycarboxylic acid and a carboxylic acid are dehydrated and condensed in a molecule or between molecules to form a cyclic structure. It includes monomers, dimers or multimers higher than trimers.
Since the cyclic ester (b) used in the present invention is not limited in the size of the ring, the hydroxycarboxylic acid (b ′), which is the precursor of the cyclic ester (b), can be ring-formed by dehydration condensation. There is no particular limitation, and an intramolecular or intermolecular condensate having one or more of aliphatic, alicyclic, aromatic and heterocyclic hydroxycarboxylic acid as a precursor can be used as the cyclic ester (b). . Below, the example of the hydroxycarboxylic acid (b ') which is a precursor of cyclic ester (b) is shown.

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

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

  The hydroxycarboxylic acid may be an organic compound having a carboxylic acid and a hydroxyl group in one molecule, and is not limited to the above examples.

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

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

The ring-opening addition of the cyclic ester (b) may be a single addition of one molecule to the hydroxyl group of the polyester main chain (I), or an addition in which a ring-opening addition of a plurality of molecules is repeated to form a polymer. It may be polymerization. If the cyclic ester (b) exceeding the equivalent with respect to the hydroxyl group of the polyester is supplied, the excess cyclic ester (b) can undergo addition polymerization to extend the side chain.
In view of the effectiveness of the side chain formed by the ring opening, in the single addition of the cyclic ester (b), the cyclic ester (b) having 4 or more carbon atoms constituting the ester ring structure is preferable. In order to efficiently perform the ring-opening addition reaction with the hydroxyl group of the polyester main chain (I), lactones of cyclic monomers having 6 to 18 carbon atoms constituting the ester ring are preferable, and ε-caprolactone Is more preferable.

Next, the sealing compound (c) for sealing a hydroxyl group is demonstrated.
The sealing compound (c) is a compound capable of sealing a hydroxyl group by reacting with a hydroxyl group and adding, and is a terminal hydroxyl group or a polyester main chain of the side chain (II) of the addition-type polyester precursor (C1, C2). It reacts with a part of the hydroxyl group directly linked to (I) to seal the hydroxyl group, and at least part of the side chain is formed to form the second side chain (II ′) having no hydroxyl group. Therefore, the use of the sealing compound (c) provides the addition type polyester resins (D1 to D3) having a smaller amount of hydroxyl groups than the addition type polyester precursor (C1). That is, the use of the sealing compound (c) makes it possible to control the amount of hydroxyl groups as functional groups that can react with the crosslinking agent (E). And by reducing the hydroxyl group in addition type polyester resin (D1-D3), the heat resistance and heat-and-moisture resistance at the time of preparing an adhesive composition and utilizing as a pressure sensitive adhesive improve.

  In addition, in the second sealing form, the compound (c) capable of reacting with a hydroxyl group was formed by a polyaddition reaction between a dibasic acid (a) and a compound (a-2) having two cyclic ether groups. It is used for reacting with a part of the secondary hydroxyl group in the polyester main chain part (I) to form the side chain part (II ′) in the addition type polyester resin (D2). The side chain part (II ′) does not have a hydroxyl group. Then, the cyclic ester compound (b) is subjected to a ring-opening addition reaction with the secondary hydroxyl group remaining in the polyester main chain part (I) to form a side chain part (II) having a hydroxyl group at the terminal. That is, the amount of the hydroxyl group in the polyester main chain (I) that becomes the reaction point with the cyclic ester (b) can be adjusted by the sealing compound (c), that is, the side chain bonded to the polyester main chain part (I). The ratio of the side chain having the ring-opening structural unit of the cyclic ester (b) in the inside can be adjusted. Therefore, it can be used for adjusting the adhesion property balance (particularly, both tack and cohesive force) when the addition-type polyester resin (D2) is used as a pressure-sensitive adhesive.

  Furthermore, sealing compound (c) reduces the hydroxyl group of the terminal of the 1st side chain (II) in addition type polyester resin (D2), and obtains addition type polyester resin (D3) of the 3rd sealing form. It can also be used for this purpose, and has the role of finally adjusting the hydroxyl group of the polyester resin.

  The sealing compound (c) used in the present invention is preferably, for example, any one of a silylating agent (c1), an acid anhydride (c2), or an isocyanate compound (c3). A compound (c ′) having a plurality of functional groups not present is more preferable. The sealing compound (c) may be used alone or in combination of two or more.

Examples of the silylating agent (c1) used in the present invention include hydrosilanes, alkoxysilanes, chlorosilanes, silanols, silylamines, and cyclic compounds thereof.
Examples of hydrosilanes include trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, trihexylsilane, diethylmethylsilane, butyldimethylsilane, dimethylphenylsilane, triphenylsilane, methylphenylvinylsilane, pentamethyldisiloxane, and allyl. Dimethylsilane, tris (trimethylsiloxy) silane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, Examples include hydrosilanes having a monofunctional Si—H group such as 1,3,5,7,9-octaphenylcyclotetrasiloxane.

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

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

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

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

Examples of the acid anhydride (c2) used in the present invention include the low molecular weight dicarboxylic acids (a-1) exemplified as the dibasic acid (a-1) used for forming the polyester main chain (I) described above. -1) and acid anhydrides in tri- or higher functional polycarboxylic acids (a-1-β) used to form high molecular weight dicarboxylic acids (a-1-3). Acid anhydrides of molecular weight dicarboxylic acids (a-1-1) are preferred.
In addition, when obtaining the addition type | mold polyester resin (D2) of a 2nd sealing form with a two-stage type manufacturing method, a silylating agent (c1) or an isocyanate compound (c3) is used as a sealing compound (c). Therefore, it is preferable to use a monofunctional one. When the acid anhydride (c2) is used as the sealing compound (c), the acid anhydride (c2) acts in the same manner as the dibasic acid (a-1) and is consumed for forming the polyester main chain (I). Therefore, the molecular design is hindered.

  Of the isocyanate compound (c3) used in the present invention, examples of the monofunctional isocyanate compound include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, and phenyl. Isocyanate, benzyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R) -(+)-Α-methylbenzyl isocyanate (S)-(−)-α-methylbenzyl isocyanate, (R)-(−)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S) — (-)-1-phenylethyl isocyanate, p-toluenesulfonyl isocyanate, etc. are mentioned.

  The polyaddition reaction between the dibasic acid (a-1) and the bicyclic ether compound (a-2) may be performed by a known and commonly used method. For example, 1) Dibasic acid (a-1) and bicyclic ether compound (a-2) are mixed and reacted together, 2) Dibasic acid (a-) in bicyclic ether compound (a-2) The reaction may be performed in such a manner that the reaction is performed while gradually adding 1) or the bicyclic ether compound (a-2) is gradually added to the dibasic acid (a-1).

A linear polyester main chain formed by polyaddition reaction of a dibasic acid (a-1) and a bicyclic ether compound (a-2) in the addition type polyester resins (D1) and (D2) of the present invention (I) has a carboxyl group or a cyclic ether group at its terminal.
The number of moles of the cyclic ether group of the bicyclic compound (a-2) with respect to 1 mole of the carboxyl group of the dibasic acid (a-1) is in the range of 0.5 to 2.0 moles, preferably 0.8 to 1. Within the range of 2 mol is preferable. When the number of moles of the cyclic ether group per mole of the carboxyl group is less than 0.5 mole or more than 2.0 mole, it is difficult to increase the molecular weight of the polyester main chain (I). It is difficult to obtain an addition-type polyester resin having characteristics as a pressure-sensitive adhesive.

  When forming the polyester main chain (I), if a bicyclic ether compound (a-2) having a secondary hydroxyl group such as a bisphenol-type diglycidyl ether compound is used, a linear polyester main chain (I) There are two types of secondary hydroxyl groups that are directly linked to the hydroxyl group: a hydroxyl group produced by ring-opening addition of a cyclic ether group and a hydroxyl group originally possessed by the bicyclic ether compound (a-2). The two kinds of secondary hydroxyl groups are both reactive base points with the cyclic ester (b) or the sealing compound (b), and the first side chain (II) having the ring-opening structural unit of the cyclic ester and the terminal hydroxyl group or A second side chain in which the hydroxyl group is sealed with the sealing compound is formed. It is considered that the hydroxyl group produced by the ring-opening addition of the cyclic ether group is more reactive with the cyclic ester (b) or the sealing compound (b) than the secondary hydroxyl group originally possessed. .

  When the polyester main chain (I) contains a large amount of aromatic groups, the resulting addition-type polyester resins (D1 to D3) have high heat resistance, but the hardness is increased and tackiness is hardly exhibited. Moreover, when many aliphatic groups are contained, the biodegradability of the resin increases, but the heat resistance decreases. Therefore, in consideration of these, the dibasic acid (a-1) and the bicyclic ether compound (a-2) used as raw materials are aromatic polyesters (I) depending on the use of the adhesive composition. The ratio of the group and the aliphatic group is appropriately selected so as to be suitable. In order for the addition-type polyester resin (D) to suitably exhibit heat resistance and tackiness, the proportion of aromatic ring groups (aromatic ring content) in the molecule of the polyester resin (D) is generally 0.01 to 60. % Is preferable, and more preferably about 1 to 50% (weight ratio). As the ratio of the aromatic ring in the resin molecule, an average value of mass (or weight) estimated from the molecular weight in each raw material used, the ratio of the mass occupied by the aromatic ring in the molecular weight, and the blending ratio can be used.

When the addition type polyester resin (D1) is prepared by the first sealing form, the cyclic ester (b) is 0. 1 mol per 1 mol of the secondary hydroxyl group directly bonded to the linear polyester main chain (I). The reaction is preferably performed at a rate of 2 mol or more, more preferably at a rate of 0.5 mol or more, and further at a rate of 0.8 to 60 mol. It is most preferable to make it react in the ratio which becomes in the range of 5-40 mol.
Moreover, when preparing addition type polyester resin (D2) by a 2nd sealing form, cyclic ester (b) with respect to 1 mol of secondary hydroxyl groups directly connected to linear polyester principal chain (I), The reaction is preferably performed at a rate of 0.15 mol or more, more preferably at a rate of 0.3 mol or more, and still more preferably within a range of 0.4 to 60 mol. It is best to cause the reaction to occur within a range of 7 to 40 moles. When the addition type polyester resin (D2) is prepared by the second sealing form, the sealing compound (c) is reacted prior to the cyclic ester (b), so that the linear polyester main chain (I) is reacted. The preferable lower limit of the amount of the cyclic ester (b) relative to 1 mol of the directly bonded secondary hydroxyl group is smaller than that when the addition type polyester resin (D1) is prepared by the first sealing form.
If it deviates from the above range, it is difficult to obtain an addition-type polyester resin (D) capable of preparing an adhesive composition that can be a pressure-sensitive adhesive satisfying both tack and cohesive strength. Therefore, the weight of the cyclic ester (b) for forming the side chain is appropriately adjusted based on the weight of the bicyclic ether compound (a-2) for forming the main chain portion so that the molar ratio is as described above. . The cyclic ester (b) in excess of the equivalent mole with respect to the hydroxyl group reacts with the terminal hydroxyl group of the side chain that has undergone ring-opening addition to form a side chain (polymer) in which a plurality of cyclic ester molecules are subjected to ring-opening polymerization. II). The side chain (II) generated by the ring opening of the cyclic ester (b) has a hydroxyl group at its terminal, and has an addition polyester precursor having a polyester main chain part (I) and a hydroxyl group-terminated side chain part (II). The body (C1) preferably has a hydroxyl value in the range of 50 to 150 mgKOH / g, more preferably in the range of 50 to 80 mgKOH / g.

When a part of the hydroxyl group at the end of the side chain of the addition-type polyester precursor (C1) is reacted with the above-mentioned sealing compound (c) to be converted into the second side chain (II ′), the polyester main chain (I ), A hydroxyl group-terminated first side chain (II), and a second side chain (II ′) having no hydroxyl group at the end, an addition type polyester resin (D1) is obtained. The hydroxyl value of the addition-type polyester resin (D1) can be adjusted to a desired value by adjusting the amount of the sealing compound (c) used, and is preferably 0.1 to 50 mgKOH / g, more preferably 0.8. It is adjusted to a range of 5 to 30 mg KOH / g. However, when the side chain has a carboxyl group and the crosslinking agent (E) reacts with the carboxyl group, the hydroxyl value of the addition-type polyester resin is allowed to about 100 mgKOH / g, and preferably 80 mgKOH / g or less. .
Depending on the sealing compound (c) used, the carboxyl group of the addition type polyester resin (D1) may be larger than the addition type polyester precursor (C1), and the sealing compound (c) is an acid anhydride, A side chain having a terminal carboxyl group is formed. When the cross-linking agent (E) reacts with a hydroxyl group, the acid value is allowed to be somewhat high, but when the cross-linking agent (E) reacts with a carboxyl group, the acid value of the addition-type polyester resin (D1) is , Preferably in the range of 0.1-50 mg KOH / g, more preferably in the range of 0.5-30 mg KOH / g.

  When the hydroxyl value or acid value is lower than 0.1 mg KOH / g, the reactivity of the crosslinking agent (E) with respect to the hydroxyl group or carboxyl group is poor, and the cohesive force of the cured resin is insufficient. Not only becomes difficult, but also adhesive residue is generated after peeling or re-peelability is insufficient. On the other hand, when the hydroxyl value or the acid value is higher than 50 mgKOH / g, the pot life of the adhesive composition containing the crosslinking agent (E) is shortened, and the workability at the time of coating and bonding is significantly reduced. This point is common to the addition type polyester resins (D1 to D3), and the value relating to the reaction target group is preferably 0.1 depending on the type of the crosslinking agent (E) (whether it reacts with a hydroxyl group or a carboxyl group). It is adjusted to ˜50 mg KOH / g, more preferably 0.5 to 30 mg KOH / g.

In the production of the addition-type polyester resin (D2), in order to adjust the acid value or the hydroxyl value as described above, the sealing compound (1 mol) is added to 1 mol of the secondary hydroxyl group of the linear polyester main chain (I). It is preferable to react the raw materials in such a ratio that the functional group capable of reacting with the hydroxyl group of c) is 0.01 to 0.85 mol, preferably 0.1 to 0.7 mol. Then, the cyclic ester (b) is reacted at a ratio of 0.8 to 40.0 mol, preferably 2.0 to 20.0, with respect to 1 mol of the unreacted hydroxyl group. It is preferable to obtain an addition type polyester resin (D2) to which the first side chain (II) derived from is added.
When the ratio of the functional group of the sealing compound (c) to the hydroxyl group of the polyester main chain (I) is less than 0.01 mol, the hydroxyl group of the addition-type polyester resin (D2) regardless of the amount of cyclic ester (b) added The price increases. Even if a large amount of the cyclic ester (b) is added when a large amount of hydroxyl groups directly bonded to the main chain remains, the cyclic ester (b) is more than the ring-opening addition of the cyclic ester (b) to the hydroxyl groups directly bonded to the main chain. This is presumed to be because the self-opening addition of) proceeds and the hydroxyl group directly linked to the main chain does not decrease so much. Since the hydroxyl value of the addition-type polyester resin (D2) is increased, the heat resistance and moist heat resistance of the cured resin are decreased. On the other hand, when the ratio of the functional group of the sealing compound (c) to the hydroxyl group of the polyester main chain (I) is more than 0.85 mol, the side chain (II) due to the cyclic ester (b) can hardly be formed, and tack In addition, it is difficult to obtain an addition-type polyester resin (D2) capable of preparing an adhesive composition that provides a pressure-sensitive adhesive that satisfies both the cohesive strength and the cohesive force.

  As described above, the addition type polyester precursor (C1, C2) can be obtained by any of the three-stage type, pseudo two-stage type, and two-stage type manufacturing methods, and the blending ratio of the raw materials is the same as described above. In the case of a two-stage type, for example, if a dibasic acid (a-1), a bicyclic ether compound (a-2) and a cyclic ester (b) or a sealing compound (c) are mixed and reacted, Well, in the case of the pseudo two-stage type, the cyclic ester (b) or the sealing compound (c) is dropped during the reaction between the dibasic acid (a-1) and the bicyclic ether compound (a-2). However, it can be obtained by reacting the three parties.

  The polyaddition reaction between the dibasic acid (a-1) and the bicyclic ether compound (a-2) proceeds even without catalyst, but a catalyst may be used as appropriate in order to make the reaction proceed more smoothly. . Usable catalysts include ammonia, amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal hydroxides, alkaline earth metal hydroxides, Lewis acids, tin, lead, titanium, iron, zinc , Zirconium, cobalt, and other organometallic compounds, metal halides, and the like. The use of quaternary ammonium salts as a reaction catalyst is preferable because colorless to light yellow addition type polyester resins (D1) and (D2) are obtained.

  Examples of amines that can be used as a catalyst for polyaddition reaction include triethylamine, pyridine, aniline, morpholine, N-methylmorpholine, pyrrolidine, piperidine, N-methylpiperidine, cyclohexylamine, n-butylamine, dimethyloxazoline, imidazole, N-methylimidazole, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethylisopropanolamine, N-methyldiethanolamine and the like can be mentioned.

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

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

  Examples of the alkali metal or alkaline earth metal hydroxide include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide; magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydroxide Mention may be made of alkaline earth metal hydroxides such as barium.

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

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

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

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

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

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

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

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

In addition to the above, Lewis acids such as boron trifluoride, aluminum trichloride, zinc chloride, and titanium chloride can also be used as the catalyst for the polyaddition reaction.
The catalyst for polyaddition reaction is not limited to the above example, and only one kind may be used or two or more kinds may be used in combination.

  The amount of the catalyst used is preferably about 10 parts by weight or less with respect to 100 parts by weight of the reaction component. If the amount exceeds 10 parts by weight, there is a disadvantage that the product is colored or acts as a negative catalyst in the ring-opening addition reaction of the cyclic ester (b).

  The polyaddition reaction is carried out at a temperature in the range of 20 to 220 ° C, preferably 50 to 200 ° C. The reaction time can usually be about 1 to 60 hours. A solvent may or may not be used. Solvents that can be used include hydrocarbon solvents such as toluene, xylene, hexane, and heptane; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as dichloromethane and chloroform Examples of such solvents include ether solvents such as diethyl ether, methoxytoluene, and dioxane. These may be used alone or in combination of two or more. However, a solvent containing a hydroxyl group cannot be used because the reaction rate in the subsequent reaction with the cyclic ester (b) is greatly reduced.

  The ring-opening addition reaction between the hydroxyl group of the polyester main chain (I) and the cyclic ester (b) can be performed using known reaction conditions. Specifically, the reaction temperature is 20 to 220 ° C, preferably 60 to 180 ° C. The reaction time can usually be about 1 to 30 hours. A catalyst may or may not be used, but is preferably used. As the catalyst for ring-opening addition, the above-mentioned catalyst for polyaddition reaction used for the reaction between the dibasic acid (a-1) and the bicyclic ether compound (a-2) can be similarly used. In particular, quaternary ammonium salts are more preferably used as a catalyst in that the addition type polyester resin (D) is difficult to be colored.

  As a catalyst when the addition compound resin (D1, D3) is obtained by reacting the sealing compound (c) with the first side chain (II) having a terminal hydroxyl group, the reactive and addition type polyester resin (D) is used. It is preferable to use a quaternary ammonium salt in that it is difficult to color.

  In obtaining the addition type polyester resin (D2), it is preferable to use a quaternary ammonium salt as a catalyst in each step for the same reason.

  The addition type polyester resins (D1 to D3) have a glass transition temperature (Tg) so that the adhesive composition can exhibit well-balanced adhesive properties as pressure-sensitive adhesives (particularly, compatibility between tack and cohesive force). Is preferably −80 to 10 ° C. When the glass transition temperature of the addition-type polyester resin (D1 to D3) is less than −80 ° C., the adhesive composition prepared using the polyester resin (D1 to D3) has a cohesive force suitable for a pressure-sensitive adhesive. It cannot be exhibited, and it becomes easy for floating to occur. On the other hand, if the glass transition temperature exceeds 10 ° C., the adhesive layer cannot sufficiently wet the adherend even if the pressure sensitive adhesive is brought into contact with the adherend, and sufficient adhesive strength cannot be obtained. there is a possibility. Therefore, the dibasic acid (a-1) and the bicyclic ring are formed so that addition polyester resins (D1 to D3) having a Tg of preferably −80 to 10 ° C., more preferably −60 to −10 ° C. can be produced. Consideration is appropriately made in selecting each component used as the ether compound (a-2), the cyclic ester (b) and the sealing compound (c).

  The weight average molecular weight (Mw) of the addition-type polyester resins (D1 to D3) is preferably in the range of 2,000 to 1,000,000 in terms of adhesiveness, and in the range of 8,000 to 500,000. More preferably. When Mw is less than 2,000, the cohesive force peculiar to the addition-type polyester resins (D1 to D3) of the present invention cannot be expressed, and heat resistance and moist heat resistance are deteriorated. On the other hand, if Mw exceeds 1,000,000, the fluidity of the adhesive composition containing the addition-type polyester resins (D1 to D3) becomes poor, and it becomes difficult to produce a pressure-sensitive adhesive sheet. .

The adhesive composition of the present invention contains a crosslinking agent (E) that can react with the functional group of the addition type polyester resin (D1 to D3) of the previous operation, and the addition type polyester resin is cured by the crosslinking reaction with the functional group. To form an adhesive layer.
The crosslinking agent (E) used in the present invention is a compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group in the addition-type polyester resin (D1 to D3) in the molecule, and acts as a crosslinking agent. A compound having two or more functional groups capable of reacting with a hydroxyl group or a carboxyl group in the molecule is preferably used. Examples of such compounds include polyisocyanate compounds, polyfunctional silane compounds, N-methylol group-containing compounds, epoxy compounds, amine compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, melamine compounds, and metal chelate compounds. These are excellent in the adhesiveness of the adhesive composition after the crosslinking reaction and the adhesiveness to the adherend / substrate. The crosslinking agent (E) capable of reacting with a hydroxyl group includes a polyisocyanate compound, a polyfunctional silane compound, an N-methylol group-containing compound, an amine compound and a melamine compound, and the crosslinking agent (E) capable of reacting with a carboxyl group. , Aziridine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds and metal chelate compounds. As described above, since there is an appropriate range of acid value or hydroxyl value of the addition type polyester resin (D) depending on the type of the crosslinking agent (E), the hydroxyl value of the addition type polyester resin (D1 to D3) is 0.1. In the case of ˜50 mg KOH / g, the crosslinking agent (E) to be combined may be a type capable of reacting with either a hydroxyl group or a carboxyl group, and the hydroxyl value of the addition type polyester resin (D1 to D3) exceeds 50 mg KOH / g. In the case of 100 mg KOH / g or less, the cross-linking agent (E) to be combined is a type capable of reacting with a carboxyl group. Is preferably 0.1 to 50 mg KOH / g.

  Examples of the polyisocyanate compound used as the crosslinking agent (E) include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate, and any compound may be used.

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

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

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

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

Trimethylolpropane adducts of the above polyisocyanate compounds, trimers having an isocyanurate ring, and the like can also be used.
Moreover, polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and these polyisocyanate modified products can also be used. As the polyisocyanate-modified product, a modified product having one or more of a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, and an isocyanurate group can be used.
A reaction product of a polyol and a diisocyanate can also be used as a polyisocyanate.

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

  When using a polyisocyanate compound as a crosslinking agent (E), reaction can be accelerated | stimulated using a well-known catalyst as needed. Examples of usable catalysts include tertiary amine compounds, organometallic compounds and the like, and these may be used alone or in combination.

  As the epoxy compound used as the crosslinking agent (E), 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, diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-di) Glycidylaminomethyl) cyclohexane and the like.

  Examples of the aziridine compound used as the crosslinking agent (E) include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridine). Carboxite), bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), tri Methylolpropane-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-aziri Dinyl) butyrate], trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate], 2,2 ′ -Bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N'-ethyleneurea, 1,6 -Hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide, etc. Is mentioned.

  The carbodiimide compound used as the crosslinking agent (E) is a compound having two or more carbodiimide groups (—N═C═N—) in the molecule, and diisocyanate in the presence of a known polycarbodiimide or carbodiimidization catalyst. A high molecular weight polycarbodiimide produced by a decarboxylation condensation reaction can be suitably used.

  As raw material isocyanate for producing high molecular weight polycarbodiimide, 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, Examples include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate, and one or a mixture of two or more of these can be used.

  As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Examples include 2-phospholene-1-oxide and phospholene oxides such as these 3-phospholene isomers.

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

  As the oxazoline compound used as the crosslinking agent (E), a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2'-methylenebis (2-oxazoline), 2,2'- Ethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-propylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline) ), 2,2'-hexamethylene bis (2-oxazoline), 2,2'-octamethylene bis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'- p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenyl Nylenebis (4-phenyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'- m-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-phenylenebis-2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline) ), 2,2'-o-phenylenebis (4-methyl-2-oxazoline), 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline) and the like. Also, vinyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline, and other monomers copolymerizable with the vinyl monomer These copolymers can also be used.

Examples of metal chelate compounds used as the crosslinking agent (E) include aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, and other polyvalent metals such as acetylacetone and acetoacetic acid. Examples thereof include compounds in which ethyl is coordinated.
The crosslinking agent (E) may be used alone or in combination.

The adhesive composition of the present invention contains a polyester resin (D) and a crosslinking agent (E) as a curable resin component, and the addition type polyester resins (D1 to D3) are used as the polyester resin (D). . As for the composition ratio, the amount of the crosslinking agent (E) with respect to 100 parts by weight of the polyester resin (D) is preferably 0.001 to 20 parts by weight, and more preferably 0.01 to 10 parts by weight. When the amount of the crosslinking agent (E) used exceeds 20 parts by weight, the adhesiveness (wetting and adhesion) when the resulting adhesive composition is used as a pressure-sensitive adhesive tends to decrease, and the resin layer Cohesive force is low, and shape retention and durability during repeated use are poor. However, it can be used as an adhesive that is bonded and fixed by curing the resin. On the other hand, when the amount is less than 0.001 part by weight, a sufficient cross-linked structure cannot be obtained, so that the cohesive force is lowered, and the heat resistance and the heat and humidity resistance tend to be lowered.
In the case of an adhesive composition or a coating composition other than the pressure-sensitive adhesive composition, most of the functional groups in the main agent can be reacted with the crosslinking agent (E) to form a cured adhesive layer or a cured coating film. However, in the case of the pressure-sensitive adhesive composition, in order for the pressure-sensitive adhesive layer already cured at the time of sticking to wet the surface of the adherend, the already cured pressure-sensitive adhesive layer has surface tackiness (tack). Must be in a semi-solid state. Therefore, in the case of a pressure-sensitive adhesive composition, a part of the crosslinkable functional groups (hydroxyl groups and carboxyl groups) in the addition type polyester resins (D1 to D3) are reacted with the crosslinker (E) to cure pressure sensitivity. It is preferable to form an adhesive layer.

      The reaction between the hydroxyl group or carboxyl group in the addition-type polyester resin (D1 to D3) and the functional group of the crosslinking agent (E) improves the shape retention by three-dimensional crosslinking of the resin, and various types of resins with side chains that are not crosslinked. Adhesion with the substrate and adherend is improved. Furthermore, since the hydroxyl value of the resin is reduced by sealing the hydroxyl group with the sealing compound (c), the heat resistance and heat and humidity resistance under severer conditions can be improved. It can be preferably used as a pressure-sensitive adhesive.

      The adhesive composition of the present invention includes various resins, coupling agents, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weather stabilizers, tackifiers, plastics, and the like within a range that does not impair the effects of the present invention. You may mix | blend an agent, a filler, anti-aging agent, etc.

Using the adhesive composition of the present invention, a laminate comprising an adhesive layer and a sheet-like substrate can be obtained, and this can be used as an adhesive sheet.
The adhesive sheet can be obtained, for example, by applying the adhesive composition of the present invention to various sheet-like substrates, and drying and curing.
When applying the adhesive composition, in order to improve workability, an appropriate liquid medium, for example, an organic solvent such as ethyl acetate, toluene, methyl ethyl ketone, isopropyl alcohol, and other hydrocarbon solvents or water is added. It is also possible to adjust the viscosity of the adhesive composition, and it is also possible to reduce the viscosity by heating the adhesive composition. However, when water or alcohols are added in a large amount, there is a possibility that the reaction between the addition type polyester resins (D1 to D3) and the crosslinking agent (E) may be inhibited.

      Examples of the sheet-like base material include cellophane, plastic, rubber, foam, cloth, rubber cloth, resin-impregnated cloth, glass, metal, wood, and the like, which are molded into a flexible flat shape. It is done. Further, the sheet-like substrate may be composed of a single material or a multilayer material in which a plurality of types of materials are laminated. Moreover, what carried out the peeling process of the surface of a sheet-like base material can also be used.

      Plastic substrates include various plastic films, such as polyvinyl alcohol films, triacetyl cellulose films, polypropylene, polyethylene, polycycloolefins, polyolefin resin films such as ethylene-vinyl acetate copolymers, polyethylene terephthalate, poly Polyester resin films such as butylene terephthalate and polyethylene naphthalate, polycarbonate resin films, polynorbornene resin films, polyarylate resin films, acrylic resin films, polyphenylene sulfide resin films, polystyrene resin films Vinyl resin film, polyamide resin film, polyimide resin film, epoxy resin film, etc. That.

There is no restriction | limiting in particular in the coating method of the adhesive composition to the said sheet-like base material, What is necessary is just to select a suitable coating means suitably according to a conventional method. Examples of the coating means include Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, spin coater and the like. When the adhesive composition contains a liquid medium such as an organic solvent or water, an adhesive layer can be formed on the sheet-like substrate by drying and removing the liquid medium after coating. When the liquid does not contain the liquid medium to be removed and the viscosity is low by heat melting, the adhesive layer is formed by cooling and solidifying the molten adhesive layer.
The drying method is not particularly limited, and examples include hot air drying, a method using infrared rays or reduced pressure. Although drying conditions depend on the cured form of the adhesive composition, the film thickness, the solvent used, and the like, usually hot air heating at about 60 to 180 ° C. is preferably used.

      The thickness of the adhesive layer on the sheet-like substrate is preferably 0.1 μm to 200 μm, and more preferably 1 μm to 100 μm. When the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained. When the thickness exceeds 200 μm, characteristics such as adhesive strength are often not improved further.

      The adhesive composition of the present invention can be used to provide a laminate in which an adhesive layer formed of an adhesive composition is laminated on an optical member, and can be used for assembling / manufacturing optical devices and components. . For example, a laminate in which an adhesive layer is laminated on a sheet-like or film-like optical member having specific optical characteristics is obtained by sticking the adhesive layer to a glass member for a liquid crystal cell so that the optical member / pressure-sensitive adhesion is achieved. A member for a liquid crystal cell having a composition composed of an agent layer / glass member can be obtained. Various optical films such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film can be cited as examples of the optical member of the laminate that can be used for the production of such an optical device. The laminate may have a sheet-like substrate that has been subjected to a release treatment for protecting the other surface of the adhesive layer before use.

  The laminate is formed by applying the adhesive composition to the release-treated surface of the release-treated sheet-like substrate and drying it to form an adhesive sheet, and laminating a sheet-like optical member on the surface of the adhesive layer. Alternatively, the adhesive composition is directly applied to a sheet-like optical member, dried, and the release-treated surface of the release-treated sheet-like substrate is laminated on the surface of the adhesive layer.

  By peeling off the peeled sheet-like substrate covering the surface of the adhesive layer from the laminate thus obtained and sticking it to the optical member, it is used for assembling and manufacturing various optical devices or components.

  Since the adhesive composition of the present invention is composed of a polyester resin, when used as a pressure-sensitive adhesive, adhesion to a substrate / adherent is improved, and plasticizer resistance and low-temperature adhesiveness are improved. Are better. Therefore, it can be suitably used for applications that require adhesion to a substrate such as a foam.

  In addition, the materials used for optical members such as optical member films and glass have a refractive index of generally about 1.50 to 1.58, and after curing of the adhesive composition used for manufacturing optical components and the like. When the refractive index is less than 1.45, the refractive index difference between the optical film and the optical member becomes large, and when the adhesive layer is provided on the optical member, total reflection occurs at a shallow angle. The effective utilization rate of light may decrease. Therefore, in order to reduce the difference in refractive index between the optical film and the optical member, it is important that the refractive index after drying and / or curing of the adhesive composition can be adjusted to a suitable value. In this regard, in the present invention, the ratio of aromatic groups contained in the polyester resin can be adjusted as appropriate by the combination of raw materials, and the refractive index of the resin is maintained at 1.45 or more by adjusting the content of the aromatic ring of the resin. It is possible. In particular, the introduction of an aromatic ring into the main chain skeleton can be easily adjusted, and the refractive index after drying and / or curing of the adhesive composition can be adjusted to a range of 1.49 to 1.60. Can be provided in the range of 1.50 to 1.55.

  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.

<< First Sealing Form: Using Silylating Agent (c1) as Sealing Compound (c) >>
In the following synthesis examples 1-20, the polyester resin was prepared using the silylating agent (c1) as a sealing compound (c). Synthesis Examples 1-6 are prepared according to a three-stage manufacturing method, Synthesis Example 7 is prepared according to a pseudo two-stage manufacturing method, Synthesis Examples 8-18 are prepared according to a two-stage manufacturing method, and Synthesis Examples 19 and 20 are prepared according to a two-stage manufacturing method. The cyclic ester (b) or the sealing compound (c) is omitted.

[Preparation of Addition Type Polyester Resin (D1) by Three-Stage Manufacturing Method]
(Synthesis Example 1)
<Step (1): Formation of polyester main chain>
A stirrer, a thermometer, a reflux condenser, a dropping device and a nitrogen introducing tube are attached to the polymerization tank to constitute a polymerization reaction device. The compound (a-2), the catalyst, and the organic solvent that were included were charged at the following ratios.

[Polymerization tank]
Adipic acid (a-1) 438 parts Isophthalic acid (a-1) 332 parts Ethyl acetate 135 parts Toluene 135 parts [Drip device]
Bisphenol A diglycidyl ether (a-2) 1995 parts Tetrabutylammonium tetrahydroborate (catalyst) 5.5 parts Ethyl acetate 135 parts Toluene 135 parts

After substituting the air in a polymerization tank with nitrogen gas, it heated up at 100 degreeC, stirring the dibasic acid solution in a tank. Subsequently, the mixture of the bicyclic ether compound was dripped at the constant rate over 1 hour from the dripping apparatus to the stirring dibasic acid mixture. After completion of the dropwise addition, the catalyst was added twice at a rate of 5.5 parts every 8 hours with stirring, and aged for 24 hours. Then, 1307 parts of ethyl acetate was added and cooled to room temperature to complete the reaction.
This reaction solution was light yellow and transparent, had a nonvolatile content of 60.5% by weight, a viscosity of 20,000 mPa · s, an acid value of 0.5 mg KOH / g, a hydroxyl value of 155 mg KOH / g, a glass transition temperature of 60 ° C., a weight average molecular weight of 50, 000 polyester resin (B) solution was obtained.

<Step (2): Ring-Opening Addition Reaction of Cyclic Ester (b)>
A polymerization reaction apparatus having a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube attached to the polymerization tank is prepared. The solution, cyclic ester (b), catalyst and organic solvent were charged in the following ratios.

[Polymerization tank]
Polyester resin (B) solution 219 parts Ethyl acetate 33 parts [Drip device]
ε-Caprolactone (b) 114 parts Tetrabutylammonium tetrahydroborate (catalyst) 1.3 parts Ethyl acetate 66 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the resin solution. Next, the cyclic ester (b) mixture was added dropwise to the stirring resin solution from the dropping device at a constant speed over 1 hour. After completion of the dropwise addition, the mixture was aged for 12 hours with further stirring, and then 66 parts of ethyl acetate was added and cooled to room temperature to complete the reaction, and a solution of the addition type polyester precursor (C1) added with the cyclic ester (b) was obtained. Obtained.
This reaction solution is light yellow and transparent, has a non-volatile content of 60.2% by weight, a viscosity of 15,000 mPa · s, an acid value of 0.05 mg KOH / g, a hydroxyl value of 74 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight. It was a resin solution of 150,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Step (3): Sealing reaction with silylating agent (c1)>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube are attached to the polymerization tank is prepared, and the addition-type polyester precursor (C1) obtained in step (2) is prepared in the polymerization tank and the dropping apparatus. A solution, a silylating agent (c1), a catalyst, and an organic solvent were charged in the following ratios.

[Polymerization tank]
Addition-type polyester precursor (C1) solution 200 parts [Drip device]
Hexamethyldisilazane (c1) 16 parts Tetrabutylammonium tetrahydroborate (catalyst) 1.2 parts Ethyl acetate 8 parts

After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 100 ° C. while stirring the addition-type polyester precursor (C1) solution. Next, the above silylating agent (c1) mixture was added dropwise to the stirring solution at a constant rate over 1 hour from a dropping device. After completion of the dropwise addition, the mixture was further aged with stirring for 8 hours, and then 3 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D1).
This reaction solution is light yellow and transparent and has a non-volatile content of 60.3% by weight and a viscosity of 18,000 mPa · s. The resin (D1) has a side chain content of 53% by weight and an aromatic ring content of about 17% by weight. The acid value was 0.05 mgKOH / g, the hydroxyl value was 5 mgKOH / g, the glass transition temperature was −10 ° C., and the weight average molecular weight was 160,000.

(Synthesis Example 2)
The dibasic acid (a-1) used in step (1) of Synthesis Example 1 was changed to isophthalic acid: 830 parts, and the bicyclic ether compound (a-2) was changed to neopentyl glycol diglycidyl ether: 1449 parts. Then, it was prepared in the same manner as in Synthesis Example 1 except that 200 parts of a polyester resin (B) solution whose non-volatile content was adjusted to about 60% by weight with ethyl acetate was used in Step (2). Thus, a solution of an addition type polyester resin (D1) having a nonvolatile content of 60.0% by weight and a viscosity of 9,000 mPa · s was obtained. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 3 mg KOH / g, a glass transition temperature of −30 ° C., and a weight average molecular weight of 80,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 3)
The bicyclic ether compound (a-2) used in the step (1) of Synthesis Example 1 is converted into 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene: 670 parts and bisphenol A diester. Glycidyl ether: prepared in the same manner as in Synthesis Example 1 except that 224 parts of the polyester resin (B) solution adjusted to 1385 parts and adjusted to a nonvolatile content concentration of about 60% by weight with ethyl acetate was used in step (2). And adjusted to a non-volatile content concentration of about 60% by weight with ethyl acetate to obtain a solution of an addition type polyester resin (D1) that is pale yellow and transparent and has a viscosity of 8,500 mPa · s. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 12 mg KOH / g, a glass transition temperature of −40 ° C., and a weight average molecular weight of 65,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.7 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 4)
Bicyclic ether compound (a-2) used in step (1) of Synthesis Example 1 was converted to bisphenol fluorenediglycidyl ether (BPFG manufactured by Osaka Gas Chemical Co., Ltd., molecular weight: 462.5, epoxy value: 3.89). (Eq / Kg)): Synthetic Example 1 except that 315 parts of a solution of polyester resin (B) adjusted to 3203 parts and adjusted to a nonvolatile content concentration of about 60% by weight with ethyl acetate was used in step (2). Preparation was carried out in the same manner, and the non-volatile content concentration was adjusted to about 60% by weight with ethyl acetate to obtain a solution of addition type polyester resin (D1) that was pale yellow and transparent and had a viscosity of 18,500 mPa · s. The resin (D1) had an acid value of 1.2 mgKOH / g, a hydroxyl value of 11 mgKOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 150,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.5 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 5)
The cyclic ester (b) used in Step (2) of Synthesis Example 1 was changed to δ-valerolactone: 100 parts, and the addition-type polyester precursor (C1) solution (nonvolatile content 60) obtained in Step (2) 0.0% by weight) was prepared in the same manner as in Synthesis Example 1 except that 200 parts were used in step (3), and was pale yellow and transparent with a non-volatile content of 60.1% by weight and a viscosity of 9,000 mPa · s. A solution of addition type polyester resin (D1) was obtained. The resin (D1) had an acid value of 1.5 mg KOH / g, a hydroxyl value of 12 mg KOH / g, a glass transition temperature of −30 ° C., and a weight average molecular weight of 110,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.7 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 6)
Preparation was carried out in the same manner as in Synthesis Example 1 except that the silylating agent (c1) used in Step (3) of Synthesis Example 1 was changed to 18 parts of trimethylsilanol. A solution of addition type polyester resin (D1) having a viscosity of 2% by weight and 13,000 mPa · s was obtained. The resin (D1) had an acid value of 1.0 mg KOH / g, a hydroxyl value of 15 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 160,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

[Preparation of Addition Type Polyester Resin (D1) by Pseudo Two-Stage Manufacturing Method]
(Synthesis Example 7)
<Steps (4) and (5): Formation of addition-type polyester precursor (C1)>
Prepare a polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dropping device and nitrogen inlet tube in the polymerization tank, and dibasic acid (a-1), bicyclic ether compound (a -2), cyclic ester (b), catalyst and organic solvent were charged at the following ratios.

[Polymerization tank]
Adipic acid (a-1) 73 parts Sebacic acid (a-1) 404 parts Bisphenol F diglycidyl ether (a-2) 875 parts Bisphenol A-based phenoxy resin (a-2) 1950 parts (manufactured by Japan Epoxy Resin Co., Ltd., product Name “JER1256”,
Glycidyl group equivalent: 7800 g / eq, Mw: 51000)
Tetrabutylammonium tetrahydroborate (catalyst) 6.6 parts Ethyl acetate 210 parts Toluene 210 parts [Drip device]
Tetrabutylammonium tetrahydroborate (catalyst) 6.6 parts ε-caprolactone (b) 800 parts Ethyl acetate 420 parts Toluene 420 parts

After the air in the polymerization tank was replaced with nitrogen gas, the dibasic acid solution was heated to 100 ° C. while stirring and reacted for 8 hours to give a polyester main chain (I) having an acid value of 5 (mg KOH / g) or less. ') Got.
Subsequently, the cyclic ester (b) mixture was dropped at a constant rate over 1 hour from the dropping device while stirring the reaction product. After completion of the dropwise addition, the mixture was further stirred for 8 hours, 6.6 parts of tetrabutylammonium tetrahydroborate was added and aged for another 8 hours, 1400 parts of ethyl acetate was added, and the reaction was terminated by cooling to room temperature. A solution of the precursor (C1) was obtained. This solution is light yellow and transparent, has a non-volatile content of 59.8% by weight and a viscosity of 30,000 mPa · s. The precursor (C1) has an acid value of 0.02 mg KOH / g, a hydroxyl value of 92 mg KOH / g, and a glass transition. It was a resin having a temperature of −15 ° C. and a weight average molecular weight of 200,000. In the above formulation, the cyclic ester (b) is in a ratio of about 0.6 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Step (6): Sealing reaction with silylating agent (c1)>
A polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device and a nitrogen introducing pipe was prepared in the polymerization tank, and the addition type polyester precursor (C1) obtained in step (5) was prepared in the polymerization tank and the dropping device. A solution (non-volatile content: 59.8%), a silylating agent (c1), a catalyst, and an organic solvent were charged in the following ratios.

[Polymerization tank]
Addition-type polyester precursor (C1) solution 200 parts [Drip device]
Diethylmethylsilane (c1) 22.5 parts Tetrabutylammonium tetrahydroborate (catalyst) 6.6 parts Ethyl acetate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the solution. Next, the above silylating agent (c1) mixture was added dropwise to the stirring solution at a constant rate over 1 hour from a dropping device. After completion of dropping, the mixture was aged for 6 hours with further stirring, and then 5 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of addition type polyester resin (D1).
This solution is light yellow and transparent, has a non-volatile content of 60.5% by weight and a viscosity of 35,000 mPa · s. The resin (D1) has a side chain content of 53% by weight and an aromatic ring content of about 17% by weight. The acid value was 0.02 mg KOH / g, the hydroxyl value was 8.5 mg KOH / g, the glass transition temperature was −15 ° C., and the weight average molecular weight was 220,000.

[Preparation of Addition Type Polyester Resin (D1) by Two-Step Manufacturing Method]
(Synthesis Example 8)
Prepare a polymerization reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube in the polymerization tank. Dibasic acid (a-1), bicyclic ether compound (a-2), cyclic ester (B) The catalyst and the organic solvent were charged at the following ratios.

[Polymerization tank]
Adipic acid (a-1) 159 parts Isophthalic acid (a-1) 120 parts Bisphenol A diglycidyl ether (a-2) 721 parts ε-caprolactone (b) 871 parts Ethyl acetate 200 parts Toluene 200 parts

<Step (7): Formation of addition-type polyester precursor (C1)>
After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 100 ° C. while stirring, and 2.0 parts of tetrabutylammonium tetrahydroborate was added to initiate the reaction. While stirring the mixture, 2.0 parts of tetrabutylammonium tetrahydroborate was added twice every 8 hours for a total of 24 hours for reaction and ripening to obtain an addition type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Step (8): Sealing reaction with silylating agent (c1)>
Ethyl acetate: 650 parts and hexamethyldisilazane: 245 parts as a silylating agent (c1) were added to the addition type polyester precursor (C1) solution and aged for 6 hours. Thereafter, 300 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D1).
This solution is light yellow and transparent, has a non-volatile content of 60.4% by weight and a viscosity of 15,000 mPa · s. The resin (D1) has an acid value of 0.4 mgKOH / g, a hydroxyl value of 6 mgKOH / g, and a glass transition temperature. It was -10 degreeC and the weight average molecular weight 150,000.

(Synthesis Example 9)
The catalyst used in Synthesis Example 8 was prepared in the same manner as in Synthesis Example 8, except that the catalyst was changed to tetrabutylammonium bromide. A solution of addition type polyester resin (D1) was obtained. The resin (D1) had an acid value of 0.8 mg KOH / g, a hydroxyl value of 10 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 120,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 10)
The dibasic acid (a-1) used in step (7) of Synthesis Example 8 was changed to succinic acid: 322 parts, and the bicyclic ether compound (a-2) was changed to neopentyl glycol diglycidyl ether: 678 parts. Then, the cyclic ester (b) was changed to ε-caprolactone: 456 parts, tetrabutylammonium nitrate was used as a catalyst three times in two parts, and the silylating agent (c1) used in the step (8) was used as methoxytrimethylsilane. : Preparation was performed in the same manner as in Synthesis Example 8 except that the amount of ethyl acetate was adjusted to 118 parts, and it was a pale yellow transparent addition type having a non-volatile content of about 60% by weight and a viscosity of 15,000 mPa · s. A solution of the polyester resin (D1) was obtained. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 12 mg KOH / g, a glass transition temperature of −35 ° C., and a weight average molecular weight of 80,000. In the above formulation, the cyclic ester (b) is in a ratio of about 0.6 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 11)
An addition type polyester which is prepared in the same manner as in Synthesis Example 8 except that the catalyst used in Synthesis Example 8 is changed to tetrabutyl titanate, is yellow and transparent, has a nonvolatile content of 60.1% by weight, and a viscosity of 8,500 mPa · s. A solution of resin (D1) was obtained. The resin (D1) had an acid value of 0.6 mg KOH / g, a hydroxyl value of 25 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 110,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 12)
This was prepared in the same manner as in Synthesis Example 8 except that the catalyst used in Synthesis Example 8 was changed to dibutyltin oxide. A solution of type polyester resin (D1) was obtained. The resin (D1) had an acid value of 2.5 mgKOH / g, a hydroxyl value of 40 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 125,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 13)
Prepared in the same manner as in Synthetic Example 8 except that the weight of the cyclic ester (b) used in Step (7) of Synthetic Example 8 was changed to 644 parts, transparent in pale yellow, non-volatile content of 60.2% by weight, A solution of an addition type polyester resin (D1) having a viscosity of 11,500 mPa · s was obtained. The resin (D1) had an acid value of 0.4 mg KOH / g, a hydroxyl value of 0.05 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 180,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 14)
Prepared in the same manner as in Synthesis Example 8 except that the weight of the cyclic ester (b) used in Step (7) of Synthesis Example 8 was changed to 16 parts and the amount of ethyl acetate was changed from 650 parts to 100 parts. As a result, a solution of addition type polyester resin (D1) which was light yellow and transparent and had a nonvolatile content of 60.5% by weight and a viscosity of 7,000 mPa · s was obtained. The resin (D1) had an acid value of 0.8 mg KOH / g, a hydroxyl value of 57.8 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 120,000. In addition, in the said prescription, a cyclic ester (b) will be a ratio of about 0.03 mol with respect to 1 mol of secondary | 2nd-class hydroxyl groups derived from a bicyclic ether compound (a-2).

(Synthesis Example 15)
In step (7) of Synthesis Example 8, dibasic acid (a-1) was added to adipic acid: 102 parts and isophthalic acid: 66 parts, and bicyclic ether compound (a-2) was added to bisphenol A diglycidyl ether: 380 parts. In the same manner as in Synthesis Example 8, except that the cyclic ester (b) was changed to 285 parts of ε-caprolactone, and the amount used at the start of the reaction and the additional amount during the reaction were changed to 0.2 parts respectively. The reaction and aging in step (7) was performed at 100 ° C. for 24 hours. Next, as step (8), 65 parts of hexamethyldisilazane as a silylating agent (c1) and 100 parts of ethyl acetate were added and aged for 4 hours, and then 90 parts of ethyl acetate was added and cooled to room temperature. A solution of addition type polyester resin (D1) was obtained.
This solution is light yellow and transparent, has a non-volatile content of 59.5% by weight and a viscosity of 3,000 mPa · s. The resin (D1) has an acid value of 78 mgKOH / g, a hydroxyl value of 20 mgKOH / g, and a glass transition temperature of −10. C. and a weight average molecular weight of 40,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.1 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 16)
In step (7) of Synthesis Example 8, dibasic acid (a-1) was added to 44 parts of adipic acid and 33 parts of isophthalic acid, and bicyclic ether compound (a-2) was added to 760 parts of bisphenol A diglycidyl ether. In the same manner as in Synthesis Example 8 except that the cyclic ester (b) was changed to 684 parts of ε-caprolactone and no catalyst was used, the reaction and aging in the step (7) was performed at 100 ° C. for 24 hours. . Next, as step (8), 290 parts of hexamethyldisilazane as the silylating agent (c1) and 665 parts of ethyl acetate were added and aged for 4 hours, and then 142 parts of ethyl acetate was added and cooled to room temperature. A solution of addition type polyester resin (D1) was obtained.
This solution is light yellow and transparent, has a nonvolatile content of 59.7% by weight and a viscosity of 95,000 mPa · s. The resin (D1) has an acid value of 0.1 mgKOH / g, a hydroxyl value of 33 mgKOH / g, and a glass transition temperature. It was -8 degreeC and the weight average molecular weight 20,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 17)
In step (7) of Synthesis Example 8, dibasic acid (a-1) is sebacic acid: 101 parts, bicyclic ether compound (a-2) is polyethylene glycol diglycidyl ether (ethylene oxide addition moles: 22): In the same manner as in Synthesis Example 8 except that the cyclic ester (b) was changed to 684 parts in 661 parts, respectively, ε-caprolactone was subjected to the reaction and aging in the step (7) for a total of 24 hours.
Next, in step (8), 245 parts of hexamethyldisilazane as a silylating agent (c1) and 427 parts of ethyl acetate were added and aged for 4 hours, and then 300 parts of ethyl acetate was added and cooled to room temperature. A solution of addition-type polyester resin (D1) that was light yellow and transparent, had a nonvolatile content of 60.5% by weight and a viscosity of 26,000 mPa · s was obtained. The resin (D1) had an acid value of 0.2 mg KOH / g, a hydroxyl value of 15 mg KOH / g, a glass transition temperature of −90 ° C., and a weight average molecular weight of 300,000. In addition, in the said prescription, cyclic ester (b) will be a ratio of about 5 mol with respect to 1 mol of secondary | 2nd-class hydroxyl groups derived from a bicyclic ether compound (a-2).

(Synthesis Example 18)
In step (7) of Synthesis Example 8, dibasic acid (a-1) is added to isophthalic acid: 83 parts, bicyclic ether compound (a-2) is added to bisphenol A diglycidyl ether: 380 parts, and cyclic ester (b) Is changed to ε-caprolactone: 342 parts, and toluene is not used as the organic solvent, and ethyl acetate is changed to only 200 parts, respectively. Reaction and aging were performed.
Next, in step (8), 245 parts of hexamethyldisilazane as a silylating agent (c1) and 200 parts of ethyl acetate were added and aged for 4 hours, and then 300 parts of ethyl acetate was added and cooled to room temperature. A solution of an addition-type polyester resin (D1) that was light yellow and transparent, had a non-volatile content of 59.3% by weight and a viscosity of 15,000 mPa · s was obtained. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 10 mg KOH / g, a glass transition temperature of 30 ° C., and a weight average molecular weight of 230,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 19)
Preparation was performed in the same manner as in Synthesis Example 8 except that the cyclic ester (b) was not used in Step (7) of Synthesis Example 8 and the amount of ethyl acetate used in Step (8) was changed from 650 parts to 100 parts. The concentration was adjusted by the amount of ethyl acetate added to obtain a light yellow transparent solution having a nonvolatile content of 60.0% by weight and a viscosity of 3,000 mPa · s. The resin contained in this solution is a polyester resin having a polyester main chain (I) and a side chain derived from the sealing compound (c), and has an acid value of 1.5 mg KOH / g, a hydroxyl value of 22 mg KOH / g, and a glass transition temperature. It was 56 degreeC and the weight average molecular weight 20,000.

(Synthesis Example 20)
In Step (8) of Synthesis Example 8, preparation was carried out in the same manner as in Synthesis Example 8 except that only 266 parts of ethyl acetate was added without using the silylating agent (c1). A solution of 60.0% by weight and a viscosity of 15,000 mPa · s was obtained. The resin contained in this solution is a polyester resin having a polyester main chain (I) and a side chain (II) resulting from addition of a cyclic ester, an acid value of 0.6 mgKOH / g, a hydroxyl value of 93 mgKOH / g, and a glass transition temperature. It was -15 degreeC and the weight average molecular weight 135,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

  Appearance, nonvolatile concentration, viscosity, resin weight average molecular weight (Mw), glass transition temperature (Tg), acid value (AV) and hydroxyl value (OHV) of each resin solution obtained in Synthesis Examples 1-20 Are summarized in Table 1. The evaluation and measurement methods for these items are described below.

<Appearance of solution>
The appearance of the resin solution was visually evaluated.

<Measurement of nonvolatile content concentration (TS)>
About 1 g of the resin solution was weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, and the residue was weighed to calculate the residual rate, thereby obtaining a non-volatile content concentration (solid content concentration, unit:%). .

<Measurement of viscosity (Vis) of solution>
The temperature of the resin solution was maintained at 25 ° C., and the viscosity (unit: mPa · s) was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) under conditions of 12 rpm and 1 minute rotation.

<Measurement of weight average molecular weight (Mw)>
Using a resin dissolved in tetrahydrofuran as a sample, separation and quantification based on the difference in molecular size is performed by liquid chromatography using GPC (gel permeation chromatograph) “HPC-8020” manufactured by Tosoh Corporation, and the weight average molecular weight of the resin ( Mw) was determined in terms of polystyrene.

<Measurement of glass transition temperature (Tg)>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.
About 10 mg of sample is weighed in an aluminum pan and set in a differential scanning calorimeter. The same type of aluminum pan with no sample is used as a reference, heated at a temperature of 300 ° C. for 5 minutes, and then −120 ° C. using liquid nitrogen. Quenched until. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the DSC chart obtained during the temperature elevation.

<Measurement of acid value (AV)>
About 1 g of a sample (polyester resin solution: concentration of about 60%) was accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution was added and dissolved. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (unit: mg KOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Non-volatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<Measurement of hydroxyl value (OHV)>
About 1 g of a sample (polyester resin solution: concentration of about 60%) was accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution was added and dissolved. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
As a numerical value of the resin in a dry state, a hydroxyl value (unit: mg KOH / g) was obtained by the following formula.
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Nonvolatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption (ml) of 0.1N alcoholic potassium hydroxide solution in the blank experiment
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

(Comparative Example 1)
50 parts of toluene is added to 100 parts by weight of the polyester resin (B) solution for the main chain obtained in the step (1) of Synthesis Example 1, and TDI / TMP (tolylene diisocyanate) is added as a crosslinking agent (E). Trimethylolpropane adduct body) 2.5 parts by weight was added and stirred well to obtain an adhesive composition. This was coated on a release-treated polyester film (hereinafter referred to as “release film”) to obtain a pressure-sensitive adhesive sheet, but the viscosity of the adhesive composition increased rapidly. I couldn't.

(Comparative Example 2)
In the same manner as in Comparative Example 1 except that the addition type polyester precursor (C1) solution obtained in the step (2) of Synthesis Example 1 was used instead of the polyester resin (B) solution for the main chain, the adhesive was used. A composition was obtained. However, since the viscosity of the adhesive composition increased rapidly as in Comparative Example 1, it could not be applied to the release film.

Example 1
50 parts of toluene is added to 100 parts by weight of the solution of the addition type polyester resin (D1) obtained in the step (3) of Synthesis Example 1, and TDI / TMP (tolylene diisocyanate) is added as a crosslinking agent (E). Trimethylolpropane adduct body) 2.5 parts by weight was added and stirred well to obtain an adhesive composition (first sealing form).
This was coated on a release film and dried at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of 25 μm to obtain an adhesive sheet.
A polarizing film having a multilayer structure in which both sides of a polyvinyl alcohol (PVA) polarizer are sandwiched between triacetyl cellulose-based protective films (hereinafter referred to as “TAC film”) is prepared, and the adhesive layer of the adhesive sheet is provided on one side. The laminated body of the structure of bonding and a "peeling film / adhesive layer / TAC film / PVA / TAC film" was obtained.
The obtained laminate was aged for one week under conditions of a temperature of 23 ° C. and a relative humidity of 50% to advance the reaction (dark reaction) of the adhesive layer, thereby obtaining a bonded polarizing plate (laminate).

(Examples 2 to 6)
Instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 1, each of the addition type polyester resin (D1) solutions obtained in Synthesis Examples 2 to 6 was used. Then, a bonded polarizing plate was produced.

(Comparative Example 3)
Similar to Comparative Example 1 except that the addition type polyester precursor (C1) solution obtained in Steps (4) and (5) of Synthesis Example 7 was used instead of the polyester resin (B) solution of Synthesis Example 1. Thus, an adhesive composition was obtained. However, as in Comparative Example 1, since the viscosity of the adhesive composition increased rapidly, it was not possible to apply a release film.

(Example 7)
To 100 parts by weight of the solution of the addition-type polyester resin (D1) obtained in the step (6) of Synthesis Example 7, 50 parts of toluene was added, and as a crosslinking agent (E), TDI / TMP (tolylene diisocyanate) was added. Trimethylolpropane adduct body) 2.5 parts by weight was added and stirred well to obtain an adhesive composition (first sealing form). Using this, a bonded polarizing plate was produced in the same manner as in Example 1.

(Example 8)
Example 7 except that the solution of the addition type polyester resin (D1) obtained in the step (8) of Synthesis example 8 was used instead of the solution of the addition type polyester resin (D1) obtained in Synthesis example 7. In the same manner as above, an adhesive composition (first sealing form) was obtained. Using this, a bonded polarizing plate was produced in the same manner as in Example 1.

(Examples 9 and 10)
Instead of the solution of addition type polyester resin (D1) obtained in Synthesis Example 8, the solution of addition type polyester resin (D1) obtained in Synthesis Example 9 (Example 9) or Synthesis Example 10 (Example 10) A bonded polarizing plate was produced in the same manner as in Example 8 except that each was used.

(Comparative Example 4)
An adhesive composition was prepared in the same manner as in Example 8 except that the polyester resin solution obtained in Synthesis Example 19 was used instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 8. Obtained. Although this adhesive composition could be applied to a release film, the adhesive layer could not be used for making a laminate because the adhesive layer did not have tack (initial adhesion).

(Comparative Example 5)
An adhesive composition was prepared in the same manner as in Example 8 except that the polyester resin solution obtained in Synthesis Example 20 was used instead of the resin solution obtained in Synthesis Example 8. Immediately after adding 2.5 parts by weight of TMP and stirring well, the viscosity rapidly increased and fluidity became poor, so that an adhesive composition could not be prepared.

(Comparative Example 6)
Adhesion processing was carried out in the same manner as in Example 10 except that the addition type polyester resin solution (D1) obtained in Synthesis Example 14 was used instead of the resin solution (D1) obtained in Synthesis Example 8. A polarizing plate was produced.

(Examples 11 and 12)
The crosslinking agent (E) was changed from TDI / TMP used in Example 8 to XDI / TMP (trimethylolpropane adduct of xylylene diisocyanate): 2.5 parts by weight (Example 11), or HMDI / Burette (Bullet Adduct of Hexamethylene Diisocyanate): An adhesive composition was obtained in the same manner as in Example 8, except that each was changed to 2.5 parts by weight (Example 12). Using this, a bonded polarizing plate was produced in the same manner as in Example 1.

(Examples 13 to 19)
In place of the solution (D1) of the addition-type polyester resin obtained in Synthesis Example 8, the additions obtained in Synthesis Examples 11 to 13 (Examples 13 to 15) and Synthesis Examples 15 to 18 (Examples 16 to 19) A bonded polarizing plate was produced in the same manner as in Example 10 except that each type polyester resin solution (D1) was used.

The pot life and coating processability of the adhesive compositions obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 2.
Moreover, about the polarizing plate (laminated body) obtained by the Example and the comparative example, the refractive index of a coating film, tack (initial adhesiveness), heat resistance, heat-and-moisture resistance, an optical characteristic, and removability were evaluated with the following method. did. The results are shown in Table 2.

<Evaluation method of pot life>
About the adhesive composition obtained by each Example and the comparative example, the viscosity in 25 degreeC was measured for every 10 hours to 10 hours, and pot life was evaluated in the following three steps. Viscosity was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) under the conditions of 12 rpm and 1 minute rotation. ○: “No problem at all.
Δ: “Slight increase in viscosity is observed and the rate of increase in viscosity up to 5 hours is less than 2 times.”
X: “A sudden increase in viscosity was observed and gelled in less than 5 hours.

<Coating process evaluation method>
The adhesive composition obtained in each Example and Comparative Example was applied on the release film at a speed of 2 m / min by adjusting the supply amount of the comma coater so that the thickness after drying was 25 μm. An adhesive layer was formed by drying in an oven at 100 ° C., and a 50 μm thick polyester film was attached and laminated to prepare an adhesive sheet. The state of the coated surface was visually observed and evaluated in three stages. In addition, about the thing whose pot life evaluation was set to "x", the coating process and the following evaluation were not performed.
○: “No problem at all”
Δ: “Slight repellency and foaming are recognized at the end of the coated surface, but there is no practical problem.”
×: “Repelling, foaming and streaking are recognized on the coated surface, and there are practical problems.”

<Evaluation method of refractive index of coating film>
The adhesive composition obtained in each Example and Comparative Example was coated on a release film, dried in an oven at 120 ° C., and provided with an adhesive layer having a thickness of 25 μm, and then bonded to a polyester film. Lamination was performed to produce an adhesive sheet.
Then, the sodium D line | wire was irradiated in 25 degreeC atmosphere with the Abbe refractometer "DR-M2" by ATAGO, and the refractive index of the adhesive bond layer on an adhesive sheet was measured.

<Evaluation method of optical characteristics>
The adhesive composition obtained in each Example and Comparative Example was coated on a release film, dried in an oven at 120 ° C., and an adhesive layer having a thickness of 25 μm was provided, and further a polyester having a thickness of 50 μm. The films were bonded together. After the adhesive layer sandwiched between the release film and the polyester film is aged for 1 week at a temperature of 23 ° C. and a relative humidity of 50%, the release film is removed, and the appearance of the adhesive layer alone is visually judged. The value was measured with a measuring device “NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd.
○: “No problem in practical use. HAZE value: less than 1.”
Δ: “No cloudiness is observed, HAZE value: 1 or more and less than 3.”
×: “Slightly cloudy or HAZE value: 3 or more (practical problem)”

<Tack (initial adhesion) evaluation method>
The adhesive composition obtained in each Example and Comparative Example was coated on a release film, dried in an oven at 120 ° C. to provide an adhesive layer having a thickness of 25 μm, and further polyester having a thickness of 50 μm. The film was laminated. After the adhesive layer taught in the release film and the polyester film was aged for one week at a temperature of 23 ° C. and a relative humidity of 50%, the release film was removed, and the adhesive layer was removed according to the J · Dow rolling ball method. The measurement was performed at 23 ° C. and 65% RH. In addition, the evaluation of the tack was “x” and the subsequent evaluation was not performed.
○: “Sufficient tack appears. Ball value: # 8 or more.”
Δ: “Tack is weak, but there is no practical problem. Ball value: # 3 to # 8.”
X: “There is almost no tack and poor initial adhesion. Ball value: less than # 3.”

<Evaluation method of heat resistance and moist heat resistance (1)>
The bonded polarizing plate (laminate) is cut into a size of 150 mm × 80 mm, the release film is peeled off, and the absorption axis of each polarizing plate is orthogonal to both surfaces of a 1.1 mm thick float glass plate. It stuck using the laminator. Subsequently, the glass plate on which the polarizing plate is attached is held in an autoclave at 50 ° C. and 5 atm for 20 minutes to firmly adhere the polarizing plate to the glass plate, and the polarizing plate and the glass plate are laminated. I got a thing.
As evaluation of heat resistance, floating peeling and deviation after leaving the laminate for 1000 hours at 120 ° C. and light leakage (white spots) when light was transmitted through the laminate were visually observed.
In addition, as an evaluation of the heat and humidity resistance, floating peeling and deviation after leaving the laminate for 1000 hours at 80 ° C. and 90% relative humidity, and light leakage (white spots) when light is transmitted through the laminate. It was observed visually. The “displacement” is a displacement of the sticking position observed around the polarizing plate attached to the glass due to contraction of the polarizing plate.
The heat resistance and moist heat resistance were evaluated based on the following four criteria.

◎: “Floating peeling, whitening, and displacement are not recognized at all, and there is no problem in practical use.”
○: “No floating peeling or whitening is observed, the displacement is less than 0.2 mm, and there is no problem in practical use.”
Δ: “Slightly floating peeling and whitening are observed, but the deviation is less than 02 to 0.5 mm, and there is no practical problem”
X: “There are floating floats and white spots on the entire surface, which is not practical”.
<Evaluation method of moisture and heat resistance (2)>
The discoloration (coloring) state of the bonded polarizing plate (laminate) before and after the test of the heat and humidity resistance (1) was observed with sight.
○: “No discoloration such as yellowing is observed, and there is no problem in practical use.”
Δ: “Slight yellowing is observed, but there is no practical problem”
×: “Significant discoloration such as yellowing is recognized and there is a problem in practical use.”

<Evaluation method of removability (reworkability)>
The bonded polarizing plate (laminated body) is cut into a size of 25 mm × 150 mm, the release film is peeled off, and is attached to a float glass plate with a thickness of 1.1 mm using a laminator. The polarizing plate was firmly adhered to the glass plate by being kept in the autoclave for 20 minutes. The test piece was left for 1 week at 23 ° C. and 50% relative humidity, and then subjected to a 180 ° peel test in which it was peeled off at a speed of 300 mm / min in the direction of 180 °, and the glass surface after peeling was visually observed. Then, the following three stages were evaluated.
○: “No cloudiness, no problem in practical use”
Δ: “Slightly cloudy, but practically no problem”
X: “Transfer of the adhesive layer is recognized over the entire surface and is not practical”.

<< First sealing form: Use of acid anhydride (c2) as sealing compound (c) >>
In the following synthesis examples 21 to 43, a polyester resin was prepared using an acid anhydride (c2) as the sealing compound (c). Synthesis Examples 21, 23 to 27 were prepared according to a three-stage manufacturing method, Synthesis Example 28 was prepared according to a pseudo two-stage manufacturing method, Synthesis Examples 29 to 43 were prepared according to a two-stage manufacturing method, and Synthesis Examples 22 and 40 were cyclic esters (b ) Is omitted.

[Preparation of Addition Type Polyester Resin (D1) by Three-Stage Manufacturing Method]
(Synthesis Example 21)
<Step (1): Formation of polyester main chain>
A stirrer, a thermometer, a reflux condenser, a dropping device and a nitrogen introducing tube are attached to the polymerization tank to constitute a polymerization reaction device. The compound (a-2), the catalyst, and the organic solvent that were included were charged at the following ratios.

[Polymerization tank]
Adipic acid (a-1) 438 parts Isophthalic acid (a-1) 332 parts Ethyl acetate 135 parts Toluene 135 parts [Drip device]
Bisphenol A diglycidyl ether (a-2) 1995 parts Tetrabutylammonium tetrahydroborate (catalyst) 5.5 parts Ethyl acetate 135 parts Toluene 135 parts

After the air in the polymerization tank was replaced with nitrogen gas, the dibasic acid (a-1) mixture was heated to 100 ° C. while stirring. Next, the bicyclic ether compound (a-2) mixture was added dropwise to the stirring dibasic acid (a-1) mixture from the dropping device at a constant rate over 1 hour. After completion of the addition, while further stirring, add 5.5 parts of catalyst twice every 8 hours, react and mature for a total of 24 hours, add 1307 parts of ethyl acetate and cool to room temperature to complete the reaction. Thus, a polyester resin (B) solution for the main chain was obtained.
This solution is light yellow and transparent, has a non-volatile content of 60.5% by weight and a viscosity of 20,000 mPa · s. The resin has an acid value of 0.5 mg KOH / g, a hydroxyl value of 155 mg KOH / g, a glass transition temperature of 60 ° C., and a weight. The average molecular weight was 50,000.

<Step (2): Ring-Opening Addition Reaction of Cyclic Ester (b)>
A polymerization reaction apparatus having a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube attached to the polymerization tank is prepared. The solution, cyclic ester (b), catalyst and organic solvent were charged in the following ratios.

[Polymerization tank]
Polyester resin (B) solution for main chain 219 parts Ethyl acetate 33 parts [Drip device]
ε-Caprolactone (b) 114 parts Tetrabutylammonium tetrahydroborate (catalyst) 1.3 parts Ethyl acetate 66 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the resin solution. Next, the cyclic ester (b) mixture was dropped at a constant rate over 1 hour from the dropping device. After completion of the dropwise addition, the mixture was further reacted and aged for 12 hours while stirring, and then 66 parts of ethyl acetate was added and cooled to room temperature to complete the reaction, thereby preparing a solution of an addition type polyester precursor (C1).
This solution is light yellow and transparent, has a nonvolatile content of 60.2% by weight and a viscosity of 15,000 mPa · s. The resin has an acid value of 0.05 mg KOH / g, a hydroxyl value of 74 mg KOH / g, a glass transition temperature of −10 ° C., The weight average molecular weight was 150,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Step (3): Sealing reaction with acid anhydride (c2)>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing pipe are attached to the polymerization tank is prepared. The solution, acid anhydride (c2), catalyst and organic solvent were charged in the following ratios.

[Polymerization tank]
200 parts of addition type polyester precursor (C1) solution obtained in the step (2) [Drip device]
Phthalic anhydride (c2) 3.6 parts Tetrabutylammonium tetrahydroborate (catalyst) 1.2 parts Ethyl acetate 1 part

After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 100 ° C. while stirring the addition-type polyester precursor (C1) solution. Subsequently, the acid anhydride mixture was dripped at this with constant velocity over 1 hour from the dripping apparatus. After completion of the dropwise addition, the mixture was further reacted and aged for 8 hours with stirring, then 5 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D1).
This solution is light yellow and transparent, has a non-volatile content of 60.2% by weight and a viscosity of 22,000 mPa · s. The resin (D1) has an acid value of 15.3 mg KOH / g, a hydroxyl value of 65 mg KOH / g, and a gas transition temperature. It was -10 degreeC and the weight average molecular weight 180,000.

(Synthesis Example 22)
In Synthesis Example 21, the main chain obtained in the step (1) was omitted in the step (3) instead of the addition type polyester precursor (C1) solution obtained in the step (2) in the step (3). Preparation was performed in the same manner as in Synthesis Example 21, except that 200 parts of a polyester resin (B) solution (non-volatile content: 60.2% by weight) was used. A polyester resin solution of 21,000 mPa · s was obtained. The resin contained in the solution had an acid value of 35 mg KOH / g, a hydroxyl value of 98 mg KOH / g, a glass transition temperature of 60 ° C., and a weight average molecular weight of 60,000.

(Synthesis Example 23)
The dibasic acid (a-1) used in the step (1) of Synthesis Example 21 was changed to isophthalic acid: 830 parts, and the bicyclic ether compound (a-2) was changed to neopentyl glycol diglycidyl ether: 1449 parts. Preparation was carried out in the same manner as in Synthesis Example 21 except that 200 parts of a solution prepared by adjusting the polyester resin for the main chain (B) to a non-volatile content of about 60% by weight with ethyl acetate was used in step (2). Then, the non-volatile content was adjusted to about 60% by weight with ethyl acetate to obtain a solution of addition type polyester resin (D1) which was light yellow and transparent and had a viscosity of 14,000 mPa · s. The resin (D1) had an acid value of 16.5 mgKOH / g, a hydroxyl value of 68 mgKOH / g, a glass transition temperature of −25 ° C., and a weight average molecular weight of 110,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.5 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 24)
1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene: 670 parts, and bisphenol A were used as the bicyclic ether compound (a-2) used in Step (1) of Synthesis Example 21. Diglycidyl ether: changed to 1385 parts and synthesized except that 224 parts of the solution obtained by adjusting the obtained polyester resin for main chain (B) to a non-volatile content of about 60% by weight with ethyl acetate was used in step (2). Preparation was carried out in the same manner as in Example 21, and the non-volatile content was adjusted to about 60% by weight with ethyl acetate to obtain a solution of addition type polyester resin (D1) having a pale yellow transparency and a viscosity of 11,500 mPa · s. The resin (D1) had an acid value of 16.8 mg KOH / g, a hydroxyl value of 72 mg KOH / g, a glass transition temperature of −35 ° C., and a weight average molecular weight of 142,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.7 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 25)
The bicyclic ether compound (a-2) used in the step (1) of Synthesis Example 21 was replaced with bisphenol fluorange glycidyl ether (BPFG manufactured by Osaka Gas Chemical Co., Ltd., alias: 9,9-bis [4- (glycidyloxy). ) Phenyl] -9H-fluorene, molecular weight: 462.5, epoxy value :: 3.89 (eq · Kg)): 3203 parts, and the obtained polyester resin (B) solution for main chain was obtained with ethyl acetate. Preparation was carried out in the same manner as in Synthesis Example 21 except that 315 parts of a solution adjusted to a nonvolatile content of about 60% by weight was used in step (2), and the nonvolatile content was adjusted to about 60% by weight with ethyl acetate. A solution of an addition type polyester resin (D1) which was yellow and transparent and had a viscosity of 35,000 mPa · s was obtained. The resin (D1) had an acid value of 13.2 mg KOH / g, a hydroxyl value of 71 mg KOH / g, a glass transition temperature of −15 ° C., and a weight average molecular weight of 165,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 26)
The cyclic ester (b) used in the step (2) of Synthesis Example 21 was changed to δ-valerolactone: 100 parts, and the obtained polyester resin for the main chain (B) solution with ethyl acetate had a nonvolatile content of about 60% by weight. Preparation was performed in the same manner as in Synthesis Example 21 except that 200 parts of the solution prepared in Step (3) was used, and the nonvolatile content was adjusted to about 60% by weight with ethyl acetate. A solution of addition type polyester resin (D1) of 1,000 mPa · s was obtained. The resin (D1) had an acid value of 15.8 mg KOH / g, a hydroxyl value of 70 mg KOH / g, a glass transition temperature of −25 ° C., and a weight average molecular weight of 120,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.6 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 27)
Preparation was performed in the same manner as in Synthesis Example 21 except that the acid anhydride (c2) used in Step (3) of Synthesis Example 21 was changed to 4 parts of anhydrous hymic acid, which was pale yellow and transparent, and had a nonvolatile content of 60 A solution of addition-type polyester resin (D1) having a viscosity of 1% by weight and a viscosity of 14,000 mPa · s was obtained. The resin (D1) had an acid value of 13.9 mg KOH / g, a hydroxyl value of 65 mg KOH / g, a glass transition temperature of −15 ° C., and a weight average molecular weight of 170,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

[Preparation of Addition Type Polyester Resin (D1) by Pseudo Two-Stage Manufacturing Method]
(Synthesis Example 28)
<Steps (4) and (5): Formation of addition-type polyester precursor (C1)>
Prepare a polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dropping device and nitrogen inlet tube in the polymerization tank, and dibasic acid (a-1), bicyclic ether compound (a -2), cyclic ester (b), catalyst and organic solvent were charged at the following ratios.

[Polymerization tank]
Adipic acid (a-1) 73 parts Sebacic acid (a-1) 404 parts Bisphenol F diglycidyl ether (a-2) 875 parts Bisphenol A-based phenoxy resin (a-2) 1950 parts (manufactured by Japan Epoxy Resin Co., Ltd., product The name “jER1256”,
Glycidyl group equivalent: 7800 g / eq, Mw: 51000)
Tetrabutylammonium tetrahydroborate (catalyst) 6.6 parts Ethyl acetate 210 parts Toluene 210 parts [Drip device]
Tetrabutylammonium tetrahydroborate (catalyst) 6.6 parts ε-caprolactone (b) 3500 parts Ethyl acetate 210 parts Toluene 210 parts

After replacing the air in the polymerization tank with nitrogen gas, the mixture was heated to 100 ° C. while stirring and reacted for 8 hours to obtain a polyester resin for main chain (I ′) having an acid value of 5 mgKOH / g or less. .
Next, the cyclic ester (b) mixture was dropped at a constant rate over 1 hour from the dropping device. After completion of dropping, 6.6 parts of tetrabutylammonium tetrahydroborate was added after stirring for 8 hours. After further reaction and aging for 8 hours, 3500 parts of ethyl acetate was added and cooled to room temperature to complete the reaction. Type polyester precursor (C1) was obtained.
This solution is light yellow and transparent, has a non-volatile content of 59.8% by weight and a viscosity of 30,000 mPa · s. The precursor (C1) has an acid value of 0.02 mgKOH / g, a hydroxyl value of 92 mgKOH / g, and a glass transition. The resin had a temperature of −15 ° C. and a weight average molecular weight of 200,000. In the above formulation, the cyclic ester (b) is in a ratio of about 0.5 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Step (6): Sealing reaction with acid anhydride (c2)>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing pipe are attached to the polymerization tank is prepared. A solution (nonvolatile content: 59.8%), an acid anhydride (c2), a catalyst, and an organic solvent were charged in the following ratios.

[Polymerization tank]
Addition-type polyester precursor (C1) solution 200 parts [Drip device]
Succinic anhydride (c2) 5.0 parts Tetrabutylammonium tetrahydroborate (catalyst) 6.6 parts Ethyl acetate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature in the tank was raised to 100 ° C. while stirring. Subsequently, the acid anhydride mixture was dropped at a constant rate over 1 hour from the dropping device. After completion of the dropwise addition, the mixture was reacted and aged for 6 hours with stirring, then 5 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D1).
This solution is light yellow and transparent and has a non-volatile content of 60.5% by weight and a viscosity of 30,000 mPa · s. The resin (D1) has an acid value of 15 mg KOH / g, a hydroxyl value of 62 mg KOH / g, and a glass transition temperature of −10. C. and a weight average molecular weight of 170,000.

[Preparation of Addition Type Polyester Resin (D1) by Two-Step Manufacturing Method]
(Synthesis Example 29)
Prepare a polymerization reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube in the polymerization tank. Dibasic acid (a-1), bicyclic ether compound (a-2), cyclic ester (B) The catalyst and the organic solvent were charged at the following ratios.

[Polymerization tank]
Adipic acid (a-1) 159 parts Isophthalic acid (a-1) 120 parts Bisphenol A diglycidyl ether (a-2) 721 parts ε-caprolactone (b) 871 parts Ethyl acetate 200 parts Toluene 200 parts

<Step (7): Formation of addition-type polyester precursor (C1)>
After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 100 ° C. while stirring, and 2.0 parts of tetrabutylammonium tetrahydroborate was added to initiate the reaction. While stirring the mixture, 2.0 parts of tetrabutylammonium tetrahydroborate was added twice every 8 hours for a total of 24 hours for reaction and ripening to obtain an addition type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Step (8): Sealing reaction with acid anhydride (c2)>
Ethyl acetate: 500 parts and phthalic anhydride: 56 parts as an acid anhydride (c2) were added to the addition-type polyester precursor (C1) solution and aged for 6 hours. Thereafter, ethyl acetate was added so that the non-volatile content was about 60% by weight, and the mixture was cooled to room temperature to obtain a solution of an addition type polyester resin (D1).
This solution is light yellow and transparent, has a nonvolatile content of 60.4% by weight and a viscosity of 37,000 mPa · s. The resin (D1) has an acid value of 11.7 mgKOH / g, a hydroxyl value of 94 mgKOH / g, and a glass transition temperature. It was -10 degreeC and the weight average molecular weight 150,000.

(Synthesis Example 30)
The dibasic acid (a-1) used in the step (7) of Synthesis Example 29 is succinic acid: 322 parts, and the bicyclic ether compound (a-2) is neopentyl glycol diglycidyl ether: 678 parts, cyclic. The ester (b) was changed to ε-caprolactone: 143 parts, the catalyst added over 3 times was changed to tetrabutylammonium nitrate: 2 parts each, and the acid anhydride (c) used in the step (8) was changed to anhydrous Succinic acid: Prepared in the same manner as in Synthesis Example 29 except that the amount was changed to 38 parts, and was a pale yellow transparent addition type polyester resin (D1) having a nonvolatile content of 59.7% by weight and a viscosity of 15,000 mPa · s. ) Was obtained. The resin (D1) had an acid value of 19.6 mg KOH / g, a hydroxyl value of 75 mg KOH / g, a glass transition temperature of −35 ° C., and a weight average molecular weight of 160,000. In the above formulation, the cyclic ester (b) is in a ratio of about 0.2 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 31)
The catalyst used in Synthesis Example 29 was prepared in the same manner as in Synthesis Example 29 except that the catalyst was changed to tetrabutylammonium bromide. It was light yellow and transparent, had a nonvolatile content of 60.2% by weight and a viscosity of 19,000 mPa · s. A solution of addition type polyester resin (D1) was obtained. The resin (D1) had an acid value of 13.8 mg KOH / g, a hydroxyl value of 88 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 130,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 32)
The catalyst used in Synthesis Example 29 was prepared in the same manner as in Synthesis Example 29 except that the catalyst was changed to tetrabutyl titanate. The addition type had a yellow transparent and non-volatile content of 60.2% by weight and a viscosity of 9,500 mPa · s. A solution of the polyester resin (D1) was obtained. The resin (D1) had an acid value of 12.8 mg KOH / g, a hydroxyl value of 85 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 80,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 33)
Prepared in the same manner as in Synthetic Example 29 except that the catalyst used in Synthetic Example 29 was changed to dibutyltin oxide, and was pale yellow translucent, non-volatile content of 60.1% by weight, and addition of viscosity of 6,000 mPa · s. A solution of type polyester resin (D1) was obtained. Resin (D1) had an acid value of 14.2 mg KOH / g, a hydroxyl value of 80 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 105,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 34)
By preparing in the same manner as in Synthesis Example 29 except that the weight of phthalic anhydride, which is the acid anhydride (c) used in Step (8) of Synthesis Example 29, was changed to 3 parts, and further adding ethyl acetate. A solution of an addition-type polyester resin (D1) that was light yellow and transparent and had a nonvolatile content of 59.8% by weight and a viscosity of 50,000 mPa · s was obtained. The resin (D1) had an acid value of 0.05 mg KOH / g, a hydroxyl value of 133.5 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 250,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 35)
Synthesis except that the weight of phthalic anhydride as the acid anhydride (c) used in Step (8) of Synthesis Example 29 was changed to 285 parts, and the weight of ethyl acetate added together with phthalic anhydride was changed to 237 parts. Prepared in the same manner as in Example 29, and added with 300 parts of ethyl acetate to obtain a solution of an addition type polyester resin (D1) having a pale yellow transparent, non-volatile content of 60.4% by weight and a viscosity of 6,000 mPa · s. It was. The resin (D1) had an acid value of 80.8 mg KOH / g, a hydroxyl value of 7.8 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 110,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 36)
The dibasic acid (a-1) used in the step (7) of Synthesis Example 29 was added to 102 parts of adipic acid and 66 parts of isophthalic acid, and the bicyclic ether compound (a-2) was used as bisphenol A diglycidyl ether: 380. In the same manner as in Synthesis Example 29, except that the cyclic ester (b) was changed to ε-caprolactone: 285 parts, and the amount used at the start of the reaction and the additional amount during the reaction were changed to 0.2 parts respectively. Then, the reaction and aging in the step (7) were performed at 100 ° C. for 24 hours. Next, as step (8), 13 parts of phthalic anhydride which is an acid anhydride (c2) and 100 parts of ethyl acetate were added and aged for 4 hours, and then 64 parts of ethyl acetate was added and cooled to room temperature. A solution of type polyester resin (D1) was obtained.
This solution is light yellow and transparent, has a non-volatile content of 59.6% by weight and a viscosity of 3,500 mPa · s. The resin (D1) has an acid value of 24.5 mgKOH / g, a hydroxyl value of 90 mgKOH / g, and a glass transition temperature. It was -10 degreeC and the weight average molecular weight 45,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.1 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 37)
The dibasic acid (a-1) used in the step (7) of Synthesis Example 29 was added to 44 parts of adipic acid and 33 parts of isophthalic acid, and the bicyclic ether compound (a-2) was added to bisphenol A diglycidyl ether: 760. In the same manner as in Synthesis Example 29 except that the cyclic ester (b) was changed to 684 parts of ε-caprolactone and no catalyst was used, the reaction and ripening in the step (7) was performed at 100 ° C. for 24 hours. went. Next, as step (8), 65 parts of phthalic anhydride as an acid anhydride (c2) and 280 parts of ethyl acetate were added and aged for 4 hours, and then 377 parts of ethyl acetate was added and cooled to room temperature. A solution of resin (D1) was obtained.
This solution is light yellow and transparent, has a non-volatile content of 60.0% by weight and a viscosity of 98,000 mPa · s. The resin (D1) has an acid value of 2.5 mgKOH / g, a hydroxyl value of 98.3 mgKOH / g, glass The transition temperature was −5 ° C. and the weight average molecular weight was 21,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 38)
The dibasic acid (a-1) used in Step (7) of Synthesis Example 29 was sebacic acid: 101 parts, and the bicyclic ether compound (a-2) was polyethylene glycol diglycidyl ether (ethylene oxide addition moles: 22 ): The reaction and ripening for 24 hours in Step (7) were carried out in the same manner as in Synthesis Example 29 except that the cyclic ester (b) was changed to 661 parts and ε-caprolactone was changed to 684 parts.
Thereafter, as step (8), 56 parts of phthalic anhydride which is an acid anhydride (c) and 500 parts of ethyl acetate are added and further reacted and aged for 6 hours. Further, 100 parts of ethyl acetate is added and cooled to room temperature. A solution of an addition-type polyester resin (D1) that was light yellow and transparent, had a nonvolatile content of 60.2% by weight and a viscosity of 27,000 mPa · s was obtained. The resin (D1) had an acid value of 12.2 mg KOH / g, a hydroxyl value of 75 mg KOH / g, a glass transition temperature of −90 ° C., and a weight average molecular weight of 350,000. In addition, in the said prescription, cyclic ester (b) will be a ratio of about 5 mol with respect to 1 mol of secondary | 2nd-class hydroxyl groups derived from a bicyclic ether compound (a-2).

(Synthesis Example 39)
The dibasic acid (a-1) used in the step (7) of Synthesis Example 29 was added to 83 parts of isophthalic acid, the bicyclic ether group compound (a-2) was added to 380 parts of bisphenol A diglycidyl ether, and a cyclic ester. The reaction and ripening for 24 hours in the step (7) were carried out in the same manner as in Synthesis Example 29 except that (b) was changed to ε-caprolactone: 342 parts.
Thereafter, as the step (8), 56 parts of phthalic anhydride which is an acid anhydride (c2) and 100 parts of ethyl acetate are added and further reacted and ripened for 6 hours, and 74 parts of ethyl acetate is added and cooled to room temperature. As a result, a solution of addition-type polyester resin (D1) that was light yellow and transparent, had a nonvolatile content of 59.5% by weight and a viscosity of 13,000 mPa · s was obtained. The resin (D1) had an acid value of 18.5 mgKOH / g, a hydroxyl value of 70.5 mgKOH / g, a glass transition temperature of 30 ° C., and a weight average molecular weight of 250,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 40)
Synthesis was performed except that the cyclic ester (b) was not used in the step (7) of Synthesis Example 29 and the amount of ethyl acetate added together with the acid anhydride (c) in the step (8) was changed from 500 parts to 204 parts. Preparation was carried out in the same manner as in Example 29, and 100 parts of ethyl acetate was added and cooled to room temperature to obtain a pale yellow transparent polyester resin solution having a nonvolatile content of 60.0% by weight and a viscosity of 5,000 mPa · s. The polyester resin contained in the solution had an acid value of 48.5 mgKOH / g, a hydroxyl value of 102 mgKOH / g, a glass transition temperature of 60 ° C., and a weight average molecular weight of 25,000.

(Synthesis Example 41)
Prepared in the same manner as in Synthetic Example 29 except that the weight of the acid anhydride (c2) used in Step (8) of Synthetic Example 29 was changed to 562 parts. A solution of addition type polyester resin (D1) having a content of 60.4% by weight and a viscosity of 40,000 mPa · s was obtained. The resin (D1) had an acid value of 120 mg KOH / g, a hydroxyl value of 0.02 mg KOH / g, a glass transition temperature of −5 ° C., and a weight average molecular weight of 220,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 42)
By further reacting phenyl isocyanate as a sealing compound (c) with 100 parts by weight of the solution of the addition type polyester resin (D1) obtained in the step (8) of Synthesis Example 29, the hydroxyl value is 94 mgKOH / g. To a hydroxyl value of 9.5 mg KOH / g, and a solution of an addition type polyester resin (D1) having a nonvolatile content of 60.2% by weight and a viscosity of 37,000 mPa · s was obtained.

(Synthesis Example 43)
By further reacting diethylmethylsilane as the sealing compound (c) with 100 parts by weight of the solution of the addition type polyester resin (D1) obtained in the step (8) of Synthesis Example 29, the hydroxyl value is 94 mgKOH / The addition value polyester resin (D1) having a non-volatile content of 59.9% by weight and a viscosity of 37,000 mPa · s was obtained by reducing the hydroxyl value from 1 g to 11.5 mg KOH / g.

  Appearance, nonvolatile content concentration, viscosity, resin weight average molecular weight (Mw), glass transition temperature (Tg), acid value (AV) and hydroxyl value (OHV) of each resin solution obtained in Synthesis Examples 21 to 43 Are summarized in Table 3.

(Comparative Example 7)
50 parts of toluene is added to 100 parts by weight of the main chain polyester resin (B) solution obtained in the step (1) of Synthesis Example 21, and TDI / TMP (tolylene diisocyanate) is added as a crosslinking agent (E). Trimethylolpropane adduct body) 2.5 parts by weight was added and stirred well to obtain an adhesive composition. This was applied onto a release film to obtain an adhesive sheet, but could not be applied because the viscosity of the adhesive composition increased rapidly.

(Comparative Example 8)
An adhesive composition was obtained in the same manner as in Comparative Example 7, except that the addition-type polyester precursor (C1) solution obtained in the step (2) of Synthesis Example 21 was used. When this was applied to a release film, foaming or the like occurred on the surface of the formed adhesive layer, but in the same manner as in Examples 1 to 19, "release film / adhesive layer / TAC film / PVA / TAC film" The laminated body of the structure of this was obtained, reaction of the adhesive bond layer was advanced, and the polarizing plate (laminated body) which carried out the adhesion process was obtained. However, since the coated surface was extremely rough, no subsequent evaluation was performed.

(Example 20)
To 100 parts by weight of the solution of the addition-type polyester resin (D1) obtained in the step (3) of Synthesis Example 21, 50 parts of toluene was added, and HBAP (2,2′-bishydroxymethyl) was further used as a crosslinking agent (E). Butanol tris [3- (1-aziridinyl) propionate]) 0.25 part by weight was added and stirred well to obtain an adhesive composition (first sealing form).
Hereinafter, in the same manner as in Examples 1 to 19 and the like, a laminate composed of “peeling film / adhesive layer / TAC film / PVA / TAC film” was produced, and the reaction of the adhesive layer was advanced, followed by adhesion processing. A polarizing plate (laminate) was obtained.

(Comparative Example 9)
An adhesive composition was obtained in the same manner as in Example 20 except that the polyester resin solution obtained in Synthesis Example 22 was used instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 21. . This could be applied to the release film, but the adhesive layer did not have tack (initial adhesion), so the adhesive layer could not be laminated to the TAC film / PVA / TAC film configuration It was.

(Examples 21 to 25)
A polarizing plate subjected to adhesion processing in the same manner as in Example 20, except that each of the resin solutions obtained in Synthesis Examples 23 to 27 was used instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 21. Was made.

(Example 26)
50 parts of toluene was added to 100 parts by weight of the solution of the addition type polyester resin (D1) obtained in the step (6) of Synthesis Example 28, and HBAP (2,2′-bishydroxymethyl) was further used as a crosslinking agent (E). Butanol tris [3- (1-aziridinyl) propionate]) 0.25 part by weight was added and stirred well to obtain an adhesive composition (second sealing form). Using this, a bonded polarizing plate was produced in the same manner as in Example 20.

(Example 27)
The adhesive composition was the same as in Example 26 except that the addition type polyester resin (D1) obtained in Synthesis Example 29 was used instead of the addition type polyester resin solution (D1) obtained in Synthesis Example 28. I got a thing. Using this, a bonded polarizing plate was produced in the same manner as in Example 26.

(Comparative Example 10)
An adhesive composition was obtained in the same manner as in Example 27 except that the polyester resin solution obtained in Synthesis Example 40 was used instead of the addition type polyester resin solution (D1) obtained in Synthesis Example 28. It was. This could be applied to the release film, but the adhesive layer did not have tack (initial adhesion), so the adhesive layer could be laminated to the TAC film / PVA / TAC film configuration. There wasn't.

(Examples 28 to 35)
Instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 28, the addition type obtained in Synthesis Examples 30 to 33 (Examples 28 to 31) and Synthesis Examples 36 to 39 (Examples 32 to 35). A bonded polarizing plate was produced in the same manner as in Example 26 except that the polyester resin (D1) was used.

(Comparative Examples 11 and 12)
Instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 28, the addition type polyester resin (D1) obtained in Synthesis Example 34 (Comparative Example 11) or Synthesis Example 35 (Comparative Example 12) was used. A bonded polarizing plate was produced in the same manner as in Example 26 except that it was.

(Examples 36 to 39)
Instead of HBAP which is the cross-linking agent (E) used in Example 27, TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) (Example 36), carbodilite V-05 ( Nisshinbo Co., Ltd. carbodiimide-based crosslinking agent) (Example 37), TMBOX [2,2′-tetramethylenebis (2-oxazoline)] (Example 38), or AlAA [aluminum tris (acetylacetonate) )] (Example 39) was used in the same manner as in Example 27 except that 0.25 parts by weight of each was used to obtain an adhesive composition. Using these, an adhesive-processed polarizing plate was produced in the same manner as in Example 28.

(Examples 40 and 41)
The addition type polyester resin (D1) used in Example 21 was changed to the addition type polyester resin (D1) obtained in Synthesis Example 35 (Example 40) or Synthesis Example 41 (Example 41), and a crosslinking agent ( A bonded polarizing plate was produced in the same manner as in Example 21 except that 2.5 parts by weight of TDI / TMP (trimethylolpropane adduct of tolylene diisocyanate) was used as E).

(Examples 42 and 43)
Implemented except that the addition type polyester resin (D1) used in Example 28 was changed to the addition type polyester resin (D1) obtained in Synthesis Example 42 (Example 42) or Synthesis Example 43 (Example 43). An adhesive composition was obtained in the same manner as in Example 28, and an adhesive-processed polarizing plate was produced in the same manner as in Example 27.

The pot life and coating processability of the adhesive compositions obtained in Examples and Comparative Examples were evaluated in the same manner as in Examples 1-19. The results are shown in Table 4.
Moreover, about the polarizing plate (laminated body) which carried out the adhesion process obtained by the Example and the comparative example, the refractive index of a coating film, heat resistance, heat-and-moisture resistance, an optical characteristic, and removability are the case of Examples 1-19. Evaluation was performed in the same manner. The results are shown in Table 4. The heat resistance evaluation test was carried out in Examples 1 to 19 except that the adjustment conditions for the samples other than Examples 42 and 43 were changed from “Leave at 120 ° C. for 1000 hours” to “Leave at 80 ° C. for 1000 hours”. As well as. The heat and humidity resistance evaluation test was carried out in the same manner as in Examples 1 to 3, except that the sample adjustment conditions were changed from “80 ° C., relative humidity 90% left for 1000 hours” to “60 ° C., relative humidity 90% left for 1000 hours”. The same as 19 was carried out. About Example 42 and 43, it carried out similarly to Examples 1-19.

<< First sealing form: Use of isocyanate compound (c3) as sealing compound (c) >>
In the following synthesis examples 44 to 63, a polyester resin was prepared using an isocyanate compound (c3) as the sealing compound (c). Synthesis Examples 44 to 49 were prepared according to a three-stage manufacturing method, Synthesis Example 50 was prepared according to a pseudo two-stage manufacturing method, Synthesis Examples 51 to 61 were prepared according to a two-stage manufacturing method, and Synthesis Examples 62 and 63 were cyclic esters (b) or The sealing compound (c) is omitted.

[Preparation of Addition Type Polyester Resin (D1) by Three-Stage Manufacturing Method]
(Synthesis Example 44)
<Step (1): Formation of polyester main chain>
A stirrer, a thermometer, a reflux condenser, a dropping device and a nitrogen introducing tube are attached to the polymerization tank to constitute a polymerization reaction device. The compound (a-2), the catalyst, and the organic solvent that were included were charged at the following ratios.

[Polymerization tank]
Adipic acid (a-1) 438 parts Isophthalic acid (a-1) 332 parts Ethyl acetate 135 parts Toluene 135 parts [Drip device]
Bisphenol A diglycidyl ether (a-2) 1995 parts Tetrabutylammonium tetrahydroborate (catalyst) 5.5 parts Ethyl acetate 135 parts Toluene 135 parts

After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 100 ° C. while stirring the dibasic acid mixture. Subsequently, the bicyclic ether compound mixture was dropped at a constant rate over 1 hour from the dropping device. Further, the catalyst was added twice in 5.5 parts each every 8 hours with stirring, and after a total of 24 hours of reaction and aging, 1307 parts of ethyl acetate was added, and the reaction was terminated by cooling to room temperature. A solution of the main chain polyester resin (B) was obtained.
This solution is light yellow and transparent, has a non-volatile content of 60.5% by weight and a viscosity of 20,000 mPa · s. The resin (B) contained in the solution has an acid value of 0.5 mgKOH / g, a hydroxyl value of 155 mgKOH / g, The glass transition temperature was 60 ° C. and the weight average molecular weight was 50,000.

<Step (2): Ring-Opening Addition Reaction of Cyclic Ester (b)>
A polymerization reaction apparatus having a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube attached to the polymerization tank is prepared. The solution, cyclic ester (b), catalyst and organic solvent were charged in the following ratios.

[Polymerization tank]
Polyester resin (B) solution for main chain 219 parts Ethyl acetate 33 parts [Drip device]
ε-Caprolactone (b) 114 parts Tetrabutylammonium tetrahydroborate (catalyst) 1.3 parts Ethyl acetate 66 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the resin solution. Subsequently, the cyclic ester (b) mixture was dropped at a constant rate over 1 hour from the dropping device. Furthermore, after reacting and aging for 12 hours with stirring, 66 parts of ethyl acetate was added and cooled to room temperature to complete the reaction, whereby an addition type polyester precursor (C1) solution was obtained.
This solution is light yellow and transparent, has a non-volatile content of 60.2% by weight and a viscosity of 15,000 mPa · s. The polyester precursor (C1) has an acid value of 0.05 mgKOH / g, a hydroxyl value of 74 mgKOH / g, and a glass transition. The resin had a temperature of −10 ° C. and a weight average molecular weight of 150,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Step (3): Sealing reaction with isocyanate compound (c3)>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing pipe are attached to the polymerization tank is prepared. The solution, isocyanate compound (c3), catalyst and organic solvent were charged in the following ratios.

[Polymerization tank]
Addition-type polyester precursor (C1) solution 200 parts [Drip device]
Phenyl isocyanate (c3) 21 parts Tetrabutylammonium tetrahydroborate (catalyst) 1.2 parts Ethyl acetate 5 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the solution. Subsequently, the mixture of the isocyanate compound was dripped at this at constant speed over 1 hour from the dripping apparatus. Furthermore, after reacting and aging for 8 hours with stirring, 8 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of addition-type polyester resin (D1).
This solution is light yellow and transparent and has a nonvolatile content of 60.4% by weight and a viscosity of 19,000 mPa · s. The resin (D1) has an acid value of 0.05 mgKOH / g, a hydroxyl value of 5 mgKOH / g, and a glass transition temperature − It was 10 ° C. and the weight average molecular weight was 170,000.

(Synthesis Example 45)
The dibasic acid (a-1) used in the step (1) of Synthesis Example 44 was changed to isophthalic acid: 830 parts, and the bicyclic ether compound (a-2) was changed to neopentyl glycol diglycidyl ether: 1449 parts. Prepared in the same manner as in Synthesis Example 44 except that 200 parts of the resulting solution of the polyester resin for main chain (B) (non-volatile content: 60.2% by weight) was used in Step (2), and ethyl acetate was added. The concentration was adjusted to obtain a solution of addition-type polyester resin (D1) that was light yellow and transparent, had a nonvolatile content of 60.1% by weight, and a viscosity of 9,500 mPa · s. The resin had an acid value of 0.6 mg KOH / g, a hydroxyl value of 4 mg KOH / g, a glass transition temperature of −30 ° C., and a weight average molecular weight of 85,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.5 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 46)
The bicyclic ether compound (a-2) used in Step (1) of Synthesis Example 44 is converted to 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene: 670 parts and bisphenol A diglycidyl. Ether: changed to 1385 parts, and in the same manner as in Synthesis Example 44, except that 224 parts of the solution (non-volatile content: 60.0% by weight) of the obtained main chain polyester resin (B) was used in step (2). The solution was prepared and ethyl acetate was added to adjust the concentration to obtain a solution of an addition type polyester resin (D1) having a pale yellow transparency, a non-volatile content of 59.9% by weight, and a viscosity of 9,000 mPa · s. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 12.5 mg KOH / g, a glass transition temperature of −40 ° C., and a weight average molecular weight of 68,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 47)
Bicyclic ether compound (a-2) used in Step (1) of Synthesis Example 44 was converted to bisphenol fluorenediglycidyl ether (manufactured by Osaka Gas Chemical Co., Ltd., BPFG, also known as: 9,9-bis [4- ( Glycidyloxy) phenyl] -9H-fluorene, molecular weight: 462.5, epoxy value: 3.89 (eq / Kg)): 3203 parts, and the resulting polyester resin (B) solution (nonvolatile content 60. 0% by weight) Prepared in the same manner as in Synthesis Example 44 except that 315 parts were used in step (2), and the concentration was adjusted by adding ethyl acetate to make it pale yellow and transparent, with a nonvolatile content of 59.8% by weight. A solution of addition-type polyester resin (D1) having a viscosity of 19,500 mPa · s was obtained. The resin (D1) had an acid value of 1.5 mg KOH / g, a hydroxyl value of 12 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 160,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 48)
The cyclic ester compound (b) used in Step (2) of Synthesis Example 44 was changed to 100 parts of δ-valerolactone, and the resulting addition-type polyester precursor (C1) solution (nonvolatile content: 60.0% by weight) ) The reaction was conducted in the same manner as in Synthesis Example 44, except that 200 parts were used in step (3), and the mixture was adjusted by adding ethyl acetate. A solution of the addition type polyester resin (D1) was obtained. The resin (D1) had an acid value of 1.8 mgKOH / g, a hydroxyl value of 12.5 mgKOH / g, a glass transition temperature of −30 ° C., and a weight average molecular weight of 115,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.6 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 49)
Prepared in the same manner as in Synthesis Example 44 except that the isocyanate compound (c3) used in Step (2) of Synthesis Example 44 was changed to 36 parts of p-toluenesulfonyl isocyanate (PTSI). Was adjusted to obtain a solution of an addition type polyester resin (D1) which was light yellow and transparent and had a nonvolatile content of 60.3% by weight and a viscosity of 13,500 mPa · s. The resin (D1) had an acid value of 1.2 mgKOH / g, a hydroxyl value of 15.4 mgKOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 165,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

[Preparation of Addition Type Polyester Resin (D1) by Pseudo Two-Stage Manufacturing Method]
(Synthesis Example 50)
<Steps (4) and (5): Formation of addition-type polyester precursor (C1)>
Prepare a polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dropping device and nitrogen inlet tube in the polymerization tank, and dibasic acid (a-1), bicyclic ether compound (a -2), cyclic ester (b), catalyst and organic solvent were charged at the following ratios.

[Polymerization tank]
Adipic acid (a-1) 73 parts Sebacic acid (a-1) 404 parts Bisphenol F diglycidyl ether (a-2) 875 parts Bisphenol A-based phenoxy resin (a-2) 1950 parts (manufactured by Japan Epoxy Resin Co., Ltd., product The name “jER1256”,
Glycidyl group equivalent: 7800 g / eq, Mw: 51000)
Tetrabutylammonium tetrahydroborate (catalyst) 6.6 parts Ethyl acetate 210 parts Toluene 210 parts [Drip device]
Tetrabutylammonium tetrahydroborate (catalyst) 6.6 parts ε-caprolactone (b) 800 parts Ethyl acetate 210 parts Toluene 210 parts

After replacing the air in the polymerization tank with nitrogen gas, the mixture was heated to 100 ° C. while stirring and reacted for 8 hours to obtain a polyester resin for main chain (I ′) having an acid value of 5 mgKOH / g or less. .
Next, the cyclic ester (b) mixture was dropped at a constant rate over 1 hour from the dropping device. After completion of dropping, 6.6 parts of tetrabutylammonium tetrahydroborate was added after stirring for 8 hours. After further reaction and aging for 8 hours, 1400 parts of ethyl acetate was added and cooled to room temperature to complete the reaction. Type polyester precursor (C1) was obtained.
This solution is light yellow and transparent, has a non-volatile content of 59.8% by weight and a viscosity of 30,000 mPa · s. The precursor (C1) has an acid value of 0.02 mg KOH / g, a hydroxyl value of 92 mg KOH / g, and a glass transition. It was a resin having a temperature of −15 ° C. and a weight average molecular weight of 200,000. In the above formulation, the cyclic ester (b) is in a ratio of about 0.1 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Step (6): Sealing reaction with isocyanate compound (c3)>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing pipe are attached to the polymerization tank is prepared. A solution (non-volatile content: 59.8%), an isocyanate compound (c3), a catalyst, and an organic solvent were charged in the following ratios.

[Polymerization tank]
Addition-type polyester precursor (C1) solution 200 parts [Drip device]
Cyclohexyl isocyanate (c3) 23 parts Tetrabutylammonium tetrahydroborate (catalyst) 6.6 parts Ethyl acetate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature in the tank was raised to 100 ° C. while stirring. Subsequently, the acid anhydride mixture was dropped at a constant rate over 1 hour from the dropping device. After completion of the dropwise addition, the mixture was reacted and aged for 6 hours with stirring, and then 4 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D1).
This solution is light yellow and transparent, has a non-volatile content of 60.2% by weight and a viscosity of 36,000 mPa · s. The resin (D1) has an acid value of 1.0 mgKOH / g, a hydroxyl value of 8.2 mgKOH / g, glass The transition temperature was −15 ° C. and the weight average molecular weight was 225,000.

[Preparation of Addition Type Polyester Resin (D1) by Two-Step Manufacturing Method]
(Synthesis Example 51)
Prepare a polymerization reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube in the polymerization tank. Dibasic acid (a-1), bicyclic ether compound (a-2), cyclic ester (B) The catalyst and the organic solvent were charged at the following ratios.

[Polymerization tank]
Adipic acid (a-1) 159 parts Isophthalic acid (a-1) 120 parts Bisphenol A diglycidyl ether (a-2) 721 parts ε-caprolactone (b) 871 parts Ethyl acetate 200 parts Toluene 200 parts

<Step (7): Formation of addition-type polyester precursor (C1)>
After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 100 ° C. while stirring, and 2.0 parts of tetrabutylammonium tetrahydroborate was added to initiate the reaction. While stirring the mixture, 2.0 parts of tetrabutylammonium tetrahydroborate was added twice every 8 hours for a total of 24 hours for reaction and ripening to obtain an addition type polyester precursor (C1) solution.

<Step (8): Sealing reaction with isocyanate compound (c3)>
Ethyl acetate: 600 parts and isocyanate useful as an isocyanate compound (c3): 200 parts were added to the addition-type polyester precursor (C1) solution and aged for 6 hours. Thereafter, 380 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D1).
This solution is light yellow and transparent, has a non-volatile content of 60.5% by weight and a viscosity of 16,000 mPa · s. The resin (D1) has an acid value of 0.5 mgKOH / g, a hydroxyl value of 5.8 mgKOH / g, glass The transition temperature was −10 ° C. and the weight average molecular weight was 160,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 52)
The reaction was carried out in the same manner as in Synthesis Example 51 except that the catalyst used in Synthesis Example 51 was changed to tetrabutylammonium bromide, and the concentration was adjusted by adding ethyl acetate to obtain a pale yellow transparent, non-volatile content of 60. An addition-type polyester resin solution having a weight of 3% by weight and a viscosity of 9,500 mPa · s was obtained. The acid value of the resin was 0.6 mg KOH / g, the hydroxyl value was 9.8 mg KOH / g, the glass transition temperature was −10 ° C., and the weight average molecular weight was 125,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 53)
Dibasic acid (a-1) used in step (7) of Synthesis Example 51 is succinic acid: 322 parts, bicyclic ether compound (a-2) is neopentyl glycol diglycidyl ether: 678 parts, cyclic ester Except that compound (b) was changed to ε-caprolactone: 143 parts, the catalyst was changed to tetrabutylammonium nitrate, and the isocyanate compound (c3) used in step (8) was changed to butyl isocyanate: 113 parts. This was prepared in the same manner as in Synthesis Example 51, and the concentration was adjusted by adding ethyl acetate. The addition type polyester resin (D1) had a pale yellow transparency, a non-volatile content of 59.6% by weight, and a viscosity of 16,000 mPa · s. A solution was obtained. The resin (D1) had an acid value of 0.3 mg KOH / g, a hydroxyl value of 12.5 mg KOH / g, a glass transition temperature of −35 ° C., and a weight average molecular weight of 85,000. In the above formulation, the cyclic ester (b) is in a ratio of about 0.2 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 54)
The catalyst was prepared in the same manner as in Synthesis Example 51 except that the catalyst used in Synthesis Example 51 was changed to tetrabutyl titanate. The concentration was adjusted by adding ethyl acetate, and it was transparent yellow and had a nonvolatile content of 60.2% by weight. A solution of an addition type polyester resin (D1) having a viscosity of 9,500 mPa · s was obtained. Resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 26.2 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 120,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 55)
The catalyst was prepared in the same manner as in Synthesis Example 51 except that the catalyst used in Synthesis Example 51 was changed to dibutyltin oxide. The concentration was adjusted by adding ethyl acetate to obtain a pale yellow translucent, non-volatile content of 60.4. A solution of addition-type polyester resin (D1) having a weight percentage of 8,500 mPa · s was obtained. The resin (D1) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 41.2 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 130,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 56)
Prepared in the same manner as in Synthesis Example 51 except that the weight of the cyclic ester compound (b) used in Step (7) of Synthesis Example 51 was changed to 644 parts, and adjusted the concentration by adding ethyl acetate, A solution of addition-type polyester resin (D1) was obtained which was light yellow and transparent and had a nonvolatile content of 60.3% by weight and a viscosity of 12,500 mPa · s. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 0.03 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 185,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 57)
Prepared in the same manner as in Synthesis Example 51 except that the weight of the cyclic ester compound (b) used in Step (7) of Synthesis Example 51 was changed to 16 parts, and adjusted the concentration by adding ethyl acetate. A solution of an addition-type polyester resin (D1) that was light yellow and transparent and had a nonvolatile content of 60.7 wt% and a viscosity of 8,000 mPa · s was obtained. Resin (D1) had an acid value of 0.6 mgKOH / g, a hydroxyl value of 58.8 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 125,000. In addition, in the said prescription, a cyclic ester (b) will be a ratio of about 0.03 mol with respect to 1 mol of secondary | 2nd-class hydroxyl groups derived from a bicyclic ether compound (a-2).

(Synthesis Example 58)
The dibasic acid (a-1) used in Step (7) of Synthesis Example 51 is adipic acid: 102 parts and isophthalic acid: 66 parts, and the bicyclic ether compound (a-2) is bisphenol A diglycidyl ether: 380 The cyclic ester (b) was changed to ε-caprolactone: 285 parts, and the additional amount of tetrabutylammonium tetrahydroborate added twice every 8 hours after the start of the reaction was changed to 0.2 parts each. In the same manner as in Synthesis Example 51, the reaction of step (7) was carried out at 100 ° C. for 24 hours, and as step (8), 54 parts of benzyl isocyanate as the isocyanate compound (c3) and ethyl acetate were further added. After aging for 4 hours, ethyl acetate was added to adjust the nonvolatile content concentration, and the mixture was cooled to room temperature to obtain a solution of an addition type polyester resin (D1).
This solution is light yellow and transparent, has a nonvolatile content of 59.6% by weight and a viscosity of 2,500 mPa · s. The resin (D1) has an acid value of 79.2 mgKOH / g, a hydroxyl value of 20.1 mgKOH / g, glass The transition temperature was −10 ° C. and the weight average molecular weight was 38,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.1 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 59)
The dibasic acid (a-1) used in the step (7) of Synthesis Example 51 is adipic acid: 44 parts and isophthalic acid: 33 parts, and the bicyclic ether compound (a-2) is bisphenol A diglycidyl ether: 760. In the same manner as in Synthesis Example 51 except that the cyclic ester (b) was changed to 684 parts of ε-caprolactone and no catalyst was used, the reaction was performed at 100 ° C. for 24 hours in the step (7). In step (8), 660 parts of benzyl isocyanate, which is an isocyanate compound (c3), and 600 parts of ethyl acetate were further added, followed by aging for 4 hours, adding ethyl acetate to adjust the nonvolatile content concentration, and cooling to room temperature. A solution of addition type polyester resin (D1) was obtained.
This reaction solution was light yellow and transparent with a non-volatile content of 59.8% by weight and a viscosity of 96,000 mPa · s.
The resin (D1) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 33.5 mg KOH / g, a glass transition temperature of −8 ° C., and a weight average molecular weight of 22,300. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 60)
The dibasic acid (a-1) used in step (7) of Synthesis Example 51 is sebacic acid: 101 parts, and the bicyclic ether compound (a-2) is polyethylene glycol diglycidyl ether (ethylene oxide addition moles: 22 ): The reaction and aging for 24 hours in the step (7) were performed in the same manner as in Synthesis Example 51 except that the cyclic ester (b) was changed to 661 parts and the ε-caprolactone was changed to 684 parts. Then, as a process (8), 200 parts of benzyl isocyanate which is an isocyanate compound (c3) and 500 parts of ethyl acetate are added, and it age | cure | ripens further for 6 hours, Ethyl acetate is added and a non volatile matter density | concentration is adjusted, It cools to room temperature. As a result, a solution of an addition type polyester resin (D1) which was transparent in pale yellow and had a nonvolatile content of 60.6% by weight and a viscosity of 26,500 mPa · s was obtained. The resin (D1) had an acid value of 0.2 mg KOH / g, a hydroxyl value of 15.6 mg KOH / g, a glass transition temperature of −90 ° C., and a weight average molecular weight of 310,000. In addition, in the said prescription, cyclic ester (b) will be a ratio of about 5 mol with respect to 1 mol of secondary | 2nd-class hydroxyl groups derived from a bicyclic ether compound (a-2).

(Synthesis Example 61)
The dibasic acid (a-1) used in Step (7) of Synthesis Example 51 was added to 83 parts of isophthalic acid, the bicyclic ether compound (a-2) was added to 380 parts of bisphenol A diglycidyl ether, and a cyclic ester ( The reaction and ripening in the step (7) was performed for 24 hours in the same manner as in Synthesis Example 50 except that b) was changed to 342 parts of ε-caprolactone. Thereafter, as step (8), 200 parts of benzyl isocyanate which is an isocyanate compound (c3) and 170 parts of ethyl acetate are added and aged for another 6 hours. Ethyl acetate is added to adjust the nonvolatile content concentration, and the mixture is cooled to room temperature. As a result, a solution of an addition type polyester resin (D1) which was light yellow and transparent and had a non-volatile content of 59.4% by weight and a viscosity of 15,500 mPa · s was obtained. The resin (D1) had an acid value of 0.6 mg KOH / g, a hydroxyl value of 10.5 mg KOH / g, a glass transition temperature of 30 ° C., and a weight average molecular weight of 235,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 62)
Synthesis Example 51 except that the cyclic ester (b) is not used in the step (7) of Synthesis Example 51, and the amount of ethyl acetate added together with the isocyanate compound (c3) in the step (8) is changed from 600 parts to 200 parts. Reaction is carried out in the same manner as in No. 51, ethyl acetate is added to adjust the nonvolatile content concentration, the solution is cooled to room temperature, and it is a pale yellow transparent polyester resin solution having a nonvolatile content of 60.1% by weight and a viscosity of 3,500 mPa · s. Got. The resin contained in this solution had an acid value of 1.6 mg KOH / g, a hydroxyl value of 22.5 mg KOH / g, a glass transition temperature of 56 ° C., and a weight average molecular weight of 21,000.

(Synthesis Example 63)
The same as in Synthesis Example 51 except that the amount of ethyl acetate added in Step (8) of Synthesis Example 51 was changed to 847 parts and the mixture was cooled to room temperature after the addition of ethyl acetate without adding the isocyanate compound (c3). Thus, a pale yellow transparent polyester resin solution having a nonvolatile content of 60.1% by weight and a viscosity of 16,000 mPa · s was obtained. The resin contained in the solution had an acid value of 0.7 mg KOH / g, a hydroxyl value of 94 mg KOH / g, a glass transition temperature of −15 ° C., and a weight average molecular weight of 140,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.8 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

  For each of the resin solutions obtained in Synthesis Examples 44 to 63, the solution appearance, nonvolatile content, resin weight average molecular weight (Mw), glass transition temperature (Tg), acid value (AV), and hydroxyl value (OHV) were synthesized. The results evaluated in the same manner as in Examples 1 to 20 are summarized in Table 5.

(Comparative Example 13)
50 parts of toluene is added to 100 parts by weight of the polyester resin (B) solution for main chain part obtained in the step (1) of Synthesis Example 44, and TDI / TMP (tolylene diisopropylene) is used as a crosslinking agent (E). 2.5 parts by weight of trimethylolpropane adduct of cinnate) was added and stirred well to obtain an adhesive composition. However, this was applied on a release film to obtain an adhesive sheet, but could not be applied because the viscosity of the adhesive composition increased rapidly.

(Comparative Example 14)
In the same manner as in Comparative Example 13, except that the addition type polyester precursor (C1) solution obtained in Step (2) of Synthesis Example 44 was used instead of the polyester resin for main chain portion (B), An adhesive composition was obtained. However, since the viscosity of the adhesive composition increased rapidly as in Comparative Example 13, it could not be applied to the release film.

(Example 44)
50 parts of toluene was added to 100 parts by weight of the solution of the addition-type polyester resin (D1) obtained in the step (3) of Synthesis Example 44, and further, TDI / TMP (tolylene diisocyanate trialuminate) Methylolpropane adduct body) 2.5 parts by weight was added and stirred well to obtain an adhesive composition of the present invention.
Using this, in the same manner as in Examples 1 to 19, a laminate having a configuration of “release film / adhesive layer / TAC film / PVA / TAC film” was prepared, and the reaction of the adhesive layer was allowed to proceed. A bonded polarizing plate (laminate) was obtained.

(Examples 45-49)
A polarizing plate subjected to adhesion processing in the same manner as in Example 44, except that the addition type polyester resin (D1) solution used was changed to the addition type polyester resin (D1) solution obtained in Synthesis Examples 45 to 49, respectively. Produced.

(Comparative Example 15)
Instead of the addition type polyester resin (D1) resin solution obtained in Step (3) of Synthesis Example 44, the addition type polyester precursor (C1) resin solution obtained in Step (5) of Synthesis Example 50 was used. Except for this, an adhesive composition was obtained in the same manner as in Example 44. However, as in Comparative Example 13, the viscosity of the adhesive composition increased rapidly, and thus could not be applied to the release film.

(Example 50)
Other than using the solution of addition type polyester resin (D1) obtained in step (6) of synthesis example 50 instead of the addition type polyester resin (D1) solution obtained in step (3) of synthesis example 44 Prepared an adhesive composition in the same manner as in Example 44 to produce a bonded polarizing plate.

(Example 51)
Adhesion was carried out in the same manner as in Example 44 except that the solution of the addition type polyester resin (D1) obtained in Synthesis Example 51 was used instead of the solution of the addition type polyester resin (D1) obtained in Synthesis Example 50. An agent composition was prepared and an adhesive processed polarizing plate was produced.

(Comparative Example 16)
An adhesive composition was obtained in the same manner as in Example 51 except that the resin solution obtained in Synthesis Example 62 was used instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 51. . This could be applied to the release film, but the adhesive layer did not have tack (initial adhesion) and could not be laminated to the TAC film / PVA / TAC film configuration with the adhesive layer.

(Comparative Example 17)
An adhesive composition was prepared in the same manner as in Example 51 except that the resin solution obtained in Synthesis Example 63 was used instead of the addition type polyester resin (D1) obtained in Synthesis Example 51. However, immediately after adding 2.5 parts by weight of TDI / TMP and stirring well, the viscosity increased and fluidity became poor, and a usable adhesive composition could not be obtained.

(Examples 52 and 53)
Instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 51, the addition type polyester resin (D1) solution obtained in Synthesis Examples 52 and 53 was used in the same manner as in Example 51. The adhesive composition was prepared and the polarizing plate which carried out the adhesion process was produced.

(Examples 54 and 55)
Instead of TDI / TMP used as the crosslinking agent (E) in Example 51, in Example 54, 2.5 parts of xylylene diisocyanate trimethylolpropane adduct (hereinafter referred to as XDI / TMP): In Example 55, an adhesive composition was obtained in the same manner as in Example 51 except that 2.5 parts of hexamethylene diisocyanate burette adduct (hereinafter referred to as HMDI / burette) was used. Using this, a bonded polarizing plate was produced in the same manner as in Example 51.

(Examples 56-58, 59-62, Comparative Example 18)
Instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 51, in Examples 56 to 58, the addition type polyester resin (D1) solution obtained in Synthesis Examples 54 to 56 was synthesized in Comparative Example 18. Example 51 except that the addition type polyester resin (D1) solution obtained in Example 57 was used in Examples 59 to 62, and the addition type polyester resin (D1) solution obtained in Synthesis Examples 58 to 61 was used. In the same manner, an adhesive composition was obtained. However, in the case of Comparative Example 18, since the viscosity of the adhesive composition increased rapidly, it could not be applied to the release film. About Examples 56-58 and 59-62, it carried out similarly to Example 51 using this, and produced the polarizing plate which carried out the adhesive process.

The pot life and coating processability of the adhesive compositions obtained in Examples and Comparative Examples were evaluated in the same manner as in Examples 1-19. The results are shown in Table 6.
Moreover, about the polarizing plate (laminated body) which carried out the adhesion process obtained by the Example and the comparative example, the refractive index of a coating film, heat resistance, heat-and-moisture resistance, an optical characteristic, and removability are the case of Examples 1-22. Evaluation was performed in the same manner. The results are shown in Table 6.

<< First sealing form: Polyamide dicarboxylic acid (a-1-4) is used as dibasic acid (a-1) >>
Polyamide dicarboxylic acid was prepared in Synthesis Example 63 below, and in Synthesis Examples 64-66, a polyester resin was prepared using polyamide dicarboxylic acid (a-1-4) as dibasic acid (a-1).

(Synthesis Example 63)
<Synthesis reaction of polyamide dicarboxylic acid>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introduction pipe are attached to a polymerization tank is prepared. In the polymerization tank, sebacic acid as a dicarboxylic acid: 462.7 parts, azelaic acid: 430.7 parts And adipic acid: 345.1 parts, hexamethylenediamine: 350.9 parts and metaxylenediamine: 410.7 parts as diamines, respectively, and the air in the polymerization tank was replaced with nitrogen gas. While stirring, the temperature was raised to 250 ° C., 2.0 parts of zinc acetate as a catalyst was added, and the mixture was reacted for 10 hours while dehydrating under reduced pressure. Thereafter, the mixture was cooled to obtain polyamide dicarboxylic acid.
This resin was pale yellow and had an acid value of 39 mg KOH / g, an amine value of 0.26 mg KOH / g and a weight average molecular weight of 30,000.

[Preparation of Addition Type Polyester Resin (D1) by Three-Stage Manufacturing Method]
<Addition type polyester resin (D1) using silylating agent (c1) as sealing compound (c)>
(Synthesis Example 64)
Except that the dibasic acid (a-1) used in the step (1) of Synthesis Example 1 was used, 1435 parts of the polyamide dicarboxylic acid obtained in Synthesis Example 63 and 747 parts of isophthalic acid were used. In the same manner as in Step (1) of Synthesis Example 1, 173 parts of a polyester resin (B) for the main chain (non-volatile content: 60.0% by weight) was prepared and used to prepare Step (2) of Synthesis Example 1. The reaction was carried out in the same manner as above to obtain a solution of an addition type polyester resin (D1) that was light yellow and transparent, had a nonvolatile content of 60.2% by weight and a viscosity of 45,000 mPa · s. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 15 mg KOH / g, a glass transition temperature of −5 ° C., and a weight average molecular weight of 180,000. In the above formulation, the cyclic ester (b) is in a ratio of about 3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Addition type polyester resin (D1) using acid anhydride (c2) as sealing compound (c)>
(Synthesis Example 65)
Except that the dibasic acid (a-1) used in the step (1) of Synthesis Example 21 was used except that 1435 parts of the polyamide dicarboxylic acid obtained in Synthesis Example 63 and 747 parts of isophthalic acid were used. In the same manner as in Step (1) of Synthesis Example 20, 173 parts of a solution of the polyester resin for main chain (B) (nonvolatile content: 60.0% by weight) was prepared, and using this, Step (2) of Synthesis Example 20 The reaction was carried out in the same manner as above to obtain a solution of an addition-type polyester resin (D1) that was light yellow and transparent, had a nonvolatile content of 60.5% by weight and a viscosity of 40,000 mPa · s. The resin (D1) had an acid value of 16 mg KOH / g, a hydroxyl value of 62 mg KOH / g, a glass transition temperature of −5 ° C., and a weight average molecular weight of 170,000. In the above formulation, the cyclic ester (b) is in a ratio of about 3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Addition type polyester resin (D1) using isocyanate compound (c3) as sealing compound (c)>
(Synthesis Example 66)
Instead of using the dibasic acid (a-1) used in Step (1) of Synthesis Example 44, the polyamide dicarboxylic acid obtained in Synthesis Example 63: 1435 parts and isophthalic acid: 747 parts were used. In the same manner as in Step (1) of Synthesis Example 44, 173 parts of a solution (non-volatile content: 60.0% by weight) of the polyester resin for main chain (B) was prepared, and this was used for Step (2) of Synthesis Example 43. The reaction is carried out in the same manner as above, and the concentration is adjusted by adding ethyl acetate to obtain a solution of an addition type polyester resin (D1) which is light yellow and transparent, has a non-volatile content of 60.3% by weight and a viscosity of 46,000 mPa · s. It was. The resin (D1) had an acid value of 0.4 mg KOH / g, a hydroxyl value of 15.5 mg KOH / g, a glass transition temperature of −5 ° C., and a weight average molecular weight of 185,000. In the above formulation, the cyclic ester (b) is in a ratio of about 3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
For each of the resin solutions obtained in Synthesis Examples 64-66, the appearance of the solution, nonvolatile content, resin weight average molecular weight (Mw), glass transition temperature (Tg), acid value (AV), and hydroxyl value (OHV) are synthesized. The results obtained in the same manner as in Examples 1 to 19 are summarized in Table 7.

(Example 63)
In Example 1, except that the addition type polyester resin (D1) solution obtained in Synthesis Example 64 was used instead of the addition type polyester resin (D1) solution obtained in Step (3) of Synthesis Example 1. An adhesive composition was prepared in the same manner as in Example 1, and an adhesive-processed polarizing plate was produced using the adhesive composition. Table 8 shows the results of evaluation conducted in the same manner.
(Example 64)
In Example 20, except that the addition type polyester resin (D1) solution obtained in Synthesis Example 65 was used instead of the addition type polyester resin (D1) solution obtained in the step (3) of Synthesis Example 21, An adhesive composition was prepared in the same manner as in Example 20, and a bonded polarizing plate was produced using the adhesive composition. Table 8 shows the results of evaluation conducted in the same manner.
(Example 65)
In Example 44, except that the addition type polyester resin (D1) solution obtained in Synthesis Example 66 was used instead of the addition type polyester resin (D1) solution obtained in Step (3) of Synthesis Example 44, An adhesive composition was prepared in the same manner as in Example 44, and an adhesive-processed polarizing plate was produced using the adhesive composition. Table 8 shows the results of evaluation conducted in the same manner.

<< First sealing form: High molecular weight dicarboxylic acid (a-1-2) used as dibasic acid (a-1) >>
In the following Synthesis Examples 67 to 107, as a dibasic acid (a-1), a high molecular weight dicarboxylic acid that is a reaction product of a low molecular weight dicarboxylic acid (a-1-1) and various polyols (a-1-α) The case where (a-1-2) is used is shown.

[Preparation of Addition Type Polyester Resin (D1) by Three-stage Manufacturing Method]
(Synthesis Example 67)
<Step (1): Formation of polyester main chain>
A polymerization reactor is constructed by attaching a stirrer, thermometer, reflux condenser, dropping device and nitrogen introducing tube to the polymerization tank. The polymerization tank and the dropping device are connected to low molecular weight dicarboxylic acids (a-1-1), polyols ( a-1-α), a compound having two cyclic ether groups (a-2), a catalyst and an organic solvent were charged in the following ratios.

[Polymerization tank]
Kuraray polyol P4010 (a-1-α) 376 parts Succinic anhydride (a-1-1) 18 parts Toluene 76 parts Ethyl acetate 30 parts Tetrabutylammonium tetrahydroborate (catalyst) 0.5 part [Drip device]
Bisphenol A diglycidyl ether (a-2) 34 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 part Ethyl acetate 36 parts

After replacing the air in the polymerization tank with nitrogen gas, the mixture was heated to 100 ° C. while stirring and subjected to a ring-opening addition reaction for 8 hours. Subsequently, the bicyclic ether compound (a-2) mixture was dripped at the constant rate over 1 hour from the dripping apparatus to the reaction material under stirring. After completion of the dropping, 0.5 parts of each catalyst was added twice every 8 hours with stirring, and the reaction and aging were carried out for a total of 24 hours. Then, 286 parts of ethyl acetate was added and cooled to room temperature to complete the reaction.
This solution is light yellow and transparent, has a non-volatile content of 50.1% by weight, a viscosity of 18,000 mPa · s, an acid value of 0.07 mg KOH / g, a hydroxyl value of 75.2 mg KOH / g, a glass transition temperature of 40 ° C., and a weight average. It contained a main chain polyester resin (B) having a molecular weight of 150,000.

<Step (2): Ring-Opening Addition Reaction of Cyclic Ester (b)>
A polymerization reaction apparatus having a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube attached to the polymerization tank is prepared. The solution, cyclic ester (b), catalyst and organic solvent were charged in the following ratios.

[Polymerization tank]
500 parts of main chain polyester resin (B) solution [Drip device]
ε-caprolactone (b) 20 parts tetrabutylammonium tetrahydroborate (catalyst) 0.5 parts ethyl acetate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the resin solution. Subsequently, the cyclic ester (b) mixture was dropped at a constant rate over 1 hour from the dropping device. Furthermore, after reacting and aging for 12 hours with stirring, 10 parts of ethyl acetate was added and cooled to room temperature to complete the reaction, whereby an addition type polyester precursor (C1) solution was obtained.
This solution is light yellow and transparent, has a non-volatile content of 50.1% by weight and a viscosity of 20,000 mPa · s. The polyester precursor (C1) has an acid value of 0.05 mgKOH / g, a hydroxyl value of 56.2 mgKOH / g, The resin had a glass transition temperature of −20 ° C. and a weight average molecular weight of 160,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.5 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Step (3): Sealing reaction with isocyanate compound (c3)>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing pipe are attached to the polymerization tank is prepared. As a solution and a sealing compound (c), an isocyanate compound, a catalyst, and an organic solvent were respectively charged in the following ratios.

[Polymerization tank]
Addition-type polyester precursor (C1) solution 500 parts [Drip device]
Phenyl isocyanate (c) 29 parts Tetrabutylammonium tetrahydroborate (catalyst) 0.1 part Ethyl acetate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the solution. Next, the mixture of the sealing compound (c) was added dropwise thereto at a constant speed over 1 hour. After completion of the dropping, the mixture was further reacted and aged for 8 hours while stirring, and then 19 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D1).
This solution is light yellow and transparent, has a nonvolatile content of 50.0% by weight and a viscosity of 18,000 mPa · s. The resin (D1) has an acid value of 0.2 mgKOH / g, a hydroxyl value of 25 mgKOH / g, and a glass transition temperature. It was -20 degreeC and the weight average molecular weight 165,000.

(Synthesis Example 68)
Step (2) in Synthesis Example 67 was omitted, and 500 parts of a solution (non-volatile content 50.1% by weight) of the polyester resin for main chain (B) obtained in step (1) was added in step (3). Prepared in the same manner as in Synthesis Example 67 except that it was used in place of the polyester precursor (C1) solution and the amount of phenyl isocyanate (c) was changed to 27 parts, and 17 parts of ethyl acetate was added and cooled to room temperature. As a result, a pale yellow transparent polyester resin solution having a nonvolatile content of 50.2% by weight and a viscosity of 17,000 mPa · s was obtained. The resin had an acid value of 0.05 mg KOH / g, a hydroxyl value of 28 mg KOH / g, a glass transition temperature of 40 ° C., and a weight average molecular weight of 155,000.

(Synthesis Example 69)
Prepared in the same manner as in Synthesis Example 67 except that the sealing compound (c) used in Step (3) of Synthesis Example 67 was changed to 23 parts of diethylmethylsilane as the silylating agent (c1). 13 parts of ethyl was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D1) which was light yellow and transparent and had a nonvolatile content of 50.0% by weight and a viscosity of 13,000 mPa · s. The resin (D1) had an acid value of 0.05 mgKOH / g, a hydroxyl value of 18.5 mgKOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 120,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.5 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 70)
The sealing compound (c) used in Step (3) of Synthesis Example 67 was prepared in the same manner as in Synthesis Example 67 except that 34 parts of phthalic anhydride as the acid anhydride (c2) was used. 24 parts of ethyl was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D1) which was light yellow and transparent and had a nonvolatile content of 50.3% by weight and a viscosity of 17,500 mPa · s. The resin (D1) had an acid value of 85.1 mgKOH / g, a hydroxyl value of 16.8 mgKOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 175,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.5 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 71)
Prepared in the same manner as in Synthesis Example 67 except that the sealing compound (c) used in Step (3) of Synthesis Example 67 was changed to 5 parts of phthalic anhydride (c) as the acid anhydride (c2). Then, the mixture was cooled to room temperature without adding ethyl acetate to obtain a solution of addition-type polyester resin (D1) that was light yellow and transparent, had a non-volatile content of 49.4% by weight and a viscosity of 11,000 mPa · s. The resin (D1) had an acid value of 5.8 mg KOH / g, a hydroxyl value of 51.5 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 105,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.5 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

[Preparation of Addition Type Polyester Resin (D1) by Two-Step Manufacturing Method]
<Synthesis of polyester polyol>
(Synthesis Example A)
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube were attached to the polymerization tank was prepared, and dicarboxylic acid, diol, and catalyst were charged into the polymerization tank at the following ratios, respectively.

[Polymerization tank]
Sebacic acid 606 parts Isophthalic acid 332 parts Neopentyl glycol 210 parts 1,4-butanediol 140 parts 1,6-hexanediol 180 parts Zinc acetate 0.5 parts

After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 200 ° C. while stirring and reacted until the acid value became 2 or less while dehydrating. Subsequently, it cooled to 50 degrees C or less, reaction was complete | finished, and the polyester polyol was obtained.
This polyester polyol was light yellow and transparent, and had an acid value of 0.3 mg KOH / g, a hydroxyl value of 21.5 mg KOH / g, a glass transition temperature of −20 ° C., and a number average molecular weight (Mn) of 4,200.

(Synthesis Example B)
Prepared in the same manner as in Synthesis Example A except that 354 parts of succinic acid, 292 parts of adipic acid, and 470 parts of 1,4-butanediol were used in place of the dicarboxylic acid and diol used in Synthesis Example A. Thus, a polyester polyol having an acid value of 0.5 mgKOH / g, a hydroxyl value of 22.3 mgKOH / g, a glass transition temperature of -20 ° C., and a number average molecular weight (Mn) of 4,000 was obtained.

(Synthesis Example 72)
[Preparation of Addition Type Polyester Resin (D1) by Two-Step Manufacturing Method]
(Synthesis Example 29)
A polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube was prepared in the polymerization tank. Low molecular weight dicarboxylic acids (a-1-1) and polyols (a-1) -α), the bicyclic ether compound (a-2), the cyclic ester (b), the catalyst and the organic solvent were charged in the following ratios.

[Polymerization tank]
Kuraray polyol P4010 (a-1-α) 376 parts Succinic anhydride (a-1-1) 18 parts Toluene 76 parts Ethyl acetate 30 parts Tetrabutylammonium tetrahydroborate (catalyst) 0.5 part [Drip device]
Bisphenol A diglycidyl ether (a-2) 34 parts ε-caprolactone (b) 32 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 part Ethyl acetate 47 parts

<Step (7): Formation of addition-type polyester precursor (C1)>
After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 100 ° C. while stirring and reacted for 8 hours to obtain a high molecular weight dicarboxylic acid (a-1-3) which is a dibasic acid (a-1). )
Subsequently, the said mixture was dripped at constant velocity over 1 hour from the dripping apparatus.
After completion of the dropwise addition, 1 part of tetrabutylammonium tetrahydroborate was added after 8 hours with further stirring. After further aging for 8 hours, 307 parts of ethyl acetate was added and cooled to room temperature, the reaction was terminated, and the cyclic ester compound ( A solution of addition type polyester precursor (C1) added with b) was obtained.
This solution is light yellow and transparent, has a non-volatile content of 50.2% by weight and a viscosity of 22,000 mPa · s. The resin (C1) has an acid value of 0.05 mgKOH / g, a hydroxyl value of 52.6 mgKOH / g, glass The transition temperature was −20 ° C. and the weight average molecular weight was 170,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

<Step (8): Sealing reaction with isocyanate compound (c3)>
A polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube was prepared, and the addition type polyester precursor (C1) obtained in step (1) was prepared in the polymerization vessel and the dropping device. A solution (non-volatile content: 50.2%), a monofunctional isocyanate compound (c3), a catalyst, and an organic solvent were charged at the following ratios.

[Polymerization tank]
Addition-type polyester precursor (C1) solution 500 parts [Drip device]
Phenyl isocyanate (c3) 21 parts Tetrabutylammonium tetrahydroborate (catalyst) 0.1 part Ethyl acetate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the solution. Subsequently, the mixture of the dripping apparatus was dripped at this at constant speed over 1 hour. After completion of the dropping, the mixture was further reacted and aged for 6 hours with stirring, and then 11 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D1).
This solution is light yellow and transparent with a non-volatile content of 50.3% by weight and a viscosity of 19,000 mPa · s. The resin (D1) has an acid value of 0.2 mgKOH / g, a hydroxyl value of 22.8 mgKOH / g, and a glass transition. The temperature was -20 ° C and the weight average molecular weight was 170,000.

(Synthesis Example 73)
It was prepared in the same manner as in Synthesis Example 72 except that 376 parts of Kuraray polyol C4090 was used instead of the polyol (a-1-α) used in Step (7) of Synthesis Example 72. A solution of an addition type polyester resin (D1) having a viscosity of 49.7% by weight and a viscosity of 16,000 mPa · s was obtained. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 20.5 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 150,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 74)
It was prepared in the same manner as in Synthesis Example 72 except that 376 parts of Kuraray polyol P4011 was used instead of the polyol (a-1-α) used in Step (7) of Synthesis Example 72. A solution of addition-type polyester resin (D1) having a viscosity of 50.2% by weight and a viscosity of 12,000 mPa · s was obtained. The resin (D1) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 22.8 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 110,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 75)
It was prepared in the same manner as in Synthesis Example 72 except that 376 parts of Kuraray polyol P4050 was used instead of the polyol (a-1-α) used in Step (7) of Synthesis Example 72. A solution of an addition-type polyester resin (D1) having a viscosity of 1.0% by weight and a viscosity of 18,500 mPa · s was obtained. The resin (D1) had an acid value of 0.8 mg KOH / g, a hydroxyl value of 21.4 mg KOH / g, a glass transition temperature of −25 ° C., and a weight average molecular weight of 140,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 76)
Instead of the polyols (a-1-α) used in step (7) of Synthesis Example 72, 478 parts of Kyowapol 5000PA was used, and the amount of toluene charged into the polymerization tank was changed to 103 parts. Prepared in the same manner as in Synthesis Example 72, and 350 parts of ethyl acetate was added to obtain a polyester resin (C1) solution to which the cyclic ester compound (b) was added. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, 500 parts of the resulting addition-type polyester precursor resin (C1) solution (non-volatile content: 50.2 wt%) was used, and the amount of phenyl isocyanate (c3) was changed to 15 parts. The reaction was carried out in the same manner as in Step (8) to obtain a solution of an addition type polyester resin (D1) having a pale yellow transparent, non-volatile content of 50.1% by weight and a viscosity of 15,500 mPa · s. The resin (D1) had an acid value of 1.2 mgKOH / g, a hydroxyl value of 19.5 mgKOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 135,000.

(Synthesis Example 77)
Prepared in the same manner as in Synthesis Example 72 except that the polyols (a-1-α) used in Step (7) of Synthesis Example 72 were changed to Kuraray polyol P6010: 188 parts and Kuraray polyol P2010: 188 parts. A solution of addition-type polyester resin (D1) having a pale yellow transparent, non-volatile content of 50.2% by weight and a viscosity of 22,500 mPa · s was obtained. The resin (D1) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 23.8 mg KOH / g, a glass transition temperature of −25 ° C., and a weight average molecular weight of 170,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 78)
Synthesis was performed except that 658 parts of TPAE-617 was used instead of the polyols (a-1-α) used in Step (7) of Synthesis Example 72, and the amount of toluene charged into the polymerization tank was changed to 152 parts. Prepared in the same manner as in step (7) of Example 72, and added 447 parts of ethyl acetate to obtain an addition type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, it carried out similarly to the process (8) of the synthesis example 8 except having changed the amount of phenyl isocyanate into 13 parts using 500 parts of obtained resin (C1) solutions (nonvolatile content 50.0 weight%). The reaction was performed to obtain a solution of an addition type polyester resin (D1) that was light yellow and transparent, had a nonvolatile content of 50.2% by weight, and had a viscosity of 20,500 mPa · s. The resin (D1) had an acid value of 0.1 mgKOH / g, a hydroxyl value of 22.6 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 175,000.

(Synthesis Example 79)
Toluene charged in the polymerization tank by using 277 parts of Kuraray polyol P6010 instead of the polyols (a-1-α) used in step (7) of Synthesis Example 72 and changing the amount of succinic anhydride to 11 parts. This was prepared in the same manner as in Synthesis Example 72 except that 12 parts of sebacic acid was added as a dicarboxylic acid to the polymerization tank, and 226 parts of ethyl acetate was added to the addition type polyester precursor (C1). A solution was obtained. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, the reaction was conducted in the same manner as in Step (8) of Synthesis Example 8 except that 500 parts of the obtained resin (C1) solution (nonvolatile content: 50.0% by weight) was used and the amount of phenyl isocyanate was changed to 17 parts. To obtain a solution of an addition-type polyester resin (D1) that is light yellow and transparent, has a nonvolatile content of 50.3% by weight, and a viscosity of 13,500 mPa · s. The resin (D1) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 21.7 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 120,000.

(Synthesis Example 80)
Instead of the polyols (a-1-α) used in Step (7) of Synthesis Example 72, a polyester polyol prepared in Synthesis Example A: prepared in the same manner as Synthesis Example 72 except that 375 parts were used, A solution of addition-type polyester resin (D1) which was light yellow and transparent and had a nonvolatile content of 50.2% by weight and a viscosity of 14,000 mPa · s was obtained. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 19.7 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 125,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 81)
Prepared in the same manner as in Synthesis Example 72 except that 377 parts of the polyester polyol prepared in Synthesis Example B was used instead of the polyols (a-1-α) used in Step (7) of Synthesis Example 72. A solution of addition-type polyester resin (D1) that was light yellow and transparent and had a nonvolatile content of 50.0% by weight and a viscosity of 12,000 mPa · s was obtained. The resin (D1) had an acid value of 0.5 mgKOH / g, a hydroxyl value of 13.5 mgKOH / g, a glass transition temperature of −40 ° C., and a weight average molecular weight of 115,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 82)
Instead of the low molecular weight dicarboxylic acids (a-1-1) used in the step (7) of Synthesis Example 72, 27 parts of phthalic anhydride was used, and the amount of toluene charged into the polymerization tank was changed to 78 parts. The reaction was conducted in the same manner as in Step (7) of Synthesis Example 72, and 281 parts of ethyl acetate was added to obtain an addition type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, it was carried out similarly to the process (8) of the synthesis example 8 except having changed the quantity of phenyl isocyanate into 22 parts using 500 parts of obtained resin (C1) solutions (nonvolatile content 50.0 weight%). The reaction was carried out to obtain a solution of an addition type polyester resin (D1) which was light yellow and transparent and had a non-volatile content of 50.2% by weight and a viscosity of 15,000 mPa · s. The resin (D1) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 18.8 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 142,000.

(Synthesis Example 83)
Other than using 30 parts of hymic acid anhydride instead of the low molecular weight dicarboxylic acids (a-1-1) used in step (7) of Synthesis Example 72, and further changing the amount of toluene charged to the polymerization tank to 80 parts. Was prepared in the same manner as in Step (7) of Synthesis Example 72, and 282 parts of ethyl acetate was added to obtain an addition-type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Next, using the obtained addition-type polyester precursor (C1) solution (nonvolatile content: 50.1% by weight) 500 parts, except that the amount of phenyl isocyanate was changed to 22 parts, step (8) of Synthesis Example 72 and The reaction was carried out in the same manner to obtain a solution of an addition type polyester resin (D1) which was light yellow and transparent, had a nonvolatile content of 50.0% by weight and a viscosity of 17,500 mPa · s. The resin (D1) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 16.5 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 165,000.

(Synthesis Example 84)
Instead of the bicyclic ether compound (a-2) used in the step (7) of Synthesis Example 72, bisphenoxyfluorange glycidyl ether (manufactured by Osaka Gas Chemical Co., Ltd., BPEFG, also known as 9,9-bis [ 2-Ethoxy-4- (glycidyloxy) phenyl] -9H-fluorene, molecular weight: 550.5, epoxy value: 3.26 (eq / Kg)): 55 parts, and the amount of ethyl acetate charged into the dropping device was The reaction was performed in the same manner as in Step (7) of Synthesis Example 72 except that the amount was changed to 54 parts, and 321 parts of ethyl acetate was added to obtain an addition type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Next, Step (8) in Synthesis Example 73 except that 500 parts of the obtained resin (C1) solution (non-volatile content: 50.1% by weight) was used and the amount of phenyl isocyanate (c3) was changed to 22 parts. The reaction was carried out in the same manner to obtain a solution of an addition type polyester resin (D1) which was light yellow and transparent and had a non-volatile content of 50.2% by weight and a viscosity of 21,000 mPa · s. The resin (D1) had an acid value of 0.1 mgKOH / g, a hydroxyl value of 15.2 mgKOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 170,000.

(Synthesis Example 85)
Instead of the compound (a-2) having two cyclic ether groups in the molecule used in the step (7) of Synthesis Example 72, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl } Using 20 parts of benzene and 10 parts of resorcinol diglycidyl ether (also known as 1,3-phenylenebis (glycidyl ether), molecular weight 222.2), except that the amount of ethyl acetate charged in the dropping apparatus was changed to 46 parts The reaction was conducted in the same manner as in Step (7) of Synthesis Example 72, and 304 parts of ethyl acetate was added to obtain an addition-type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.7 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, the reaction was performed in the same manner as in Step (8) of Synthesis Example 72 except that 500 parts of the obtained addition-type polyester precursor (C1) solution (nonvolatile content: 49.8% by weight) was used. A solution of an addition type polyester resin (D1) having a viscosity of 49.7% by weight and a viscosity of 11,000 mPa · s was obtained. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 25.3 mg KOH / g, a glass transition temperature of −25 ° C., and a weight average molecular weight of 100,000.

(Synthesis Example 86)
Instead of the bicyclic ether compound (a-2) used in the step (7) of Synthesis Example 72, a bisphenol A-based high molecular weight glycidyl resin “JER1002” (manufactured by Japan Epoxy Resin, epoxy equivalent: 635 (g / eq) The reaction was carried out in the same manner as in the step (7) of Synthesis Example 72 except that 130 parts were used and the amount of ethyl acetate charged in the dropping device was changed to 80 parts. 370 parts of ethyl was added to obtain an addition type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 0.5 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Next, using the obtained addition-type polyester precursor (C1) solution (nonvolatile content: 50.2% by weight) 500 parts, except that the amount of phenyl isocyanate was changed to 25 parts, step (8) of Synthesis Example 72 and By reacting in the same manner, a light yellow transparent solution of addition type polyester resin (D1) having a non-volatile content of 50.2% by weight and a viscosity of 25,000 mPa · s was obtained. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 12.1 mg KOH / g, a glass transition temperature of −15 ° C., and a weight average molecular weight of 180,000.

(Synthesis Example 87)
Instead of the bicyclic ether compound (a-2) used in the step (7) of Synthesis Example 72, 28 parts of neopentyl glycol diglycidyl ether was used, and the amount of ethyl acetate charged in the dropping device was changed to 45 parts. Reacted in the same manner as in Step (7) of Synthesis Example 73, and 303 parts of ethyl acetate was added to obtain an addition-type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.1 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, the reaction was performed in the same manner as in Step (8) of Synthesis Example 72 except that 500 parts of the obtained addition-type polyester precursor (C1) solution (non-volatile content: 50.0% by weight) was used. A solution of addition type polyester resin (D1) having a viscosity of 50.2% by weight and a viscosity of 12,500 mPa · s was obtained. The acid value of the resin (D1) was 0.2 mgKOH / g, the hydroxyl value was 23.4 mgKOH / g, the glass transition temperature was −50 ° C., and the weight average molecular weight was 120,000.

(Synthesis Example 88)
Instead of the bicyclic ether compound (a-2) used in Step (7) of Synthesis Example 72, 100 parts of bis- (3,4-epoxycyclohexyl) adipate (molecular weight 366.5) was used as a dropping device. The reaction was performed in the same manner as in Step (7) of Synthesis Example 72 except that the amount of ethyl acetate charged was changed to 80 parts, and 370 parts of ethyl acetate was added to obtain an addition-type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 0.5 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, using the obtained addition-type polyester precursor (C1) solution (non-volatile content: 50.2% by weight) 500 parts, and changing the amount of phenyl isocyanate to 25 parts, step (8) of Synthesis Example 72 and The reaction was conducted in the same manner to obtain a solution of an addition type polyester resin (D1) which was light yellow and transparent and had a nonvolatile content of 50.5% by weight and a viscosity of 19,000 mPa · s. Resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 13.5 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 165,000.

(Synthesis Example 89)
Instead of the bicyclic ether compound (a-2) used in the step (7) of Synthesis Example 72, biphenyl-4,4′-diglycidyl ether (also known as 4,4′-bis (glycidyloxy) -1, 1′-biphenyl, molecular weight: 298.3) The reaction was conducted in the same manner as in Step (7) of Synthesis Example 72 except that 30 parts of ethyl acetate was used and the amount of ethyl acetate charged into the dropping device was changed to 44 parts. Part was added to obtain an addition-type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, using the obtained addition-type polyester precursor (C1) solution (nonvolatile content 50.1% by weight) 500 parts, and changing the amount of phenyl isocyanate to 20 parts, the step (8) of Synthesis Example 72 and The reaction was carried out in the same manner to obtain a solution of an addition type polyester resin (D1) which was light yellow and transparent, had a nonvolatile content of 50.0% by weight and a viscosity of 15,000 mPa · s. The resin (D1) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 17.2 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 145,000.

(Synthesis Example 90)
Instead of the cyclic ester (b) used in Step (7) of Synthesis Example 72, 28 parts of δ-valerolactone was used, and the amount of ethyl acetate charged into the dropping device was changed to 46 parts. Reaction was performed in the same manner as in step (7), and 304 parts of ethyl acetate was added to obtain an addition type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, the reaction was performed in the same manner as in Step (8) of Synthesis Example 72 except that 500 parts of the obtained addition-type polyester precursor (C1) solution (non-volatile content: 50.0% by weight) was used. A solution of an addition type polyester resin (D1) having a viscosity of 50.2% by weight and a viscosity of 21,000 mPa · s was obtained. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 18.9 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 195,000.

(Synthesis Example 91)
Step of Synthesis Example 72, except that 24 parts of γ-butyrolactone was used in place of the cyclic ester (b) used in Step (7) of Synthesis Example 72 and the amount of ethyl acetate charged into the dropping device was changed to 45 parts. It reacted like (7), 301 parts of ethyl acetate was added, and the addition type polyester precursor (C1) solution was obtained. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, the reaction was performed in the same manner as in Step (8) of Synthesis Example 72 except that 500 parts of the obtained addition-type polyester precursor (C1) solution (non-volatile content: 50.1% by weight) was used. An addition type polyester resin solution having a viscosity of 50.1% by weight and a viscosity of 22,500 mPa · s was obtained. The resin had an acid value of 0.5 mg KOH / g, a hydroxyl value of 24.3 mg KOH / g, a glass transition temperature of −15 ° C., and a weight average molecular weight of 200,000.

(Synthesis Example 92)
Step (7) of Synthesis Example 72, except that the amount of cyclic ester (b) used in Step (7) of Synthesis Example 72 was changed to 10 parts and the amount of ethyl acetate charged in the dropping device was changed to 40 parts. And 292 parts of ethyl acetate was added to obtain an addition type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 0.4 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Subsequently, the reaction was performed in the same manner as in Step (8) of Synthesis Example 72 except that 500 parts of the obtained addition-type polyester precursor (C1) solution (non-volatile content: 50.1% by weight) was used. A solution of an addition type polyester resin (D1) having a viscosity of 50.0% by weight and a viscosity of 32,000 mPa · s was obtained. The resin (D1) had an acid value of 0.6 mgKOH / g, a hydroxyl value of 48.4 mgKOH / g, a glass transition temperature of −15 ° C., and a weight average molecular weight of 290,000.

(Synthesis Example 93)
The step (7) of the synthesis example 72 except that the amount of the cyclic ester compound (b) used in the step (7) of the synthesis example 72 was changed to 80 parts and the amount of ethyl acetate charged in the dropping device was changed to 63 parts. And 339 parts of ethyl acetate was added to obtain an addition-type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 3.5 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Next, the reaction was performed in the same manner as in Step (8) of Synthesis Example 72 except that 500 parts of the obtained addition-type polyester precursor (C1) solution (nonvolatile content: 50.5% by weight) was used. A solution of an addition type polyester resin (D1) having a weight of 50.3% by weight and a viscosity of 6,500 mPa · s was obtained. The resin (D1) had an acid value of 1.2 mgKOH / g, a hydroxyl value of 3.5 mgKOH / g, a glass transition temperature of −35 ° C., and a weight average molecular weight of 80,000.

(Synthesis Example 94)
Instead of the sealing compound (c) used in Step (8) of Synthesis Example 72, 35 parts of p-toluenesulfonyl isocyanate, which is a monofunctional isocyanate compound (c3), was used, and the amount of ethyl acetate charged into the dropping device was 12 The reaction was carried out in the same manner as in Synthesis Example 72 except that the content was changed to parts, and 13 parts of ethyl acetate was added. The addition type polyester resin (D1) had a pale yellow transparent, non-volatile content of 50.3% by weight and a viscosity of 12,000 mPa · s. Solution was obtained. The resin (D1) had an acid value of 21.3 mg KOH / g, a hydroxyl value of 14.2 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 105,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 95)
Instead of the sealing compound (c) used in Step (8) of Synthesis Example 72, 19 parts of trimethylchlorosilane as the silylating agent (c1) was used, and the amount of ethyl acetate charged in the dropping device was changed to 9 parts. The reaction was conducted in the same manner as in Synthesis Example 72, and 10 parts of ethyl acetate was added, and a solution of addition-type polyester resin (D1) having a pale yellow transparent, non-volatile content of 50.1% by weight and a viscosity of 12,500 mPa · s was obtained. Obtained. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 15.8 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 110,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 96)
Instead of the sealing compound (c) used in Step (8) of Synthesis Example 72, 13 parts of triethylsilanol as the silylating agent (c1) was used, and the amount of ethyl acetate charged into the dropping device was changed to 6 parts. The reaction was conducted in the same manner as in Synthesis Example 72, and 7 parts of ethyl acetate was added to obtain a solution of an addition type polyester resin (D1) having a pale yellow transparent, non-volatile content of 50.2% by weight and a viscosity of 11,500 mPa · s. It was. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 17.2 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 98,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 97)
The reaction was conducted in the same manner as in Synthesis Example 72 except that 20 parts of hexamethyldisilazane as the silylating agent (c1) was used instead of the sealing compound (c) used in Step (8) of Synthesis Example 72. Then, 10 parts of ethyl acetate was added to obtain a light yellow transparent solution of addition type polyester resin (D1) having a non-volatile content of 50.2% by weight and a viscosity of 9,500 mPa · s. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 20.5 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 85,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 98)
Instead of the sealing compound (c) used in Step (8) of Synthesis Example 72, 15 parts of phthalic anhydride, which is an acid anhydride (c2), was used, and the amount of ethyl acetate charged in the dropping device was changed to 12 parts. The reaction was performed in the same manner as in Synthesis Example 72 except that 13 parts of ethyl acetate was added, and the solution was a yellowish transparent, non-volatile content of 50.5% by weight, and a viscosity of 15,500 mPa · s addition type polyester resin (D1). Got. The resin (D1) had an acid value of 78.5 mgKOH / g, a hydroxyl value of 15.7 mgKOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 160,000.

(Synthesis Example 99)
Synthesis Example except that 2 parts of phthalic anhydride was used as the acid anhydride (c2) instead of the sealing compound (c) used in Step (8) of Synthesis Example 72, and ethyl acetate was not charged into the dropping device. The reaction was carried out in the same manner as in No. 72, and 2 parts of ethyl acetate was added to obtain a solution of an addition type polyester resin (D1) having a pale yellow transparent, non-volatile content of 50.3% by weight and a viscosity of 10,500 mPa · s. The resin (D1) had an acid value of 6.2 mg KOH / g, a hydroxyl value of 52.7 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 100,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 100)
Synthesis was performed except that 2 parts of hymic acid anhydride, which is an acid anhydride (c2), was used instead of the sealing compound (c) used in the step (8) of Synthesis Example 72, and ethyl acetate was not charged into the dropping device. The reaction was conducted in the same manner as in Example 72, and 2 parts of ethyl acetate was added to obtain a solution of an addition type polyester resin (D1) having a pale yellow transparent, non-volatile content of 50.3% by weight and a viscosity of 11,000 mPa · s. The resin (D1) had an acid value of 5.2 mg KOH / g, a hydroxyl value of 54.2 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 95,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 101)
Instead of the polyols (a-1-α) used in the step (7) of Synthesis Example 72, 276 parts of the polyester polyol produced in Synthesis Example A was used, and the amount of succinic anhydride was changed to 11 parts. The same procedure as in Step (7) of Synthesis Example 72 except that the amount of toluene was changed to 30 parts, and 5 parts of adipic acid and 5 parts of isophthalic acid were added to the polymerization tank as dicarboxylic acid (a-1-1). After the reaction, 226 parts of ethyl acetate was added to obtain an addition type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Next, 500 parts of the obtained addition-type polyester precursor fat (C1) solution (non-volatile content: 50.1% by weight) was used, and an acid anhydride was used instead of the sealing compound (c) used in the step (8). The reaction was the same as in Step (8) of Synthesis Example 72 except that 2 parts of phthalic anhydride as (c2) was used, and the mixture was adjusted with ethyl acetate to be pale yellow and transparent with a nonvolatile content of 50.4% by weight and a viscosity of 14 A solution of addition type polyester resin (D1) of 1,000 mPa · s was obtained. The resin (D1) had an acid value of 5.7 mgKOH / g, a hydroxyl value of 58.2 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 130,000.

(Synthesis Example 102)
Instead of the polyol (a-1-α) used in Step (7) of Synthesis Example 72, 377 parts of the polyester polyol prepared in Synthesis Example B was used instead of the bicyclic ether compound (a-2). The reaction was conducted in the same manner as in Step (7) of Synthesis Example 72 except that 24 parts of 1,4-butanediol diglycidyl ether was used and the amount of ethyl acetate charged into the dropping device was changed to 15 parts. Part was added to obtain an addition-type polyester precursor (C1) solution. In the above formulation, the cyclic ester (b) has a ratio of about 1.2 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Next, 500 parts of the obtained resin (C1) solution (non-volatile content: 50.3% by weight) is used, and instead of the sealing compound (c) used in step (8), the acid anhydride (c2) is used. The reaction was carried out in the same manner as in Synthesis Example 72 except that 2 parts of succinic anhydride was used, and it was adjusted with ethyl acetate to give a pale yellow transparent addition-free polyester resin having a non-volatile content of 49.7% by weight and a viscosity of 9,500 mPa · s ( A solution of D1) was obtained. The resin (D1) had an acid value of 8.3 mg KOH / g, a hydroxyl value of 16.2 mg KOH / g, a glass transition temperature of −45 ° C., and a weight average molecular weight of 90,000.

(Synthesis Example 103)
The reaction was conducted in the same manner as in Synthesis Example 72 except that the amount of phenyl isocyanate (c3) used in Step (8) of Synthesis Example 72 was changed to 30 parts and the amount of ethyl acetate charged in the dropping device was changed to 15 parts. Then, 15 parts of ethyl acetate was added to obtain a solution of an addition type polyester resin (D1) having a pale yellow transparent, non-volatile content of 50.1% by weight and a viscosity of 17,000 mPa · s. The resin (D1) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 0.05 mg KOH / g, a glass transition temperature of −15 ° C., and a weight average molecular weight of 155,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 104)
The reaction was conducted in the same manner as in Synthesis Example 72 except that 20 parts of phthalic anhydride as the acid anhydride (c2) was used in place of the sealing compound (c) used in Step (8) of Synthesis Example 72. 10 parts of ethyl was added to obtain a solution of an addition type polyester resin (D1) which was light yellow and transparent and had a nonvolatile content of 50.4% by weight and a viscosity of 28,000 mPa · s. The resin (D1) had an acid value of 86.4 mg KOH / g, a hydroxyl value of 0.02 mg KOH / g, a glass transition temperature of −15 ° C., and a weight average molecular weight of 230,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 105)
The reaction was carried out in the same manner as in Synthesis Example 72 except that the catalyst used in Synthesis Example 72 was changed to tetrabutylammonium nitrate, and the mixture was adjusted by adding ethyl acetate. A solution of addition type polyester resin (D1) of 17,000 mPa · s was obtained. The resin (D1) had an acid value of 0.2 mg KOH / g, a hydroxyl value of 23.5 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 165,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

(Synthesis Example 106)
The reaction was carried out in the same manner as in Synthesis Example 72 except that the catalyst was omitted in Synthesis Example 72, adjusted by adding ethyl acetate, pale yellow transparent, non-volatile content of 50.1% by weight, viscosity of 17,500 mPa · s. A solution of the polyester resin (D1) was obtained. The resin (D1) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 26.5 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 150,000. In the above formulation, the cyclic ester (b) is in a ratio of about 1.4 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

  For each of the resin solutions obtained in Synthesis Examples 67 to 106, the appearance of the solution, nonvolatile content, resin weight average molecular weight (Mw), glass transition temperature (Tg), acid value (AV), and hydroxyl value (OHV) were synthesized. The results evaluated in the same manner as in Examples 1 to 19 are summarized in Tables 9 and 10.

(Comparative Example 19)
Polyester resin (B) solution for main chain obtained in step (1) of Synthesis Example 67: 25 parts of toluene is added to 100 parts by weight, and TDI / TMP (tolylene diisocyanate) is used as a crosslinking agent (E). Of trimethylolpropane adduct) was added and stirred well to obtain an adhesive composition. This was applied onto a release film to obtain an adhesive sheet, but could not be applied because the viscosity of the adhesive composition increased rapidly.

(Comparative Example 20)
An adhesive composition was obtained in the same manner as in Comparative Example 16 except that the addition type polyester precursor (C1) solution obtained in the step (2) of Synthesis Example 67 was used. However, as in Comparative Example 16, the viscosity of the adhesive composition increased rapidly, and thus could not be applied to the release film.

(Example 63)
25 parts of toluene was added to 100 parts by weight of the solution of the addition type polyester resin (D1) obtained in the step (3) of Synthesis Example 67, and TDI / TMP (tolylene diisocyanate) was added as a crosslinking agent (E). Trimethylolpropane adduct body) 2.5 parts by weight was added and stirred well to obtain the adhesive composition of the present invention. This was coated on a release film so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form an adhesive layer.
Further, in the same manner as in Examples 1 to 19 and the like, a laminate having a configuration of “peeling film / adhesive layer / TAC film / PVA / TAC film” was obtained, and the reaction of the adhesive layer was allowed to proceed for adhesion. A polarizing plate (laminate) was obtained.

(Comparative Example 21)
An adhesive composition was prepared in the same manner as in Example 63 except that the resin solution obtained in Synthesis Example 68 was used instead of the addition type polyester resin (D1) obtained in Step (3) of Synthesis Example 67. Prepared. When an adhesion process was attempted using this, the coating was completed, but the adhesive layer did not exhibit tack (initial adhesion), and an adhesive-processed polarizing plate could not be produced.

(Examples 64 and 65)
Instead of the addition-type polyester resin (D1) solution obtained in the step (3) of Synthesis Example 67, the adhesive solution obtained in Synthesis Example 69 (Example 64) or Synthesis Example 70 (Example 65) was used. An adhesive composition was prepared in the same manner as in Example 67 except that it was used, and a bonded polarizing plate was produced.

(Comparative Example 22)
An adhesive composition was prepared in the same manner as in Example 67 except that the resin solution obtained in Synthesis Example 71 was used instead of the addition type polyester resin (D1) obtained in Step (3) of Synthesis Example 67. An attempt was made to prepare a prepared and bonded polarizing plate. However, since the viscosity of the adhesive composition suddenly increased, it could not be applied to the release film.

(Comparative Example 23)
The addition type polyester precursor (C1) solution obtained in step (7) of synthesis example 72 was used in place of the addition type polyester precursor (C) solution obtained in step (2) of synthesis example 72. Except for this, an adhesive composition was obtained in the same manner as in Comparative Example 20. However, as in Comparative Example 20, the viscosity of the adhesive composition increased sharply, so that it was possible to apply, but streaks and repellency occurred on the coated surface to produce a bonded polarizing plate. could not.

Example 66
25 parts of toluene was added to 100 parts by weight of the solution of the addition type polyester resin (D1) obtained in the step (8) of Synthesis Example 72, and TDI / TMP (tolylene diisocyanate) was added as a crosslinking agent (E). Trimethylolpropane adduct body) 2.5 parts by weight was added and stirred well to obtain the adhesive composition of the present invention. Using this, a bonded polarizing plate was produced in the same manner as in Example 63.

(Examples 67 to 92)
Adhesion was carried out in the same manner as in Example 66 except that each of the resin (D1) solutions obtained in Synthesis Examples 73 to 98 was used instead of the resin (D1) solution obtained in Step (8) of Synthesis Example 72. An agent composition was prepared and an adhesive processed polarizing plate was produced.
(Examples 93 to 97)
Adhesion was carried out in the same manner as in Example 66 except that each of the resin (D1) solutions obtained in Synthesis Examples 102 to 106 was used instead of the resin (D1) solution obtained in Step (8) of Synthesis Example 72. An agent composition was prepared and an adhesive processed polarizing plate was produced.

(Comparative Examples 24-26)
Instead of the resin (D1) solution obtained in Step (8) of Synthesis Example 72, the resin (D1) solution obtained in Synthesis Examples 99 to 101 was used in the same manner as in Example 66. An adhesive composition was prepared and an attempt was made to produce a bonded polarizing plate. However, since the viscosity of the adhesive composition suddenly increased, it could not be applied to the release film.

(Examples 98 and 99)
The crosslinking agent (E) used in Example 66 was changed from TDI / TMP to 2.5 parts of XDI / TMP (trimethylolpropane adduct of xylylene diisocyanate) (Example 98) or HMDI / burette ( An adhesive composition was obtained in the same manner as in Example 66 except that it was changed to 2.5 parts (Example 99) of hexamethylene diisocyanate burette adduct). Using these materials, a bonded polarizing plate was produced in the same manner as in Example 66.

(Example 100)
To 100 parts by weight of the solution of the addition-type polyester resin (D1) obtained in Synthesis Example 99 was added 25 parts of toluene, and HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) 0.25 parts by weight was added and stirred well to obtain the adhesive composition of the present invention. Using this, a bonded polarizing plate was produced in the same manner as in Example 66.

(Comparative Examples 27 and 28)
Instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 99, the addition type polyester resin (D1) solution obtained in Synthesis Example 98 or Synthesis Example 104 was used in the same manner as in Example 100. Thus, an adhesive composition was prepared. At this time, although the viscosity of the resin solution was increased, a polarizing plate that could be applied and bonded was prepared.

(Examples 101 to 103)
Adhesive composition in the same manner as in Example 100 except that the resin (D1) solution obtained in Synthesis Examples 100 to 102 was used in place of the addition type polyester resin (D1) solution obtained in Synthesis Example 99. A polarizing plate was prepared by preparing a product and bonding.

(Example 104)
25 parts of toluene was added to 100 parts by weight of the solution of the addition-type polyester resin (D1) obtained in Synthesis Example 99, and TGMXDA (N, N, N ′, N′-tetraglycidyl- m-xylylenediamine) 0.25 part by weight was added and stirred well to obtain the adhesive composition of the present invention. Using this, a bonded polarizing plate was produced in the same manner as in Example 100.

(Comparative Examples 29 and 30)
Adhesive composition in the same manner as in Example 104 except that the resin (D1) solution obtained in Synthesis Examples 98 and 99 was used in place of the addition type polyester resin (D1) solution obtained in Synthesis Example 99, respectively. A product was prepared. . However, since the viscosity of the adhesive composition suddenly increased, it could not be applied to the release film.

(Examples 105 to 107)
Adhesive composition in the same manner as in Example 104 except that each of the resin (D1) solutions obtained in Synthesis Examples 100 to 102 was used instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 99. The polarizing plate which prepared the thing and carried out the adhesion process was produced, and was evaluated.

(Example 108)
25 parts of toluene was added to 100 parts by weight of the addition-type polyester resin (D1) solution obtained in Synthesis Example 99, and “carbodilite V-05” (Nisshinbo Industries, Ltd.), which is a carbodiimide compound, as a crosslinking agent (E). 0.25 parts by weight were added and stirred well to obtain an adhesive composition of the present invention. Using this, a bonded polarizing plate was produced in the same manner as in Example 100.

(Comparative Examples 31, 32)
Instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 99, the resin (D1) solution obtained in Synthesis Example 98 or Synthesis Example 99 was used in the same manner as in Example 108. An adhesive composition was prepared. . However, since the viscosity of the adhesive composition suddenly increased, it could not be applied to the release film.

(Examples 109 to 111)
Adhesive composition as in Example 108 except that the resin (D1) solution obtained in Synthesis Examples 100 to 102 was used in place of the addition-type polyester resin (D1) solution obtained in Synthesis Example 99, respectively. A polarizing plate was prepared by preparing a product and bonding.

(Example 112)
25 parts of toluene was added to 100 parts by weight of the solution of the addition type polyester resin (D1) obtained in Synthesis Example 99, and HMoxz (2,2′-hexamethylenebis (2-oxazoline) was used as a crosslinking agent (E). ) 0.25 part by weight was added and stirred well to obtain the adhesive composition of the present invention. Using this, a bonded polarizing plate was produced in the same manner as in Example 100.

(Comparative Examples 33 and 34)
In the same manner as in Example 112, except that the resin (D1) solution obtained in Synthesis Examples 98 and 99 was used instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 99, respectively. A composition was prepared. However, since the viscosity of the adhesive composition suddenly increased, it could not be applied to the release film.

(Examples 113 to 116)
Adhesive composition as in Example 112 except that the resin (D1) solution obtained in Synthesis Examples 100 to 102 was used instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 99, respectively. The polarizing plate which prepared the thing and carried out the adhesion process was produced, and was evaluated.

(Example 118)
25 parts of isopropyl alcohol (IPA) is added to 100 parts by weight of the solution of the addition type polyester resin (D1) obtained in Synthesis Example 99, and AlAA (aluminum tris (acetylacetonate)) 0 is added as a crosslinking agent (E). .25 parts by weight was added and stirred well to obtain an adhesive composition of the present invention. Using this, a bonded polarizing plate was produced in the same manner as in Example 100.

(Comparative Examples 35 and 36)
Instead of the addition type polyester resin (D1) solution obtained in Synthesis Example 99, the resin (D1) solution obtained in Synthesis Example 98 or Synthesis Example 99 was used in the same manner as in Example 118, respectively. An adhesive composition was prepared. However, since the viscosity of the adhesive composition suddenly increased, it could not be applied to the release film.

(Examples 119 to 121)
Adhesive composition as in Example 118 except that the resin (D1) solution obtained in Synthesis Examples 100 to 102 was used in place of the addition type polyester resin (D1) solution obtained in Synthesis Example 99, respectively. A product was prepared, and a polarizing plate bonded using the product was prepared.

The pot life and coating processability of the adhesive compositions obtained in Examples and Comparative Examples were evaluated in the same manner as in Examples 1-19. The results are shown in Tables 11-13.
Moreover, about the polarizing plate (laminated body) which carried out the adhesion process obtained by the Example and the comparative example, the refractive index of a coating film, heat resistance, heat-and-moisture resistance, an optical characteristic, and removability are the case of Examples 1-22. Evaluation was performed in the same manner. The results are shown in Tables 11-13.

<< 2nd sealing form: addition type polyester resin (D2) >>
In the following synthesis examples 107 to 113, a method for producing an addition-type polyester resin (D2), in which formation of the main chain (I), hydroxyl group sealing reaction, and side chain formation with a cyclic ester are sequentially performed in three steps, will be described. To do.

[Preparation of Addition Type Polyester Resin (D2) by Three-Step Mold Manufacturing Method]
(Synthesis Example 107)
<Step (9): Formation of polyester main chain (I)>
A polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube was prepared. In the polymerization tank and the dropping device, dicarboxylic acid (a-1) was added as a dibasic acid (a-1). a-1-1), a compound having two cyclic ether groups in the molecule (a-2), a catalyst and an organic solvent were respectively charged in the following ratios.

[Polymerization tank]
Adipic acid (a-1-1) 438 parts Isophthalic acid (a-1-1) 332 parts Ethyl acetate 192 parts Toluene 384 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 part [Drip device]
Bisphenol A diglycidyl ether (a-2) 1919 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 part Ethyl acetate 192 parts Toluene 384 parts

After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 100 ° C. while stirring the contents. Subsequently, the mixture of the bicyclic ether compound (a-2) was dripped at this with constant velocity over 1 hour from the dripping apparatus. After completion of the dropping, 0.5 parts of the catalyst was added twice every 8 hours with stirring. After 24 hours of reaction and aging, 1537 parts of ethyl acetate was added and cooled to room temperature to complete the reaction. A solution of the chain polyester resin (B) was obtained.
This solution is light yellow and transparent with a non-volatile content of 50.1% by weight and a viscosity of 18,000 mPa · s. Resin (I) has an acid value of 1.2 mfKOH / g, a hydroxyl value of 175.2 mgKOH / g, and a glass transition temperature. The temperature was 40 ° C. and the weight average molecular weight was 150,000.

<Step (10): Addition reaction of sealing compound (c)>
A polymerization reaction apparatus having a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube attached to the polymerization tank was prepared, and the polyester resin for the main chain (B) prepared in step (9) was prepared in the polymerization tank and the dropping apparatus. The solution, the sealing compound (c), the catalyst, and the organic solvent were charged at the following ratios.

[Polymerization tank]
500 parts of main chain polyester resin (B) solution [Drip device]
Phenyl isocyanate (c3) 90 parts Tetrabutylammonium tetrahydroborate (catalyst) 0.1 part Ethyl acetate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the solution. Next, the mixture of the sealing compound (c) was dropped into the solution at a constant rate over 1 hour from the dropping device. After completion of the dropwise addition, the mixture was reacted and aged for 12 hours with stirring, and then 80 parts of ethyl acetate was added and cooled to room temperature to complete the reaction, whereby a solution of the polyester resin (C2) to which the sealing compound (c) was added was obtained. It was.
This solution is light yellow and transparent, has a non-volatile content of 50.1% by weight, a viscosity of 20,000 mPa · s, an acid value of the resin of 0.5 mg KOH / g, a hydroxyl value of 37.2 mg KOH / g, a glass transition temperature of 40 ° C., and a weight. The average molecular weight was 160,000.

<Step (11): Ring-opening addition reaction of cyclic ester (b)>
A polymerization reaction apparatus having a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube attached to the polymerization tank is prepared, and the polyester resin (C2) solution prepared in step (10), cyclic Lactone (b-1) which is ester (b), catalyst and organic solvent were charged at the following ratios.

[Polymerization tank]
500 parts of the polyester resin (C2) solution obtained in the step (10) [Drip device]
ε-Caprolactone (b-1) 32 parts Tetrabutylammonium tetrahydroborate (catalyst) 0.5 parts Ethyl acetate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the solution. Next, the cyclic ester (b-1) mixture was dropped into the solution at a constant rate over 1 hour from a dropping device. After completion of the dropwise addition, the mixture was further reacted and aged for 8 hours while stirring, and then 22 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of an addition type polyester resin (D2).
This solution is light yellow and transparent with a non-volatile content of 50.0% by weight and a viscosity of 18,500 mPa · s. The resin (D2) has an acid value of 0.2 mg KOH / g, a hydroxyl value of 15 mg KOH / g, a glass transition temperature − It was 10 ° C. and the weight average molecular weight was 165,000.

(Synthesis Example 108)
Step (10) in Synthesis Example 107 was omitted, and in Step (11), instead of the addition-type polyester resin (C2) solution, a solution (nonvolatile) of the polyester resin for the main chain (B) obtained in Step (9) 50.1% by weight), 500 parts, and the same procedure as in Synthesis Example 107 except that the amount of ε-caprolactone (b) was changed to 44 parts. 34 parts of ethyl acetate was added and cooled to room temperature. As a result, a pale yellow transparent polyester resin solution having a nonvolatile content of 50.2% by weight and a viscosity of 17,000 mPa · s was obtained. The resin contained in the solution had an acid value of 0.5 mg KOH / g, a hydroxyl value of 77 mg KOH / g, a glass transition temperature of 40 ° C., and a weight average molecular weight of 155,000.

(Synthesis Example 109)
Instead of the dibasic acid (a-1) used in Synthesis Example 107, 1000 parts of sebacic acid as the dicarboxylic acid (a-1-1) and high molecular weight polyester dicarboxylic acid (a-1-2) 800 parts of a certain Byron GK110 (number average molecular weight: 16,000, acid value: 6; manufactured by Toyobo Co., Ltd.) was used, and the amount of the solvent charged into the reaction vessel and the dropping device was 265 parts of ethyl acetate and 530 parts of toluene. The reaction was conducted in the same manner as in Step (9) of Synthesis Example 107 except that the content was changed to parts, and 2129 parts of ethyl acetate was added to obtain a polyester resin (B) solution for main chain.
Next, 500 parts of the obtained resin (B) solution (nonvolatile content: 50.2% by weight) was used, and the amount of phenyl isocyanate as the sealing compound (c3) was changed to 65 parts. Reaction was performed in the same manner as in step (10), and 55 parts of ethyl acetate was added and cooled to room temperature to obtain a polyester resin (C2) solution to which the sealing compound (c) was added.
Furthermore, except that 500 parts of the obtained resin (C2) solution (non-volatile content: 50.0% by weight) was used, and the amount of ε-caprolactone as the cyclic ester (b) was changed to 23 parts, Synthesis Example 107 Reaction was carried out in the same manner as in step (11), and 13 parts of ethyl acetate was added and cooled to room temperature. It was a pale yellow transparent addition type polyester resin (D2) having a nonvolatile content of 50.1% by weight and a viscosity of 15,500 mPa · s. Solution was obtained. The resin (D2) had an acid value of 1.2 mgKOH / g, a hydroxyl value of 19.5 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 135,000.

(Synthesis Example 110)
Instead of dibasic acid (a-1) used in Synthesis Example 107, 910 parts of sebacic acid as dicarboxylic acid (a-1-1) and TXM80B as high molecular weight polyamide dicarboxylic acid (a-1-2b) (Number average molecular weight: 1,600, acid value: 20; manufactured by Fuji Kasei Kogyo Co., Ltd.) 800 parts are used, and the amount of solvent charged in the reaction vessel and the dropping device is changed to 260 parts ethyl acetate and 520 parts toluene. Except for this, the reaction was carried out in the same manner as in Step (9) of Synthesis Example 107, and 2069 parts of ethyl acetate was added to obtain a polyester resin (B) solution for main chain.
Next, 500 parts of the obtained resin (B) solution (nonvolatile content: 50.2% by weight) was used, and the amount of phenyl isocyanate as the sealing compound (c3) was changed to 67 parts. It reacted like the process (10), 57 parts of ethyl acetate was added, it cooled to room temperature, and the solution of the polyester resin (C2) which added the sealing compound (c) was obtained.
Furthermore, except that 500 parts of the obtained resin (C2) solution (non-volatile content: 50.0% by weight) was used and the amount of ε-caprolactone as the cyclic ester (b) was changed to 24 parts, Reaction was carried out in the same manner as in step (11), and 14 parts of ethyl acetate was added and cooled to room temperature. It was a pale yellow transparent, non-volatile content of 50.1% by weight, viscosity of 15,000 mPa · s of addition type polyester resin (D2) A solution was obtained. The resin (D2) had an acid value of 1.5 mgKOH / g, a hydroxyl value of 18.3 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 130,000.

(Synthesis Example 111)
A polymerization reaction apparatus having a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube attached to the polymerization tank was prepared, and the low molecular weight dicarboxylic acids (a-1-) used in Synthesis Example 107 were prepared in the polymerization tank and the dropping apparatus. Instead of 1), low molecular weight dicarboxylic acids (a-1-1), polyester polyol (a-1-α), compound having two cyclic ether groups (a-2), catalyst, and organic solvent Prepared with.

[Polymerization tank]
Kuraray polyol P4010 (a-1-α) 2078 parts Succinic anhydride (a-1-1) 50 parts Ethyl acetate 165 parts Toluene 330 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 part [Drip device]
Bisphenol A diglycidyl ether (a-2) 192 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 part Ethyl acetate 165 parts Toluene 330 parts

After the air in the polymerization tank was replaced with nitrogen gas, the contents were heated to 100 ° C. while stirring, and reacted for 8 hours to obtain a high molecular weight dicarboxylic acid (a-1-) as a dibasic acid (a-1). 3) got.
Subsequently, the mixture of the bicyclic ether compound (a-2) was dripped at constant speed over 1 hour from the dripping apparatus. After completion of the dropwise addition, the catalyst was added twice at 0.5 parts each every 8 hours with further stirring. After 24 hours of reaction and aging, 1330 parts of ethyl acetate was added and cooled to room temperature to complete the reaction. A main chain polyester resin (B) was prepared.

Next, 500 parts of the obtained resin (B) solution (non-volatile content: 50.1% by weight) was used, and the amount of phenyl isocyanate as the sealing compound (c3) was changed to 12 parts. It reacted like the process (10), 2 parts of ethyl acetate was added, it cooled to room temperature, and the polyester resin (C2) solution which added the sealing compound (c) was obtained.
The process of Synthesis Example 107, except that 500 parts of the obtained resin (C2) solution (non-volatile content: 50.2% by weight) was used and the amount of ε-caprolactone as the cyclic ester (b) was changed to 5 parts. Reaction was carried out in the same manner as in (11), and the mixture was cooled to room temperature without adding ethyl acetate to obtain a solution of addition-type polyester resin (D2) having a pale yellow transparent, non-volatile content of 49.7% by weight and a viscosity of 15,500 mPa · s. It was. The resin (D2) had an acid value of 1.2 mgKOH / g, a hydroxyl value of 7.5 mgKOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 135,000.

(Synthesis Example 112)
Instead of the sealing compound (c3) used in Step (10) of Synthesis Example 107, the reaction was performed in the same manner as Synthesis Example 107 except that 77 parts of diethylmethylsilane was used as the silylating agent (c1). 67 parts of ethyl acetate was added and cooled to room temperature to obtain a polyester resin (C2) solution to which the sealing compound (c) was added.
In step (11), except that 500 parts of the obtained resin (C2) solution (non-volatile content: 50.0% by weight) was used, and the amount of ε-caprolactone as the cyclic ester (b) was changed to 33 parts. It reacts similarly to the synthesis example 107, 23 parts of ethyl acetate is added, and it cools to room temperature, The solution of addition type polyester resin (D2) of 50.0 weight% of non volatile matters and viscosity 13,000 mPa * s is pale yellow transparent. Obtained. The resin (D2) had an acid value of 0.05 mgKOH / g, a hydroxyl value of 18.5 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 120,000.

(Synthesis Example 113)
The reaction was conducted in the same manner as in Synthesis Example 107 except that 112 parts of phthalic anhydride (c2) was used instead of the sealing compound (c3) used in Step (10) of Synthesis Example 107, and 102 parts of ethyl acetate was added. In addition, it was cooled to room temperature to obtain a polyester resin (C2) solution to which the sealing compound (c) was added.
In step (11), except that 500 parts of the obtained resin (C2) solution (non-volatile content: 50.2% by weight) was used, and the amount of ε-caprolactone as the cyclic ester (b) was changed to 31 parts. Reaction was carried out in the same manner as in Synthesis Example 107, and 21 parts of ethyl acetate was added and cooled to room temperature. Obtained. The resin (D2) had an acid value of 85.1 mg KOH / g, a hydroxyl value of 12.8 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 175,000.

[Preparation of Addition Type Polyester Resin (D2) by Pseudo Two-Stage Manufacturing Method]
In the following synthesis examples 114 to 115, a main chain (I ′) having an acid value of 5 (mg KOH / g) or less is generated, and then completion of the main chain (I) and a sealing reaction are simultaneously performed. A method for obtaining an addition type polyester resin (D2) through a pseudo two-stage process for adding a chain will be described.

(Synthesis Example 114)
<Process (12) (13): Synthesis | combination of polyester resin (C2) which added sealing compound (c)>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube are attached to the polymerization tank is prepared, and dicarboxylic acid (a-1) is added to the polymerization tank and the dropping apparatus as dibasic acid (a-1). -1), compound (a-2) having two cyclic ether groups, compound (b), catalyst and organic solvent were charged in the following ratios.

[Polymerization tank]
Adipic acid (a-1-1) 438 parts Isophthalic acid (a-1-1) 332 parts Bisphenol A diglycidyl ether (a-2) 1919 parts Ethyl acetate 260 parts Toluene 520 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 Part [Drip device]
Phenyl isocyanate (c3) 952 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 part Ethyl acetate 260 parts Toluene 520 parts

After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 100 ° C. while stirring the contents, and the reaction was carried out for 8 hours, for the main chain (I ′) having an acid value of 5 (mgKOH / g) or less. Polyester was obtained.
Subsequently, the isocyanate mixture was dripped at constant speed over 1 hour from the dropping device.
After completion of dropping, 1 part of tetrabutylammonium tetrahydroborate was added after 8 hours with further stirring, and after further reaction and aging for 8 hours, 2081 parts of ethyl acetate was added and cooled to room temperature to complete the reaction. A polyester resin (C2) to which (c3) was added was prepared.
This reaction liquid is light yellow and transparent with a non-volatile content of 50.1% by weight and a viscosity of 20,000 mPa · s. The resin (C2) has an acid value of 0.5 mgKOH / g, a hydroxyl value of 37.2 mgKOH / g, glass The transition temperature was 40 ° C. and the weight average molecular weight was 160,000.

<Step (14): Addition reaction of cyclic ester (b)>
A polymerization reaction apparatus having a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube attached to the polymerization tank was prepared, and the polyester resin (C2) solution (nonvolatile) prepared in step (13) was prepared in the polymerization tank and the dropping apparatus. Min. 50.2%), cyclic ester (b), catalyst and organic solvent were charged at the following ratios.

[Polymerization tank]
500 parts of the polyester resin (C2) solution obtained in the step (13) [Drip device]
ε-Caprolactone (b-1) 16 parts Tetrabutylammonium tetrahydroborate (catalyst) 0.5 part Ethyl acetate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. while stirring the solution. Next, the cyclic ester mixture was dropped into this solution at a constant speed from a dropping device over 1 hour. After completion of the dropwise addition, the mixture was further reacted and aged for 6 hours while stirring, and then 6 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of addition type polyester resin (D2).
This solution is light yellow and transparent and has a non-volatile content of 50.3% by weight and a viscosity of 19,000 mPa · s. The resin (D2) has an acid value of 0.2 mgKOH / g, a hydroxyl value of 16.8 mgKOH / g, and a glass transition. The temperature was −10 ° C. and the weight average molecular weight was 170,000.

(Synthesis Example 115)
Instead of the dibasic acid (a-1) used in Synthesis Example 114, 1000 parts of sebacic acid as the dicarboxylic acid (a-1-1) and Byron as the high molecular weight polyester dicarboxylic acid (a-1-2a) Similar to Steps (12) and (13) of Synthesis Example 114, except that 800 parts of GK110 were used and the amounts of the solvent charged into the reaction vessel and the dropping device were changed to 333 parts of ethyl acetate and 666 parts of toluene, respectively. After the reaction, 2673 parts of ethyl acetate was added to obtain a polyester resin (C2) solution to which the compound (c3) was added.
Next, Synthetic Example 114 except that 500 parts of the obtained resin (C2) solution (non-volatile content: 50.0% by weight) was used and the amount of ε-caprolactone as the cyclic ester (b) was changed to 12 parts. The reaction was carried out in the same manner as in step (14), and 2 parts of ethyl acetate was added and cooled to room temperature. It was a pale yellow transparent addition-type polyester resin (D2) having a nonvolatile content of 50.2% by weight and a viscosity of 20,500 mPa · s. A solution was obtained. Resin (D2) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 22.6 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 185,000.

[Two-step synthesis of addition-type polyester resin (D2)]
In the following synthesis example 116, the formation reaction of the main chain part (I) and the addition of the sealing compound (c) proceed in parallel, and then the side chain formation by the ring-opening addition of the cyclic ester proceeds. A method for producing the addition-type polyester resin (D2) will be described.

(Synthesis Example 116)
<Step (15): Preparation of polyester resin (C2) to which sealing compound (c) has been added>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube are attached to a polymerization tank is prepared. A low molecular weight dicarboxylic acid (a-1-1), a polyol (a -1-α), a compound having two cyclic ether groups in the molecule (a-2), a sealing compound (c), a catalyst and an organic solvent were respectively charged in the following ratios.

[Polymerization tank]
Kuraray polyol P4010 (a-1-α) 2078 parts
50 parts of succinic anhydride (a-1-1)
173 parts of ethyl acetate
345 parts of toluene
Tetrabutylammonium tetrahydroborate (catalyst) 1 part [Drip device]
192 parts of bisphenol A diglycidyl ether (a-2)
95 parts of phenyl isocyanate (c3)
Tetrabutylammonium tetrahydroborate (catalyst) 1 part
173 parts of ethyl acetate
345 parts of toluene

After replacing the air in the polymerization tank with nitrogen gas, the contents are heated to 100 ° C. while stirring and reacted for 8 hours to form the dibasic acid (a-1) for forming the main chain (I). A high molecular weight dicarboxylic acid (a-1-3) was obtained.
Next, the mixture of the bicyclic ether compound (a-2) and the sealing compound (c) was dropped from the dropping device at a constant rate over 1 hour. After completion of the addition, the catalyst was added twice in 0.5 parts each every 8 hours with further stirring. After 24 hours of reaction and aging, 1379 parts of ethyl acetate was added and cooled to room temperature to complete the reaction. A polyester resin (C2) solution to which the sealing compound (c) was added was obtained.

<Step (16): Ring-Opening Addition Reaction of Cyclic Ester (b)>
500 parts of the polyester resin (C2) solution (non-volatile content: 50.2% by weight) was placed in a polymerization tank. Under the same conditions as in the second stage of Synthesis Example 114, a mixture of (b-1) ε-caprolactone: 24 parts, tetrabutylammonium tetrahydroborate (catalyst): 0.5 part, and ethyl acetate 10 parts. The reaction was dropped from the dropping tank to the polymerization tank, 14 parts of ethyl acetate was added, and the mixture was cooled to room temperature. It was a pale yellow transparent addition-type polyester resin (D2 having a non-volatile content of 49.7 wt% and a viscosity of 15,000 mPa · s). ) Was obtained. The resin (D2) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 7.5 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 130,000.

[Pseudo two-step synthesis of addition-type polyester resin (D2)]
In the following synthesis examples 117 to 137, a polyester for the main chain (I ′) having an acid value of 5 (mg KOH / g) or less is obtained, and then the formation of the main chain (I) and the sealing reaction proceed simultaneously. A method for obtaining an addition type polyester resin (D2) by a pseudo two-stage process for adding side chains will be described.

(Synthesis Example 117)
Instead of the bicyclic ether compound (a-2) used in Synthesis Example 114, 2778 parts of bisphenoxyethanol fluorenediglycidyl ether were used, and the amount of the solvent charged into the reaction vessel and the dropping device was 321 parts of ethyl acetate, toluene. The reaction was the same as in Steps (12) and (13) of Synthesis Example 114 except that the amount was changed to 642 parts, and 2575 parts of ethyl acetate was added to obtain a polyester resin (C2) solution to which the sealing compound (c3) was added. It was.
Subsequently, Synthesis Example 114 was used except that 500 parts of the obtained resin (C2) solution (nonvolatile content: 50.1% by weight) was used and the amount of ε-caprolactone as the cyclic ester compound (b) was changed to 13 parts. The reaction was carried out in the same manner as in step (14) to obtain a solution of an addition type polyester resin (D2) having a pale yellow transparent, non-volatile content of 50.2 wt% and a viscosity of 21,000 mPa · s. Resin (D2) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 8.2 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 190,000.

(Synthesis Example 118)
Instead of the bicyclic ether compound (a-2) used in Synthesis Example 114, 685 parts of 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene and resorcinol diglycidyl ether 702 The reaction was conducted in the same manner as in Steps (12) and (13) of Synthesis Example 114 except that the amount of the solvent charged into the reaction vessel and the dropping device was changed to 222 parts of ethyl acetate and 444 parts of toluene, respectively. 1777 parts were added to obtain a polyester resin (C2) solution to which the sealing compound (c3) was added.
Next, a synthesis example except that 500 parts of the obtained resin (C2) solution (non-volatile content: 49.8% by weight) was used and that the amount of ε-caprolactone as the cyclic ester compound (c) was changed to 19 parts. The reaction was conducted in the same manner as in step (14) of 114, and 9 parts of ethyl acetate was added and cooled to room temperature. Solution was obtained. Resin (D2) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 9.3 mg KOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 100,000.

(Synthesis Example 119)
In place of the bicyclic ether compound (a-2) used in Synthesis Example 114, 6060 parts of bisphenol A-based high molecular weight glycidyl resin “JER1002” (manufactured by Japan Epoxy Resin Co., Ltd.) was used, and the solvent charged into the reaction vessel and the dropping device, respectively. The reaction was conducted in the same manner as in Steps (12) and (13) of Synthesis Example 114, except that 556 parts of ethyl acetate and 1112 parts of toluene were changed, and 4446 parts of ethyl acetate was added to the sealing compound (c3). An added polyester resin (C2) solution was obtained.
Next, Synthesis Example 114 except that 500 parts of the obtained resin (C2) solution (nonvolatile content: 50.2% by weight) was used and the amount of ε-caprolactone as the cyclic ester compound (b) was changed to 40 parts. The reaction was carried out in the same manner as in the second stage reaction step (14), 30 parts of ethyl acetate was added and cooled to room temperature, light yellow and transparent, non-volatile content 50.2% by weight, viscosity 25,000 mPa · s addition type polyester A solution of resin (D2) was obtained. Resin (D2) had an acid value of 0.5 mgKOH / g, a hydroxyl value of 12.1 mgKOH / g, a glass transition temperature of −5 ° C., and a weight average molecular weight of 195,000.

(Synthesis Example 120)
Instead of the compound (a-2) having two cyclic ether groups in the molecule used in Synthesis Example 114, 526 parts of neopentyl glycol diglycidyl ether was used, and the amount of the solvent charged respectively into the reaction vessel and the dropping device was changed. The reaction was carried out in the same manner as in Steps (12) and (13) of Synthesis Example 114 except that 106 parts of ethyl acetate and 212 parts of toluene were used, and 1042 parts of ethyl acetate was added to add the sealing compound (c3). A resin (C2) solution was obtained.
Next, Synthesis Example 114 except that 500 parts of the obtained resin (C2) solution (nonvolatile content: 50.2% by weight) was used, and the amount of ε-caprolactone as the cyclic ester (b) was changed to 39 parts. The reaction was conducted in the same manner as in step (14), and 29 parts of ethyl acetate was added, and the mixture was cooled to room temperature. It was a pale yellow transparent, non-volatile content of 50.2% by weight, and a viscosity of 12,500 mPa · s A solution was obtained. Resin (D2) had an acid value of 0.2 mgKOH / g, a hydroxyl value of 10.4 mgKOH / g, a glass transition temperature of −25 ° C., and a weight average molecular weight of 120,000.

(Synthesis Example 121)
In place of the bicyclic ether compound (a-2) used in Synthesis Example 114, 960 parts of bis- (3,4-epoxycyclohexyl) adipate was used, and the amount of the solvent charged into the reaction vessel and the dropping device was adjusted to ethyl acetate. Except for changing to 192 parts and 384 parts of toluene, the reaction was carried out in the same manner as in Steps (12) and (13) of Synthesis Example 114, 1530 parts of ethyl acetate was added, and the polyester resin (C2) solution to which compound (c3) was added Got.
Next, Synthesis Example 114 except that 500 parts of the obtained resin (C2) solution (nonvolatile content: 50.2 wt%) was used and the amount of ε-caprolactone as the cyclic ester compound (c) was changed to 22 parts. The reaction was conducted in the same manner as in step (14), and 12 parts of ethyl acetate was added and cooled to room temperature. A solution was obtained. Resin (D2) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 9.5 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 175,000.

(Synthesis Example 122)
In place of the bicyclic ether compound (a-2) used in Synthesis Example 114, 1505 parts of biphenyl-4,4′-diglycidyl ether was used, and the amount of the solvent charged into the reaction vessel and the dropping device was adjusted to ethyl acetate 230. The polyester resin (C2) added with a sealing compound (c3) was reacted in the same manner as in Steps (12) and (13) of Synthesis Example 114 except that 1 part of toluene and 460 parts of toluene were changed. A solution was obtained.
Subsequently, using the obtained resin (C2) solution (nonvolatile content: 50.1% by weight) 500 parts, and changing the amount of the cyclic ester (b) ε-caprolactone to 18 parts, the process of Synthesis Example 114 Reaction was carried out in the same manner as in (14), and 8 parts of ethyl acetate was added and cooled to room temperature. Obtained. Resin (D2) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 11.2 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 145,000.

(Synthesis Example 123)
Instead of the sealing compound (c3) used in Synthesis Example 114, 1578 parts of p-toluenesulfonyl isocyanate was used, and the amounts of the solvents charged in the reaction vessel and the dropping device were changed to 305 parts of ethyl acetate and 610 parts of toluene, respectively. The reaction was performed in the same manner as in Steps (12) and (13) of Synthesis Example 114, and 2435 parts of ethyl acetate was added to obtain a polyester resin (C2) solution to which a sealing compound (c3) was added.
Next, 500 parts of the obtained resin (C2) solution (nonvolatile content: 50.0% by weight) was used, and the amount of ε-caprolactone as the cyclic ester (b) was changed to 14 parts. Reaction was performed in the same manner as in step (14), and 4 parts of ethyl acetate was added and cooled to room temperature. Got. Resin (D2) had an acid value of 80.5 mgKOH / g, a hydroxyl value of 13.9 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 195,000.

(Synthesis Example 124)
Instead of the compound (c3) used in Synthesis Example 114, 864 parts of trimethylchlorosilane was used as the silylating agent (c1), and the amounts of the solvents charged in the reaction vessel and the dropping device were respectively 254 parts of ethyl acetate and 508 parts of toluene. Except for the change, the reaction was performed in the same manner as in Steps (12) and (13) of Synthesis Example 114, and 2029 parts of ethyl acetate was added to obtain a polyester resin (C2) solution to which compound (c1) was added.
Next, Synthesis Example 114 except that 500 parts of the obtained resin (C2) solution (nonvolatile content: 49.7% by weight) was used and the amount of ε-caprolactone as the cyclic ester compound (b) was changed to 17 parts. The reaction was conducted in the same manner as in step (14), and 7 parts of ethyl acetate was added and cooled to room temperature. A solution was obtained. Resin (D2) had an acid value of 1.5 mgKOH / g, a hydroxyl value of 10.2 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 165,000.

(Synthesis Example 125)
Instead of the compound (c3) used in Synthesis Example 114, 1056 parts of triethylsilanol was used as the silylating agent (c1), and the amount of the solvent charged into the reaction vessel and the dropping device was adjusted to 268 parts of ethyl acetate and 535 parts of toluene. Except for the change, the reaction was performed in the same manner as in Steps (12) and (13) of Synthesis Example 114, and 2029 parts of ethyl acetate was added to obtain a polyester resin (C2) solution to which the sealing compound (c1) was added.
Subsequently, the reaction was conducted in the same manner as in the step (14) of Synthesis Example 114 except that 500 parts of the obtained resin (C2) solution (nonvolatile content: 49.8% by weight) was used. A solution of addition-type polyester resin (D2) having a weight percentage of 14,000 mPa · s was obtained. Resin (D2) had an acid value of 0.8 mgKOH / g, a hydroxyl value of 12.6 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 130,000.

(Synthesis Example 126)
Instead of the compound (c3) used in Synthesis Example 114, 725 parts of hexamethyldisilazane was used as the silylating agent (c1), and the amount of the solvent charged into the reaction vessel and the dropping device was 244 parts of ethyl acetate and toluene 488, respectively. The reaction was conducted in the same manner as in Steps (12) and (13) of Synthesis Example 114, except that 1950 parts of ethyl acetate was added to obtain a polyester resin (C2) solution to which compound (c1) was added.
Subsequently, 500 parts of the obtained resin (C2) solution (nonvolatile content: 49.6% by weight) was used, and the amount of ε-caprolactone as the cyclic ester (b) was changed to 15 parts. Reaction was carried out in the same manner as in step (14), 5 parts of ethyl acetate was added, and the mixture was cooled to room temperature. Got. Resin (D2) had an acid value of 1.1 mg KOH / g, a hydroxyl value of 10.3 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 110,000.

(Synthesis Example 127)
Instead of the compound (c3) used in Synthesis Example 114, 862 parts of methoxytrimethylsilane was used as the silylating agent (c1), and the amount of the solvent charged into the reaction vessel and the dropping device was 233 parts of ethyl acetate and 466 parts of toluene, respectively. The reaction was conducted in the same manner as in Steps (12) and (13) of Synthesis Example 114 except that 1867 parts of ethyl acetate was added to obtain a polyester resin (C2) solution to which the sealing compound (c3) was added.
Next, 500 parts of the obtained resin (C2) solution (nonvolatile content: 49.8% by weight) was used, and the amount of ε-caprolactone as the cyclic ester (b) was changed to 14 parts. Reaction was performed in the same manner as in step (14), and 4 parts of ethyl acetate was added and cooled to room temperature. A solution of addition-type polyester resin (D2) having a pale yellow transparent, non-volatile content of 49.7% by weight and a viscosity of 12,500 mPa · s. Got. Resin (D2) had an acid value of 0.5 mg KOH / g, a hydroxyl value of 8.5 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 120,000.

(Synthesis Example 128)
Instead of the sealing compound (c3) used in Synthesis Example 114, 1184 parts of phthalic anhydride was used as the acid anhydride (c2), and the amount of the solvent charged into the reaction vessel and the dropping apparatus was 276 parts of ethyl acetate, toluene The reaction was conducted in the same manner as in Steps (12) and (13) of Synthesis Example 114 except that the amount was changed to 554 parts, and 2213 parts of ethyl acetate was added to obtain a polyester resin (C2) solution to which compound (c2) was added.
Next, 500 parts of the obtained resin (C2) solution (nonvolatile content: 50.2% by weight) was used, and the amount of ε-caprolactone as the cyclic ester (b) was changed to 15 parts. Reaction was carried out in the same manner as in step (14), and 5 parts of ethyl acetate was added and cooled to room temperature. A solution of addition-type polyester resin (D2) having a pale yellow transparent, non-volatile content of 49.7% by weight and a viscosity of 16,000 mPa · s. Got. Resin (D2) had an acid value of 85.5 mgKOH / g, a hydroxyl value of 7.3 mgKOH / g, a glass transition temperature of −5 ° C., and a weight average molecular weight of 145,000.

(Synthesis Example 129)
Instead of the sealing compound (c3) used in Synthesis Example 114, 148 parts of phthalic anhydride, which is an acid anhydride (c2), was used, and the amount of the solvent charged into the reaction vessel and the dropping device was 202 parts of ethyl acetate, The reaction was conducted in the same manner as in Steps (12) and (13) of Synthesis Example 114 except that the content was changed to 404 parts of toluene. Obtained.
Next, Synthesis Example 114 except that 500 parts of the obtained resin (C2) solution (nonvolatile content: 50.2% by weight) was used and the amount of ε-caprolactone as the cyclic ester compound (b) was changed to 50 parts. The reaction was conducted in the same manner as in step (14), and 40 parts of ethyl acetate was added and cooled to room temperature. The reaction mixture was cooled to room temperature. A solution was obtained. Resin (D2) had an acid value of 12.5 mgKOH / g, a hydroxyl value of 62.3 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 140,000.

(Synthesis Example 130)
Instead of the sealing compound (c3) used in Synthesis Example 114, 100 parts of succinic anhydride, which is an acid anhydride (c2), was used, and the amount of the solvent charged in each of the reaction vessel and the dropping device was 139 parts of ethyl acetate, Except for changing to 278 parts of toluene, the reaction was conducted in the same manner as in Steps (12) and (13) of Synthesis Example 114, 2233 parts of ethyl acetate was added, and the polyester resin (C2) solution to which the sealing compound (c2) was added was added. Obtained.
Next, 500 parts of the obtained resin (C2) solution (nonvolatile content: 50.0% by weight) was used, and the amount of ε-caprolactone as the cyclic ester (b) was changed to 49 parts. Reaction was performed in the same manner as in step (14), and 39 parts of ethyl acetate was added and cooled to room temperature. A solution of addition-type polyester resin (D2) having a pale yellow transparent, non-volatile content of 50.1% by weight and a viscosity of 12,500 mPa · s. Got. Resin (D2) had an acid value of 13.8 mgKOH / g, a hydroxyl value of 68.7 mgKOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 130,000.

(Synthesis Example 131)
Instead of the sealing compound (c3) used in Synthesis Example 114, 164 parts of anhydrous hymic acid which is an acid anhydride (c2) was used, and the amount of the solvent respectively charged in the reaction vessel and the dropping device was 204 parts of ethyl acetate, Except for changing to 408 parts of toluene, the reaction was conducted in the same manner as in Steps (12) and (13) of Synthesis Example 114, and 1635 parts of ethyl acetate was added, and the polyester resin (C2) solution added with the sealing compound (c2) Obtained.
Next, 500 parts of the obtained resin (C2) solution (nonvolatile content: 49.7% by weight) was used, and the amount of ε-caprolactone as the cyclic ester (b) was changed to 50 parts. Reaction was carried out in the same manner as in step (14), and 40 parts of ethyl acetate was added and cooled to room temperature. Got. Resin (D2) had an acid value of 10.8 mgKOH / g, a hydroxyl value of 58.5 mgKOH / g, a glass transition temperature of −20 ° C., and a weight average molecular weight of 130,000.

(Synthesis Example 132)
Prepared in the same manner as in Synthesis Example 114 except that 14 parts of δ-valerolactone was used in place of the cyclic ester (b) used in Step (14) of Synthesis Example 114, and 4 parts of ethyl acetate was added and cooled to room temperature. As a result, a light yellow transparent solution of addition type polyester resin (D2) having a nonvolatile content of 50.0% by weight and a viscosity of 20,000 mPa · s was obtained. Resin (D2) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 18.5 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 190,000.

(Synthesis Example 133)
The reaction was the same as in Synthesis Example 114 except that the cyclic ester (b) used in Step (14) of Synthesis Example 114 was changed to 12 parts of γ-butyrolactone, and 2 parts of ethyl acetate was added and cooled to room temperature. A solution of addition-type polyester resin (D2) having a transparent yellow color and a non-volatile content of 50.2% by weight and a viscosity of 21,000 mPa · s was obtained. Resin (D2) had an acid value of 0.3 mg KOH / g, a hydroxyl value of 19.2 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 205,000.

(Synthesis Example 134)
The reaction was conducted in the same manner as in Synthesis Example 114 except that the catalyst used in Synthesis Example 114 was changed to tetrabutylammonium hydrogen sulfate. The reaction was light yellow and transparent with a nonvolatile content of 49.7 wt% and a viscosity of 17,000 mPa · s. A solution of addition-type polyester resin (D2) was obtained. Resin (D2) had an acid value of 0.2 mgKOH / g, a hydroxyl value of 15.5 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 155,000.

(Synthesis Example 135)
The reaction was conducted in the same manner as in Synthesis Example 114 except that the catalyst used in Synthesis Example 114 was changed to tetraethylammonium-p-toluenesulfonate. The reaction was light yellow and transparent with a nonvolatile content of 50.0% by weight and a viscosity of 18,000 mPa · s. A solution of addition-type polyester resin (D2) was obtained. Resin (D2) had an acid value of 0.2 mg KOH / g, a hydroxyl value of 15.8 mg KOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 160,000.

(Synthesis Example 136)
The reaction was conducted in the same manner as in Synthesis Example 114 except that the catalyst used in Synthesis Example 114 was changed to tetrabutylammonium pearlate, and the reaction was pale yellow and transparent, with a nonvolatile content of 50.1 wt% and a viscosity of 15,000 mPa · s. A solution of type polyester resin (D2) was obtained. Resin (D2) had an acid value of 0.2 mgKOH / g, a hydroxyl value of 14.3 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 150,000.

(Synthesis Example 137)
The reaction was conducted in the same manner as in Synthesis Example 114 except that the catalyst was not used, and a solution of an addition type polyester resin (D2) having a pale yellow transparent, non-volatile content of 49.7% by weight and a viscosity of 14,500 mPa · s was obtained. Resin (D2) had an acid value of 0.1 mgKOH / g, a hydroxyl value of 17.2 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 125,000.

[Third Sealing Mode: Synthesis of Addition Type Polyester Resin (D3)]
In the following Synthesis Examples 138 to 140, a method of obtaining the addition type polyester resin (D3) by reacting the hydroxyl group in the addition type polyester resin (D2) obtained in the synthesis example 114 with the sealing compound (c) will be described.

(Synthesis Example 138)
A polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was prepared, and a 16.8 mg KOH / g hydroxyl group-added polyester resin prepared in Synthesis Example 114 was prepared in the polymerization tank. (D2) The solution, the sealing compound (c2) and the catalyst were respectively charged in the following ratios.

[Polymerization tank]
Addition-type polyester resin (D2) solution obtained in Synthesis Example 114 500 parts Phthalic anhydride (c2) 3 parts Tetrabutylammonium tetrahydroborate (catalyst) 0.1 part

  After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 90 ° C. while stirring the solution. Furthermore, after 6 hours of reaction and aging with stirring, 2 parts of ethyl acetate was added and cooled to room temperature to complete the reaction. The reaction was light yellow and transparent, with a nonvolatile content of 50.1% by weight and a viscosity of 19,500 mPa · s. A solution of type polyester resin (D3) was obtained. Resin (D3) had an acid value of 4.5 mgKOH / g, a hydroxyl value of 12.1 mgKOH / g, a glass transition temperature of −10 ° C., and a weight average molecular weight of 180,000.

(Synthesis Example 139)
The reaction was the same as in Synthesis Example 138 except that the sealing compound (c2) used in Synthesis Example 138 was changed to 4 parts of stearyl isocyanate (c3), and 4 parts of ethyl acetate was added and cooled to room temperature. A transparent solution of an addition type polyester resin (D3) having a nonvolatile content of 50.0% by weight and a viscosity of 17,500 mPa · s was obtained. Resin (D3) had an acid value of 0.1 mg KOH / g, a hydroxyl value of 8.5 mg KOH / g, a glass transition temperature of −15 ° C., and a weight average molecular weight of 160,000.

(Synthesis Example 140)
The reaction was performed in the same manner as in Synthesis Example 138 except that the sealing compound (c2) used in Synthesis Example 138 was changed to 3 parts of dimethyloctylchlorosilane (c1), and 3 parts of ethyl acetate was added and cooled to room temperature. A solution of addition-type polyester resin (D3) having a transparent yellow color, a non-volatile content of 49.8% by weight, and a viscosity of 17,000 mPa · s was obtained. Resin (D3) had an acid value of 0.1 mgKOH / g, a hydroxyl value of 9.3 mgKOH / g, a glass transition temperature of −15 ° C., and a weight average molecular weight of 165,000.

  For each resin solution obtained from Synthesis Examples 107 to 140, the appearance of the solution, nonvolatile content, resin weight average molecular weight (Mw), glass transition temperature (Tg), acid value (AV) and hydroxyl value (OHV) were synthesized. The results evaluated in the same manner as in Examples 1 to 20 are summarized in Tables 14 and 15.

(Comparative Example 37)
Polyester resin (B) solution for main chain obtained in step (9) of Synthesis Example 107: 25 parts of toluene is added to 100 parts by weight, and TDI / TMP (tolylene diisocyanate) is used as a crosslinking agent (E). Of trimethylolpropane adduct) was added and stirred well to obtain an adhesive composition. This was applied onto a release film to obtain an adhesive sheet, but could not be applied because the viscosity of the adhesive composition increased rapidly.

(Comparative Example 38)
An adhesive composition was obtained in the same manner as in Comparative Example 19 except that the addition type polyester resin (C2) solution obtained in the step (10) of Synthesis Example 107 was used. This was coated on a release film and dried. After drying, an attempt was made to bond one side of a polarizing film having a multilayer structure of TAC / PVA / TAC to the adhesive layer. However, since the adhesive layer did not show tack (initial adhesiveness), it could not be attached.

(Example 122)
25 parts of toluene was added to 100 parts by weight of the solution of the addition-type polyester resin (D2) obtained in the step (11) of Synthesis Example 107, and TDI / TMP (tolylene diisocyanate) was added as a crosslinking agent (E). Trimethylolpropane adduct body) 2.5 parts by weight was added and stirred well to obtain an adhesive composition of the present invention. This was coated on the release film so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form an adhesive layer.
Further, in the same manner as in Examples 1 to 19 and the like, a laminate having a configuration of “peeling film / adhesive layer / TAC film / PVA / TAC film” was obtained, and the reaction of the adhesive layer was allowed to proceed to perform adhesion processing. A polarizing plate (laminate) was obtained.

(Comparative Example 39)
Adhesion processing was carried out in the same manner as in Example 121 except that the resin solution obtained in Synthesis Example 108 was used instead of the addition type polyester resin (D2) solution obtained in Step (11) of Synthesis Example 107. An attempt was made to produce a polarizing plate. However, since the viscosity of the adhesive composition suddenly increased, it could not be applied to the release film.

(Examples 123-127)
Implemented except that the addition type polyester resin (D2) solutions obtained in Synthesis Examples 109 to 113 were used in place of the addition type polyester resin (D2) solution obtained in the step (11) of Synthesis Example 107, respectively. In the same manner as in Example 122, a bonded polarizing plate was produced.

(Comparative Example 40)
An adhesive composition was prepared in the same manner as in Example 121 except that the addition type polyester resin (C2) solution obtained in Step (13) of Synthesis Example 114 was used. Although the viscosity of the product rapidly increased and could be applied, streaks and repellency occurred on the coated surface, and the adhesive layer did not exhibit tack (initial adhesiveness). It could not be produced.

(Example 128)
To 100 parts by weight of the solution of the addition type polyester resin (D2) obtained in the step (14) of Synthesis Example 114, 25 parts of toluene was added, and TDI / TMP (tolylene diisocyanate trisene was added as a crosslinking agent (E). Methylolpropane adduct body) 2.5 parts by weight was added and stirred well to obtain the adhesive composition of the present invention. Using this, a bonded polarizing plate was produced in the same manner as in Example 122.

(Example 129)
Example 128 and Example 128 except that the addition-type polyester resin (D2) solution obtained in Synthesis Example 115 was used instead of the addition-type polyester resin (D2) solution obtained in Step (14) of Synthesis Example 114, respectively. Similarly, a bonded polarizing plate was produced.

(Example 130)
Example 128 and Example 128 except that the addition-type polyester resin (D2) solution obtained in Synthesis Example 116 was used instead of the addition-type polyester resin (D2) solution obtained in Step (14) of Synthesis Example 114, respectively. Similarly, a bonded polarizing plate was produced.

(Examples 131-148)
The addition type polyester resin (D3) solutions obtained in Synthesis Examples 117 to 128 and 132 to 137 were used in place of the addition type polyester resin (D2) solution obtained in the step (14) of Synthesis Example 114, respectively. A bonded polarizing plate was produced in the same manner as in Example 128 except that.

(Comparative Examples 41-43)
Example except that the addition type polyester resin (D2) solution obtained in Synthesis Examples 129 to 131 was used in place of the addition type polyester resin (D2) solution obtained in the step (14) of Synthesis Example 114. In the same manner as in 127, an adhesive processed polarizing plate was prepared. However, since the viscosity of the adhesive composition suddenly increased, it could not be applied to the release film.

(Examples 149 and 150)
Instead of TDI / TMP used as the crosslinking agent (E) in Example 114, in Example 149, 2.5 parts of XDI / TMP (trimethylolpropane adduct of xylylene diisocyanate) were used. , HMDI / burette (hexamethylene diisocyanate burette adduct) 2.5 parts were used in the same manner as in Example 128, except that 2.5 parts of each was used. Using these, in the same manner as in Example 128, a bonded polarizing plate was produced.

(Examples 151 to 153)
Implementation was carried out except that the addition type polyester resin (D3) solution obtained in Synthesis Examples 138 to 140 was used instead of the addition type polyester resin (D2) solution obtained in Step (14) of Synthesis Example 114. In the same manner as in Example 150, a bonded polarizing plate was produced.

(Comparative Examples 44 and 45) (Examples 154 to 156)
25 parts of toluene was added to 100 parts by weight of each of the addition-type polyester resin (D2) solutions obtained in Synthesis Examples 123 and 128 to 131, and HBAP (2,2′-bishydroxymethyl) was used as a crosslinking agent (E). 0.25 parts by weight of butanol tris [3- (1-aziridinyl) propionate]) was added and stirred well to obtain the adhesive composition of the present invention. However, in the case of Comparative Examples 44 and 45, the viscosity of the adhesive composition increased rapidly, and thus could not be applied to the release film. About Examples 154-156, it carried out similarly to Example 128, and produced the polarizing plate which carried out the adhesion process.

(Comparative Examples 46 and 47) (Examples 157 to 159)
25 parts of toluene was added to 100 parts by weight of each of the addition-type polyester resins (D2) obtained in Synthesis Examples 123 and 128 to 131, and TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) 0.25 part by weight was added and stirred well to obtain the adhesive composition of the present invention. However, in the case of Comparative Examples 46 and 47, the viscosity of the adhesive composition increased rapidly, and thus could not be applied to the release film. About Examples 156-158, it carried out similarly to Example 122, and produced the polarizing plate which carried out the adhesion process.

(Comparative Examples 48 and 49) (Examples 160 to 162)
25 parts of toluene was added to 100 parts by weight of the solution of each of the addition type polyester resins (D2) obtained in Synthesis Examples 123 and 128 to 131, and “carbodilite V-05 which is a carbodiimide compound as a crosslinking agent (E). ”(Nisshinbo Industries, Ltd.) 0.25 part by weight was added and stirred well to obtain the adhesive composition of the present invention. However, in the case of Comparative Examples 48 and 49, the viscosity of the adhesive composition increased rapidly, and thus could not be applied to the release film. About Examples 159-161, it carried out similarly to Example 122 using this, and produced the polarizing plate which carried out the adhesive process.

(Comparative Examples 50 and 51) (Examples 163 to 165)
25 parts of isopropyl alcohol (IPA) is added to 100 parts by weight of the solution of each addition type polyester resin (D2) obtained in Synthesis Examples 123 and 128 to 131, and AlAA (aluminum tris ( Acetylacetonate))) 0.25 parts by weight was added and stirred well to obtain the adhesive composition of the present invention. However, in Comparative Examples 50 and 51, the viscosity of the adhesive composition increased rapidly, and thus could not be applied to the release film. About Examples 162-163, it carried out similarly to Example 122 using this, and produced the polarizing plate which carried out the adhesive process.

The pot life and coating processability of the adhesive compositions obtained in Examples and Comparative Examples were evaluated in the same manner as in Examples 1 to 19 and the like. The results are shown in Tables 16 and 17.
Moreover, about the polarizing plate (laminated body) which carried out the adhesion process obtained by the Example and the comparative example, the refractive index of a coating film, heat resistance, heat-and-moisture resistance, an optical characteristic, and removability are the case of Examples 1-19 etc. And evaluated in the same manner. The results are shown in Table 17.

(Synthesis Example 141)
<Synthesis of polyester polyol>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube were attached to the polymerization tank was prepared, and dicarboxylic acid, diol, and catalyst were charged into the polymerization tank at the following ratios, respectively.

[Polymerization tank]
Terephthalic acid 392.8 parts Isophthalic acid 392.8 parts Ethylene glycol 210 parts Neopentyl glycol 236.6 parts Dibutyltin oxide 0.5 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature of the mixture was increased to 180 ° C. while stirring, and the temperature was gradually increased to 260 ° C. over 4 hours while dehydrating to perform ester reaction. In order to promote the reaction, 30 parts of xylene was added dropwise, and the reaction was continued at 230 ° C. for 6 hours. Next, the reaction was terminated by cooling to 50 ° C. or lower, and ethyl acetate was added so that the non-volatile content was 50% to obtain a solution of polyester polyol (a-1-α).
This polyester polyol was a light yellow transparent resin having an acid value of 22 mgKOH / g, a hydroxyl value of 2.5 mgKOH / g, a glass transition temperature of 40 ° C., and a number average molecular weight (Mn) of 5,000.

<Step (1): Formation of polyester main chain>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introduction tube are attached to the polymerization tank is prepared, and the polymerization tank has the polyester polyol (a-1-α) and two cyclic ether groups. The compound (a-2) and the catalyst were respectively charged in the following ratio.

[Polymerization tank]
200 parts of the above polyester polyol (a-1-α) bisphenol A diglycidyl ether type epoxy resin (a-2)
“JER 828 (epoxy equivalent: 184-194 g / eq,
3.7 parts bisphenol A diglycidyl ether high molecular weight glycidyl resin (a-2)
"JER 1001 (epoxy equivalent: 450-500 g / eq,
9.4 parts 2-methylimidazole (catalyst) 0.06 parts

After replacing the air in the polymerization tank with nitrogen gas, the contents were heated to 135 ° C. while stirring the contents and reacted for 15 hours. Next, ethyl acetate was added to adjust the nonvolatile content to 40%, and the reaction was terminated by cooling to room temperature to obtain a solution of the polyester resin for main chain (B).
This solution is light yellow and transparent and has a non-volatile content of 40.1% by weight and a viscosity of 3,000 mPa · s. The resin contained in the solution has an acid value of 3.8 mg KOH / g, a hydroxyl value of 50.5 mg KOH / g, and a glass transition. The temperature was 60 ° C. and the weight average molecular weight was 30,000.

<Synthesis of addition type polyester precursor (C1) to which cyclic ester (b) is added>
100 parts of the main chain polyester resin (B) solution obtained above (non-volatile content: 40.1% by weight) was charged into a polymerization tank, and 1.9 parts of ε-caprolactone as a cyclic ester (b) was used as a catalyst. Zinc acetylacetone: 0.02 part was added, and the reaction was carried out at 80 ° C. for 1 hour and further at 130 ° C. for 8 hours, and the non-volatile content was reduced using a mixed solvent of toluene / ethyl acetate = 85/15 (weight ratio). The concentration was adjusted to 40% to obtain an addition type polyester precursor (C) solution. This solution had a viscosity of 3,500 mPa · s, and the resin contained in the solution had an acid value of 3.5 mgKOH / g, a hydroxyl value of 48.2 mgKOH / g, a glass transition temperature of 50 ° C., and a weight average molecular weight of 35,000. It was.

(Synthesis Example 142)
The process of Synthesis Example 72 (except that the amount of the cyclic ester compound (b) used in Step (7) of Synthesis Example 72 was changed to 5 parts and that the amount of ethyl acetate charged in the dropping device was changed to 90 parts) The reaction was conducted in the same manner as in 7), and 260 parts of ethyl acetate was added to obtain a polyester resin (C1) solution to which a cyclic ester compound was added. In the above formulation, the cyclic ester (b) is in a ratio of about 0.2 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
Next, the process of Synthesis Example 72 except that 500 parts of the obtained resin (C1) solution (nonvolatile content 50.1% by weight) was used and the amount of phenyl isocyanate as the sealing compound (c) was changed to 6 parts. Reaction was performed in the same manner as in (8), and 1 part of ethyl acetate was added to obtain a solution of an addition type polyester resin (D1) having a pale yellow transparent, non-volatile content of 49.8% by weight and a viscosity of 15,000 mPa · s. The resin (D1) had an acid value of 1.5 mgKOH / g, a hydroxyl value of 48.5 mgKOH / g, a glass transition temperature of −5 ° C., and a weight average molecular weight of 130,000.

(Comparative Examples 52 and 53)
25 parts of toluene was added to 100 parts by weight of each of the addition-type polyester resin solutions obtained in Synthesis Examples 141 and 142, and TDI / TMP (trimethylolpropane adduct of tolylene diisocyanate) was used as a crosslinking agent (E). ) 2.5 parts by weight was added and stirred well to obtain an adhesive composition. This was coated on the release film so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form an adhesive layer.
Further, in the same manner as in Examples 1 to 19 and the like, a laminate having a configuration of “peeling film / adhesive layer / TAC film / PVA / TAC film” was obtained, and the reaction of the adhesive layer was allowed to proceed to perform adhesion processing. A polarizing plate (laminate) was obtained and evaluated in the same manner. The results are shown in Tables 18 and 19.

As described above, the adhesive composition of the present invention is easy to adjust coating processability, heat resistance, moist heat resistance, optical properties, removability and refractive index when used as a pressure sensitive adhesive, and is pressure sensitive. It turns out that the outstanding characteristic can be exhibited as an adhesive agent.
On the other hand, in each comparative example, the pot life as a pressure sensitive adhesive is short, and it may not be able to be applied to a release film or may not be applied even if it can be applied.

The pressure-sensitive adhesive composition of the present invention cannot form an acrylic resin because it can form a polymer having an aromatic ring or an alicyclic ring in the main chain skeleton while maintaining the cohesive force unique to the polyester resin. The adhesive properties can be expressed. Examples thereof include heat resistance, moist heat resistance, optical characteristics, removability, and the like as described above. Especially for optical laminate applications, it is important that there is no light leakage as an optical property. With the recent increase in size of displays, the required performance is increasing, such as controlling the refractive index and preventing charging during rework. It is getting stricter. Therefore, the adhesive composition of the present invention is very promising because it can exhibit characteristics that have been difficult to realize until now.
The adhesive composition of the present invention is suitable for use as an optical member, as well as general labels and seals, paints, elastic wall materials, waterproof coating materials, flooring materials, tackifiers, adhesives, and laminated structures. Adhesives, sealing agents, molding materials, surface modification coating agents, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.), urethane foam (hard, Semi-rigid, soft), urethane RIM, UV / EB curable resin, high solid paint, thermosetting elastomer, microcellular, textile processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent, artificial marble Resin, impact resistance agent for artificial marble, resin for ink, film (laminate adhesive, protective film, etc.), Laminated glass resin, reactive diluent, various molding materials, elastic fiber, artificial leather, as a raw material for synthetic leather is also very useful as various resin additives and a raw material thereof or the like.

Claims (33)

A polyester resin (D) having a polyester main chain (I) and a plurality of side chains branched from the polyester main chain (I), wherein the plurality of side chains are selected from the group consisting of a hydroxyl group and a carboxyl group The first side chain (II) having a functional group and the second side chain (II ′) not having a hydroxyl group, and the proportion of the plurality of side chains in the molecule of the polyester resin (D) Is a polyester resin (D) that is 5 to 80% in average value by weight ratio,
An adhesive composition containing a crosslinking agent (E) capable of crosslinking the polyester resin (D),
When the crosslinking agent (E) can react with a hydroxyl group, the hydroxyl value of the polyester resin (D) is 50 mgKOH / g or less, and the crosslinking agent (E) can react with a carboxyl group. In some cases, the polyester resin (D) has a hydroxyl value of 100 mgKOH / g or less and an acid value of 50 mgKOH / g or less.   The ring-opening structural unit of cyclic ester (b) is contained in the plurality of side chains, and the second side chain has a structure in which a hydroxyl group is sealed with a sealing compound (c). Adhesive composition.   The adhesive composition according to claim 1 or 2, wherein both the first side chain and the second side chain contain a ring-opening structural unit of the cyclic ester (b).   The adhesive composition according to claim 1 or 2, wherein the first side chain contains a ring-opening structural unit of the cyclic ester (b), and the second side chain does not contain a ring-opening structural unit of the cyclic ester (b). .   The adhesive composition according to claim 3 or 4, wherein the crosslinking agent (E) is capable of reacting with a hydroxyl group.   The first side chain has a structure in which a hydroxyl group is sealed with a sealing compound (c), the functional group of the first side chain is a carboxyl group, and the crosslinking agent (E) is The adhesive composition according to claim 1 or 2, which can react.   The adhesive composition according to any one of claims 1 to 6, wherein the cyclic ester (b) is a compound having 6 to 18 carbon atoms constituting the ester ring.   The adhesive composition according to claim 1, wherein the cyclic ester (b) is a lactone.   The said sealing compound (c) has at least 1 type selected from the group which consists of a silylating agent (c1), an acid anhydride (c2), and an isocyanate compound (c3). Adhesive composition.   The adhesive composition according to claim 9, wherein the silylating agent (c1) includes at least one selected from the group consisting of hydrosilane, alkoxysilane, chlorosilane, silanol, and silylamine.   The adhesive composition according to claim 9, wherein the acid anhydride (c2) includes an anhydride of a dicarboxylic acid (a-1-1) having a molecular weight of 90 to 500.   The adhesive composition according to claim 9, wherein the isocyanate compound (c3) is a monofunctional isocyanate compound.   In the polyester main chain (I), structural units of the dibasic acid (a-1) and the compound (a-2) having two cyclic ether groups are alternately and repeatedly bonded via ester bonds. The adhesive composition according to any one of 12 above.   The dibasic acid (a-1) is a dicarboxylic acid (a-1-1) having a molecular weight of 90 to 500 or a tri- or higher functional polycarboxylic acid (a-1-2) and a polyol (a-1-α). The adhesive composition according to claim 13, which is a dehydration condensate under acid-excess conditions.   The adhesion according to claim 13 or 14, wherein the polyol (a-1-α) contains at least one diol having a number average molecular weight of 500 to 50,000, which is selected from the group consisting of polyester diol, polycarbonate diol, and polyamide diol. Agent composition.   The adhesive composition according to any one of claims 1 to 15, wherein the polyester resin (D) has a glass transition temperature of -80 to 10 ° C.   The adhesive composition according to any one of claims 1 to 16, wherein the polyester resin (D) has a weight average molecular weight of -2000 to 1000000.   The adhesive composition according to claim 5, wherein the crosslinking agent (E) contains a polyisocyanate compound.   The adhesive composition according to claim 6, wherein the cross-linking agent (E) includes at least one selected from the group consisting of an epoxy compound, an aziridine compound, a carbodiimide compound, an oxazoline compound, and a metallate compound.   The laminated body which has an optical member and the layer of the adhesive composition in any one of Claims 1-19 laminated | stacked on the said optical member.   The member for liquid crystal cells in which the layer of the adhesive composition in any one of Claims 1-19 and the glass member for liquid crystal cells was laminated | stacked. The polyester main chain (I) has a first side chain (II) and a second side chain (II ′) branched from the polyester main chain (I), and the first side chain (II) is a hydroxyl group And a functional group selected from the group consisting of carboxyl groups, the second side chain (II ′) is a polyester resin (D) having a structure in which a hydroxyl group is sealed with the sealing compound (c). A preparation process to prepare comprising:
Formation of a polyester main chain having a plurality of hydroxyl groups by ring-opening addition polymerization of a dibasic acid (a-1) and a compound (a-2) having two cyclic ether groups;
A side chain formation reaction by ring-opening addition of the cyclic ester compound (b) to a hydroxyl group of the polyester main chain; and
The manufacturing method of the adhesive composition which has the preparation process which performs the sealing reaction of the hydroxyl group by sealing compound (c).   The method for producing an adhesive composition according to claim 22, wherein the side chain formation reaction is performed before the sealing reaction.   The method for producing an adhesive composition according to claim 23, wherein the side chain formation reaction is started in the middle of the polyester main chain formation reaction.   The method for producing an adhesive composition according to claim 23, wherein the side chain formation reaction is started substantially simultaneously with the formation reaction of the polyester main chain.   The said sealing reaction is a manufacturing method of the adhesive composition of Claim 22 performed before the said side chain formation reaction.   The said sealing reaction is a manufacturing method of the adhesive composition of Claim 26 started in the middle of the formation reaction of the said polyester principal chain.   27. The method for producing an adhesive composition according to claim 26, wherein the sealing reaction is started substantially simultaneously with the formation reaction of the polyester main chain.   The method for producing an adhesive composition according to any one of claims 26 to 28, wherein the sealing reaction is also performed after the side chain formation reaction.   In the preparation step, selected from the group consisting of ammonia, amine, quaternary ammonium salt, quaternary phosphonium salt, alkali metal hydroxide, alkaline earth metal hydroxide, Lewis acid, organometallic compound and metal halide. The method for producing an adhesive composition according to any one of claims 22 to 29, wherein a reaction catalyst is used.   Furthermore, the manufacturing method of the adhesive composition in any one of Claims 22-30 which has the process of mix | blending a crosslinking agent (E) with the said addition type polyester resin (D).   The first side chain (II) is formed by the side chain formation reaction, and the second side chain (II ') is formed from the hydroxyl group or the first side chain (II) by the sealing reaction. The manufacturing method of the adhesive composition in any one of 22-31.   The method for producing an adhesive composition according to any one of claims 22 to 31, wherein the first side chain (II) and the second side chain (II ') are formed by the sealing reaction.