Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

• Adhesive composition method for producing the same, and laminate using adhesive composition TECHNICAL FIELD
• 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, and heat and humidity resistance. And an adhesive composition that is excellent in transparency 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 used in the production of various optical devices and the like It is about.
• FPD flat panel displays
• LCD liquid crystal displays
• PDP plasma displays
• RPJ rear projection displays
• EL displays and light emitting diode displays 1
• LCD liquid crystal displays
• RPJ rear projection displays
• EL displays EL displays
• light emitting diode displays 1 It has come to be used in a wide range of fields as a display device.
• FPDs are used when they are mounted on a vehicle and used in a moving state, such as a car navigation display that can be used when fixed indoors, such as personal computer displays and LCD TVs. To do.
• Such display devices usually have various antireflection films for preventing reflection from an external light source, and protective films (protective films) for preventing scratches on the surface of the display device.
• protective films for preventing scratches on the surface of the display device.
• a liquid crystal cell member constituting an LCD a polarizing film or a retardation film is laminated.
• the FPD may be used as an input device by providing a touch panel function on its surface as well as being used as a display device.
• a touch panel function on its surface as well as being used as a display device.
• protective films, antireflection films, ITO vapor-deposited resin films, etc. are also used.
• Such a film is attached to an adherend with a pressure-sensitive adhesive and used in a display device. Since pressure sensitive adhesives used in display devices are required to have excellent transparency, pressure sensitive adhesives based on acrylic resins are generally used.
• the polarizing film is made of polybulal alcohol. It presents a three-layer structure in which both sides of a polarizer are sandwiched between protective films of triacetylcellulose-based cycloolefin. For this reason, in the polarizing film, due to the characteristics of the material constituting each layer, a significant dimensional change due to expansion and contraction accompanying changes in temperature and humidity occurs.
• 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 around 1.52 for glass, for example.
• the difference in refractive index between the resins is about 1.51 for the methacrylic resin, about 1.54 for the polycarbonate resin, and about 1.60 for the polyethylene terephthalate (PET) resin.
• PET polyethylene terephthalate
• 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.
• the polarizing film undergoes dimensional changes during the long-term use of the liquid crystal panel, and the stress is accumulated in the adhesive layer. If the stress continues to accumulate in the adhesive layer, the distribution of the adhesive force between the polarizing film and the liquid crystal cell glass member becomes non-uniform. During long-term use, stress is concentrated especially on the periphery of the polarizing film. As a result, the periphery 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.
• the polarizing film or the like is peeled off to remove the polarizing film etc. A polarizing film or the like is reapplied.
• the laminated body is generally inspected after being stored at a high temperature for a certain period of time in order to improve adhesion, if the peel strength becomes high during that time and it becomes difficult to peel off the polarizing film or the like. Adhesive residue is generated after peeling due to reduced strength and resilience.
• 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 heat-and-moisture resistance, good stress relaxation properties, Refractive index controllability, removability, etc. are required. Similar performance is required for pressure sensitive adhesives for laminating retardation film and various display power bar films.
• a pressure-sensitive adhesive comprising an acrylic resin mainly composed of an alkyl ester of (meth) atalinoleic acid having 1 to 12 carbon atoms in the alkyl group
• a pressure-sensitive adhesive comprising a talinole-based 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. It has been known.
• the following document 2 describes a high molecular weight (meth) atari having a weight average molecular weight of 1 million or more.
• a polarizing plate consisting of 100 parts by weight of a copolymer and 200 parts by weight of a low molecular weight (meth) atalinole copolymer having a weight average molecular weight of 30,000 or less and 0.005 part by weight of a polyfunctional compound.
• a pressure adhesive is described.
• Proposed pressure-sensitive adhesives for polarizing films comprising low molecular weight acrylic resins having a molecular weight of 30,000 to 100,000 and polyfunctional compounds having functional groups capable of forming a crosslinked structure therewith
• an acrylic ring-containing monomer is used as a copolymerization component, and the copolymerization ratio of the aromatic ring-containing monomer component is 40 90 wt% of the total monomer components.
• a pressure-sensitive adhesive having a controlled refractive index and containing a copolymer as a component is known.
• Reference 5 below describes a pressure-sensitive adhesive in which the refractive index is controlled by adding 4060% by weight of tack-eye resin to 90% by weight of acrylic pressure-sensitive adhesive.
• the acrylic pressure-sensitive adhesive containing an acrylic resin and a crosslinking agent there are pressure-sensitive adhesives in which an acrylic resin and a polyester resin or a polyurethane resin are used in combination.
• a viscoelastic resin having a glass transition temperature (Tg) of ⁇ 60 ⁇ 5 ° C. and an elastic resin such as a polyurethane resin having a glass transition temperature (Tg) of ⁇ 5 ° C. or less are used.
• Tg glass transition temperature
• Tg glass transition temperature
• Tg glass transition temperature
• Tg glass transition temperature
• the following document 8 discloses a pressure-sensitive adhesive containing an acrylic resin and a hydroxyl group-containing polyurethane resin.
• the pressure-sensitive adhesive obtained by mixing a plurality of types of resins compensates for the shortcomings of each resin to improve the adhesion to the adherend and increase the refractive index. It is generally considered that performance can be improved.
• acrylic resin is poorly compatible with polyester resin and polyurethane resin. If a small amount of polyester resin or polyurethane resin is mixed with acrylic resin, transparency will be greatly impaired. No power 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 with poor compatibility as described above. Even if it is attached to glass for liquid crystal cells, there is a problem that phase separation or fluctuation occurs in the adhesive layer.
• the following document 10 comprises a copolymerized polyester resin of dimer acid and a glycol component having an alkyl group in 30 mol% or more side chain, and has a glass transition temperature ( Tg ) of -60 to 0
• Tg glass transition temperature
• the following Document 11 discloses a dicarboxylic acid essentially comprising a diol component essentially comprising a polycarbonate diol and a dicarboxylic acid having a molecular skeleton of an aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms.
• a pressure-sensitive adhesive containing a polyester having a weight average molecular weight of 10,000 or more synthesized from an acid component is described!
• the following Document 12 discloses a pressure-sensitive adhesive characterized by containing a biodegradable polyester having a polylatatatone structure in the main chain and having a weight average molecular weight of 10,000 or more.
• pressure-sensitive adhesives using these polyester resins can improve the disadvantages of acrylic resins, particularly heat resistance or moist heat resistance.
• the functions required for pressure-sensitive adhesives are impaired, for example, the initial adhesiveness (tack) is too low and there is no cohesive force.
• these have insufficient compatibility, when applied to an optical film such as a polarizing film or a phase difference film, phase separation, fluctuation, and protrusion occur in the pressure-sensitive adhesive layer.
• the peel strength after sticking increases excessively as long as it causes a phenomenon such as foam misalignment, and if it is difficult to peel off the polarizing film, etc., the adhesive residue remains after peeling with a force. Arise.
• the polarizing film is not suitable as a pressure-sensitive adhesive for attaching an optical film such as a retardation film.
• polyester-based resin composition for example, there are the following documents 14 to 16; Reference 14 has a structure in which latatones are subjected to ring-opening addition polymerization in the side chain of the linear polyester resin. Modified polyester resin compositions are described.
• Document 15 discloses a method for producing a hydroxyl group-containing polyester resin, characterized by ring-opening addition of latathone to a secondary hydroxyl group of a compound produced by a polyaddition reaction of a diglycidyl compound and a dicarboxylic acid compound. /!
• Document 16 describes a rataton graft copolymer characterized by ring-opening addition polymerization of a latatin monomer to a hydroxyl group produced by reacting a carboxylic acid compound with a glycidyl group in a polymer. The manufacturing method is described!
• Document 18 describes an unsaturated group-containing resin obtained by reacting a reaction product of an epoxy resin with an unsaturated group-containing carboxylic acid or its anhydride with a polybasic carboxylic acid or its anhydride. Has been.
• an adhesive resin composition comprising a polyester resin, a glycidyl resin and a block-free isocyanate having a glass transition temperature (Tg) force in the range of 5 to 80 ° C. Is disclosed.
• a resin composition for an adhesive mainly comprising a resin obtained by reacting a polyester resin having a hydroxyl group and / or a carboxyl group at a molecular end, a glycidyl resin and a diisocyanate compound. It has been known.
• polyester resins have excellent adhesion to a wide range of adherends, and have durability such as chemical resistance. It is used in various fields as an adhesive. However, these generally have a high resin melting temperature and melt viscosity, are difficult to dissolve in low-boiling solvents, and have a short pot life when a crosslinking agent is added. Workability is considerably 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 melted or dissolved in a solvent is applied to the adherend and cooled, wetting of the adherend will occur. There are problems such as poor adhesion. Furthermore, the peel strength after sticking becomes too high and the re-peelability is insufficient, so it is not suitable for a pressure sensitive adhesive.
• Tg glass transition temperature
• tack initial adhesiveness
• Reference 8 Japanese Patent Laid-Open No. 2004-083648
• Reference 10 Japanese Patent Laid-Open No. 04-328186
• Reference 12 Japanese Patent Application Laid-Open No. 11 158452
• Reference 15 Japanese Patent Laid-Open No. 08-165337
• Reference 16 Japanese Patent Laid-Open No. 09-0777855
• Reference 17 Japanese Patent Laid-Open No. 2003-107694
• An object of the present invention is to form an adhesive layer excellent in initial adhesiveness (tack), adhesion to an adherend (that is, a base material), heat resistance, moist heat resistance and transparency, and pressure sensitive adhesion
• An adhesive composition that can be suitably used as an agent, a method for producing the same, and a laminate using the adhesive composition.
• 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 ( ⁇ ) having a functional group selected from the group consisting of a hydroxyl group and a carboxyl group, and has no hydroxyl group!
• a second side chain ( ⁇ ′) The polyester resin (D), wherein the polyester resin (D) has a ratio force S occupied by the plurality of side chains in the molecule of the polyester resin (D), and an average value by weight ratio of 5 to 80%; and the polyester resin
• the hydroxyl value of the tellurium resin (D) is 100 mgKOH / g or less, and the acid value is 50 mgKOH / g or less.
• the laminate includes an optical member and the layer of the adhesive composition laminated on the optical member.
• the liquid crystal cell member can 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.
• a method for producing an adhesive composition comprises a polyester main chain (I) and
• the second side chain ( ⁇ ′) is a preparation step for preparing a polyester resin (D) having a structure in which a hydroxyl group is sealed with the sealing compound (c): dibasic acid (a- Formation reaction of a polyester main chain having a plurality of hydroxyl groups by ring-opening addition polymerization of 1) with a compound having two cyclic ether groups (a-2); a cyclic ester compound to a hydroxyl group of the polyester main chain (b A side chain formation reaction by ring-opening addition; and a hydroxyl group sealing reaction with the sealing compound (c).
• the side chain formation reaction may be performed before the capping reaction, or the capping reaction may be performed before the side chain formation reaction. Is possible.
• the cured resin forms a layer having a shape-retaining force (that is, an appropriate hardness) that does not collapse by pressure, and the resin. It is necessary to have an affinity for the adherend so that the surface of the layer can develop an adhesive force (tack).
• the main chain of the polyester has an affinity for an adherend such as a glass substrate, wettability, and the like due to the polarity of the ester group (particularly the carbonyl bond) compared to the main chain of the acrylic polymer. It can be said that polyester is basically useful as an adhesive material because it has tackiness and the durability and shape retention of the formed resin layer is increased due to the rigidity of the carbonyl bond.
• the non-crosslinked side chain has a function of improving shape retention by acting elastically against the pressure applied to the cured resin layer from the outside. 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, crystallization may occur due to the orientation of the side chains, so molecules with an appropriate interval between the side chains. A structure is preferred.
• Polyesters with side chains that cause moderate constraints 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 bonded to the polyester main chain.
• a functional group for branching for example, a polyester (C) having a secondary hydroxyl group is subjected to, for example, ring-opening addition polymerization of a dicarboxylic acid (a-1) and a bicyclic ether compound (a-2).
• a branched side chain in which a ring-opening structure is bonded to the polyester main chain via an ester bond is prepared by ring-opening addition of a cyclic ester such as acid anhydride or rataton.
• the side chain of the addition-type polyester produced by such a ring-opening addition reaction has a carboxyl group or a hydroxyl group at the terminal, and can react with the crosslinking agent through this functional group.
• the side chain having an ester bond also enhances the shape retention of the cured resin layer by increasing the affinity with the adherend by means of a carbonyl bond that is not limited only by the binding between the polyester molecules, and the adherence to the adherend. The tack of this is also expressed. 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.
• a highly flexible side chain is formed, and when the ring-opening addition is multiplexed, the ester is repeated in the ring-opening structural unit of the cyclic ester.
• Side chains are composed of polyester chains with intervening groups. This is preferable in terms of increasing the affinity of the side chain to the adherend and the affinity between adjacent molecules, and it also facilitates the involvement of the adjacent molecule by the extension of the side chain. In order for the side chain to work effectively, it is preferred that the length is equivalent to a straight-chain hydrocarbon group having about 4 or more carbon atoms, and that a flexible saturated bond is mainly used.
• Ring-opening addition of cyclic esters is a technique for forming branched side chains. Is preferred.
• the adhesive composition is used so that the cured resin layer can suitably exhibit shape retention and tack, which are basic characteristics as a pressure-sensitive adhesive.
• the addition type polyester resin (D) having a side chain branched from the polyester main chain is used as the main component of the curable resin constituting the.
• the side chain branched from the polyester main chain has a ring-opening structural unit of the cyclic ester (b) and is a side chain using a sealing agent (c).
• this side chain content is an average value by weight ratio of 5 to 80%, preferably 7 to 70%, more preferably 10 to 60%, side chains can be contained in a suitable ratio.
• the cured resin exhibits a good function as a pressure-sensitive adhesive that acts elastically against external pressure and has high shape retention.
• the ratio between the side chain to be crosslinked and / or the side chain can be adjusted by the ratio of the crosslinking agent blended in the polyester resin. Focusing on the relationship between the functional groups in the resin and the decrease in performance as a pressure-sensitive adhesive, we found that the properties as a pressure-sensitive adhesive can be improved by improving the side chains of the polyester resin. Specifically, in the case where the side chain has a hydroxyl group as a functional group, a cured resin is obtained when there is a large amount of hydroxyl groups remaining without crosslinking or hydroxyl groups remaining in the polyester main chain without forming side chains.
• 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 is not more than a predetermined amount.
• This polyester resin (D) is used as the main component of the curable resin, and a crosslinking agent (E) is blended with the curable resin to constitute an adhesive composition.
• a side chain having no hydroxyl group derived from the structure of the sealing compound (c) is formed.
• the sealing compound (c) may be a compound in which a group having a functional group other than a hydroxyl group is bonded only by a compound in which a group having no functional group is bonded by hydroxyl group sealing.
• the adhesive composition can be combined 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).
• the sealing compound (c) include a silylating agent, an acid anhydride, and an isocyanate compound. The acid anhydride and the isocyanate compound do not have a hydroxyl group! /, And are compounds.
• an acid anhydride is used as the sealing compound (c)
• a carboxyl group is generated instead of the hydroxyl group being blocked, 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.
• the crosslinking agent (E) that is blended in the adhesive composition.
• the compounded crosslinking agent reacts with a hydroxyl group
• a decrease in wet heat resistance is suppressed if the hydroxyl value of the polyester resin (D) is about 50 mgKOH / g or less.
• the hydroxyl value of the polyester resin (D) is about 100 mgKOH / g. It becomes as follows.
• 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, up to about 100 mgKOH / g. It is considered acceptable.
• the side chain branched from the polyester main chain of the polyester resin (D) includes a cross-linked side chain and a non-crosslinked side chain (sealed) side chain. And exist. That is, the polyester resin (D) of the present invention has a side chain (first side chain) having a crosslinkable functional group and a hydroxyl group! /, (Sealed) side chain (second side chain). ) Is 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 contain a ring-opening structure of a cyclic ester with an ester bond (carbonyl bond), It is preferably 30% or more.
• each of the first and second side chains may or may not contain a cyclic ester ring-opening structure.
• the hydroxyl groups directly bonded to the polyester main chain remain, because the polyester molecules easily aggregate in a lump due to the association of the hydroxyl groups, and the coating of the adhesive composition becomes difficult. Therefore, in the present invention, 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 become extremely small. Adopt an appropriate preparation method.
• the total number of side chains is assumed to be 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 secondary ethers of the cyclic ether groups and cyclic ethers of the raw material. Equal to the total number of hydroxyl groups. Therefore, in determining the ratio of the number of side chains containing a ring-opening structure of a cyclic ester, it can be estimated based on the number of secondary hydroxyl groups of the main chain polyester.
• the molecular structure of the polyester resin (D) can be roughly classified into the following forms depending on the form of hydroxyl group sealing.
• side chains first side chains
• Polyester resin (D1) which has been converted to the second side chain by sealing the hydroxyl group with compound (c).
• a part of the hydroxyl group bonded to the polyester main chain is sealed with the sealing compound (c).
• 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 third form is useful in that it makes it possible to correct the hydroxyl amount of the polyester resin (D2) of the second form.
• an acid anhydride is used as the capping compound (c)
• the pot life of the adhesive composition is shortened due to the progress of the cross-linking reaction, and the coating processability is lowered, so when sealing with an acid anhydride,
• the hydroxyl group is sealed so that the hydroxyl group remains within the range of 50 mgKOH / 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 reacted to react with the acid value.
• the crosslinking agent for carboxyl groups is used.
• the hydroxyl value of the polyester resin (D) is 0. !
• the acid value is preferably about 0.;! ⁇ 50 mg KOH / g is more preferable. Therefore, in any of the above sealing forms, depending on the type of crosslinking agent to be blended, The reaction conditions and the mixing ratio of raw materials are adjusted so that the acid value and hydroxyl value of the reester resin are appropriate.
• the cross-linking agent (E) when the cross-linking agent (E) is reactive with hydroxyl groups, the cross-linking agent (E) is reactive with the carboxyl group so that the hydroxyl value of the polyester resin (D) is 50 mgKOH / g or less.
• the sealing compound (c) and its use amount are appropriately adjusted so that the hydroxyl value of the polyester resin (D) is lOOmgK OH / g or less and the acid value is 50 mgKOH / g or less.
• the method of adjusting the polyester resin (D) is appropriately selected according to the sealing form. 1st to 1st
• the polyester resin (D) is produced by three reactions: a polyester main chain formation reaction, a side chain formation reaction, and a hydroxyl group blocking reaction.
• the polyester main chain formation reaction is a polyaddition reaction of dicarboxylic acid (a-1) and bicyclic ether compound (a-2).
• the dicarboxylic acid (a-1) is a dibasic acid compound having two carboxyl groups (hereinafter sometimes referred to as dibasic acid (a-1))
• the bicyclic ether (a-2) is A compound having two cyclic ether 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.
• the polymer main chain (I) is elongated by polymerization and a hydroxyl group directly connected to the polyester main chain (I) is generated.
• a hydroxyl group is increased 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. Since it has at least one ring-opening structural unit of the cyclic ester (b) bonded to the polyester main chain (I) via an ester bond and a terminal hydroxyl group, the first side chain having a crosslinkable functional group Can act as (II). Since this ring-opening addition is more reactive when the ratio of the cyclic ester (b) to the hydroxyl group is higher, the efficiency of side chain formation is improved by devising the preparation process, and a production method is provided.
• the hydroxyl group capping reaction is an addition reaction of the capping 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 in which a hydroxyl group is sealed with a sealing compound (c), that is, hydroxide Without a group! /, A second side chain ( ⁇ ') is formed.
• 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 ( ⁇ ).
• the hydroxyl group of the side chain is more reactive than the hydroxyl group of the polyester main chain
• the hydroxyl group is added before the side chain addition reaction.
• a sealing reaction is preferably performed.
• 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 with the group, the remaining hydroxyl group directly bonded to the polyester main chain can also be sealed with the sealing compound (c).
• Such an addition-type polyester resin (D1) can be obtained by the following three production methods: a three-stage type, a pseudo two-stage type, and a two-stage type.
• the three-stage production method is a method of obtaining an addition type polyester resin (D1) stepwise by the following three steps (1) to (3).
• Step (1) Dibasic acid (a-1) and bicyclic ether compound, that is, dicyclic acid (a-1) and bicyclic ether compound by ring-opening addition polymerization with compound (a-2) having two cyclic ether groups.
• a polyester main chain (I) in which each structural unit derived from the bicyclic ether compound (a-2) is alternately and repeatedly connected via an ester bond, and a plurality of hydroxyl groups directly connected to the polyester main chain (I).
• Step (2) The side chain composed of the ring-opening structural unit of the cyclic ester (b) is obtained by subjecting the hydroxyl group directly linked to the polyester main chain (I) of the polyester to a ring-opening addition reaction of the cyclic ester (b).
• Step (3) A part of the terminal hydroxyl group of the side chain ( ⁇ ) of the addition-type polyester precursor (C1) is reacted with the sealing compound (c) to have no hydroxyl group (sealed). A step of reducing the hydroxyl value of the polyester resin (D1) by forming a side chain ( ⁇ ′).
• 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).
• step (2) the hydroxyl group power for adding cyclic ester (b) is present in the polyester in a dense state in the polyester produced as a result of step (1), so hydrogen bonding occurs, and step (1) As a result, the resulting polyester becomes extremely viscous and agglomerates, hindering the efficiency of the addition reaction in step (2).
• the pseudo two-stage type and the two-stage type manufacturing method described later are more advantageous.
• the pseudo two-stage production method is a method of obtaining an addition-type polyester resin (D1) stepwise by the following three steps (4) to (6).
• Step (4) Opening of 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)
• a polyester having an acid value of about 5 gKOH / g is obtained by cycloaddition polymerization.
• This polyester is composed of ester units composed of dibasic acid (a-1) and bicyclic ether compound (a-2). It is the same as the polyester in step (1) in that it has a polyester main chain ( ⁇ ) alternately and repeatedly connected through a bond and a plurality of hydroxyl groups directly connected to the polyester main chain ( ⁇ ).
• Step (5) The cyclic ester (b) is added to the polyester main chain ( ⁇ ), and the cyclic ester (b) is added to the hydroxyl group of the polyester main chain ( ⁇ ) to form a side chain ( ⁇ ).
• the polyester main chain ( ⁇ ) is extended by addition polymerization of the remaining dibasic acid (a-1) and the bicyclic ether compound (a-2) to complete the formation of the main chain, thereby adding the addition type polyester precursor.
• Step (6) A part of the terminal hydroxyl group of the side chain ( ⁇ ) of the addition type polyester precursor (C1) is reacted with the sealing compound (c) to have no hydroxyl group! /, (Sealed) ) A step of obtaining a polyester resin (D1) having a side chain ( ⁇ ′).
• the steps (4) and (5) may be a series of work steps.
• 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 ( ⁇ ) increases in the step (5). Therefore, the reaction efficiency of the ring-opening addition of the cyclic ester (b) is improved, and a side chain is easily formed. Therefore, the quasi-two-stage type is more suitable for the polyester of the addition type polyester precursor (C1) than the previous three-stage type. It is easy to reduce unreacted hydroxyl groups remaining in the tell main chain.
• the hydroxyl group of the polyester main chain ( ⁇ ) produced in the step (5) also contributes to the formation of hydrogen bonds, so that the viscosity becomes higher than in the case of the three-stage type. Although it is difficult, the two-stage type described later is more preferable.
• the two-stage production method is a method of obtaining the addition type polyester resin (D1) stepwise by the following two 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.
• a polyester main chain (I) in which structural units derived from a basic acid (a-1) and a bicyclic ether compound (a-2) are alternately connected via an ester bond and a polyester main chain (I)
• Step (8) A part of the terminal hydroxyl group of the side chain ( ⁇ ) of the addition-type polyester precursor (C1) is reacted with the sealing compound (c) to have no hydroxyl group (sealed). A step of obtaining a polyester resin (D1) having a side chain ( ⁇ ′).
• 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 side chain ( ⁇ ) The degree of formation of the polyester main chain (I) at the start of the formation is in the complete, in the middle of formation, or not formed, and the reaction efficiency in the ring-opening addition of the cyclic ester (b) is different.
• the addition type polyester resin (D2) in the second sealing form has a hydroxyl group directly bonded to the polyester main chain (I) partially sealed with the sealing compound (c) and has no hydroxyl group! /,
• the second side chain (2 ′) is formed (sealed), and the first side chain ( ⁇ ) containing the ring-opening unit of the cyclic ester (b) is added to the remaining hydroxyl group.
• the second side chain ( ⁇ ′) does not contain the ring-opening structural unit of the cyclic ester (b).
• the hydroxyl group directly bonded to the polyester main chain and the sealing compound (c) are reacted in advance.
• the reason why the sealing reaction is performed first is that the residual hydroxyl group after the side chain is formed by the cyclic ester (b) can remain after the sealing reaction because the reaction is easily inhibited by the side chain.
• the method for producing the addition type polyester resin (D2) in the second sealing form is the same as in the first sealing form, and the formation of the second side chain ( ⁇ ') by the sealing compound (c) is started. It can be obtained by three different production methods depending on the degree of formation of the polyester main chain.
• the three-stage production method is a method of obtaining the addition type polyester resin (D2) stepwise by the following three steps (9) to (11).
• Step (9) From the polyaddition of the dibasic acid (a-1) and the bicyclic ether compound (a-2), each derived from the dibasic acid (a-1) and the 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 via ester bonds, and a plurality of hydroxyl groups directly connected to the polyester main chain (I).
• Step (11) Ring-opening structure of cyclic ester (b) by reacting cyclic ester (b) with residual hydroxyl group of addition-type polyester precursor (C2) in which the second side chain ( ⁇ ') is formed
• step (10) the hydroxyl group is reduced by reacting a part of the hydroxyl group directly bonded to the main chain (I) with the sealing compound (c). ) In which the first side chain is formed is controlled by the degree of sealing in the step (10).
• the pseudo two-stage manufacturing method is a method of obtaining the addition type polyester resin (D2) stepwise by the following three steps (12) to (14).
• a polyester having an acid value of about 5 gKOH / g is obtained by cycloaddition polymerization.
• This polyester is composed of ester units composed of dibasic acid (a-1) and bicyclic ether compound (a-2). It is the same as the polyester in the step (9) in that it has a polyester main chain ( ⁇ ) alternately and repeatedly connected through a bond and a plurality of hydroxyl groups directly connected to the polyester main chain ().
• Step (13) The sealing compound (c) is added to the polyester main chain ( ⁇ ), and the second side chain ( ⁇ ) is reacted by reacting the sealing compound (c) with the hydroxyl group of the polyester main chain ( ⁇ ).
• the polyester main chain ( ⁇ ) is extended by polyaddition of the remaining dibasic acid (a-1) and the bicyclic ether compound (a-2) to complete the formation of the main chain, thereby adding the addition type polyester.
• the steps (12) and (13) may be a series of work steps.
• the formation of the polyester main chain in the step (12) is in progress, so that the amount of hydroxyl groups in the polyester main chain ( ⁇ ) in the step (13) is the previous three-stage manufacturing. 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 hydroxyl groups directly bonded to the polyester main chain, and the addition type polyester precursor (C2)
• the reaction efficiency of the ring-opening addition of the cyclic ester (b) to is relatively good.
• the two-stage production method is a method of obtaining an addition-type polyester resin (D2) stepwise by the following two steps (15) to (; 16).
• a polyester main chain (I) in which structural units derived from a dibasic acid (a-1) and a bicyclic ether compound (a-2) are alternately and repeatedly connected via an ester bond and a polyester main chain (I) Seals directly connected hydroxyl groups
• the hydroxyl groups are sealed simultaneously with the formation of the polyester main chain in the step (15), and the association and agglomeration of the polyester molecules by the hydroxyl groups directly connected to the polyester main chain are performed. Since it does not occur substantially, the reaction system is easy to homogenize and reacts very easily. 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 a precursor-added polyester (C2) having a polyester main chain (I) and a side chain ( ⁇ ') is obtained, the side chain ( ⁇ ) starts to form.
• the degree of formation of the polyester main chain (I) at this time is either complete, in the middle of formation, or not formed.
• the sealing compound (c ′) is a monofunctional compound. There must be.
• the production method of the polyester resin (D) may be appropriately selected from the above production methods as necessary.
• the addition type polyester resin (D3) in the third sealing form is prepared by further reacting the addition type polyester resin (D2) in the second sealing form with the sealing compound (c). It can be obtained by the step (17) of sealing a part of the hydroxyl group at the terminal of the first side chain ( ⁇ ) containing the ring-opening structural unit of the cyclic ester (b) in 2). That is, the manufacturing method according to the third sealing form includes any one of the three-stage type, pseudo two-stage type, or two-stage type process of the manufacturing method according to the second sealing form, and the above-described step (17).
• Such addition type polyester resin (D3) is composed of dibasic acid (a-1) and bicyclic ether.
• a polyester main chain (I) in which structural units derived from the compound (a-2) are alternately and repeatedly bonded via ester bonds, and a first side chain having a ring-opening structural unit and a terminal hydroxyl group of the cyclic ester (b) ( ⁇ ) the side chain in which the hydroxyl group directly bonded to the polyester main chain (I) is sealed with the sealing compound (c) and the terminal hydroxyl group of the first side chain ( ⁇ ) are sealed with the sealing compound (c).
• It has two types of second side chains ( ⁇ ).
• 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 can have is a cyclic ester. It is preferable to prepare an addition-type polyester resin so as to contain the ring-opening structural unit of (b), more preferably 30% or more of the total number of side chain hydroxyl groups contains the ring-opening structural unit. It is preferable because the properties derived from the ester ester (b) are effectively exhibited! /.
• the sealing compound (c) when an acid anhydride is used as the sealing compound (c), a compound that undergoes a crosslinking reaction with respect to a carboxyl group is combined as a crosslinking agent (E).
• the sealed second side chain ( ⁇ ′) also functions as the first side chain (I) having a functional group, and may be completely sealed in terms of hydroxyl value.
• the dibasic acid (a-1) used for forming the polyester main chain (I) is a known dicarboxylic acid compound (a-1-l) having a relatively low molecular weight (for example, a molecular weight of about 90 to 500). It can be used as it is, and includes the following various dicarboxylic acids, anhydrides and derivatives thereof, and may be any of aliphatic compounds, aromatic compounds and alicyclic compounds.
• 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, and pimeline.
• Examples thereof include acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, and the like, and these aliphatic dicarboxylic acids and anhydrides thereof can be used.
• succinic anhydride methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl hydrous succinic anhydride, dodecenyl succinic anhydride, Phenyl succinic anhydride, etc.
• glutaric anhydride dialtaric anhydride, 3-aryl daltaric anhydride, 2,4 dimethyl daltaric anhydride, 2,4 jetyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc.
• Maleic anhydride derivatives (2 methyl maleic anhydride, 2,3 dimethyl maleic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl Maleic anhydride, 2,3 dichloromaleic anhydride, phenylmaleic anhydride, 2,3 diphenyl Anhydrous derivatives such as maleic anhydride) can also be used.
• aromatic dicarboxylic acids include: o phthalic acid, isophthalic acid, terephthalic acid
• Hexahydrophthalic anhydride derivatives ((3-methylxahydrophthalic anhydride, 4-methylxahydrophthalic anhydride), tetrahydrophthalic anhydride derivatives (1, 2, 3, 6 tetrahydrophthalenoic anhydride, 3-methylolene) 1, 2, 3, 6 Tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,2,3,6-tetrahydrophthalic anhydride, etc.) it can.
• 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. Acids and their anhydrides can be used.
• These low molecular weight dicarboxylic acid compounds (a-1-l) can be used alone or in combination of two or more as dibasic acid (a-1).
• 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).
• 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).
• Polyamide dicarboxylic acid (a-1-4) obtained by reacting polyamines (a-1- ⁇ ) described later with carboxylic acid in excess can be used as the dibasic acid (a-1).
• the polyol component (a-l- ⁇ ) used for the preparation of the high molecular weight dicarboxylic acid (a-1-2, a-1-3) includes a relatively low number average molecular weight of about 50 to 500.
• Examples of relatively low molecular weight diols include, for example, ethylene glycol, propylene glycolanol, dipropylene glycolanol, diethylene glycolanol, triethylene glycolone, butylene glycol, 3 methyl-1, 5 Pentanediol, 2,4 Getinole 1,5 Pentanediol, 2 Methyl-1,8 Octanediol, 3,3 'Dimethylolheptane, 2 Butyl-2 Ethyl-1,3 Propanediol, Polyoxyethylene glycol ), Polyoxypropylene glycol (additional mole number of 10 or less), propanediol, 1,3-butanediol, 1,4 butanediol, 1,5 pentanediol, 1,6 hexanediol, 1,9 Nangionore, Neo Pentinore Glicorenore, Octannionore, Pu, Chin
• the relatively low molecular weight diols described above may be used alone or in combination of two or more.
• Examples of relatively high molecular weight polyols 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 above-described reaction of relatively low molecular weight diols with carbonates or phosgene.
• polyester polyols obtained by ring-opening polymerization of latatones such as poly-force prolatatone diol, poly (13-methyl- valero latatatone) diol, polyvalero latatatone diol, and the like are also used for the above high molecular weight polyols. Included in high molecular weight diols that can be used as (a-1-a-2).
• the above high molecular weight polyols (a-1-a-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.
• these polyols when a bifunctional diol is used, a pressure-sensitive adhesive having excellent adhesiveness, heat resistance, heat and moisture resistance and transparency can be obtained, and therefore a bifunctional diol is most preferable.
• the molecular weight of the high molecular weight polyols (a-1-a-2) is not particularly limited as long as it is soluble in the solvent used, but the number average molecular weight (Mn) is in the range of 500 to 50,000.
• the high molecular weight polyol (a-l_3b) is preferred. When such a high molecular weight polyol (a-l_3b) is used, a pressure-sensitive adhesive having excellent adhesion and wettability can be obtained. More preferably 1,000 -30, 000, most preferred ⁇ (or 1,000 -10, 000 is used. Polymer !: Positive
• the number average molecular weight (Mn) of the process (a-1-a-2) is less than 500!
• addition-type polyester resins (D1) to (D3) become excessively hard and bonded.
• initial adhesiveness (tack) becomes difficult to develop.
• a plastic sheet or a glass plate and a plastic film are laminated using a pressure-sensitive adhesive composition containing addition-type polyester resins (D1) to (D3) that are too hard, the adhesive strength becomes weak. It becomes easier to peel off when the laminate is kept under high temperature and high humidity for a long time.
• the Mn of the high molecular weight polyols (a_l-a_2) exceeds 50,000, the solubility of the addition type polyester resins (D 1) to (D3) in the solvent is reduced. 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-a-2) is also not particularly limited! /, But is preferably -70 to 80 ° C, more preferably -50 to 20 °. C.
• Tg glass transition temperature
• the adhesiveness and cohesive strength of the adhesive composition may be insufficient, and cohesive failure may occur after lamination and peeling may occur.
• the temperature exceeds 80 ° C the coating film becomes too hard, and may affect the strength, slippage, and coating processability of initial adhesion (tack).
• the glass transition temperature of the high molecular weight polyols (a-1-a-2) can be adjusted by appropriately selecting the types of the raw materials polycarboxylic acid, polyamine and low molecular weight polyol. It is also possible to adjust to a suitable glass transition temperature using two or more kinds of polyols having different glass transition temperatures.
• the hydroxyl value of the high molecular weight polyols (a-1- ⁇ -2) is preferably in the range of 5 to 200 mgKOH / g, more preferably in the range of 10 to 100 mgKOH / g. If the hydroxyl value exceeds 200 mgKOH / g, the addition-type polyester resins (D 1) to (D3) may become too hard, and initial adhesiveness (tack) may be difficult to develop. When the hydroxyl value is less than 5 mgKOH / g, the solubility of the addition-type polyester resins (D1) to (D3) in the solvent decreases, and the viscosity of the prepared adhesive composition increases. Handling at the time of processing becomes difficult, resulting in trouble with calorie properties.
• the tri- or higher functional polycarboxylic acids (a-1- ⁇ ) used to obtain (a-1-3) are described below.
• the trifunctional or higher polycarboxylic acids (a-1- ⁇ ) are preferably those having an anhydride ring, and the trifunctional or higher polycarboxylic acids (a_l_ / 3) having one anhydride ring are preferably trimerized anhydride.
• Ritnic acid is mentioned.
• Examples of the trifunctional or more polycarboxylic acids having two or more anhydride rings include 1, 2, 3, 4 butanetetracarboxylic dianhydride, 1, 2, 3, 4 -Cyclobutane tetracarboxylic dianhydride, 1, 3 dimethyl 1, 2, 3, 4 cyclobutane tetracarboxylic dianhydride, 1, 2, 3, 4 cyclopentane tetracarboxylic dianhydride, 2, 3, 5 Tricanolepoxycyclopentinoleacetic acid dianhydride, 2, 3, 5, 6 Tetracanoleoxycyclohexane dianhydride, 2, 3, 5, 6 Tetracarboxynorbornane anhydride, 3, 5, 6 Tricanolepoxino levono Rennan 2 Acetic dianhydride, 2, 3, 4, 5 Tetrahydrofuran tetracarboxylic dianhydride, 5- (2, 5 Dioxotetrahydrofural) -3 Methyl 3 Cyclohex
• the low molecular weight dicarboxylic acids (a-1-l) and the polycarboxylic acids (a-1- ⁇ ) are each reacted alone or in combination of two or more with the polyol (a-1- ⁇ ).
• the low molecular weight dicarboxylic acids are used as the dibasic acid (a-1) for forming the polyester main chain (I) rather than the low molecular weight dicarboxylic acid (a-1-l) as it is.
• 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) -1) is used as it is, because the distance between the ester bonds in the polyester main chain (I) caused by polyaddition is longer and a suitable distance is generated between the secondary hydroxyl groups.
• the agglomeration of the polyester is suppressed, and at the same time, addition type polyester resin (D l), (D2) Reduction of hydroxyl value is facilitated.
• polyester main chain (I) using a high molecular weight dicarboxylic acid (a-1-2, a-1-3) as the dibasic acid (a-1).
• the polyamide dicarboxylic acid (a-1-4) that can be used as the dibasic acid (a-1) includes the low molecular weight dicarboxylic acid (a-1-l) and the polyamine (a-1- ⁇ ).
• the polyamine (a-1- ⁇ ) used for the preparation of polyamide dicarboxylic acid, which is condensed under the condition of excess carboxylic acid, has two carboxyl groups at the end and is linked by an amide bond, Any polyamine having two or more primary amino groups can be used without particular limitation.
• aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene at both ends of the molecule.
• Polypropylene glycol with amino groups bonded to branched carbon (propylene skeleton diamine, products from Jeffermine D230 and Jeffamine D400 from Sun Techno Chemical Co., Ltd., propylene skeleton triamine, products from Sun Techno Chemical Co., T403 '', ethylenediamine, propylenediamine, butylenediamine, triethylenetetramine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, ⁇ ⁇ ⁇ -aminoethylphenyl Perazine, 1, 2-amineaminopropane, iminobispropylamine, methyliminobispropylamine, HN (CH 2 CH 2 O) (CH 2) NH (an amine nitrogen such as ethylene glycol skeletal diamine “Jeffamine EDR148” manufactured by San Techno Chemanol) Diamine of polyether skeleton with methylene group
• Ketimine which is a reaction product of the above polyamine and ketone, is also polyamine (a-1- ⁇ ).
• Reaction product of dimethyleneamine (NBDA) with norbornane skeleton Reaction product of acetophenone or propiophenenone and methylylylenediamine; Jeffer, acetophenone or propiofenenone, and ethylene glycol skeleton or propylene skeleton diamine Min EDR148, Jeffamine D230, Jeffamine D400, etc.! /, And the like are reaction products with a propylene skeleton triamine such as Jeffamine T403.
• Each of the above polyamines may be used alone or in combination of two or more.
• the dibasic acid (a-1) used to form the polyester main chain (I) having a hydroxyl group at the side chain position is the above-mentioned low molecular weight dicarboxylic acid (a-1-l),
• a-1-l low molecular weight dicarboxylic acid
• One or two or more kinds of molecular weight dicarboxylic acids (a-1-2, a-l-3) and polyamide dicarboxylic acids (a-l-4) can be appropriately selected and used.
• 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 form 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.
• 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 a high molecular weight resin that may be any of an aliphatic compound, an aromatic compound, and an alicyclic compound.
• Examples of the aliphatic diglycidyl compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycol.
• Shijinoleatenore Dipropyleneglyconoresigrisinoreatenore, Tripropyleneglycol Monoresidinoglyceinoreatenore, Polypropyleneglyconoresiniginoreatenore, Butandi Pentinoreglyconoresiglicidinoreethenole, 1,6 hexanediol diglycidyl ether, glycerin diglycidyl ether, diglycidylamine, butadiene dioxide, diglycidyl ether of dimer acid, and the like.
• 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, Bisphenol Monore S Diglycidinoreateoret, 2, 2 Bis (4-hydroxyphenenole) propanediglycidinorenotere, Bis (4-hydroxyphenenole) methanediglycidinoreatenore, 1, 1 Bis (4-hydroxyfenenole) Ethanediglycidyl ether, 3, 3 ', 5, 5'-tetramethyl-4,4'-dihydroxybiphenyldiglycidyl ether, 2,2bis (4 ((4-hydroxypropoxy) phenyl) propanediglycidyl ether, resorcinol di Glycidge tenor, Fueninore 4,4'-Glycidinoreatenore, 1,5-
• Examples of the alicyclic diglycidyl ether compound include cyclohexane dimethanol diglycidino reetenole, dicyclopentadiene dioxide, 3, 4-glycidino cyclohexyl methyl-3, 4-glycidyl cyclo Hexanecarboxylate, 3,4-Glycidinole 6-Methylcyclohexylmethyl- 3,4-Glycidileu 6-Methylcyclohexane power Norevoxylate, Vininolecyclohexenedioxide, Dicyclogeno-Noleepoxide glycidyl ether, Tetrahydrophthalic acid diglycidyl ether , Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 2, 2 bis (4 hydroxycyclohexenole) propane diglycidino reetenol, bis (3,4-epoxycyclohexyl) azimuth
• Examples of the high molecular weight diglycidyl resin include bisphenol A type high molecular weight glycidyl resin. Resin, bisphenol F type high molecular weight glycidyl resin, or phenoxy resin obtained by reacting the above diglycidyl compound.
• Bisphenol resin-based (A-type, F-type, etc.) diglycidyl compounds have a secondary hydroxyl group, and this secondary hydroxyl group is a cyclic ether group (glycidyl group) with a dibasic acid (a-1). It acts as a starting point for forming a side chain, like a secondary hydroxyl group produced by polyaddition of a carboxyl group.
• Examples of the compound having an oxetanyl group include carbonate bisoxetane, adipate bisoxetane, xylylene bisoxetane, terephthalate bisoxetane, bisoxetane cyclohexanedicarboxylate, and bis ( Examples include 3-ethyl-3-oxetanylmethyl) ether, 1,4bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and diethyl ( 3- oxetanyl) ⁇ methyl ether.
• the bicyclic ether compound (a-2) can be used alone or in combination of two or more.
• 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 (Dl, 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 can react with the crosslinking agent (E) described later to cure the polyester resin (D) and form a pressure-sensitive adhesive layer.
• the amount of the cyclic ester (b) to be reacted with the secondary hydroxyl group of the polyester main chain (I) can be controlled, and based on the amount of side chains introduced. ! / In addition, it is possible to ensure the balance of adhesive properties (especially both tack and cohesiveness) as pressure-sensitive adhesives of adhesive compositions containing addition-type polyester resins (D1) to (D3) It becomes.
• the addition-type polyester resins (D1 to D3) can be obtained by a three-stage, pseudo-two-stage, or two-stage production method.
• the progress of the formation reaction (polyaddition reaction) of the polyester main chain (I) at the start of addition of the sealing compound (c) is different.
• Polyesters that have completed the polyaddition reaction have a large number of hydroxyl groups, so there is a possibility that hydroxyl groups with high viscosity may associate with each other or side reactions, and cyclic esters (b)
• the addition reaction of the cyclic ester (b) or the sealing compound (c) which tends to lower the reaction efficiency by inhibiting the uniform mixing with the sealing compound (c), is suppressed.
• the cyclic ester (b) used for forming the side chain in the present invention is an ester in which a hydroxyl group of a hydroxycarboxylic acid and a carboxylic acid are dehydrated and condensed in a molecule or between molecules to form a ring structure. It includes carboxylic acid cyclic monomers, dimers or multimers of trimers or higher.
• the hydroxycarboxylic acid (b ′) which is a precursor of the cyclic ester
• the hydroxycarboxylic acid (b ′) can be used as long as it can form a ring by dehydration condensation.
• Intramolecular or intermolecular condensates with one or more of aliphatic, alicyclic, aromatic and heterocyclic hydroxycarboxylic acids as precursors can be used as cyclic ester (b).
• Examples of hydroxycarboxylic acid (b ′) which is a precursor of cyclic ester (b) are shown below.
• Examples of the aliphatic hydroxycarboxylic acid include glycolic acid, lactic acid, hydroacrylic acid, a-oxybutyric acid, ⁇ -hydroxyisobutyric acid, hydroxyvaleric acid, ⁇ -hydroxycaproic acid, ⁇ -hydroxycaproic acid, glyceric acid, tartronic acid, malic acid, Kuen acid, capric acrylic acid, lauric acid, Rishinonore acid, a- hydroxide triacontyl Tan acid, alpha-hydroxy Tet Ratoria proximal acid, alpha - hexa triacontyl Tan acid to hydroxy, alpha-hydroxy Octatriacontanic acid, a-hydroxytetraacontanic acid, hydroxypiparic acid, hydroxypropionic acid, 6 hydroxypentanoic acid, ⁇ -hydroxyheptanoic acid, 10 hydroxystearic acid, 12-hydroxystearic acid, 10- Hydroxydecanoic acid, 12-hydroxystearic
• Alicyclic, aromatic and heterocyclic hydroxycarboxylic acids include, for example, salicylic acid,
• 2-hydroxybenzoic acid 3-hydroxybenzoic acid, 3,4 dihydroxybenzoic acid, 4-hydroxy-3-phenyl benzoic acid, 4-hydroxy-3-methoxybenzoic acid, 4-hydroxy-3,5-dimethoxybenzoic acid, 4, -hydroxy-4 carboxy Biphenyl, 6-hydroxy 2 naphthoic acid, 3 hydroxy-2 naphthoic acid, 5 hydroxy 1 naphthoic acid and the like.
• the hydroxycarboxylic acid is not limited to the above examples as long as it is an organic compound having a carboxylic acid and a hydroxyl group in one molecule.
• ratatones can be used, and there is no particular limitation.
• Examples of the cyclic dimer of hydroxycarboxylic acid that can be used as the cyclic ester (b) in the present invention include lattide 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 a polymer obtained by repeating the ring-opening addition of a plurality of molecules. It may be an addition polymerization to form. 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. From the viewpoint of the effectiveness of the side chain formed by ring opening, in the single addition of the cyclic ester (b), a cyclic ester (b) having a carbon number force or more constituting the ester ring structure is preferred.
• an ester ring Preferred is a cyclic monomeric ratatatone having a carbon number of 6 to 18;
• the capping compound (c) is a compound that can clog a hydroxyl group by reacting with a hydroxyl group and adding it, and is a terminal hydroxyl group or a polymer of the side chain ( ⁇ ) of the addition-type polyester precursor (CI, C2). It reacts with a part of the hydroxyl group directly bonded to the ester main chain (I) to seal the hydroxyl group, and at least a part of the side chain is formed to form a second side chain ( ⁇ ′) 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).
• 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 when an adhesive composition is prepared and used as a pressure sensitive adhesive improves.
• the compound (c) capable of reacting with a hydroxyl group is a polyaddition reaction between a dibasic acid (a) and a compound (a-2) having two cyclic ether groups. It is used to form a side chain part ( ⁇ ′) in the addition-type polyester resin (D2) by reacting with a part of the secondary hydroxyl group in the polyester main chain part (I) produced.
• the side chain part ( ⁇ ′) has no hydroxyl group! /.
• 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 ( ⁇ ) 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 proportion of the side chain having the ring-opening structural unit of the cyclic ester (b) can be adjusted. Therefore, it can be used to adjust the adhesive property balance (particularly, both tack and cohesive force) when the addition-type polyester resin (D2) is used as a pressure-sensitive adhesive.
• the sealing compound (c) is obtained by reducing the hydroxyl group at the terminal of the first side chain ( ⁇ ) in the addition type polyester resin (D2) to reduce the addition type polyester resin (D3 ) And can also be used to finally adjust the hydroxyl group of the polyester resin.
• sealing compound (c) used in the present invention examples include a silylating agent (cl) and an acid anhydride. Monofunctional or bridging action that is preferred to be either (c2) or isocyanate compound (c3)! / Compound (c ′) having a plurality of functional groups is more preferred! /.
• the sealing compound (c) may be used alone or in combination of two or more.
• silylating agent (cl) used in the present invention examples include hydrosilanes, alkoxysilanes, chlorosilanes, silanols, silylamines, and cyclic compounds thereof.
• hydrosilanes include trimethylsilane, triethylsilane, tripropylsilane, dimethylphenylsilane, triphenylsilane, methylphenylvinylsilane, penta
• alkoxysilanes examples include methoxytrimethylsilane, methoxytriethylsilane, methoxydimethinolevinolesilane, dimethylenoethoxyethoxytinolesilane, and ethoxytrimethyl.
• Examples thereof include dimethylethoxyphenylsilane, benzyloxytrimethylsilane, methoxytripropyl silane, penzinoresimethino ethoxysilane, 2-ethino hexeno genino xytrimethino silane and alkoxysilanes having a alkoxy group.
• chlorosilanes include trimethylchlorosilane and dimethylvinylchlorosilane. Simple substances such as rolosilane, methinolevenolevininorechlorosilane, penzinoresimethinolechlorosilane, triprotylchlorosilane, diphenylvinylchlorosilane, triphenylchlorosilane, trihexylenochlorosilane, dimethyloctadecylchlorosilane, tribenzylchlorosilane, etc. Examples include chlorosilanes that possess a chlorosilyl group of public function.
• silanols include silanol compounds having a monofunctional silanol group such as trimethylsilanol, triethylsilanol, and triphenylsilanol.
• silylamines include trimethylsilyldimethylamine, trimethylsilyldimethylamine, dimethylaminotrimethylsilane, arylaminotrimethylsilane, N-methylolene-N-trimethylsilylacetamide, anilinotrimethylsilane, 1-trimethylsilylpyrrole.
• Silylamines possessing monofunctional silylamino groups such as 1-trimethylsilinorepyrrolidone, 1-trimethylsilinoreimidazole, 1-trimethylolylsilyl-1,2,4triazole
• 1, 3, 3, 3-tetramethyldisilazane N, N bis (trimethylsilyl) N-phenylurea and other silylamines having a bifunctional silylamino group; 1, 1, 3, 3, 5, 5 hexamethyl
• silylamines having a trifunctional or higher cyclic silylamino group such as norecyclotrisilazane and 1,1,1,3,3,5,5,7,7-year-old kutamethinolecyclotetrasilazane.
• Examples of the acid anhydride (c2) used in the present invention include the low molecular weight dicarboxylic acids exemplified as the dibasic acid (a-1) used for forming the polyester main chain (I) described above ( acid anhydrides in (a-1-1) and acid anhydrides in tri- or higher functional polycarboxylic acids (a-1- ⁇ ) used to form high molecular weight dicarboxylic acids (a-1-3).
• the acid anhydrides of low molecular weight dicarboxylic acids (a-1-l) are preferred!
• the silylating agent (cl) or the isocyanate compound (c3) is used as the sealing compound (c). Therefore, it is preferable to use a monofunctional one.
• acid anhydride (c2) is used as the sealing compound (c)
• the acid anhydride (c 2) acts in the same manner as the dibasic acid (a-1) to form the polyester main chain (I). As a result, the molecular design is hindered.
• examples of monofunctional isocyanate compounds include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, Cutyl isocyanate, Decyl isocyanate, Octadecyl isocyanate, Stearyl isocyanate, Cyclohexyl isocyanate, Phenyl isocyanate, Benzyl isocyanate, p Black phenyl isocyanate, p Nitto Phenyl isocyanate, 2 chloroethyl isocyanate, 2, 4 dichlorophenyl isocyanate, 3-chloro-4-methyl phenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)- «methyl Benzyl isocyanate, (S) (1) ⁇ -methylbenzyl isocyanate,
• 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) A dibasic acid (a-1) and a bicyclic ether compound (a-2) are mixed and reacted together. 2) A dibasic acid (a-2) is added to the bicyclic ether compound (a-2). The reaction may be carried out while gradually adding -1) or by reacting the dibasic acid (a-1) while gradually adding the bicyclic ether compound (a-2).
• the linear polyester produced by the polyaddition reaction of the dibasic acid (a-1) and the bicyclic ether compound (a-2) The polyester main chain (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. It should be in the range of 2 mol. If 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 the characteristics as a pressure-sensitive adhesive.
• polyester main chain (I) When the polyester main chain (I) is formed, 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 is used.
• the secondary hydroxyl group directly connected to the reester main chain (I) includes 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)! / There are two types.
• the two types of secondary hydroxyl groups are both reactive bases with the cyclic ester (b) or the encapsulating compound (b), and the first side chain (II) having the ring-opening structural unit of the cyclic ester and the terminal hydroxyl group.
• the 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.
• 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 have increased hardness and are less likely to exhibit tack.
• the biodegradability of the resin increases, but the heat resistance decreases.
• 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.
• the proportion of aromatic ring groups in the molecule of the polyester resin (D) is generally from 0.01 to About 60% is more preferable than about 1 to 50% (weight ratio).
• 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.
• the cyclic ester (b) is added to 1 mol of the secondary hydroxyl group directly bonded to the linear polyester main chain (I). Is preferably reacted at a rate of 0.2 mol or more, more preferably at a rate of 0.5 mol or more, and further at a rate within the range of 0.8 to 60 mol. Preferably, the reaction is carried out at a rate within the range of 1.5 to 40 mol.
• the cyclic ester (b) is added to 1 mol of the secondary hydroxyl group directly bonded to the linear polyester main chain (I). It is preferable to react at a ratio of 0.1 mol or more. It is more preferable to react at a ratio of 0.3 mol or more, more preferably at a ratio within the range of 0.4 to 60 mol. It is best to carry out the reaction at a ratio within the range of 7 to 40 mol.
• the linear polyester main chain (I) The preferable lower limit of the amount of the cyclic ester (b) relative to 1 mol of the secondary hydroxyl group directly bonded to the base is smaller than that when the additive-type polyester resin (D1) is prepared by the first sealing form.
• 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 so that the molar ratio is as described above. .
• the cyclic ester (b) in an amount exceeding the mole equivalent to the hydroxyl group reacts with the terminal hydroxyl group of the ring-opened side chain to form a side chain composed of a polymer obtained by ring-opening polymerization of a plurality of cyclic ester molecules ( ⁇ ).
• the side chain ( ⁇ ) produced by the ring opening of the cyclic ester (b) has a hydroxyl group at its end, and has a polyester main chain part (I) and a hydroxyl group-terminated side chain part ( ⁇ ).
• the precursor (C1) preferably has a hydroxyl value in the range of 50 to 150 mg KOH / g, more preferably in the range of 50 to 80 mg KOH / g! /.
• the polyester main chain (I) an addition type polyester resin (D1) having a hydroxyl group-terminated first side chain ( ⁇ ) and a terminal hydroxyl group! /, And a second side chain ( ⁇ ′).
• 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, preferably from 0.;! To 50 mg KOH / g, Preferably, it is adjusted to a range of 0.5 to 30 mg KOH / g.
• 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 up to about 100 mgKOH / g and not more than 80 mgKOH / g. Is preferred.
• 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-free product. As a result, a side chain having a terminal carboxyl group is formed.
• the cross-linking agent (E) reacts with a hydroxyl group, the acid value is allowed to be somewhat high, but the cross-linking agent (E) is When reacting with a boxyl group, the acid value of the addition-type polyester resin (D1) is preferably in the range of 0.5 ;! to 50 mg KOH / g, more preferably in the range of 0.5 to 30 mg KOH / g.
• the cyclic ester (b) can be added to the addition type polyester resin (D2) regardless of the addition amount.
• the hydroxyl value increases. This is because, even when a large amount of cyclic ester (b) is added when a large amount of hydroxyl groups directly bonded to the main chain remain, cyclic ester (b) rather than ring-opening addition of cyclic ester (b) to hydroxyl groups directly bonded to the main chain. It is presumed that the self-opening addition of b) proceeds and the hydroxyl groups directly connected to the main chain do not decrease so much.
• the hydroxyl value of the addition-type polyester resin (D2) increases, the heat resistance and moist heat resistance of the cured resin decrease.
• the ratio of the functional group of the capping compound (c) to the hydroxyl group of the polyester main chain (I) is more than 0.85 mol, side chains ( ⁇ ) due to the cyclic ester (b) can hardly be formed. Tack and cohesion It is difficult to obtain an addition-type polyester resin (D2) capable of preparing an adhesive composition that can be used as a pressure-sensitive adhesive.
• the addition type polyester precursor (CI, C2) can be obtained by any of the three-stage type, pseudo-two-stage type and two-stage type manufacturing methods, and the mixing ratio of the raw materials is the same as described above. It is.
• the two-stage type for example, the dibasic acid (a-1), the bicyclic ether compound (a-2) and the cyclic ester (b) or the sealing compound (c) can be combined and reacted.
• 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). 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 a catalyst, but a catalyst is used to make the reaction proceed more smoothly. It may be used as appropriate.
• 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 oxides, and rogens.
• the use of quaternary ammonium salts as a reaction catalyst is preferable because colorless to light yellow addition type polyester resins (Dl) and (D2) can be obtained.
• Examples of amines that can be used as a catalyst for polyaddition reaction include triethylamine, pyridine, aniline, morpholine, N-methylmorpholine, pyrrolidine, piperidine, N-methylbiperidine, cyclohexylamine, n- Butylamine, dimethyloxazoline, imidazole, N-methylimidazole, N, N-dimethylethanolamine, N, N-jetinoethanolamine, N, N-dimethylisopropanolamine, N-methyljetanol, etc. Can be mentioned.
• the quaternary ammonium salts include, for example, tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium fluoride trihydrate, tetramethylammonium hexafluorophosphate, Tetramethylammonium hydrogen phthalate, tetramethylammonium hydroxide pentahydrate, tetramethylammonium hydroxide, tetramethylammonium iodide, tetramethylammonium nitrate, tetramethylammonium park mouth Rate, tetramethylammonium tetrafluoroborate, tetramethylammonium tribromide, phenyltrimethylammonium Umbromide, tetraethynoleammonum bromide, tetraethynoleammonum chloride, tetraethylammonium fluoride trihydrate, tetraethylammonium
• quaternary phosphonium salts include benzyl triphenyl phosphonium chloride, tetraphenyl phosphonium bromide, ethenoret triphenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, tetrabutyl phosphonium.
• alkali metal or alkaline earth metal hydroxide examples include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; magnesium hydroxide, calcium hydroxide, Alkaline earth metal hydroxides such as strontium hydroxide and barium hydroxide can be mentioned.
• organic tin compounds examples include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBT DU, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, Examples thereof include rebutyl tin oxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate, and 2-ethyl hexyl hexanoate.
• DBT DU dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide
• Examples thereof include re
• Examples of the organic dinoreconium compounds include dinoleconium acetate, zirconium benzoate, and zirconium naphthenate.
• organic titanium compounds examples include dibutyltitanium dichloride, tetrapeptinoretitanate, tetrabutoxytitanate, tetraethyltitanate, butoxytitanium trichloride.
• organic lead compounds examples include lead acetate, lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate and the like.
• organic iron compounds examples include iron 2-ethylhexanoate, iron acetylethyl acetate and the like.
• 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.
• metal halides examples include stannous chloride, stannous bromide, stannous iodide, and the like.
• 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-mentioned examples, 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 per 100 parts by weight of the reaction components. When 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 performed 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; And halogenated hydrocarbon solvents such as ether 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 it greatly reduces the reaction rate in the subsequent reaction with the cyclic ester (b).
• the ring-opening addition reaction between the hydroxyl group of the polyester main chain (I) and the cyclic ester (b) can be carried out 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.
• the catalyst may or may not be used, but is preferably used.
• the above-mentioned catalyst for polyaddition reaction used for the reaction of dibasic acid (a-1) and bicyclic ether compound (a-2) can be used in the same manner.
• the quaternary ammonium salt is more preferably used as a catalyst because the addition type polyester resin (D) is difficult to be colored.
• Addition-type polyester resins (D1 to D3) have a glass transition temperature so that the adhesive composition can exhibit well-balanced adhesive properties as pressure-sensitive adhesives (particularly, compatibility between tack and cohesiveness).
• the degree (Tg) is preferably from -80 to 10 ° C.
• 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 strength suitable for pressure-sensitive adhesives. Will not be able to be exhibited, and floating will easily occur.
• the dibasic acid (a-1) can be produced so that an addition type polyester resin (D1 to D3) having a Tg of preferably ⁇ 80 to; 10 ° C., more preferably ⁇ 60 to ⁇ 10 ° C. Consideration should be given to the selection of each component used as the bicyclic ether compound (a_2), the cyclic ester (b) and the sealing compound (c).
• the addition-type polyester resins (D1 to D3) preferably have a weight average molecular weight (Mw) in the range of 2,000—1,000,000 in terms of adhesion, and 8,000- More preferably, it is in the range of 500,000.
• Mw weight average molecular weight
• Mw weight average molecular weight
• the cohesive force peculiar to the addition-type polyester resins (D1 to D3) of the present invention cannot be expressed, and heat resistance and heat-and-moisture resistance are reduced.
• Mw exceeds 1,000,000, the fluidity of the adhesive composition containing the addition-type polyester resins (D1 to D3) becomes poor, making it difficult to produce a pressure-sensitive adhesive sheet. .
• the adhesive composition of the present invention contains a crosslinking agent (E) capable of reacting with a functional group of the addition type polyester resin (D1 to D3) of the previous operation, and the addition type polyester is obtained by a crosslinking reaction with the functional group.
• the resin hardens and forms an adhesive layer.
• the crosslinking agent (E) used in the present invention is a compound having in its molecule a functional group capable of reacting with a hydroxyl group or a carboxyl group in the addition type polyester resin (D1 to D3), 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.
• Such compounds include polyisocyanates. Examples thereof include silicate compounds, polyfunctional silane compounds, N methylol group-containing compounds, epoxy compounds, amine compounds, aziridine compounds, carpositimide compounds, oxazoline compounds, melamine compounds, and metal chelate compounds.
• 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.
• the hydroxyl value of the addition type polyester resin (D1 to D3) is 0. ;
• the cross-linking agent (E) to be combined may be of any type that can react with either a hydroxyl group or a carboxyl group, and the hydroxyl value of the addition type polyester resin (D1-D3) is 50mgKOH /
• the combined crosslinking agent (E) is a type capable of reacting with strong lpoxyl groups, and from the viewpoint of pot life and the like, addition type polyester resin (D1 to It is desirable that the acid value of D3) is 0.;!-50 mgKOH / g.
• Polyisocyanate compounds used as the crosslinking agent (E) include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and the like. Any compound may be used.
• aromatic polyisocyanate examples include 1,3 phenylene diisocyanate, 4,4'-dipheninoresin isocyanate, 1,4 phenylene diisocyanate, 4, 4 '-Diphenylmethane diisocyanate, 2, 4 Tolylene diisocyanate, 2, 6 Tolylene diisocyanate, 4, 4, Torenoleidine diisocyanate, 2, 4, 6 Triisocyanate tonorene 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether ether diisocyanate, 4,4,4 "triphenylmethane triisocyanate, etc. Can be mentioned.
• Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylenediocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate. And hexamethylene diisocyanate.
• Examples of the araliphatic polyisocyanate include ⁇ , ⁇ '-diisocyanate 1,3-dimethylbenzene, ⁇ , ⁇ , -diisocyanate 1,4-dimethylbenzene, ⁇ , ⁇ , Examples include isocyanate 1,4-jetylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.
• Examples of the alicyclic polyisocyanate include, for example, 3-isocyanate methyl 1,3,5,5 trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylolene 2,4 cyclohexane diisocyanate, methyl-2,6 cyclohexane diisocyanate, 4,4'-methylenebis (cyclo Hexyl isocyanate), 1,4 bis (isocyanate methyl) cyclohexane, and the like.
• IPDI 3-isocyanate methyl 1,3,5,5 trimethylcyclohexyl isocyanate
• 1,3-cyclopentane diisocyanate 1, 3-cyclohexane diisocyanate
• 1,4-cyclohexane diisocyanate 1,4-cyclohexane diisocyanate
• a trimethylolpropane adduct of the above polyisocyanate compound, a trimer having an isocyanurate ring, or the like can also be used.
• Polyphenylmethane polyisocyanate PAPI
• naphthylene diisocyanate modified polyisocyanate
• modified polyisocyanate and the like can also be used.
• PAPI Polyphenylmethane polyisocyanate
• a modified product having one or more of any force selected from a carpositimide group, a uretdione group, a uretoimine group, a bullet group reacted with water, and an isocyanurate group can be used. Noh.
• a reaction product of a polyol and a diisocyanate can also be used as a polyisocyanate.
• polyisocyanate compounds 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl Non-yellowing or non-yellowing type such as isocyanate (also known as isophorone diisocyanate), xylylene diisocyanate, 4,4, -methylenebis (cyclohexyl isocyanate) (also known as hydrogenated MDI)
• isocyanate also known as isophorone diisocyanate
• xylylene diisocyanate also known as xylylene diisocyanate
• 4,4, -methylenebis (cyclohexyl isocyanate) also known as hydrogenated MDI
• the use of a polyisocyanate compound is particularly preferred from the viewpoint of weather resistance, heat resistance and heat and moisture resistance.
• a known A catalyst can be used to promote the reaction.
• usable catalysts include tertiary amine compounds and organometallic compounds. These may be used alone or in combination of two or more.
• Epoxy compounds used as the cross-linking agent (E) include bisphenol A-epoxychlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glyconoresin glycidino enoate, glycerin diglycidino enoate.
• Glycerin triglycidinoreatenore 1,6-hexanedioresinglycidinoreatenore, trimethylonerepro pantriglycidyl ether, diglycidyl dilin, N, N, N ', N'-tetraglycidyl m xylyl
• Examples include diamamine, 1,3-bis (N, N, -diglycidinoreaminomethinole) cyclohexane.
• the aziridine compounds used as the crosslinking agent (E) include N, N'-diphenylmethane 1,4,4,1bis (1 aziridinecarboxite), N, N, 1 toluene 2,4bis (1 aziridine) Carboxite), bisisophthaloyl 1- (2-methylaziridine), tri-1-diazidinylphosphine oxide, N, N'-hexamethylene 1,6-bis (1 aziridin carboxite), tri ⁇ -aziridinylpropionate, methylolpropane tritriol ⁇ -aziridinylpropionate, ⁇ -aziridinylpropionate, tris 2, 4, 6-(1 —aziridinyl) -1,3,5-triazine, Trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3 (1 aziridinyl) butylate], trimethylolpropane tri
• the raw material isocyanate that produces the high molecular weight polycarpositimide includes 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy 4,4'-diphenylmethane diisocyanate, 3, 3, 1-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3,1 dimethyl-4,4'-diphenyl ether diisocyanate, 2,4 tolylene diisocyanate Cyanate, 2, 6 Tolylene diisocyanate, 1-methoxyphenol, 2, 4 diisocyanate, isophorone diisocyanate, 4, 4 'dicyclic, one or a mixture of two or more of these be able to.
• Carposimidization catalysts include 1-phenyl-2-phospholene-1-oxide, 3-methylol-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene 1-oxide. And phospholenoxides such as these 3-phospholene isomers.
• Examples of commercially available high-molecular-weight polycalpositimides include the Calposlite series manufactured by Nisshinbo Industries, Ltd. Of these, calpositrite V— 01, 03, 05, 07, 0 9 is excellent because it has excellent compatibility with organic solvents!
• 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 'Ethylene bis (2-oxazoline), 2, 2' Ethylene bis (4-methyl-1-oxazoline), 2, 2 '-Propylene bis (2-oxazoline), 2, 2'-Tetramethylene bis (2-oxazoline) 2, 2 'monohexamethylene bis (2-oxazoline), 2, 2' — otatamethylene bis (2-oxazoline), 2, 2 '— p phenylene bis (2-oxazoline), 2, 2' —P—Phenylenebis (4,4'-dimethylenole-2-oxazoline), 2, 2 '—p Phenylenebis (4-methyl-2-oxazoline), 2, 2' —p Phenylenebis (4-phenyl-2-oxazoline), 2, 2'
• copolymers of butyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4 dimethyl-2-oxazoline with other monomers that can be copolymerized with bulur monomers. It can be used.
• Examples of the metal chelate compound used as the crosslinking agent (E) include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Examples include compounds coordinated with acetylacetone or acetyl acetate.
• 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 above-mentioned addition-type polyester resins (D1 to D3) as a polyester resin (D). Is used.
• the composition ratio is such that the amount of the crosslinking agent (E) relative to 100 parts by weight of the polyester resin (D) is 0.00;! To 20 parts by weight, preferably S, and 0.01 to 10 parts by weight. More preferable.
• the amount of the crosslinking agent (E) used exceeds 20 parts by weight, the adhesiveness (wetting and adhesion) tends to decrease when the resulting adhesive composition is used as a pressure sensitive adhesive.
• 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 cause a curing sensation. It is preferable to form a pressure-bonding layer! [0174]
• 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) increases the shape retention by three-dimensional crosslinking of the resin, and the side chain that is not crosslinked. Adhesion between the resin and various substrates is improved.
• the hydroxyl value of the resin is reduced by sealing the hydroxyl group with the sealing compound (c), the heat resistance and heat and moisture resistance under severer conditions than before 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, weathering stabilizers, taters and the like within a range not impairing the effects of the present invention. You may mix
• the adhesive sheet can be obtained by, for example, applying the adhesive composition of the present invention to various sheet-like base materials and drying and curing the adhesive composition.
• an appropriate liquid medium for example, an organic solvent such as ethyl acetate, toluene, methyl ethyl ketone, isopropyl alcohol, and other hydrocarbon solvents. It is also possible to adjust the viscosity of the adhesive composition by adding water, and it is also possible to reduce the viscosity by heating the adhesive composition. However, if water or alcohols are added in a large amount, it may cause a reaction inhibition between the addition type polyester resins (D1 to D3) and the crosslinking agent (E), so it is necessary to pay attention to the addition amount.
• an organic solvent such as ethyl acetate, toluene, methyl ethyl ketone, isopropyl alcohol, and other hydrocarbon solvents
• the sheet-like base material cellophane, plastic, rubber, foam, fabric, rubber cloth, resin-impregnated cloth, glass, metal, wood, etc. were formed into a flexible flat shape.
• the power S is mentioned.
• the sheet-like base material may be composed of a single material or a multilayer material in which a plurality of materials are laminated. Further, the surface of the sheet-like base material that has been subjected to the recording IJ separation treatment can also be used.
• Plastic base materials include various plastic films, such as polyolefin alcohol resins, triacetinol resinolose resin, polypropylene, polyethylene, polychloroolefin, ethylene acetate resin, and other polyolefin resins.
• the film Polyester resin film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate resin film, polynorbornene resin film, polyarylate resin film, acrylic resin film, polyphenylene sulfide resin Film, polystyrene resin film, bull resin film, polyamide resin film, polyimide resin film, epoxy resin film, and the like.
• the method for applying the adhesive composition to the sheet-like substrate is not particularly limited and may be carried out by appropriately selecting suitable application means according to a conventional method.
• suitable application means include Myano, applicator, bureau
• the adhesive composition contains a liquid medium such as an organic solvent or water
• the adhesive layer can be formed on the sheet-like substrate by drying and removing the liquid medium after coating.
• the adhesive layer is formed by cooling and solidifying the molten adhesive layer.
• drying method including hot air drying and methods using infrared rays or reduced pressure.
• drying conditions force depending on the cured form of the adhesive composition, the film thickness, the solvent used, etc.
• Hot air heating of usually about 60 to 180 ° C is preferably used.
• the thickness of the adhesive layer on the sheet-like substrate is preferably 0.1 / m to 200, im, more preferably m to 100m. 0.; If it is less than 1 m, sufficient adhesive strength may not be obtained, and even if it exceeds 200 in, properties such as adhesive strength often do not improve further.
• the adhesive composition of the present invention it is possible to provide a laminate in which an adhesive layer formed of an adhesive composition is laminated on an optical member, and assembling optical devices and components. Can be used for manufacturing.
• a laminate in which an adhesive layer is laminated on a sheet-like or film-like optical member having specific optical characteristics can be obtained by sticking the adhesive layer to a glass member for a liquid crystal cell, thereby forming an optical member / pressure-sensitive adhesive.
• a member for a liquid crystal cell having a composition composed of an agent layer / glass member can be obtained.
• Laminate optics available for the manufacture of such optical instruments examples include various optical films such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
• 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 was prepared by applying an adhesive composition to the release-treated surface of the release-treated sheet-like substrate and drying it to form an adhesive sheet.
• the surface of the adhesive layer was a sheet-like optical member.
• the adhesive composition is directly applied to a sheet-like optical member and dried, and the release-treated surface of the release-treated sheet-like substrate is laminated on the surface of the adhesive layer. Is obtained.
• the laminate strength obtained in this way is used to assemble various optical devices or components by peeling off the peeled sheet-like substrate covering the surface of the adhesive layer and sticking it to the optical member. Is done.
• the adhesive composition of the present invention is composed of a polyester resin! /, When used as a pressure-sensitive adhesive, adhesion to a substrate and an adherend is improved, and a plasticizer Excellent in heat resistance and low temperature adhesion. Therefore, it can be suitably used in applications that require adhesion to a substrate such as a foam.
• 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 are used for the production of optical components and the like. If the refractive index after curing of the object is less than 1.45, the difference in refractive index from the optical film or optical member becomes large, and when the adhesive layer is provided on the optical member, the shallow angle In some cases, total reflection occurs and the effective utilization rate of light decreases. 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.
• the ratio of aromatic groups contained in the polyester resin can be adjusted as appropriate depending on 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 to do.
• 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 1.49-1.60, which is a problem.
• Adhesive layers with rates ranging from 1.50 to; 1.55 can be provided.
• Example [0186] 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.
• “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
• a polymerization reactor is constructed by attaching a stirrer, thermometer, reflux condenser, dropping device and nitrogen introducing tube to the polymerization tank.
• Dibasic acid (a-1) and 2 cyclic ether groups are added to the polymerization tank and the dropping device.
• Each compound (a-2), catalyst and organic solvent were charged in the following ratios.
• This reaction solution is light yellow and transparent, has a non-volatile content of 60.5% by weight, a viscosity of 20, OOOmPa's, an acid value of 0.5 mgKOH / g, a hydroxyl value of 155 mgKOH / g, a glass transition temperature of 60 ° C, and a weight average molecular weight.
• a solution of 50,000 polyester resin (B) was obtained.
• a polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dripping device and nitrogen inlet tube was prepared in the polymerization tank, and the main chain polyester resin obtained in step (1) (B ) Solution, cyclic ester (b), catalyst and organic solvent were charged at the following ratios:
• the resin solution was heated to 100 ° C while stirring.
• the cyclic ester (b) mixture was added dropwise to the stirring resin solution at a constant rate over 1 hour from a dropping device.
• 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 the addition type polyester precursor (C1) added with the cyclic ester (b) A solution was obtained.
• This reaction solution is light yellow and transparent, has a non-volatile content of 60.2% by weight, a viscosity of 15, OOOmPa's, an acid value of 0.05 mgKOH / g, a hydroxyl value of 74 mgKOH / g, a glass transition temperature of 10 ° C, and a weight.
• the cyclic ester (b) causes about 1 • 8 monoleic harm IJ to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound ( a- 2).
• This reaction solution is light yellow and transparent, has a non-volatile content of 60.3% by weight, a viscosity of 18, OOOmPa's, the side chain content of the resin (D1) is 53% by weight, and the aromatic ring content is 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.
• step (1) of Synthesis Example 1 change the dibasic acid (a-1) to 830 parts of isophthalic acid and change the bicyclic ether compound (a-2) to neopentyldaricol.
• a solution of addition type polyester resin (D1) having a pale yellow transparent, non-volatile content of 60.0% by weight and a viscosity of 9, OOOmPa's was obtained.
• the resin (D1) had an acid value of 0.5 mgKOH / g, a hydroxyl group value of 3 mgKOH / g, a glass transition temperature of 30 ° C., and a weight average molecular weight of 80,000.
• the cyclic ester (b) is in a ratio of about 1.3 mol to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2). [0198] (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 nore A diglycidyl 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 non-volatile content of about 60% by weight with ethyl acetate was used in step (2).
• the non-volatile content concentration was adjusted to about 60% by weight with ethyl acetate to obtain a solution of an addition type polyester resin (D1) that was light yellow and transparent and had a viscosity of 8,500 mPa's.
• the resin (D1) had an acid value of 0.5 mgKOH / g, a hydroxyl value of 12 mgKOH / g, a glass transition temperature of 40 ° C., and a weight average molecular weight of 65,000.
• the cyclic ester (b) is in a ratio of about 1.7 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the bicyclic ether compound (a-2) used in step (1) of Synthesis Example 1 was converted into bisphenol alcohol orange glycidyl 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 non-volatile content of about 60% by weight with ethyl acetate was used in step (2).
• BPFG bisphenol alcohol orange glycidyl ether
• the mixture was prepared in the same manner as described above 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 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 1 mgKOH / g, a glass transition temperature of 20 ° C., and a weight average molecular weight of 150,000.
• the amount of cyclic ester (b) is about 1.5 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the cyclic ester (b) used in the step (2) of Synthesis Example 1 was changed to ⁇ valerolataton: 100 parts, and the addition type polyester precursor (C1) solution (nonvolatile content 60.0) obtained in the step (2). (Weight%) Except that 200 parts was used in step (3), it was prepared in the same manner as in Synthesis Example 1 and was pale yellow transparent, non-volatile content 60.1% by weight, viscosity 9, OOOmPa's added.
• a solution of type polyester resin (D1) was obtained.
• the resin (D1) has an acid value of 1.5 mgKOH / g, hydroxy acid
• the base value was 12 mgKOH / g
• the glass transition temperature was 30 ° C.
• the weight average molecular weight was 110,000.
• the cyclic ester (b) is in a ratio of about 1 ⁇ 7 mol to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the dibasic acid solution was heated to 100 ° C with stirring and reacted for 8 hours to give a polyester having an acid value of 5 (mgKOH / g) or less.
• the main chain ( ⁇ ) was obtained.
• the cyclic ester (b) mixture was added dropwise 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 tetraptyl ammonium tetrahydroborate was added and aged for another 8 hours, and then the reaction was terminated by adding 1400 parts of ethyl acetate and cooling to room temperature. A solution of type polyester precursor (C1) was obtained.
• This solution is light yellow and transparent, has a nonvolatile content of 59.8% by weight, a viscosity of 30, OOOmPa's, and the precursor (C1) has an acid value of 0.02 mgKOH / g, a hydroxyl value of 92 mgKOH / g, glass
• the resin had a transition temperature of 15 ° C and a weight average molecular weight of 200,000.
• the cyclic ester (b) is in the ratio of about 0.6 mol to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• This solution is light yellow and transparent, has a non-volatile content of 60.5% by weight, a viscosity of 35, OOOmPa's, the side chain content of the resin (D1) is 53% by weight, and the aromatic ring content is 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.
• the temperature of the mixture was raised to 100 ° C. while stirring, and 2.0 parts of tetraptyl ammonium tetrahydroborate was added to initiate the reaction. Addition of tetraptylammonium tetrahydroborate every 2 hours, 2 parts in total, for 2 hours, and agitation for a total of 24 hours, stirring the mixture, adding type polyester precursor (C1) A solution was obtained.
• the cyclic ester (b) is in a ratio of about 1.8 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• addition type polyester precursor (C1) solution 650 parts of ethyl acetate, silylating agent (cl ) Hexamethyldisilazane: 245 parts was added and aged for 6 hours. Thereafter, 300 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 60.4% by weight, a viscosity of 15, and OOOmPa'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. The temperature was 10 ° C and the weight average molecular weight was 150,000.
• a solution of addition type polyester resin (D1) of OOOmPa's was obtained.
• the resin (D1) had an acid value of 0.8 mgKOH / g, a hydroxyl value of 10 mgKOH / g, a glass transition temperature of ⁇ 10 ° C., and a weight average molecular weight of 120,000.
• 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).
• the dibasic acid (a_l) 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 neopentyldaricol diglycidyl ether: 678 parts.
• the cyclic ester (b) was changed to ⁇ -force prolatatone: 456 parts, tetrabutylammonium nitrate was used 3 times in 2 parts as a catalyst, and the silylating agent (cl) used in step (8) was methoxylated.
• Trimethylsilane Prepared in the same manner as in Synthesis Example 8 except that the amount of ethyl acetate was changed to 118 parts, and was pale yellow transparent, non-volatile content of about 60% by weight, viscosity 15, OOOmPa's A solution of the addition type polyester resin (D1) was obtained.
• the resin (D1) had an acid value of 0.5 mgKOH / g, a hydroxyl value of 12 mgKOH / g, a glass transition temperature of 35 ° C., and a weight average molecular weight of 80,000.
• the cyclic ester (b) is in a ratio of about 0.6 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the catalyst used in Synthesis Example 8 was changed to tetrabutyl titanate, it was prepared in the same manner as in Synthesis Example 8, and it was transparent yellow, non-volatile content 60.1% by weight, and an addition type polyester with a viscosity of 8,500 mPa-s.
• a solution of resin (Dl) was obtained.
• the resin (D1) has an acid value of 0.6 mgKOH / g, a hydroxyl value of 25 mgKOH / g, a glass transition temperature of 10 ° C., and a weight average molecular weight of 110, 00. 0.
• 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).
• the resin (D1) had an acid value of 2.5 mgK OH / g, a hydroxyl value of 40 mgKOH / g, a glass transition temperature of 10 ° C., and a weight average molecular weight of 125,000.
• 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).
• the dibasic acid (a-1) in Step (7) of Synthesis Example 8 is adipic acid: 102 parts and isophthalic acid: 66 parts, and the bicyclic ether compound (a-2) is bisphenol A diglycidyl ether: 3 80
• the cyclic ester (b) was changed to ⁇ -force prolatatone: 285 parts each for catalyst reaction.
• the reaction and maturation of step (7) was carried out at 100 ° C for 24 hours in the same manner as in Synthesis Example 8 except that the starting amount used and the additional amount in the middle were each changed to 0.2 parts.
• step (8) 65 parts of hexamethyldisilazane as a silylating agent (cl) and 100 parts of ethyl acetate are aged for 4 hours, then 90 parts of ethyl acetate is added and cooled to room temperature. As a result, a solution of addition-type polyester resin (D1) was obtained.
• 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.
• the weight average molecular weight was 40,000 ° C.
• the cyclic ester (b) has a ratio of about 1.1 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• step (7) of Synthesis Example 8 dibasic acid (a-1) is adipic acid: 44 parts and isophthalic acid: 33 parts, and bicyclic ether compound (a-2) is bisphenol A diglycidyl ether: 76 0
• cyclic ester (b) was changed to ⁇ -force prolatatone: 684 parts and the catalyst was used, and the reaction / ripening in step (7) was 100 °. C went for 24 hours.
• step (8) silyl methylating agent (cl) hexamethyldisilazane: 290 parts and ethyl acetate 665 parts were added and aged for 4 hours, and then ethyl acetate: 142 parts were added and cooled to room temperature. As a result, a solution of addition-type polyester resin (D1) was obtained.
• the resin (D1) has an acid value of 0.1 mgKOH / g, a hydroxyl value of 33 mgKOH / g, a glass transition temperature. Degree—8 ° C., weight average molecular weight 20,000.
• the cyclic ester (b) has a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• Dibasic acid (a_l) in step (7) of Synthesis Example 8 is sebacic acid: 101 parts, and bicyclic ether compound (a-2) is polyethylene glycol diglycidyl ether (ethylene oxide addition moles: 22): 661
• the reaction (age) for a total of 24 hours in Step (7) was performed. I got it.
• step (8) 245 parts of hexamethyldisilazane as a silylating agent (cl) and 427 parts of ethyl acetate are added and aged for 4 hours, and then 300 parts of ethyl acetate is added and cooled to room temperature.
• a solution of addition-type polyester resin (D1) which was light yellow and transparent, had a nonvolatile content of 60.5% by weight and a viscosity of 26, OOOmPa's was obtained.
• the resin (D1) had an acid value of 0.2 mgKOH / g, a hydroxyl value of 15 mgKOH / g, a glass transition temperature of 90 ° C., and a weight average molecular weight of 300,000.
• the cyclic ester (b) is in a ratio of about 5 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• step (7) of Synthesis Example 8 dibasic acid (a-1) is added to 83 parts of isophthalic acid, bicyclic ether compound (a-2) is added to 380 parts of bisphenol A diglycidyl ether, and cyclic ester ( In the same manner as in Synthesis Example 8 except that b) was changed to ⁇ -force prolatatone: 342 parts, and toluene was not used as the organic solvent, but only ethyl acetate: 200 parts. A total of 24 hours of reaction and maturation.
• step (8) hexamethyldisilazane as a silylating agent (cl): 245 parts and 200 parts of ethyl acetate are aged for 4 hours, then 300 parts of ethyl acetate is added and cooled to room temperature.
• a solution of addition-type polyester resin (D1) which was light yellow and transparent and had a non-volatile content of 59.3% by weight and a viscosity of 15, OOOmPa's was obtained.
• the resin (D1) had an acid value of 0.5 mgKOH / g, a hydroxyl value of 10 mgKOH / g, a glass transition temperature of 30 ° C., and a weight average molecular weight of 230,000.
• the cyclic ester (b) is in a ratio of about 1.3 mol to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the same procedure as in Synthesis Example 8 was carried out except that only 266 parts of ethyl acetate was added without using a silylating agent (cl) in the step (8) of Synthesis Example 8, and it was light yellow and transparent, and was non-volatile.
• a solution of 60.0% by weight, viscosity 15, OOOmPa's was obtained.
• the resin contained in this solution is a polyester resin having a polyester main chain (I) and a side chain (II) by addition of a cyclic ester, an acid value of 0.6 mgKOH / g, a hydroxyl value of 93 mgKOH / g, and a glass transition.
• the temperature was 15 ° C and the weight average molecular weight was 135,000.
• the cyclic ester (b) is about 1.8 moles per mole of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• 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.) at 12 rpm for 1 minute.
• the weight-average molecular weight of the resin is determined by liquid chromatography using GPC (gel permeation chromatograph) “HPC-8020” manufactured by Tosoh Corporation. (Mw) was determined in terms of polystyrene.
• Tg glass transition temperature
• the acid value (unit: mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
• Phex Bisphenol A-based phenoxy resin Side chain content (wt%): Side chain content in addition type polyester resin (wt%)
• Methylolpropane adduct body 2.5 parts by weight were added and stirred well to obtain an adhesive composition.
• release film a release-treated polyester film
• a polarizing film with a multilayer structure is prepared by sandwiching both sides of a polybulal alcohol (PVA) polarizer with a triacetylcellulose-based protective film (hereinafter referred to as “TAC film”).
• PVA polybulal alcohol
• TAC film triacetylcellulose-based protective film
• the obtained laminate was aged at a temperature of 23 ° C. and a relative humidity of 50% for 1 week to advance the reaction of the adhesive layer (soot reaction) to obtain a bonded polarizing plate (laminate).
• Example 7 was used 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.
• an adhesive composition (first sealing form) was obtained. Using this, in the same manner as in Example 1, a bonded polarizing plate was produced.
• 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.
• the adhesive layer could not be used for making a laminate because the force adhesive layer that could be applied to the release film did not have tack (initial adhesion).
• 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. TMP2. Immediately after adding 5 parts by weight and stirring well, the viscosity increases rapidly and fluidity is poor. Therefore, it was impossible to produce an adhesive composition.
• 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 prepared.
• the cross-linking agent (E) was changed from TDI / TMP used in Example 8 to XDI / TMP (trimethylolpropane adduct of xylylene disulfonate): 2.5 parts by weight (Example 11) or HM DI / 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.
• the viscosity at 25 ° C was measured every 10 hours for up to 10 hours, and the pot life was measured in the following three steps. evaluated. Viscosity was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 12 rpm for 1 minute.
• the adhesive composition obtained in each Example and Comparative Example was coated on the release film at a speed of 2 m / min by adjusting the supply rate of the comma coater so that the thickness after drying was 25 m. Then, it was dried in an oven at 100 ° C. to form an adhesive layer, and a 50 m thick polyester film was adhered and laminated to prepare an adhesive sheet. The state of the coated surface was visually observed and evaluated in three stages. In addition, the coating process and the following evaluations were not performed for those whose pot life evaluation was “X”.
• ⁇ “Slight repellency is observed at the edge of the coated surface, but there is no problem in practical use.”
• X “Repelling and foaming on the coated surface are recognized, and there is a practical problem.”
• 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 mm, and then a polyester film
• the adhesive sheet was produced by bonding and laminating.
• the Abbe refractometer “DR-M2” manufactured by ATAGO was irradiated with sodium D-ray in an atmosphere of 25 ° C., and the refractive index of the adhesive layer on the adhesive sheet was measured.
• the adhesive compositions obtained in each Example and Comparative Example were applied to a release film and dried in an oven at 120 ° C to provide an adhesive layer having a thickness of 25 m. m polyester film was laminated. After aging the adhesive layer sandwiched between the release film and polyester film for 1 week at a temperature of 23 ° C and a relative humidity of 50%, the release finale is removed and the appearance of the adhesive layer alone is visually judged.
• the HAZE value was measured using a measuring device “NDH-300AJ” manufactured by Nippon Denshoku Industries Co., Ltd.
• ⁇ “No cloudiness is observed, HAZE value: 1 or more and less than 3”
• Tack (initial adhesion) evaluation method The adhesive composition obtained in each example and comparative example was applied to a release film, dried in an oven at 120 ° C. to form an adhesive layer having a thickness of 25 m, and then further coated with a thickness of 50 m polyester film was laminated.
• the adhesive layer taught in the release film and polyester film was aged at a temperature of 23 ° C and a relative humidity of 50% for 1 week, after which the release finale was removed and the adhesive layer was removed using the J 'Dow rolling ball method. Measured under the conditions of 23 ° C and 65% RH. If the evaluation result of tack was “X”, no further evaluation was made.
• the bonded polarizing plate (laminate) is cut to a size of 25mm x 150mm, the release film is peeled off, and it is attached to a float glass plate with a thickness of 1.1mm using a laminator.
• the polarizing plate was firmly adhered to the glass plate by holding in an autoclave under the conditions for 20 minutes. After leaving this specimen at 23 ° C and 50% relative humidity for 1 week, a 180 ° peel test was performed to peel it off at a speed of 300 mm / min in the direction of 180 °. It was visually observed and evaluated in the following three stages.
• Synthesis Examples 21 and 23 to 27 are prepared according to a three-stage manufacturing method
• Synthesis Example 28 is prepared according to a pseudo two-stage manufacturing method
• Synthesis Examples 29 to 43 are prepared according to a two-stage manufacturing method
• Synthesis Examples 22 and 40 are cyclic esters ( b) is omitted.
• a polymerization reactor is constructed by attaching a stirrer, thermometer, reflux condenser, dropping device and nitrogen introducing tube to the polymerization tank.
• Dibasic acid (a-1) and 2 cyclic ether groups are added to the polymerization tank and the dropping device.
• Each compound (a-2), catalyst and organic solvent were charged in the following ratios.
• This solution is light yellow and transparent, has a non-volatile content of 60.5% by weight, a viscosity of 20, OOOmPa's, and 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, The weight average molecular weight was 50,000.
• Step (2) Ring-opening addition reaction of cyclic ester (b)>
• a polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dripping device and nitrogen inlet tube was prepared in the polymerization tank, and the main chain polyester resin obtained in step (1) (B ) Solution, cyclic ester (b), catalyst and organic solvent were charged at the following ratios:
• This solution is light yellow and transparent with a non-volatile content of 60.2% by weight and a viscosity of 15, OOOmPa's.
• the resin has an acid value of 0.05 mgKOH / g, a hydroxyl value of 74 mgKOH / g, and a glass transition temperature of ⁇ 10 ° C.
• the weight average molecular weight was 150,000.
• the cyclic ester (b) is in a ratio of about 1.8 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• a polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dripping device and nitrogen inlet tube was prepared in the polymerization tank, and the addition type polyester precursor (C1) obtained in step (2) was placed in the polymerization tank and the dripping device. ) Solution, acid anhydride (c2), catalyst and organic solvent are charged at the following ratios.
• addition-type polyester precursor (C1) solution was raised to 100 ° C while stirring.
• acid anhydride mixture was dropped at a constant rate over 1 hour from the dropping device.
• the reaction was aged for 8 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).
• 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. The temperature was 10 ° C and the weight average molecular weight was 180,000.
• step (2) is omitted, and in step (3), instead of the addition-type polyester precursor (C 1) solution obtained in step (2), the main product obtained in step (1) is used.
• a chain polyester resin solution (B) nonvolatile content: 60.2% by weight
• a polyester resin solution having a viscosity 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.
• the dibasic acid (a_l) used in 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.
• D1 addition-type polyester resin
• the resin (Dl) had an acid value of 16.5 mg KOH / g, a hydroxyl value of 68 mg KOH / g, a glass transition temperature of 25 ° C., and a weight average molecular weight of 110,000.
• 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).
• the bicyclic ether compound (a-2) used in the step (1) of Synthesis Example 21 was replaced with 1,4 bis ⁇ [(3 ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene: 670 parts, and bisphenol A diglycidyl Ether: Synthesized except that 385 parts of the main chain polyester resin (B) solution was adjusted to about 60% by weight non-volatile content with ethyl acetate in step (2).
• B main chain polyester resin
• Step (2) preparedd in the same manner as in Example 21 and adjusted the non-volatile content to about 60% by weight with ethyl acetate to obtain a solution of addition-type polyester resin (D1) that is pale yellow and transparent and has a viscosity of 11,500 mPa's. .
• the resin (D1) had an acid value of 16.8 mgKOH / g, a hydroxyl value of 72 mgKOH / g, a glass transition temperature of 35 ° C., and a weight average molecular weight of 142,000.
• the cyclic ester (b) is in a ratio of about 1 ⁇ 7 mol to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the bicyclic ether compound (a-2) used in the step (1) of Synthesis Example 21 was converted to bisphenol alcohol glycidyl ether (BPFG manufactured by Osaka Gas Chemorole Co., Ltd., 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 main chain polyester resin (B) solution obtained with ethyl acetate Prepare a solution in the same manner as in Synthesis Example 21 except that 315 parts of a solution adjusted to a nonvolatile content of approximately 60% by weight was used in step (2).
• BPFG bisphenol alcohol glycidyl ether
• a solution of ethyl acetate to reduce the nonvolatile content by approximately 60% by weight.
• 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.
• the cyclic ester (b) is in a ratio of about 1 ⁇ 3 mol to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the resin (D1) had an acid value of 15.8 mgKOH / g, a hydroxyl value of 70 mgKOH / g, a glass transition temperature of ⁇ 25 ° C., and a weight average molecular weight of 120,000.
• the cyclic ester (b) accounts for about 1.6 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• a solution of addition type polyester resin (D1) having a weight of 1 and a viscosity of 14, OOOmPa's was obtained.
• the resin (D1) had an acid value of 13.9 mgKOH / g, a hydroxyl value of 65 mgKOH / g, a glass transition temperature of 15 ° C., and a weight average molecular weight of 170,000.
• the cyclic ester (b) is in a ratio of about 1.8 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the mixture was heated to 100 ° C while stirring and reacted for 8 hours to obtain a polyester resin for the main chain ( ⁇ ) having an acid value of 5 mgKOH / g or less.
• the cyclic ester (b) mixture was dropped at a constant rate over 1 hour from the dropping device. After completion of dropping, add 6 ⁇ 6 parts of tetraptyl ammonium tetrahydroborate after stirring for 8 hours, and further react for 8 hours. After aging, add 3500 parts of ethyl acetate and cool to room temperature. After completion, an addition-type polyester precursor (C1) was obtained.
• This solution is light yellow and transparent, has a non-volatile content of 59.8% by weight, a viscosity of 30, OOOmPa's, and 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 transfer temperature of 15 ° C and a weight average molecular weight of 200,000.
• the cyclic ester (b) has a ratio of about 0.5 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• This solution is light yellow and transparent, has a non-volatile content of 60.5% by weight, a viscosity of 30, OOOmPa's, and 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, weight average molecular weight 170,000.
• the temperature of the mixture was raised to 100 ° C. while stirring, and 2.0 parts of tetraptyl ammonium tetrahydroborate was added to initiate the reaction. While stirring the mixture, add 20 parts of tetraptyl ammonium tetrahydroborate every 8 hours. By adding two times in total, the reaction and aging were carried out for a total of 24 hours to obtain an addition type polyester precursor (C1) solution.
• the cyclic ester (b) is in a ratio of about 1.8 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• 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 nonvolatile 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 non-volatile content of 60.4% by weight, a viscosity of 37, OOOmPa's, and the resin (D1) has an acid value of 11.7 mg KOH / g, a hydroxyl value of 94 mg KOH / g, and a glass transition temperature.
• the temperature was 10 ° C and the weight average molecular weight was 150,000.
• 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.
• the product was prepared in the same manner as in Synthesis Example 29 except that the acid anhydride (c) was changed to 38 parts of succinic anhydride, and was pale yellow transparent, non-volatile content 59.7% by weight, viscosity 15, A solution of addition type polyester resin (D1) of OOOmPa's was obtained.
• the resin (D1) had an acid value of 19.6 mgKOH / g, a hydroxyl group value of 75 mgKOH / g, a glass transition temperature of 35 ° C., and a weight average molecular weight of 160,000.
• the cyclic ester (b) has a ratio of about 0.2 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the resin (D1) had an acid value of 13.8 mgKOH / g, a hydroxyl value of 88 mgKOH / g, a glass transition temperature of 10 ° C., and a weight average molecular weight of 130,000.
• the bicyclic ether compound The cyclic ester (b) has a ratio of about 1 to 8 moles per mole of the secondary hydroxyl group derived from (a-2).
• 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.
• 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).
• the weight of phthalic anhydride which is the acid anhydride (c) used in step (8) of Synthesis Example 29, was changed to 285 parts, and the weight of ethyl acetate added with phthalic anhydride was changed to 237 parts.
• a solution of addition-type polyester resin (D1) was obtained which was light yellow and transparent and had a non-volatile content of 60.4% by weight and a viscosity of 6, OOOmPa's.
• the resin (D1) had an acid value of 80.8 mgKOH / g, a hydroxyl value of 7.8 mgKOH / g, a glass transition temperature of ⁇ 10 ° C., and a weight average molecular weight of 110,000.
• 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).
• Dibasic acid (a_l) used in step (7) of Synthesis Example 29 was added to adipic acid: 102 parts and isophthalic acid: 66 parts, and bicyclic ether compound (a-2) was added to bisphenol A diglycidyl ester: 380 The cyclic ester (b) was changed to ⁇ -force prolatatone: 285 parts, and the amount of catalyst used at the start of the reaction and the amount added in the middle were changed to 0.2 parts respectively. Similarly, the reaction and aging in step (7) was carried out at 100 ° C. for 24 hours.
• step (8) 13 parts of phthalic anhydride as 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 addition-type polyester resin (D1) was obtained.
• the resin (D1) has an acid value of 24.5 mgKOH / g, a hydroxyl value of 90 mgKOH / g, and a glass transition temperature. The temperature was 10 ° C and the weight average molecular weight was 45,000.
• the cyclic ester (b) has a ratio of about 1 ⁇ 1 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• Dibasic acid (a-1) used in step (7) of Synthesis Example 29 was added to adipic acid: 44 parts and isophthalic acid: 33 parts, and bicyclic ether compound (a-2) was added to bisphenol A diglycidyl ester. : In 760 parts, cyclic ester (b) is changed to ⁇ -force prolatatone: 684 parts, respectively. Except for using a catalyst and using a catalyst, the same as in Synthesis Example 29, except that the reaction (maturation) For 24 hours at 100 ° C.
• 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, a viscosity of 98, OOOmPa's,
• the resin (Dl) had an acid value of 2.5 mgKOH / g, a hydroxyl value of 98.3 mgKOH / g, a glass transition temperature of 5 ° C., and a weight average molecular weight of 21,000.
• the cyclic ester (b) has a ratio of about 1.3 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the dibasic acid (a_l) 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 conducted in the same manner as in Synthesis Example 29, except that the cyclic ester (b) was changed to 684 parts in 661 parts, respectively ⁇ -force prolatatone: 684 parts.
• step (8) 56 parts of phthalic anhydride, which is an acid anhydride (c), and 500 parts of ethyl acetate are added and reacted and aged for another 6 hours. Further, 100 parts of ethyl acetate is added and cooled to room temperature.
• 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.
• the cyclic ester (b) is in a ratio of about 5 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the dibasic acid (a_l) used in step (7) of Synthesis Example 29 is isophthalic acid: 83 parts, and the bicyclic ether group compound (a-2) is bisphenol A diglycidyl ether: 380 parts.
• the reaction and aging for 24 hours in Step (7) was carried out in the same manner as in Synthesis Example 29 except that (b) was changed to ⁇ -force prolatatatone: 342 parts.
• step (8) 56 parts of phthalic anhydride, which is an acid anhydride (c2), and 100 parts of ethyl acetate are added, and the reaction is further aged for 6 hours. Then, 74 parts of ethyl acetate is added and cooled to room temperature.
• a solution of addition type polyester resin (D1) which was light yellow and transparent and had a nonvolatile content of 59.5% by weight and a viscosity of 13, OOO 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.
• the cyclic ester (b) has a ratio of about 1 ⁇ 3 mol.
• Synthesis was performed except that cyclic ester (b) was not used in step (7) of synthesis example 29, and the amount of ethyl acetate added with acid anhydride (c) was changed from 500 parts to 204 parts in step (8). 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 polyester resin solution that was light yellow and transparent and had a nonvolatile content of 60.0% by weight and a viscosity of 5, OOOmPa'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.
• step (8) of Synthesis Example 29 100 parts by weight of the solution of the addition-type polyester resin (D 1) obtained in this way is further reacted with phenyl isocyanate as a sealing compound (c). As a result, a hydroxyl group value was reduced from 94 mgKOH / g to a hydroxyl value of 9.5 mgKOH / g, and a solution of addition type polyester resin (D1) having a nonvolatile content of 60.2% by weight and a viscosity of 37, OOOmPa's was obtained.
• step (8) of Synthesis Example 29 100 parts by weight of the solution of the addition-type polyester resin (D 1) obtained in this step is further reacted with jetylmethylsilane as the sealing compound (c). As a result, the hydroxyl value decreased from 94 mgKOH / g to 11.5 mgKOH / g, and a solution of addition-type polyester resin (D1) having a nonvolatile content of 59.9 wt% and a viscosity of 37, OOOmPa's was obtained. .
• toluene 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 21, and TDI / TMP (tolylene diisocyanate) is used as a crosslinking agent (E). 2. 5 parts by weight was added and stirred well to obtain an adhesive composition. 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.
• TDI / TMP tolylene diisocyanate
• 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; “Peeling film / adhesive layer / TAC film / PVA / TAC film” was obtained, and the reaction of the adhesive layer was allowed to proceed to obtain a bonded polarizing plate (laminate). However, since the coated surface was extremely rough, no further evaluation was performed.
• 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 is because the force that could be applied to the release film did not have tack (initial adhesion), so the adhesive layer could not be laminated to the TAC film / PVA / TAC finome structure It was.
• Example 21 to 25 A polarizing plate bonded and processed 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.
• 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 is because the force that could be applied to the release film was a force that the adhesive layer had no tack (initial adhesion), so the adhesive layer was made into a TAC film / PVA / TAC film configuration. could not be laminated.
• HBAP cross-linking agent (E) used in Example 27
• TGMXDA N, N, N ′, N′-tetraglycidyl-m-xylylenediamine
• carpolite V-0 5 Nisshinbo Co., Ltd.
• Carposiimide Crosslinker Example 37
• TMBOXC2, 2'-tetramethylenebis (2-oxazoline)] Example 38
• A1AA Alluminum Tris (acetyl) Acetate
• 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).
• TDI / TMP trimethylolpropane adduct of tolylene diisocyanate
• Example 28 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.
• Example 1 the refractive index, heat resistance, moist heat resistance, optical properties, and removability of the coating film are shown in Examples 1 to 19; Evaluation was conducted in the same manner as above. The results are shown in Table 4.
• the heat resistance evaluation test was conducted in the same manner as in Example 1 except that the adjustment conditions for samples other than Examples 42 and 43 were changed from "Leave for 1000 hours at 120 ° C" to "Leave for 1000 hours at 80 ° C".
• a polymerization reactor is constructed by attaching a stirrer, thermometer, reflux condenser, dropping device and nitrogen introducing tube to the polymerization tank.
• Dibasic acid (a-1) and 2 cyclic ether groups are added to the polymerization tank and the dropping device.
• Each compound (a-2), catalyst and organic solvent were charged in the following ratios.
• This solution is light yellow and transparent, has a non-volatile content of 60.5 wt%, a viscosity of 20, OOOmPa's, and the resin (B) contained in the solution has an acid value of 0.5 mgKOH / g, a hydroxyl value of 155 mgKOH / g, Ga
• the glass transition temperature was 60 ° C and the weight average molecular weight was 50,000.
• a polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dripping device and nitrogen inlet tube was prepared in the polymerization tank, and the main chain polyester resin obtained in step (1) (B ) Solution, cyclic ester (b), catalyst and organic solvent were charged at the following ratios:
• polyester precursor (C1) has an acid value of 0.05 mgKOH / g, a hydroxyl value of 74 mgKOH / g, glass.
• the resin had a transition temperature of 10 ° C and a weight average molecular weight of 150,000.
• the amount of cyclic ester (b) is about 1 ⁇ 8 mol with respect to 1 mol of secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• a polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dripping device and nitrogen inlet tube was prepared in the polymerization tank, and the addition type polyester precursor (C1) obtained in step (2) was placed in the polymerization tank and the dripping device.
• Solution, isocyanate compound (c3), catalyst and organic solvent were charged at the following ratios.
• the resin (D1) has an acid value of 0.05 mgKOH / g, a hydroxyl value of 5 mgKOH / g, and a glass transition temperature of 10
• the weight average molecular weight was 170,000 ° C.
• Dibasic acid (a-1) used in step (1) of synthesis example 44 is isophthalic acid: 830 parts, and bicyclic ether compound (a-2) is neopentylglycol diglycidyl ether: 14 49 parts, respectively.
• a modified solution was prepared in the same manner as in Synthesis Example 44 except that 200 parts of the solution of the obtained polyester resin for main chain (B) (nonvolatile content: 60.2% by weight) was used in step (2).
• the resin had an acid value of 0.6 mgKOH / g, a hydroxyl value of 4 mgKOH / g, a glass transition temperature of 30 ° C., and a weight average molecular weight of 85,000.
• 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).
• the bicyclic ether compound (a-2) used in the step (1) of Synthesis Example 44 was converted to 1,4 bis ⁇ [(3 ethyl-3 oxetanyl) methoxy] methyl ⁇ benzene: 670 parts and bisphenol no A diglycidyl ether: 1385
• 224 parts of the obtained main chain polyester resin (B) solution non-volatile content: 60.0% by weight
• step (2) Adjust the concentration by adding ethyl acetate, light yellow transparent and non-volatile A solution of addition type polyester resin (D1) having a starting weight of 59.9% by weight and a viscosity of 9, OOOmPa's was obtained.
• the resin (D1) had an acid value of 0.5 mgKOH / g, a hydroxyl value of 12.5 mgKOH / g, a glass transition temperature of 40 ° C., and a weight average molecular weight of 68,000.
• the cyclic ester (b) causes about 1 • 8 monoleic harm IJ to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound ( a- 2).
• the bicyclic ether compound (a-2) used in Step (1) of Synthesis Example 44 was converted to bisphenol alcohol orange glycidino 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 ( (Non-volatile content: 60.0% by weight) Prepared in the same manner as in Synthesis Example 44, except that 315 parts were used in step (2).
• a solution of addition type polyester resin (D1) having a content of 59.8% by weight and a viscosity of 19,500 mPa's was obtained.
• the resin (D1) had an acid value of 1.5 mgKOH / g, a hydroxyl value of 12 mgKOH / g, a glass transition temperature of ⁇ 20 ° C., and a weight average molecular weight of 160,000.
• the cyclic ester (b) accounts for about 1.3 moles per mole of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the cyclic ester compound (b) used in Step (2) of Synthesis Example 44 was changed to ⁇ -valerolactone: 100 parts, 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), adjusted by adding ethyl acetate, pale yellow and transparent, non-volatile content 60.2% by weight, viscosity 9,500 mPa '
• a solution of addition type polyester resin (D1) of s was obtained.
• the resin (D1) had an acid value of 1.8 mg KOH / g, a hydroxyl value of 12.5 mg KOH / g, a glass transition temperature of 30 ° C., and a weight average molecular weight of 115,000.
• the cyclic ester (b) is in a ratio of about 1.6 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the isocyanate compound (c3) used in step (2) of Synthesis Example 44 was converted to p Honylisocyanate (PTSI): Prepared in the same manner as in Synthesis Example 44, except that it was changed to 36 parts. Adjusted the concentration by adding ethyl acetate, pale yellow and transparent, nonvolatile content 60.3% by weight A solution of addition-type polyester resin (D1) having a viscosity of 13,500 mPa's was obtained.
• 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.
• 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).
• This solution is light yellow and transparent, has a non-volatile content of 59.8% by weight, a viscosity of 30, OOOmPa's, and 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 transfer temperature of 15 ° C and a weight average molecular weight of 200,000.
• the cyclic ester (b) has a ratio of about 0.1 mol per mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• This solution is light yellow and transparent, has a non-volatile content of 60.2% by weight, a viscosity of 36, OOOmPa's,
• the resin (Dl) had an acid value of 1.0 mgKOH / g, a hydroxyl value of 8.2 mgKOH / g, a glass transition temperature of 15 ° C., and a weight average molecular weight of 225,000.
• the temperature of the mixture was raised to 100 ° C. while stirring, and 2.0 parts of tetraptyl ammonium tetrahydroborate was added to initiate the reaction. While stirring the mixture, the reaction and aging were carried out for 24 hours in total by adding 2 parts of tetraptyl ammonium tetrahydroborate every 8 hours for a total of 24 hours, and the addition type polyester precursor (C 1 ) A solution was obtained.
• addition type polyester precursor (C1) solution 600 parts of ethyl acetate and 200 parts of isocyanate useful as an isocyanate ester compound (c3) were added and aged for 6 hours. Thereafter, 380 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, a viscosity of 16, OOOmPa's, and 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.
• bicyclic The cyclic ester (b) has a ratio of about 1 ⁇ 8 moles per mole of the secondary hydroxyl group derived from the ether compound (a-2).
• the reaction was the same as in Synthesis Example 51 except that the catalyst used in Synthesis Example 51 was changed to tetraptyl ammonium bromide, and the concentration was adjusted by adding ethyl acetate to produce a pale yellow transparent, non-volatile component. 60.
• a solution of an addition type polyester resin 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 mgKOH / g
• the hydroxyl value was 9.8 mgKOH / g
• the glass transition temperature was 10 ° C.
• the weight average molecular weight was 125,000.
• the cyclic ester (b) is a harm IJ of about 1.8 monole to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the dibasic acid (a_l) used in the step (7) of Synthesis Example 51 is succinic acid: 322 parts
• the bicyclic ether compound (a-2) is neopentyl glycol diglycidyl ether: 678 parts
• the cyclic ester compound (except that b) is changed to ⁇ -force prolatatatone: 143 parts
• the catalyst is changed to tetrabutyl ammonium nitrate
• the isocyanate compound (c3) used in step (8) is changed to ptyl isocyanate: 113 parts.
• the addition-type polyester resin (D1) was pale yellow and transparent with a nonvolatile content of 59.6% by weight and a viscosity of 16, OOOmPa's. Solution was obtained.
• the resin (D1) had an acid value of 0.3 mgKOH / g, a hydroxyl value of 12.5 mgKOH / g, a glass transition temperature of 35 ° C., and a weight average molecular weight of 85,000.
• the cyclic ester (b) has a ratio of about 0.2 mol per mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• a solution of addition type polyester resin (D1) having a nonvolatile content of 60.4% by weight and a viscosity of 8,500 mPa's was obtained.
• the resin (D1) had an acid value of 0.1 mgKOH / g, a hydroxyl value of 41.2 mgKOH / g, a glass transition temperature of 10 ° C., and a weight average molecular weight of 130,000.
• 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).
• the dibasic acid (a_l) used in step (7) of Synthesis Example 51 was replaced with adipic acid: 102 parts and iso Phthalic acid: 66 parts, bicyclic ether compound (a-2) changed to bisphenol A diglycidyl ether: 380 parts, cyclic ester (b) changed to ⁇ -force prolatatone: 285 parts. Except for changing the additional amount of tetraptylammonium tetrahydroborate added twice every 8 hours to 0.2 parts each, the same procedure as in Synthesis Example 51 was performed at 100 ° C in step (7).
• step (8) 54 parts of isocyanate compound (c3) benzylisocyanate and ethyl acetate were added, followed by aging for 4 hours. Ethyl acetate was added to adjust the non-volatile concentration. The solution was adjusted and cooled to room temperature to obtain a solution of addition type polyester resin (D1).
• the resin (D1) has an acid value of 79.2 mgKOH / g, a hydroxyl value of 20. lmgKOH / g, glass
• the transition temperature was 10 ° C and the weight average molecular weight was 38,000.
• the cyclic ester (b) has a ratio of about 1 ⁇ 1 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• Dibasic acid (a-1) used in step (7) of Synthesis Example 51 was mixed with adipic acid: 44 parts and isophthalic acid: 33 parts, and bicyclic ether compound (a-2) with bisphenol A diglycidyl ester. : In 760 parts, cyclic ester (b) was changed to ⁇ -force prolatatone: 684 parts, respectively, except that a catalyst was used.
• step (8) 660 parts of isocyanate compound (c3) and 600 parts of ethyl acetate are aged, followed by aging for 4 hours, and then adding ethyl acetate to adjust the non-volatile concentration. The solution was adjusted and cooled to room temperature to obtain a solution of addition type polyester resin (D1).
• This reaction solution is light yellow and transparent, has a non-volatile content of 59.8% by weight and a viscosity of 96,000 mPa-s.
• the resin (D1) has an acid value of 0.1 mgKOH / g, a hydroxyl value of 33.5 mgKOH / g, and a glass transition. The temperature was 8 ° C and the weight average molecular weight was 22,300.
• the cyclic ester (b) causes about 1 • 3 monoleic harm IJ per mole of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• step (8) 200 parts of isocyanate compound (c3) benzyl isocyanate and 500 parts of ethyl acetate are aged for further 6 hours, and then the ethyl acetate is added to adjust the non-volatile concentration and cool to room temperature.
• a solution of addition-type polyester resin (D1) which was light yellow and transparent, 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 mgKOH / g, a hydroxyl value of 15.6 mgKOH / g, a glass transition temperature of 90 ° C., and a weight average molecular weight of 310,000.
• the cyclic ester (b) is in a ratio of about 5 mol per 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• the dibasic acid (a-1) used in step (7) of Synthesis Example 51 is isophthalic acid: 83 parts
• the bicyclic ether compound (a-2) is bisphenol A diglycidyl ether: 380 parts
• cyclic The reaction and aging in step (7) was carried out for 24 hours in the same manner as in Synthesis Example 50 except that ester (b) was changed to ⁇ -force prolatatatone: 342 parts.
• step (8) 200 parts of isocyanate compound (c3) benzylisocyanate and 170 parts of ethyl acetate were added and aged for another 6 hours. Ethyl acetate was added to adjust the nonvolatile content concentration.
• 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.
• the cyclic ester (b) is in a ratio of about 1 ⁇ 3 mol to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• AdA Adipic acid (SV and d- / Lerolactone)
• the addition type polyester precursor (C1) resin solution obtained in step (5) of synthesis example 50 was used instead of the addition type polyester resin (D1) resin solution obtained in step (3) of synthesis example 44. 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 suddenly increased, and could not be applied to the release film.
• Example 50 Instead of the addition type polyester resin (D1) solution obtained in step (3) of synthesis example 44, the solution of addition type polyester resin (D1) obtained in step (6) of synthesis example 50 was used. Except for this, an adhesive composition was prepared in the same manner as in Example 44, and a bonded polarizing plate was produced.
• 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.
• Example 51 except that the addition-type polyester resin (D 1) solution obtained in Synthesis Examples 52 and 53 was used instead of the addition-type polyester resin (D1) solution obtained in Synthesis Example 51.
• An adhesive composition was prepared in the same manner as described above, and a bonded polarizing plate was produced.
• Example 54 trimethylolpropane adduct of xylylene diisocyanate (hereinafter referred to as XDI / TMP and! /) Is: 2. 5 parts, in Example 55 hexamethylene diisocyanate burette adduct (hereinafter referred to as HMDI / burette): 2. Same as Example 51 except that 5 parts were each used. Thus, an adhesive composition was obtained. Using this, a bonded polarizing plate was produced in the same manner as in Example 51.
• This resin was pale yellow and had an acid value of 39 mgKOH / g, an amine value of 0.26 mgKOH / g and a weight average molecular weight of 30,000.
• the resin (D1) had an acid value of 0.5 mgKOH / g, a hydroxyl value of 15 mgKOH / g, a glass transition temperature of 5 ° C., and a weight average molecular weight of 180,000.
• 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).
• Step (1) of Synthesis Example 21 1435 parts of polyamide dicarboxylic acid obtained in Synthesis Example 63 and 747 parts of isophthalic acid were used.
• Step (2) of Synthesis Example 20 173 parts of a polyester resin for main chain (B) (non-volatile content: 60.0% by weight) was prepared and used to prepare Step (2) of Synthesis Example 20 and Reaction was carried out in the same manner to obtain a solution of a caropolyester resin (D1) with light yellow and transparent, non-volatile content of 60.5% by weight, viscosity of 40, OOOmPa.s.
• D1 caropolyester resin with light yellow and transparent, non-volatile content of 60.5% by weight, viscosity of 40, OOOmPa.s.
• the resin (D1) had an acid value of 16 mgKOH / g, a hydroxyl group value of 62 mgKOH / g, a glass transition temperature of 5 ° C., and a weight average molecular weight of 170,000.
• 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).
• Step (1) of Synthesis Example 44 1435 parts of the polyamide dicarboxylic acid obtained in Synthesis Example 63 and 747 parts of isophthalic acid were used.
• Step (2) of Synthesis Example 43 173 parts of a polyester resin for main chain (B) (non-volatile content: 60.0% by weight) was prepared and used to prepare Step (2) of Synthesis Example 43.
• Perform the same reaction adjust the concentration by adding ethyl acetate, and add a solution of addition-type polyester resin (D1) that is light yellow, transparent, non-volatile content 60.3 wt%, viscosity 46, OOOmPa's. Obtained.
• D1 addition-type polyester resin
• the resin (D1) had an acid value of 0.4 mgKOH / g, a hydroxyl value of 15.5 mgKOH / g, a glass transition temperature of 5 ° C., and a weight average molecular weight of 185,000.
• the cyclic ester (b) is in a ratio of about 3 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).
• Example 1 instead of the addition-type polyester resin (D1) solution obtained in step (3) of Synthesis Example 1, the addition-type polyester resin (D1) solution obtained in Synthesis Example 64 was used. Except for the above, 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 similar evaluations.
• Example 20 except that the addition type polyester resin (D1) solution obtained in Synthesis Example 65 was used in place of the addition type polyester resin (D1) solution obtained in Step (3) of Synthesis Example 21.
• An adhesive composition was prepared in the same manner as in Example 20, and an adhesive-processed polarizing plate was produced using the adhesive composition. Table 8 shows the results of similar evaluations.
• Example 44 instead of the addition type polyester resin (D1) solution obtained in step (3) of synthesis example 44, the addition type polyester resin (D1) solution obtained in synthesis example 66 was used.
• An adhesive composition was prepared in the same manner as in Example 44 except that it was used, and an adhesive-processed polarizing plate was produced using this. Table 8 shows the results of similar evaluations.
• TDI / TMP Trimethylolpropane adduct of tolylene diisocyanate
• High molecular weight dicarboxylic acid (a-1-2) is used as dibasic acid (a-1)
• the following synthesis examples 67 to 107 include dibasic acid (a-1 ) Shows a case where a high molecular weight dicarboxylic acid (a-1-2), which is a reaction product of a low molecular weight dicarboxylic acid (a_l_l) and various polyols (a-1- ⁇ ), is used.
• a polymerization reactor is configured by attaching a stirrer, thermometer, reflux condenser, dropping device, and nitrogen inlet tube to the polymerization tank, and the low molecular weight dicarboxylic acids (a-l_l) and polyols (a -1-a), a compound having two cyclic ether groups (a-2), a catalyst and an organic solvent were charged in the following ratios.
• Kuraraypolio-Nore P4010 (a— 1— ⁇ ) 3763 ⁇ 4
• This solution is light yellow and transparent, has a non-volatile content of 50.1% by weight, a viscosity of 18, and OOOmPa's, an acid value of 0.07 mgKOH / g, a hydroxyl value of 75.2 mgKOH / g, a glass transition temperature of 40 ° C, and a weight.
• a polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dripping device and nitrogen inlet tube was prepared in the polymerization tank, and the main chain polyester resin obtained in step (1) (B ) Solution, cyclic ester (b), catalyst and organic solvent were charged at the following ratios:
• This solution is light yellow and transparent, has a nonvolatile content of 50.1% by weight, a viscosity of 20, OOOmPa's, and has a polyester precursor (C1) having an acid value of 0.05 mgKOH / g, a hydroxyl value of 56.2 mgKOH / g, The resin had a glass transition temperature—20 ° C. and a weight average molecular weight of 160,000.
• 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).
• the resin (D1) has an acid value of 0.2 mg KOH / g, a hydroxyl value of 25 mg KOH / g, and a glass transition temperature. The temperature was 20 ° C and the weight average molecular weight was 165,000.
• Step (2) in Synthesis Example 67 was omitted, and 500 parts of the solution (B. 1% by weight of non-volatile content) of the polyester resin for main chain (B) obtained in step (1) was added in step (3).
• Upon cooling a pale yellow transparent solution of polyester resin having a non-volatile content of 50.2% by weight and a viscosity of 17, OOOmPa's was obtained.
• the resin had an acid value of 0.05 mgKOH / g, a hydroxyl value of 28 mgKOH / g, a glass transition temperature of 40 ° C., and a weight average molecular weight of 155,000.
• the sealing compound (c) used in Step (3) of Synthesis Example 67 was the same as Synthesis Example 67 except that 34 parts of phthalic anhydride as the acid anhydride (c2) was used. 24 parts of ethyl acetate was added and cooled to room temperature to obtain a solution of addition-type polyester resin (D1) that was light yellow and transparent, had a nonvolatile content of 50.3% by weight and a viscosity of 17, 50 OmPa'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.
• 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 67 except that the sealing compound (c) used in Step (3) of Synthesis Example 67 was changed to 5 parts of phthalic anhydride (c), which is the acid anhydride (c2). Prepared in the same manner as above, and cooled to room temperature without adding ethyl acetate.
• the resin (D1) had an acid value of 5.8 mgKOH / g, a hydroxyl value of 51.5 mgKOH / g, a glass transition temperature of 20 ° C., and a weight average molecular weight of 105,000.
• 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).
• a polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dropping device and nitrogen inlet tube was prepared in the polymerization tank, and dicarboxylic acid, diol and catalyst were charged into the polymerization tank at the following ratios.
• the reaction was continued while dehydrating until the acid value was 2 or less. Next, the reaction was terminated by cooling to 50 ° C. or lower to obtain a polyester polyol.
• This polyester polyol was light yellow and transparent, and had an acid value of 0.3 mgKOH / g, a hydroxyl group value of 21.5 mgKOH / g, a glass transition temperature of 20 ° C., and a number average molecular weight (Mn) of 4,200.
• Kuraraypolio-Nore P4010 (a— 1— a) 376 copies
• the mixture was heated to 100 ° C. while stirring, and reacted for 8 hours to obtain a high molecular weight dicarboxylic acid (a-1-) that is a dibasic acid (a-1). 3) was obtained. Next, the above mixture was dropped at a constant rate over 1 hour from the dropping device.
• This solution is light yellow and transparent, has a nonvolatile content of 50.2% by weight, a viscosity of 22, OOOmPa's, and 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.
• the cyclic ester (b) is in a ratio of about 1.4 mol with respect to 1 mol of the secondary hydroxyl group derived from the bicyclic ether compound (a-2).

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