JP2017171802A - Bisphenol f skeleton-containing phenoxy resin, manufacturing method therefor and resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenoxy resin excellent in low viscosity, transparency, adhesiveness and storage stability and suitably usable in a dry film type adhesive used when a touch panel and a frame printed cover panel are laminated, and a composition thereof.SOLUTION: There is provided a bisphenol F skeleton-containing phenoxy resin having a structure represented by the following general formula (1) in a main chain, weight average molecular weight of 30000 to 60000 in terms of polystyrene, ratio of weight average molecular weight and number average molecular weight of 3.5 to 6.5 and ratio of molecular weight at maximum intensity by a static polygonal light scattering method and molecular weight of maximum intensity by specific refractive index of 3.0 to 15.SELECTED DRAWING: None

Description

  The present invention relates to a bisphenol F skeleton-containing phenoxy resin, a method for producing the same, and a resin composition using the same, and in particular, low viscosity, low temperature thermocompression bonding, and transparency that can be suitably used as an adhesive for display element-related members. The present invention relates to provision of a bisphenol F skeleton-containing phenoxy resin, a resin varnish, and a resin composition using the same.

  Conventionally, a thermoplastic polyhydroxy polyether resin is generally known as a phenoxy resin, and has excellent flexibility, impact resistance, insulation, adhesion, mechanical properties, etc. It is used in a wide range of applications such as magnetic tape binders, base films for film capacitors, insulating varnishes for electric machines such as motors, adhesives and films for circuit boards, and the like. And it is applied also to the adhesive agent etc. of display element related members, such as a liquid crystal display panel, according to the expansion of a use.

  The adhesive used as the display element-related member may have a use process close to the final process at the time of assembly, such as bonding of panels, and is often restricted when bonded by heat. This is because the already assembled display element material, its related members, and the casing surrounding the display element are easily damaged by heat.

  As the adhesive as the display element-related member, a study on a photo-curing adhesive is widely studied so as not to damage the display element, its related member, and the casing. Commonly used materials are liquid acrylic adhesives or adhesive films in which an acrylic polymer having tackiness at room temperature is applied to a base film. In the case of liquid adhesives, Problems such as poor appearance due to exudation and peeling of the adhesion interface due to curing shrinkage during photocuring occur. In the case of an adhesive film having tackiness at room temperature, there are defects in the handling surface due to stickiness, There are problems in terms of peeling, whitening in a moisture resistance test, and electrical reliability.

  In order to improve this problem, a dry film type adhesive having no tack at room temperature has been studied as an adhesive as a related member of the display element. The dry film type adhesive is used in such a manner that the related member of the display element is pressure-bonded to the base material using heat that does not cause thermal damage, and is temporarily bonded for alignment and then subjected to light or heat treatment. In general, this bonding is performed.

  The required properties of dry film type adhesives are transparency enough to achieve visibility as a display element, high adhesion to various general-purpose substrates, no tackiness at room temperature, and dry film itself Therefore, a phenoxy resin having a glass transition temperature of room temperature or higher may be applied.

  On the other hand, with the recent development of information devices, display devices represented by smartphones have also been diversified. In particular, a cover panel on which a touch panel and frame printing are applied needs to conceal circuit materials and electronic components connected to the touch panel, and the printing thickness may be increased depending on the decorativeness of the frame printing. For this reason, the dry film type adhesive used in this application is required to follow a step of about 100 μm derived from frame printing and to adhere the interface without a gap. At this time, as a dry film type adhesive, it is flexible enough to be wound in a roll form from its product form, sufficient light transmittance after adhesion, and has no tackiness at room temperature, and it damages display element related members It is required that it melts with heat that does not give heat, exhibits high fluidity that can follow a step, and has good adhesion to an adherend.

  As an application of a phenoxy resin as an adhesive to a display element-related member that is vulnerable to heat, an organic EL element laminate sealing film as described in Patent Document 1 can be cited. Examples of the phenoxy resin having excellent optical characteristics include phenoxy resins as described in Patent Documents 2 and 3.

  Patent Document 1 discloses an organic EL sealing resin composition that can be cured at low temperature, using a phenoxy resin containing bisphenol A or bisphenol S skeleton, an epoxy resin, and a blocked isocyanate. However, since the thickness of the organic EL display element is on the order of nm, there is no description for lowering the viscosity that requires step following ability. Since the phenoxy resin having a condensed ring such as a fluorene structure as disclosed in Patent Document 2 has a high glass transition point and a high melt viscosity due to its rigid structure, it is an adhesive for display element-related members that are vulnerable to heat. As inappropriate. A phenoxy resin using an epoxy resin having an alicyclic structure as disclosed in Patent Document 3 as a raw material must pass through a nuclear hydrogenation reaction using a noble metal catalyst, and is economically disadvantageous. When an alcoholic hydroxyl group and epichlorohydrin are used as starting materials, a chlorohydrin compound as an impurity is likely to be generated, and the purity of the epoxy at both ends is lowered, so that a polymer chain does not grow to a desired molecular weight during the synthesis of the phenoxy resin. Further, performing purification such as distillation to increase the purity of the terminal group leads to a decrease in economy. In addition, the phenoxy resin described in Patent Document 3 is described as a polymerizable resin composition having a transmittance of 80% or more at a wavelength of 400 nm when formed into a cured film of 50 μm thickness. No mention is made of transparency as a resin alone or application of adhesives for display element-related members.

  As a general phenoxy resin, a resin composed only of a bisphenol A skeleton is well known and can be obtained economically advantageously. However, since the phenoxy resin composed only of the bisphenol A skeleton has a glass transition temperature of about 90 ° C. and has a high flow start temperature for use as an adhesive for heat-sensitive display element-related members, Is difficult to apply. In order to improve this defect, a phenoxy resin into which a bisphenol F skeleton excellent in fluidity is introduced is also well known. However, in general, phenoxy resin is a linear polymer synthesized from a resin having a divalent glycidyl group and a divalent phenolic hydroxyl group, and since there are few branches, the viscosity is almost unambiguous depending on the target molecular weight. Will be determined. For this reason, even if the bisphenol F skeleton is introduced, there is a limit to lowering the viscosity of the phenoxy resin, and it can be applied when the requirement for further step following and the requirement for low-temperature thermocompression accompanying the change of members are realized. It becomes difficult.

  As a method of reducing the viscosity of the phenoxy resin having a bisphenol F skeleton, a method of increasing the degree of branching while reducing the inertia radius of the polymer while maintaining the same molecular weight can be considered. Specifically, a method of branching a polymer chain by utilizing a secondary alcoholic hydroxyl group generated by ring opening of a glycidyl group during the reaction as a reaction point with the glycidyl group can be considered. However, these methods are difficult to control the degree of branching and the growth reaction of the polymer chains, and it is difficult to achieve low viscosity, often resulting in high molecular weight dispersion, resulting in high viscosity and, in some cases, a crosslinked structure. Is insolubilized by locally occurring.

  In addition, the phenoxy resin using the bisphenol F skeleton as a divalent phenolic compound as a raw material is likely to be colored by oxidation during the production of the phenoxy resin. This is because the methylene group connecting the aromatic rings is easily oxidized to form a carbonylation or another structure that forms a chromophore, and the phenoxide that is an intermediate during the reaction is oxidized to form a quinoid structure. It is thought to be derived from the fact that it is easy to take.

  On the other hand, attempts have been made to use an epoxy resin as a hyper-branched polymer. A hyperbranched polymer is a polymer in which the main chain is branched and branched in the polymerization of monomers, and since it is nearly spherical, it has a shorter inertia radius and lower viscosity than a linear polymer of the same molecular weight. There is.

  In Patent Document 4, glycerin-1,3-diglycidyl ether is used as a monomer, the self-polymerization is performed using an acid or a basic catalyst, and the absolute molecular weight measured by a multi-angle light scattering detector is measured by gel permeation chromatography. An epoxy group-containing hyperbranched polymer that is at least twice the measured weight average molecular weight is disclosed. However, although there is a useful description as a high hardness, a curing rate, and a low shrinkage when acrylated with an acrylic acid halide or anhydride, the glycerin-1,3-diglycidyl ether which is a precursor to acrylate is used. As for polyepoxides, there is no description about lowering the viscosity when compared with the same molecular weight. In addition, glycerin-1,3-diglycidyl ether itself, unlike epoxy resins composed of aromatics, has a high flexibility of the main chain, so the distance between the secondary hydroxyl group and the epoxy group is easily accessible in the molecule. As described therein, proton exchange equilibrium at the time of ring opening is likely to occur, and primary alcohol is likely to be generated. This means that the quality at the time of storage or reaction is likely to deteriorate, and selectively synthesizes a normal alternating copolymer type phenoxy resin from glycerin-1,3-diglycidyl and bisphenols as raw materials. Is quite difficult to implement.

  Patent Document 5 discloses an epoxy adhesive film for an additive printed wiring board using a high molecular weight epoxy polymer having a weight average molecular weight of 70000 or more by gel permeation chromatography and a weight average molecular weight of 70000 or more by a light scattering method. Is disclosed. However, there is no difference between the weight average molecular weight determined by gel permeation chromatography and the weight average molecular weight determined by the light scattering method, and there is no description regarding the comparison of fluidity at low temperatures.

JP 2011-84667 A JP 2013-32549 A International Publication No. 2007/106795 JP 2010-150325 A JP-A-6-108016

  For this reason, in the phenoxy resin of the prior art and its manufacturing method, it is difficult to reduce the viscosity when the same raw material is used, and it has transparency and low viscosity suitable as a dry film type adhesive for a display element member. A method is desired.

  As a result of intensive studies by the present inventors, the bisphenol F skeleton-containing phenoxy resin synthesized using a certain catalyst and an aromatic organic solvent has a molecular weight in terms of polystyrene equivalent to that of a conventional bisphenol F skeleton-containing phenoxy resin. However, the molecular weight measured by the static light scattering method has shifted to the higher molecular weight side than usual, and more terminal epoxy groups of this phenoxy resin remain than before, and varnishes using this have been conventional The present inventors have found that the viscosity is reduced as compared with the technology, and have reached the present invention.

That is, the present invention is a bisphenol F skeleton-containing phenoxy resin having a structure represented by the following general formula (1) in the main chain, and the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is polystyrene. The conversion value is 30000 to 60000, the ratio (Mw / Mn) of Mw to the number average molecular weight (Mn) of polystyrene conversion value is 3.5 to 6.5, and the light scattering intensity by the static polygonal light scattering method The absolute molecular weight (M _LS ) at which the intensity of the molecular weight distribution indicated by is the maximum intensity and the weight average molecular weight (M _RI ) in terms of polystyrene where the intensity of the molecular weight distribution indicated by the relative refractive index based on tetrahydrofuran is the maximum intensity, The ratio (M _LS / M _RI ) of the bisphenol F skeleton-containing phenoxy resin is 3.0 to 15.

  In general formula (1), A is a divalent organic residue. Y is a group represented by the following general formula (1a). However, 80 mol% or more of Y is a k = 0 component. n is the average number of repetitions of 10-200.

In general formula (1a), Z is a group represented by the following general formula (1b) or (1c). R ₁ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different. m is independently a number from 0 to 4, and m ₁ is independently a number from 0 to 3. k is an average value of 0 to 0.6.

In general formulas (1b) and (1c), A is a divalent organic residue. Y is the same as Y in the general formula (1). n ₁ and n ₂ are the average repeating number of 0 to 200.

  The epoxy equivalent of the bisphenol F skeleton-containing phenoxy resin is 4000-8500 g / eq. The phenolic hydroxyl group equivalent is 7000 to 17000 g / eq. Is preferred.

  A in the general formula (1) is preferably a divalent aromatic group represented by the following general formula (2).

In General Formula (2), X is a 1,1-cyclohexylene group which may have a single bond, a methylene group, a dimethylmethylene group, or an alkyl substituent having 1 to 4 carbon atoms. R ₂ is a monovalent hydrocarbon group having 1 to 8 carbon atoms and may be the same or different. m ₂ is independently a number from 0 to 4.

  Examples of the divalent aromatic group represented by the general formula (2) include groups represented by the following general formulas (2a) to (2d).

In general formulas (2a) to (2d), R _{2 to} R ₅ and m _{2 to} m ₅ are the same as R ₂ and m _{2 in} general formula (2), respectively.

  Furthermore, the present invention uses, as raw materials, a divalent epoxy resin represented by the following general formula (3) and a bisphenol F compound represented by the following general formula (4), and in the presence of an onium salt catalyst, an aromatic system is used. In the solvent, the ratio of the number of moles of the epoxy group (E1) in the divalent epoxy resin to the number of moles of the phenolic hydroxyl group (F1) in the bisphenol F compound is (E1) :( F1) = 1.035 It is a manufacturing method of the bisphenol F frame | skeleton containing phenoxy resin represented by the said General formula (1) characterized by making it react in the range of 1.005: 1.

  In general formula (3), A is a divalent organic residue.

In the general formula (4), R ₁ is a monovalent hydrocarbon group having 1 to 8 carbon atoms may each be the same or different. m is independently a number from 0 to 4, and m ₁ is independently a number from 0 to 3. k is an average value of 0 to 0.6, but the component of k = 0 occupies 80% (area%) or more.

Moreover, this invention is obtained with the manufacturing method of the said bisphenol F frame | skeleton containing phenoxy resin, Mw by GPC measurement is 30000-60000 by a polystyrene conversion value, and the ratio (Mw / Mn) of Mw and Mn is 3.5. The molecular weight distribution indicated by the light scattering intensity of the weight average molecular weight by static polygonal light scattering method is the maximum molecular weight (M _LS ) and the relative refractive index based on tetrahydrofuran. It is a bisphenol F skeleton-containing phenoxy resin having a ratio (M _LS / M _RI ) of 3.0 to 15 with respect to the weight average molecular weight (M _RI ) in terms of polystyrene in which the strength of the molecular weight distribution is the maximum strength.

  The onium salt catalyst is preferably an organic phosphonium salt represented by the following general formula (5), and the aromatic solvent preferably has a boiling point of 80 to 145 ° C. under normal pressure.

ここで、Ｒ₇は１価の炭化水素基を表し、それぞれ同一でも異なっていてもよい。Ｘ₁は１価の陰イオンを形成する原子及び原子団である。

Here, R ₇ represents a monovalent hydrocarbon group, which may be the same or different. X ₁ is an atom and atomic group forming a monovalent anion.

R ₇ preferably satisfies any one of the following conditions (A) to (C).
(A) all R ₇ are alkyl groups having 1 to 10 carbon atoms,
(B) All R ₇ may have an aryl group which may have a substituent or an aralkyl group which may have a substituent,
(C) three R ₇ is an aryl group which may have a substituent group, one R ₇ is an alkyl group having 1 to 10 carbon atoms.

X ₁ is preferably a halogen atom or any one of the following general formulas (5a) to (5c).

In the general formulas (5a) to (5c), R ₈ and R ₉ each represent an alkyl group having 1 to 4 carbon atoms, and may be the same or different. R ₁₀ represents an alkyl group having 1 to ₁₀ carbon atoms.

  In the structure represented by the general formula (4), the component of k = 0 is preferably 96.5 area% or more.

  Furthermore, the present invention is a resin varnish prepared by using the above bisphenol F skeleton-containing phenoxy resin to a resin concentration of 15 to 90% by mass using an organic solvent.

  Furthermore, this invention is a resin composition which contains the hardening agent which has the said bisphenol F frame | skeleton containing phenoxy resin or the said resin varnish, and a phenoxy resin as an essential component. In addition, a composition in which the bisphenol F skeleton-containing phenoxy resin or the resin varnish is used as a thermoplastic resin and a curable resin, for example, a thermosetting resin such as an epoxy resin, or a photocurable resin such as an acrylate is blended in the composition. is there. Further, it is a cured product obtained by subjecting the resin composition to light and / or heat treatment.

  Furthermore, the present invention is an optical adhesive, a coating agent, or a display device using the bisphenol F skeleton-containing phenoxy resin, the resin composition, or the resin varnish.

  The bisphenol F skeleton-containing phenoxy resin of the present invention is excellent in low viscosity, transparency, adhesiveness, and storage stability, and its composition is useful for optical materials, coating materials, and electronic materials. In the dry film type adhesive used when bonding the frame-printed cover panel, improvement of the problem such as the step following property which is a problem can be expected.

It is a GPC chart shown by the relative refractive index difference of resin of an Example. It is a GPC chart shown by the relative refractive index difference of resin of a comparative example. It is a GPC chart shown by the light scattering intensity | strength of resin of an Example. It is a GPC chart shown by the light scattering intensity | strength of resin of a comparative example.

Hereinafter, embodiments of the present invention will be described in detail. The bisphenol F skeleton-containing phenoxy resin of the present invention is represented by the above general formula (1), Mw by GPC measurement is 30000-60000 in terms of polystyrene, Mw / Mn = 3.5-6.5, static Of absolute molecular weight (M _LS ) where the intensity of the molecular weight distribution indicated by the light scattering intensity by the dynamic polygon light scattering method is the maximum intensity and polystyrene intensity where the intensity of the molecular weight distribution indicated by the relative refractive index based on tetrahydrofuran is the maximum intensity the weight average molecular weight by (M _RI) and the ratio of (M _LS / M _RI) is 3.0 to 15.

In general formula (1), A represents a divalent organic residue. Examples of the divalent organic residue include aliphatic hydrocarbon groups such as ethylene group, propylene group, butylene group, hexylene group, and octylene group, cyclohexylene group, 1,4-dimethylenecyclohexyl group, and decahydronaphthylene group. , Bicyclohexylene group, alicyclic hydrocarbon group such as 4,4′-dimethylenebicyclohexyl group, phenylene group, m-xylylene group, p-xylylene group, naphthylene group, dimethylenenaphthyl group, biphenylene group, bisphenol Examples thereof include aromatic-containing organic residues derived from the above, but are not limited thereto, and may be the same or different. These divalent organic residues may have a monovalent hydrocarbon group having 1 to 8 carbon atoms as a substituent. Preferred examples of the substituent include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a phenyl group, and a styryl group. Preferable A is a divalent aromatic group represented by the above general formula (2) from the viewpoint of physical properties such as low viscosity, transparency, adhesiveness, and economy when a bisphenol F skeleton-containing phenoxy resin is used. It is.
In the general formulas (1) to (4), common symbols are synonymous unless otherwise specified.

In General Formula (2), X is a 1,1-cyclohexylene group which may have a single bond, a methylene group, a dimethylmethylene group, or an alkyl group having 1 to 4 carbon atoms as a substituent.
R ₂ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different. Examples include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a phenyl group, and a styryl group. m ₂ is independently a number from 0 to 4. A preferred embodiment is a structure in which m ₂ is represented by 0 from the viewpoints of availability, low viscosity, and transparency.

In general formula (1), Y is a group represented by the above general formula (1a). In General Formula (1a), Z is a group represented by General Formula (1b) or (1c). A and Y in the general formulas (1b) and (1c) are the same as A and Y in the general formula (1). n ₁ and n ₂ is an average repeating number is from 0 to 200 range.
In the general formula (1a), R ₁ is a monovalent hydrocarbon group having 1 to 8 carbon atoms may each be the same or different. Examples thereof include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a phenyl group, and a styryl group. m is any number from 0 to 4. A preferred embodiment is a structure represented by m = 0 from the viewpoint of availability, low viscosity, and transparency.

In general formula (1), n is an average number of repetitions, and is the range of 10-200. By being in this range, flexibility as a dry film type adhesive for display members, sufficient light transmittance after bonding, non-tack property at room temperature, low heat melting property, low fluidity to follow a step, coverage It is possible to obtain a bisphenol skeleton-containing phenoxy resin that exhibits good adhesion to a dressing. A preferable range of n is 12 to 150, and more preferably 15 to 120. When n is less than 10, the flexibility is poor and it is difficult to wind in a roll shape. When n exceeds 200, the molecular weight is too large, resulting in high viscosity, making it difficult to achieve level difference tracking. For the same reason, the range of n + n ₁ + n ₂ is preferably 10 to 200.

  Mw of the bisphenol F skeleton containing phenoxy resin of this invention is 30000-60000 in polystyrene conversion value. When Mw is less than 30000, the flexibility is poor and it is difficult to wind in a roll shape. On the other hand, when Mw exceeds 60000, the molecular weight is too large, resulting in high viscosity, making it difficult to achieve step following ability. Within this range, flexibility as a dry film type adhesive for display members, sufficient light transmittance after bonding, non-tack property at room temperature, low heat melting property, low fluidity to follow a step, adhesion A bisphenol skeleton-containing phenoxy resin showing good adhesion to the material can be obtained. The preferable range of Mw is 32000-58000, and the more preferable range is 35000-55000. Here, Mw is calculated | required by GPC measurement, and GPC measurement conditions depend on the conditions described in the Example.

  The ratio (Mw / Mn) of Mw and Mn of the bisphenol F skeleton-containing phenoxy resin of the present invention is 3.5 to 6.5. When Mw / Mn is low, the production may be difficult because the epoxy equivalent exceeds the range of the present invention in the production method of the present invention. When Mw / Mn is high, it is in a state of containing a large amount of branched structure generated as a side reaction, and since the degree of freedom of the polymer main chain is limited by the branched structure, brittleness as a film appears. There is a fear. Within this range, flexibility as a dry film type adhesive for display members, sufficient light transmittance after bonding, non-tack property at room temperature, low heat melting property, low fluidity to follow a step, adhesion It is possible to obtain a bisphenol skeleton-containing phenoxy resin that exhibits better properties, such as good adhesion to the material. A preferable range of Mw / Mn is 3.6 to 6.4, a more preferable range is 3.7 to 6.3, and a further preferable range is 3.8 to 6.0. Here, Mw and Mn are obtained by GPC measurement, and GPC measurement conditions are based on the conditions described in the examples.

The bisphenol F skeleton-containing phenoxy resin of the present invention is represented by the absolute molecular weight (M _LS ) at which the intensity of the molecular weight distribution indicated by the light scattering intensity by the static polygonal light scattering method is the maximum intensity and the relative refractive index based on tetrahydrofuran. The ratio (M _LS / M _RI ) to the polystyrene-equivalent weight average molecular weight (M _RI ) at which the intensity of the molecular weight distribution is the maximum intensity is 3.0-15. When M _LS / M _RI is low, this is a case where the degree of branching of the polymer main chain is small, and as a result, the melt viscosity becomes high and the effect of the present invention cannot be obtained. When M _LS / M _RI is high, the absolute molecular weight increases, resulting in an increase in melt viscosity and an increase in the number of branched structures that facilitates the formation of a cross-linked structure, leading to poor storage stability and insolubilization in solvents. Therefore, it is not preferable. Within this range, flexibility as a dry film type adhesive for display members, sufficient light transmittance after bonding, non-tack property at room temperature, low heat melting property, low fluidity to follow a step, adhesion It is possible to obtain a bisphenol skeleton-containing phenoxy resin that exhibits better properties, such as good adhesion to the material. A preferable range of M _LS / M _RI is 3.5 to 12, and a more preferable range is 4.0 to 10. Here, M _LS and M _RI are determined by GPC measurement, and GPC measurement conditions depend on the conditions described in the examples.

  The inventors consider as follows that a specific bisphenol F skeleton-containing phenoxy resin having many branched structures could be created.

  In general GPC measurement, a calibration curve is prepared using a standard substance such as polystyrene having a known molecular weight, and is used as a method of converting to a molecular weight by elution time. Since molecular weight fractionation is performed by the exclusion phenomenon derived from the molecular volume of the polymer when penetrating the gel packed in the column, the molecular weight calculation from the calibration curve is based on the molecular volume in the polystyrene solution. Become. In other words, a calibration curve consisting of elution time and molecular weight is created from the molecular volume in the solution, but for polymers with different main chain skeletons and polymers with a branched structure, the molecular volume in the solution is different from the standard substance. Therefore, only the molecular weight as a relative value using the molecular volume of polystyrene as an index can be expressed.

  On the other hand, the molecular weight measurement by the static polygonal light scattering method considers a polymer as one particle and applies a scattering phenomenon that occurs when light is applied to one particle. It is known that it is proportional to the concentration dependency of concentration, molecular weight, and refractive index. The molecular weight can be determined by measuring the concentration dependency of the refractive index in advance and measuring the concentration dependency and angle dependency of the scattering intensity. Theoretically, when the chemical potential of a solution is derived from the obtained scattering intensity and the solution concentration is approximated to 0 in the differential equation with respect to the concentration of the chemical potential, the chemical potential is expressed theoretically by the reciprocal of the molecular weight. Therefore, the molecular weight obtained by the molecular weight measurement by the static polygonal light scattering method can be handled as an absolute molecular weight.

The absolute molecular weight (M _LS ) at which the intensity of the molecular weight distribution indicated by the light scattering intensity by the static polygonal light scattering method is the maximum intensity defined by the present invention and the intensity of the molecular weight distribution indicated by the relative refractive index based on tetrahydrofuran In other words, the ratio (M _LS / M _RI ) to the weight average molecular weight (M _RI ) in terms of polystyrene that gives the maximum strength can be expressed as (absolute molecular weight) / (molecular volume). When comparing polymers with the same main chain skeleton, when the molecular volume is kept constant, the absolute molecular weight changes depending on the degree of branching of the main chain, so (absolute molecular weight) / (molecular volume) is the degree of branching. It can be regarded as an indicator. That is, the higher this value, the higher the degree of branching.

  The phenoxy resin itself is synthesized from a bifunctional epoxy resin and a bifunctional bisphenol, and usually has an epoxy equivalent of 10,000 g / eq. Although the epoxy group has been consumed up to the above, the bisphenol F skeleton-containing phenoxy resin of the present invention has an Mn and Mw in the GPC method, and a molecular weight distribution similar to that of ordinary phenoxy, but usually has an epoxy group and a phenolic hydroxyl group. It was found that more remained than phenoxy resin. In order to investigate this phenomenon in detail, a molecular weight measurement using a static polygonal light scattering method was performed. As a result, the absolute weight average molecular weight was higher than that of a normal phenoxy resin, and the peak of the molecular weight distribution indicated by the light scattering intensity was found. It turned out that it shifted to the high molecular weight side. In view of the fact that the molecular weight distribution by the GPC method is almost the same as that of a normal bisphenol F skeleton-containing phenoxy resin, a branching reaction proceeds at a position other than the functional group of the epoxy group and the phenolic hydroxyl group, resulting in an absolute molecular weight of Although it increases, it is presumed that as a result of the increase in the number of branched structures, the molecular volume has become comparable. And since such a bisphenol F skeleton containing phenoxy resin has more branched structures than a normal phenoxy resin, if it is the same volume, it must be closer to a rounder structure than the linear structure of the phenoxy resin. Is guessed. Since the viscosity of a polymer basically depends on the “spread” of the structure, the viscosity of a molecule having a rounded structure is lower than that of a linear molecule at the same volume. The phenoxy resin obtained in the present invention is considered to have been able to obtain the effects of the present invention by increasing the components having such a rounded structure and decreasing the viscosity at the time of melting.

  Therefore, 4000-8500 are preferable, as for the epoxy equivalent (g / eq.) Of the bisphenol F frame | skeleton containing phenoxy resin of this invention, 4200-8300 are more preferable, and 4500-8000 are further more preferable. When the epoxy equivalent is low, the film forming property when used alone is weak. On the other hand, when the epoxy equivalent is high, a sufficient effect cannot be obtained even when a curing agent having reactivity with the epoxy group is used. If it is this range, not only the film forming property at the time of using the phenoxy resin of this invention alone but hardened | cured material can be created by making it harden | cure using the hardening | curing agent reactive with an epoxy group. The conventional phenoxy resin has a very large epoxy equivalent, that is, the number of epoxy groups contained in the resin is very small. Therefore, even if a curing agent having reactivity with the epoxy group is used, it is not incorporated into the reaction. Since it remains as a reaction product, heat resistance and the like tend to deteriorate. Since the bisphenol F skeleton-containing phenoxy resin of the present invention can be polymerized with the epoxy group remaining, it can be designed as a thermosetting film resin composition. A curable film can be obtained.

  The phenolic hydroxyl group equivalent (g / eq.) Of the bisphenol F skeleton-containing phenoxy resin of the present invention is preferably from 7000 to 17000, more preferably from 7500 to 16500, and even more preferably from 8000 to 16000. If it is this range, when it is used as a dry film type adhesive for display element members, more suitable transparency and low viscosity are shown. When the phenolic hydroxyl group equivalent is small, the epoxy group is not sufficiently consumed, and a sufficient effect may not be obtained, such as an increase in viscosity and molecular weight in terms of storage stability. On the other hand, when the phenolic hydroxyl group equivalent is large, the reaction with the epoxy group is sufficiently advanced, and the effect of the present invention may not be obtained from the viewpoint of low melt viscosity.

  A general phenoxy resin is synthesized from a bifunctional epoxy resin, a bifunctional resin that is reactive with an epoxy group, and a monomer. From the characteristics of the reaction, an epoxy group or a functional group that is reactive with an epoxy group is The reaction is complete when almost disappeared. On the other hand, the bisphenol F skeleton-containing phenoxy resin obtained by the production method of the present invention undergoes a high molecular weight reaction with both epoxy groups and phenolic hydroxyl groups remaining, and as a result, both functional groups coexist. have.

  This is because, in addition to the reaction of the phenolic hydroxyl group present in the epoxy resin and the bisphenol F compound, an addition or condensation reaction between the polymer main chains occurs at a site other than the epoxy group and the phenolic hydroxyl group. It is presumed that the high molecular weight reaction proceeds as a side reaction while the functional hydroxyl group remains. For example, hydrogen abstraction occurs on the secondary carbon produced by the reaction of the methylene group in the dihydroxydiphenylmethane moiety or the epoxy group with the phenolic hydroxyl group, and a cation or anion is generated on the benzyl position or the secondary carbon. Thus, it is presumed that side reactions that do not involve an epoxy group and a phenolic hydroxyl group such as electrophilic addition, nucleophilic substitution reaction, dimerization reaction on a benzene ring and a methylene moiety or secondary carbon occur. The inventors speculate that this phenomenon appears by selecting a bisphenol F compound having a bisphenol F skeleton, a specific solvent and a specific catalyst. For this reason, even if the molecular weight is the same, the radius of inertia of the molecule is shortened, and as a result, the viscosity is reduced during melting. And if the method of this invention is used, even if the functional group which reacts mutually exists, the phenoxy resin and its varnish which have favorable storage stability can be obtained, without resin changing during storage.

  Next, the manufacturing method of the bisphenol F skeleton containing phenoxy resin of this invention is described.

  The production method of the bisphenol F skeleton-containing phenoxy resin of the present invention comprises a divalent epoxy resin represented by the above general formula (3) and a bisphenol F compound represented by the above general formula (4) as an onium salt catalyst. In the aromatic solvent, the ratio of the number of moles of epoxy group (E1) in the divalent epoxy resin to the number of moles of phenolic hydroxyl group (F1) in the bisphenol F compound is (E1) :( F1) is reacted in the range of 1.035 to 1.005: 1.

By reacting at this ratio, a bisphenol F skeleton-containing phenoxy resin excellent in low viscosity, transparency, adhesiveness, film properties, and storage stability can be obtained. When the ratio exceeds 1.035, it is difficult to control Mw within the range of the present invention, and as a result, it becomes difficult to obtain the effect of the present invention. When the ratio is less than 1.005, M _LS / M _RI is out of the range, the melt viscosity becomes high, and a branched structure is easily obtained due to an increase in the branched structure, resulting in deterioration of storage stability and the like. It is not preferable because it causes insolubilization. Further, if the phenolic hydroxyl group equivalent is out of this ratio, it may be out of the preferred range. A preferable range of (E1) :( F1) is 1.032 to 1.010: 1, and a more preferable range is 1.030 to 1.012: 1.

  As the divalent epoxy resin represented by the general formula (3), various compounds can be applied as long as they are known compounds. For example, ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, or 1, Epoxy resins derived from chain aliphatic diols such as 6-hexanediol; Cycloaliphatic diols such as cyclohexanediol, cyclodecanediol, bicyclohexanediol, decalindiol, cyclohexanedimethanol, or bicyclohexanedimethanol An epoxy resin derived from: an epoxy resin derived from a polyalkylene ether glycol such as polyethylene ether glycol, polyoxytrimethylene ether glycol, or polypropylene glycol; and bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol C, bisphenol K, bisphenol AP, bisphenol BP, bisphenol E, bisphenol P, bisphenol PH, bisphenol AD, bisphenol AF, bisphenol fluorene, biscresol fluorene, bisphenol Z, bisphenol TMC , Dimethyl bisphenol A, tetramethyl bisphenol A, dimethyl bisphenol F, tetramethyl bisphenol F, dimethyl bisphenol S, tetramethyl bisphenol S, tetramethyl bisphenol Z, hydroquinone, resorcin, catechol, methyl hydroquinone, dimethyl hydroquinone, trimethyl hydroquinone, butyl hydroquinone Dibutylha Droquinone, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydiphenyl ether, dihydroxybenzophenone, dihydroxydiphenyl sulfide, thiodiphenol, brominated bisphenol A, or a compound having a monofunctional phenol and one aldehyde group An aromatic group-containing epoxy resin derived from a bisphenol obtained by a condensation reaction of bisphenols obtained by a condensation reaction of a monofunctional phenol and a compound having one carbonyl group, or the like, is not limited thereto. A preferable epoxy resin is a divalent epoxy resin derived from bisphenol A, bisphenol F, biphenol, or bisphenol Z from the viewpoint of availability, transparency, and low melt viscosity.

  In addition, bisphenol F diglycidyl ether [4,4′-methylenebis (glycidyloxybenzene), 2,2′-methylenebis (glycidyloxybenzene) obtained by further distilling an epoxy resin obtained from a bisphenol F compound and epihalohydrin and 2,4′-methylenebis (glycidyloxybenzene) mixture] is an epoxy resin having a content of 98% by mass or more, or a component of k = 0 in the above general formula (4) is 99% by area or more of a bisphenol F compound and an epihalohydrin. The structure of the general formula (1) can also be obtained by reacting the resulting epoxy resin with a divalent phenolic compound. However, it is preferable from the economical viewpoint to use the bivalent epoxy resin represented by the general formula (3) and the bisphenol F compound represented by the general formula (4).

In the general formula (4), R ₁ independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of such a hydrocarbon group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a phenyl group, or a styryl group. m is independently a number from 0 to 4, and m ₁ is independently a number from 0 to 3. A preferable embodiment is a structure represented by m = 0 and m ₁ = 0 from the viewpoint of availability, low viscosity, and transparency. k is an average value of 0 to 0.6, but the component of k = 0 is 80% (area%) or more, preferably 95% or more, and more preferably 96.5% or more. When the component of k = 0 is less than 80%, the number of trifunctional or higher components increases, so that the number of reaction points increases. As the reaction proceeds, insolubilization tends to occur and the effects of the present invention are hardly obtained. In some cases, the k = 0 component is expressed as a binuclear body, the k = 1 component is expressed as a trinuclear body, the k = 2 component is expressed as a 4-nuclear body, and the k = 3 component is expressed as a 5-nuclear body. The bisphenol F skeleton-containing phenoxy resin of the present invention is most preferably a bisphenol F compound in which the value of k in the general formula (4) is 0. This is economically disadvantageous because it involves processing by an analysis operation. The range of k for obtaining the effect of the present invention is 0 to 0.6, and may be a bisphenol F compound with a polynuclear body in this range. Preferably it is 0.0005-0.05, More preferably, it is 0.001-0.01. In addition,%, such as a component of k = 0, is area% based on GPC measurement, and GPC measurement conditions are the same conditions as the molecular weight measurement conditions described in the Examples.

  Moreover, it is preferable that an isomer exists in the binuclear substance in the bisphenol F compound used in the present invention. In the present invention, it is important to control the ratio of three isomers of 4,4′-isomer, 2,2′-isomer, and 2,4′-isomer, and other isomers may be ignored. . This isomer ratio is an area ratio measured by liquid chromatography (HPLC), and the 4,4′-isomer is preferably 40% or less, more preferably 29 to 37%. The 2,2'-form is preferably 20% or less, more preferably 14 to 19%. The 2,4'-form is preferably 40 to 100%, more preferably 44 to 60%. When these isomers exceed the above ratio, the above-described reaction is difficult to occur, and the bisphenol F skeleton-containing phenoxy resin of the present invention having a high molecular weight while the epoxy group and the phenolic hydroxyl group remain cannot be obtained. There is a fear. The HPLC measurement conditions are the same as those described in the examples.

  Further, when the reaction between the divalent epoxy resin and the bisphenol F compound is performed, a divalent phenolic compound can be used in combination as long as the effects of the present invention are not affected. The amount that can be used is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 25 parts by mass or less with respect to 100 parts by mass of the bisphenol F compound.

  When a divalent phenolic compound is used in combination, the total number of moles of phenolic hydroxyl groups in the bisphenol F compound and the number of moles of phenolic hydroxyl groups in the divalent phenolic compound is 2 (F1). It reacts in a molar ratio (E1: F1) = 1.035 to 1.005: 1 with the number of moles (E1) of epoxy groups in the valent epoxy resin.

  Specific examples of divalent phenolic compounds that can be used in combination include bisphenol A, bisphenol S, bisphenol B, bisphenol C, bisphenol K, bisphenol AP, bisphenol BP, bisphenol E, bisphenol P, bisphenol PH, bisphenol AD, and bisphenol. AF, bisphenol fluorene, biscresol fluorene, bisphenol Z, bisphenol TMC, dimethyl bisphenol A, tetramethyl bisphenol A, dimethyl bisphenol S, tetramethyl bisphenol S, tetramethyl bisphenol Z, hydroquinone, resorcin, catechol, methyl hydroquinone, dimethyl hydroquinone, Trimethylhydroquinone, butylhydroquinone, dibutylhydro Non, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydiphenyl ether, dihydroxybenzophenone, dihydroxydiphenyl sulfide, thiodiphenol, brominated bisphenol A, or a compound having a monofunctional phenol and one aldehyde group And bisphenols obtained by a condensation reaction between a monofunctional phenol and a compound having one carbonyl group.

  Catalysts used in the method for producing a bisphenol F skeleton-containing phenoxy resin of the present invention are onium salts such as phosphonium salts, ammonium salts, iodonium salts and sulfonium salts, and organic phosphonium salts represented by the general formula (5) are preferable, You may use 2 or more types as needed.

In general formula (5), R ₇ represents a monovalent hydrocarbon group, which may be the same or different. Moreover, what satisfy | fills any one of the following (I)-(C) is preferable.
(A) All R ₇ are alkyl groups having 1 to 10 carbon atoms.
(B) All R ₇ may have an aryl group which may have a substituent or an aralkyl group which may have a substituent.
(C) three R ₇ is an aryl group which may have a substituent group, one R ₇ is an alkyl group having 1 to 10 carbon atoms.

  Examples of the alkyl group having 1 to 10 carbon atoms described in the above (a) or (c) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, or a decyl group. However, it is not limited to these.

  Examples of the aryl group which may have a substituent described in (b) or (c) above include, for example, a phenyl group, a toluyl group, a dimethylphenyl group, a tert-butylphenyl group, a methoxyphenyl group, a dimethoxyphenyl group, Examples thereof include, but are not limited to, a tert-butoxyphenyl group. Examples of the aralkyl group which may have a substituent include, but are not limited to, benzyl group, 2-phenylethyl group, 1-phenylethyl group, 3-phenylpropyl group, 4-isopropylbenzyl group and the like. Not.

In the general formula (5), X ₁ is an atom or atomic group forming a monovalent anion. Further, a halogen _{^{atom, (R 8 O) 2 PO}} 2 -, (R 9 O) 2 PS 2 - or R ¹⁰ CO ₂ ^- in which is preferable. However, R < ⁸ > and R < ⁹ > represents a C1-C4 alkyl group, and may be same or different, respectively. R ¹⁰ represents an alkyl group having 1 to ¹⁰ carbon atoms. ^{_{(R 8 O) 2 PO 2}} -, (R 9 O) 2 PS 2 - or R ¹⁰ CO ₂ ^- is represented by the general formula (5a) ~ (5c).
R ₈ and R ₉ represent an alkyl group having 1 to 4 carbon atoms, and may be the same or different. A methyl group or an ethyl group is preferable. R ₁₀ represents an alkyl group having 1 to ₁₀ carbon atoms, preferably a methyl group.

Illustrative examples of the organic phosphonium salts represented by the general formula (5) include the following when R ₇ satisfies the above (i).
When X ₁ is halogen: tetramethylphosphonium chloride, tetramethylphosphonium iodide, tetraethylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium iodide, tetra-n-propylphosphonium chloride, tetra-n-propylphosphonium bromide, tetra- n-propylphosphonium iodide, methyltributylphosphonium chloride, methyltributylphosphonium bromide, methyltributylphosphonium iodide, tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium iodide, tetra- n-hexylphosphonium chloride, tetra-n-hexylphosphonium bromide, tetra-n-hexylphosphonium Iodide, tetra-n-octylphosphonium chloride, tetra-n-octylphosphonium bromide, tetra-n-octylphosphonium iodide, tetra-n-decylphosphonium chloride, tetra-n-decylphosphonium bromide, tetra-n-decylphosphonium iodide , Limethylcyclohexylphosphonium bromide, trimethylcyclohexylphosphonium iodide and the like.
When X ₁ is the general formula (5a): tetramethylphosphonium dimethyl phosphate, tetramethylphosphonium diethyl phosphate, tetraethylphosphonium dimethyl phosphate, tetraethylphosphonium diethyl phosphate, methyltripropylphosphonium dimethylphosphate, methyltripropylphosphonium diethylphosphate, methyltributylphosphonium Dimethyl phosphate, methyl tributyl phosphonium diethyl phosphate, tetra-n-butyl phosphonium dimethyl phosphate, tetra-n-butyl phosphonium diethyl phosphate, tetra-n-hexyl phosphonium dimethyl phosphate, tetra-n-hexyl phosphonium diethyl phosphate, methyl trihexyl phosphonium dimethyl Sufeto, and methyl tri-hexyl phosphonium diethylphosphate.
When X ₁ is the general formula (5b): tetramethylphosphonium-o, o-dimethyl phosphorodithioate, tetramethylphosphonium-o, o-diethyl phosphorodithioate, tetraethylphosphonium-o, o-dimethyl phosphorodithioate , Tetraethylphosphonium-o, o-diethyl phosphorodithioate, tetrapropylphosphonium-o, o-dimethyl phosphorodithioate, tetrapropylphosphonium-o, o-diethyl phosphorodithioate, methyltributylphosphonium-o, o -Dimethyl phosphorodithioate, methyltributylphosphonium-o, o-diethyl phosphorodithioate, tetra-n-butylphosphonium-o, o-dimethylphosphorodithioate, tetra-n-butylphosphonium-o, o-die Ruphosphorodithioate, tetra-n-hexylphosphonium-o, o-dimethylphosphorodithioate, tetra-n-hexylphosphonium-o, o-diethylphosphorodithioate, methyltree n-hexylphosphonium-o, o -Dimethyl phosphorodithioate, methyltri n-hexylphosphonium-o, o-diethyl phosphorodithioate, etc.
When X ₁ is the general formula (5c): tetraethylphosphonium acetate, tetraethylphosphonium propionate, tetrabutylphosphonium acetate, tetrabutylphosphonium propionate, tetrabutylphosphonium hexanoate, tetrabutylphosphonium decanoate and the like.

The case where R ₇ satisfies the above (b) is as follows.
When X ₁ is halogen: tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium iodide, tetraphenylphosphonium bromide, tetraphenylphosphonium Iodide etc.
When X ₁ is the general formula (5a): tetraphenylphosphonium dimethyl phosphate, tetraphenylphosphonium diethyl phosphate, benzyltriphenylphosphonium dimethyl phosphate, benzyltriphenylphosphonium diethyl phosphate, etc.
When X ₁ is the general formula (5b): tetraphenylphosphonium-o, o-dimethyl phosphorodithioate, tetraphenylphosphonium-o, o-diethyl phosphorodithioate, benzyltriphenylphosphonium-o, o-dimethylphospho Lodithioate, benzyltriphenylphosphonium-o, o-diethyl phosphorodithioate, and the like.
When X ₁ is the general formula (5c): tetraphenylphosphonium acetate, tetraphenylphosphonium propionate, tetraphenylphosphonium butanoate, tetraphenylphosphonium hexanoate, tetraphenylphosphonium octanoate, tetraphenylphosphonium decanoate Benzyltriphenylphosphonium acetate, benzyltriphenylphosphonium propionate, benzyltriphenylphosphonium butanoate, benzyltriphenylphosphonium hexanoate, benzyltriphenylphosphonium octanoate, benzyltriphenylphosphonium decanoate and the like.

The case where R ₇ satisfies the above (c) is as follows.
When X ₁ is halogen: methyltriphenylphosphonium chloride, methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, propyltriphenylphosphonium chloride , Propyltriphenylphosphonium bromide, propyltriphenylphosphonium iodide, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, hexyltriphenylphosphonium chloride, hexyltriphenylphosphonium bromide, hexyltriphenylphosphonium iodide De etc.
When X ₁ is the general formula (5a): methyl triphenyl phosphonium dimethyl phosphate, methyl triphenyl phosphonium diethyl phosphate, ethyl triphenyl phosphonium dimethyl phosphate, ethyl triphenyl phosphonium diethyl phosphate, propyl triphenyl phosphonium dimethyl phosphate, propyl triphenyl phosphonium Diethyl phosphate, butyl triphenyl phosphonium dimethyl phosphate, butyl triphenyl phosphonium diethyl phosphate, hexyl triphenyl phosphonium dimethyl phosphate, hexyl triphenyl phosphonium diethyl phosphate and the like.
When X ₁ is the general formula (5b): methyltriphenylphosphonium-o, o-dimethylphosphorodithioate, methyltriphenylphosphonium-o, o-diethylphosphorodithioate, ethyltriphenylphosphonium-o, o- Dimethyl phosphorodithioate, ethyltriphenylphosphonium-o, o-diethyl phosphorodithioate, propyltriphenylphosphonium-o, o-dimethyl phosphorodithioate, propyltriphenylphosphonium-o, o-diethyl phosphorodithioate Butyltriphenylphosphonium-o, o-dimethyl phosphorodithioate, butyltriphenylphosphonium-o, o-diethyl phosphorodithioate, hexyltriphenylphosphonium-o, o-dimethyl phosphorodithioate, Sill triphenylphosphonium -o, o-diethyl phosphorodithioate and the like.
When X ₁ is the general formula (5c): methyltriphenylphosphonium acetate, methyltriphenylphosphonium propionate, methyltriphenylphosphonium butanoate, methyltriphenylphosphonium hexanoate, methyltriphenylphosphonium octanoate, methyl Triphenylphosphonium decanoate, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium propionate, ethyltriphenylphosphonium butanoate, ethyltriphenylphosphonium hexanoate, ethyltriphenylphosphonium octanoate, ethyltriphenylphosphonium decane Acid salt, propyltriphenylphosphonium acetate, propyltriphenylphosphonium propionate, propyltriphenylphospho Umbutanoate, propyltriphenylphosphonium hexanoate, propyltriphenylphosphonium octanoate, propyltriphenylphosphonium decanoate, butyltriphenylphosphonium acetate, butyltriphenylphosphonium propionate, butyltriphenylphosphonium butanoate, Butyltriphenylphosphonium propionate, Butyltriphenylphosphonium hexanoate, Butyltriphenylphosphonium propionate, Butyltriphenylphosphonium octanoate, Butyltriphenylphosphonium propionate, Butyltriphenylphosphonium decanoate, Hexyltri Phenylphosphonium acetate, hexyltriphenylphosphonium propionate, hexyltriphenylphos Honium butanoate, hexyltriphenylphosphonium propionate, hexyltriphenylphosphonium hexanoate, hexyltriphenylphosphonium propionate, hexyltriphenylphosphonium octanoate, hexyltriphenylphosphonium propionate, hexyltriphenylphosphonium decanoic acid Salt etc.

The organic phosphonium salts represented by the general formula (5) are not limited to the above.
Among these, more preferable organic phosphonium salts are those in which R ₇ is any one of a methyl group, a butyl group, and a phenyl group, and satisfies the above conditions (a), (b), and (c). X ₁ is a halogen atom. Further preferred organic phosphonium salts are tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetraphenylphosphonium bromide, methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide.

  Examples of onium salts other than the above include organic phosphonium salts such as benzyltriethylphosphonium bromide, phenyltriethylphosphonium bromide, (tert-butoxycarbonylmethyl) triphenylphosphonium bromide, 2-dimethylaminoethyltriphenylphosphonium bromide; Ammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutyl Ammonium Organic ammonium salts such as lithium, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltributylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride; diphenyliodonium iodide, phenyl (2-methylphenyl) iodonium iodide Organic iodonium salts such as phenyl (4-methylphenyl) iodonium iodide, phenyl (2,5-dimethylphenyl) iodonium iodide; triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide, trimethylsulfonium chloride , Trimethylsulfonium bromide, trimethylsulfonium iodide, dimethylphenylsulfide Nium chloride, dimethylphenylsulfonium bromide, dimethylphenylsulfonium iodide, 4-tert-butylphenyldiphenylsulfonium bromide, 4-tert-butylphenyldiphenylsulfonium iodide, 4-tert-butoxyphenyldiphenylsulfonium bromide, 4-tert-butoxy Phenyldiphenylsulfonium iodide, tris (4-tert-butylphenyl) sulfonium bromide, tris (4-tert-butylphenyl) sulfonium iodide, tris (4-tert-butoxyphenyl) sulfonium bromide, tris (4-tert-butoxy) And organic sulfonium salts such as phenyl) sulfonium iodide and p-tolyldiphenylsulfonium bromide.

  Moreover, you may use together the catalyst which can make an epoxy group and a phenolic hydroxyl group react within the grade which does not impair the scope of the present invention. For example, alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride, sodium methoxide, sodium ethoxide Alkali metal alkoxides such as alkali metal phenoxides, alkali metal halide compounds such as sodium hydride and lithium hydride, alkali metal salts of organic acids such as sodium acetate and sodium stearate, tri-n-propylphosphine, and tri-n Organic phosphine compounds such as -butylphosphine, triphenylphosphine, tri-p-tolylphosphine, tri-2,5-xylylphosphine, tri- (p-methoxyphenylphosphine), triethylamine, tri-n-propylamine, Tertiary amine compounds such as ri-n-butylamine and benzyldimethylamine, and nitrogen atom-containing complexes such as pyridine, quinoline, isoquinoline, piperazine, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. A ring compound etc. are mentioned.

  The catalyst concentration in the production of the bisphenol F skeleton-containing phenoxy resin of the present invention is not particularly limited, but is usually 5 ppm to 100,000 ppm. If it is 5 ppm or less, the reaction rate is very slow and economically disadvantageous. If it exceeds 100,000 ppm, the progress of side reactions cannot be ignored, and in some cases the resin becomes insoluble, which is not preferable.

  The solvent used in the method for producing the bisphenol F skeleton-containing phenoxy resin of the present invention may be an aromatic solvent. Such a solvent is not particularly limited as long as it is a known one. Examples include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, benzyl chloride, anisole, methoxytoluene and the like, but are not limited thereto, and two or more kinds may be used in combination. Among these, more preferable aromatic solvents are solvents having a boiling point of 80 to 145 ° C. under normal pressure, such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like. A particularly preferred solvent is toluene from the viewpoints of safety, energy required for drying and time.

  By using the above aromatic solvent, the bisphenol F skeleton-containing phenoxy resin of the present invention can be obtained relatively easily. In the case of other solvents, it may be difficult to control the reaction and to determine the reaction end point. Moreover, when using together solvents other than an aromatic solvent, it is preferable to use 70 mass% or more of aromatic solvents with respect to the whole solvent. If it is this quantity, the bisphenol F frame containing phenoxy resin of this invention can be obtained comparatively easily. As the solvent other than the aromatic solvent that can be used in combination, various solvents can be applied as long as they do not affect the epoxy group and the phenolic hydroxyl group. For example, aliphatic hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, Ketone solvents such as cyclopentanone, ether solvents such as dioxane, ethyl phenyl ether, ethyl benzyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, cellosolv solvents such as methyl cellosolve, ethyl cellosolve, Alkylene glycol mono, such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate Ruki and ethers acetate-based solvents, dimethyl formamide, various solvents such as dimethyl sulfoxide not limited thereto, may be used in combination of two or more.

  The reaction temperature in the production of the bisphenol F skeleton-containing phenoxy resin of the present invention is not particularly limited, but is usually 50 ° C to 230 ° C, and particularly preferably the present invention is an aromatic hydrocarbon having a boiling point of 80 ° C to 145 ° C. Since it uses, it is 80 to 160 degreeC. Below 50 ° C., the reaction rate is very slow and economically disadvantageous. When the reaction temperature exceeds 230 ° C., the progress of side reactions cannot be ignored, and in some cases the resin becomes insoluble, which is not preferable.

  In particular, the effect of the present invention can be obtained by using a catalyst represented by the organic phosphonium salt compound described in the general formula (5) and an aromatic hydrocarbon solvent having a boiling point of 80 ° C. to 145 ° C. under normal pressure during the reaction. A bisphenol F skeleton-containing phenoxy resin that can be expressed to the maximum can be produced. For this reason, the inventors consider as follows.

  In the production of phenoxy resin, it is individually known that an aromatic organic solvent is used as a reaction solvent and an organic phosphonium salt is used as a catalyst. There is no. A general phenoxy resin is a relatively highly polar polymer having a secondary alcoholic hydroxyl group in the side chain, and an aromatic solvent having a low polarity is poor in the solubility of the phenoxy resin. On the other hand, when a bisphenol F structure containing a structural isomer was used as a raw material, the polymer main chain structure was randomly asymmetric, and it was thought that the solvent could be increased even with a low polarity solvent. In the F skeleton-containing phenoxy resin, no phenomenon of the macroscopic aggregation and separation of the resin was observed even during the reaction. As described above, the bisphenol F compound used in the present invention generally has three kinds of structural isomers as a binuclear body, and has an asymmetric structure, so that the dissolving power is improved, and the aromatic solvent contains the bisphenol F skeleton of the present invention. It is considered that a behavior like a θ solvent is expressed with respect to the phenoxy resin, and it is considered that an aromatic hydrocarbon having a boiling point of 80 ° C. to 145 ° C. is particularly optimal under normal pressure.

  In such a reaction system, it is considered that the part in which the organic solvent is compatible and the part incompatible with the organic solvent are microscopically separated, and the catalyst used in the production of the phenoxy resin acts as a phase transfer catalyst. It is estimated that the behavior is different from that of a homogeneous system using a solvent. In the method of the present invention, a solvent having poor solubility in a phenoxy resin such as an aromatic solvent, a specific quaternary phosphonium salt, and a bisphenol F compound having a structural isomer are added to the above-described benzylic position or secondary carbon. Due to the generation of a cation or anion, side reactions that do not involve an epoxy group and a phenolic hydroxyl group such as electrophilic addition, nucleophilic substitution reaction, dimerization reaction, etc. on the benzene ring and the methylene moiety or secondary carbon proceed. It is presumed that the bisphenol F skeleton-containing phenoxy resin of the present invention was obtained by increasing the molecular weight while the group and the phenolic hydroxyl group coexisted. The bisphenol F skeleton-containing phenoxy resin obtained by the production in the presence of such a θ solvent coexists with an epoxy group and a phenolic hydroxyl group, and is excellent in storage stability. In addition, no reported examples of bisphenol F skeleton-containing phenoxy resins having such properties have been found so far. In the present invention, it is presumed that a specific reaction field is created by using the onium salts in combination with an aromatic catalyst, and the bisphenol F skeleton-containing phenoxy resin of the present invention is obtained. In particular, it is presumed that the most effective bisphenol F skeleton-containing phenoxy resin was obtained by using the organic phosphonium salt in combination with an aromatic catalyst having a boiling point of 80 ° C. to 145 ° C. in an optimal state. Yes.

  As described above, the phenoxy resin using the bisphenol F compound as a divalent phenolic compound as a raw material easily changes to another structure in which a methylene group is oxidized during the reaction to form a chromophore by carbonylation or conjugation. The phenoxide form, which is an intermediate of the time, is easily oxidized and is likely to be colored due to the fact that it easily takes a quinoid structure. The reason why a resin varnish with little coloration is obtained when onium salts are used as a catalyst is not known in detail, but when a base such as an alkali metal catalyst or amines is used as a catalyst, the polymerization initiation species is phenoxide. It is an ion, and the reaction by nucleophilic substitution with the epoxy group starts, but until the nucleophilic addition reaction starts, the conjugated structure extends to the methylene site, so that a color group due to side reaction tends to occur, When an onium salt is used as a catalyst, a polymerization initiating species is formed by coordination of an onium cation to an epoxy group, and then polymerization is initiated by an electrophilic addition reaction with phenol, so that an intermediate phenoxide ion is formed. It is presumed that good transparency was obtained without forming a color group as a result.

  Next, the divalent epoxy resin represented by the general formula (3) and the bisphenol F compound represented by the general formula (4) are mixed in the presence of an onium salt catalyst in an aromatic solvent. The ratio (E1 / F1) of the number of moles (E1) of epoxy groups in the epoxy resin and the number of moles (F1) of phenolic hydroxyl groups in the bisphenol F compound is 1.035 to 1.005. The epoxy equivalent is 4000-8500 g / eq. The phenolic hydroxyl group equivalent is 7000 to 17000 g / eq. A bisphenol F skeleton-containing phenoxy resin (A2) having a weight average molecular weight of 30000 to 60000 in terms of polystyrene as measured by gel permeation chromatography will be described.

  The divalent epoxy resin represented by the general formula (3), the bisphenol F compound represented by the general formula (4), the onium salt catalyst, and the aromatic solvent used are those shown in the production method of the present invention. The preferred ones are also the same. Regarding the reaction conditions such as the molar ratio, the conditions shown in the production method of the present invention are used, and preferable conditions are also the same. The epoxy equivalent, phenolic hydroxyl group equivalent, and weight average molecular weight of the bisphenol F skeleton-containing phenoxy resin thus obtained are the same as those of the bisphenol F skeleton-containing phenoxy resin (A1) of the present invention represented by the general formula (1). The same is true for the preferable range, and it is considered that the main chain has a structure represented by the above general formula (1) but cannot be represented by the general formula (1). Hereinafter, when it is necessary to distinguish the bisphenol F skeleton-containing phenoxy resin of the present invention represented by the general formula (1) from the bisphenol F skeleton-containing phenoxy resin of the present invention obtained by the above production method, the former is referred to as bisphenol. The F skeleton-containing phenoxy resin (A1) is used, and the latter is the bisphenol F skeleton-containing phenoxy resin (A2).

  Next, the resin varnish of the present invention will be described.

  The resin varnish of the present invention comprises an aromatic organic solvent (A) having a boiling point of 80 to 145 ° C. and a ketone organic solvent (B) having a boiling point of 60 to 120 ° C. as essential components, and a resin concentration of 20 to 80. % By mass. By using these solvents, it is possible to obtain a resin varnish that has both good transparency and good drying properties when producing a dry film type adhesive for display element members. This resin is a bisphenol F skeleton-containing phenoxy resin, and the bisphenol F skeleton-containing phenoxy resins (A1) and (A2) can be used in the same manner.

  As the organic solvent (A), various solvents can be applied as long as they are known ones. Examples include benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like, but are not limited thereto, and two or more kinds may be used. A particularly preferable solvent is toluene from the viewpoints of safety, solubility and energy and time required for drying.

  As the organic solvent (B), various solvents can be applied as long as they are known ones. Examples include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 2-methyl-3-pentanone, tert-butyl methyl ketone, and the like, but not limited thereto, and two or more kinds may be used. . A particularly preferred solvent is methyl ethyl ketone from the viewpoints of solubility, energy required for drying and time.

  The resin concentration of the resin varnish of the present invention is 20 to 80% by mass. When the resin concentration is less than 20% by mass, the high molecular weight component of the bisphenol F skeleton-containing phenoxy resin of the present invention may be excluded, and it may be difficult to obtain a uniform varnish. When the resin concentration exceeds 80% by mass, fluidity at normal temperature is lost, and handling as a solution may be difficult. By setting the resin concentration in the range of 20 to 80% by mass, handling as a resin varnish can be facilitated. A preferable range of the resin concentration is 25 to 70% by mass, and a more preferable range is 30 to 60% by mass.

  The resin varnish of the present invention may be a known organic solvent in addition to the organic solvent (A) and the organic solvent (B), and the resin concentration may be 20 to 80% by mass, and two or more of them are used in combination. Also good. Such an organic solvent can be appropriately selected by those skilled in the art according to its use and purpose. However, the boiling point is 60 to 145 ° C. and the amount used is based on the total amount of the solvent in that the scope of the present invention is not impaired. It is preferable that it is less than 50 mass%. When an organic solvent having a boiling point of less than 60 ° C. is used in combination, the quality may change due to varnish skinning and evaporation during storage. When an organic solvent having a boiling point of 145 ° C. or higher is used in combination, the solvent remains when the film adhesive for display members is produced, and the adhesive properties may be deteriorated.

  Although it does not specifically limit about the solvent composition of the organic solvent (A) used for the resin varnish of this invention, and an organic solvent (B), Usually, (A) / {Total amount of the solvent containing (A) and (B)} Is less than 0.8. Preferably it is less than 0.75, More preferably, it is less than 0.65. By being in this range, the resin varnish of the present invention can maintain uniformity. When the value of (A) / {total amount of solvent including (A) and (B)} exceeds 0.8, the organic solvent (A) is too much and the uniformity of the resin varnish of the present invention There is a fear that cannot be kept. In particular, it is preferable to use toluene as the organic solvent (A) and methyl ethyl ketone as the organic solvent (B) in a composition of (A) / (B) = 8/2 to 1/9 by mass ratio. It is more preferable to use (B) = 6/4 to 1/9. If the proportion of (A) is too large, the mixed solvent becomes a poor solvent and the compatibility may be deteriorated. On the other hand, if the proportion of (A) is too small, the proportion of (B), which is a good solvent, increases too much, and the inertial radius increases due to incorporation between the molecules of the phenoxy resin, resulting in an increase in viscosity and the desired effect. There is a risk that it will not be obtained.

  It does not specifically limit about the manufacturing method of the resin varnish of this invention, It can implement in a preferable aspect for those skilled in the art. For example, the bisphenol F skeleton-containing phenoxy resin of the present invention obtained by a reaction using an arbitrary solvent is recovered and solidified under normal pressure or reduced pressure, and then the aromatic boiling point of 80 to 145 ° C. is obtained. A boiling point of 80 to 145 ° C. in advance, together with a process of redissolving using an organic solvent (A) and a ketone organic solvent (B) having a boiling point of 60 to 120 ° C. and a raw material of the bisphenol F skeleton-containing phenoxy resin of the present invention. The aromatic solvent (A) and / or the ketone organic solvent (B) having a boiling point of 60 to 120 ° C. can be used for the reaction to dilute to a predetermined concentration. Preferably, the reaction is performed using an aromatic organic solvent (A) having a boiling point of 80 to 145 ° C., and particularly preferably an aromatic organic solvent (A) having a boiling point of 80 to 145 ° C. This is a technique using toluene.

  The resin varnish of the present invention has a viscosity at 25 ° C. of preferably 500 to 7000 mPa · s, and more preferably 1000 to 4000 mPa · s. When the viscosity is low, the molecular weight of the bisphenol F skeleton-containing phenoxy resin of the present invention is not sufficiently grown or the degree of branching is very high, and the desired flexibility may not be obtained sufficiently. . When the viscosity is high, when used as a dry film type adhesive for a display element member, the melt viscosity becomes high and the step following property may be deteriorated.

  The transmittance at a wavelength of 400 nm using a 10 mm quartz cell of the resin varnish of the present invention is preferably 90% or more, more preferably 93% or more, and further preferably 95% or more. If the transmittance is within this range, more suitable transparency can be obtained when a dry film adhesive for display members is used.

  In particular, by using the organic phosphonium salts described in the present invention as a catalyst for the reaction, toluene as the organic solvent (A), methyl ethyl ketone as the organic solvent (B), and (A) / ( B) When the composition is 3/7 and the resin concentration is diluted to 50% by mass, a resin varnish can be suitably obtained, and compatibility, viscosity and drying properties suitable as a film adhesive for display members can be obtained. Can do.

  Next, applications using the bisphenol F skeleton-containing phenoxy resin and the resin varnish of the present invention will be described.

  Since the bisphenol F skeleton-containing phenoxy resin and the resin varnish of the present invention are excellent in transparency, flexibility, adhesiveness, etc., they can be suitably used for optical adhesives, coatings, and electronic materials. .

  As the optical adhesive use, various uses can be selected as long as they are known. For example, adhesives for image sensors of cameras (vehicle cameras, digital cameras, PC cameras, mobile phone cameras, surveillance cameras, etc.), eyeglass lenses, optical filters, diffraction gratings, prisms, light guides, light beam condensing lenses , Light diffusion lens, photo sensor, photo switch, LED, light emitting element, optical waveguide, optical splitter, adhesive for optical elements such as optical fiber, display glass for display device, resin for display device, substrate for display element, color Examples include a filter substrate, a touch panel substrate, a display protective film, a display backlight, a light guide plate, an optical laminate such as an antireflection film, and an adhesive for the laminate film.

  As the coating application, various applications can be selected as long as they are known. For example, for protection of rust prevention and gloss, building for decoration, insulation, etc., flooring application, metal primer coating application, precoat metal application, glass coating application, ceramic coating application, fiber, tape, cloth, etc. The composite material coating use etc. which are manufactured by impregnating a composition are mentioned.

  As electronic material applications, various applications can be selected as long as they are publicly known. For example, circuit board use, interlayer adhesive for bonding circuit boards together, coverlay film, coverlay film adhesive, copper-clad film adhesive, electromagnetic wave shielding adhesive, semiconductor encapsulant application, die attach film, etc. Is mentioned.

  Since the bisphenol F skeleton-containing phenoxy resin and its varnish of the present invention have an epoxy group at the terminal, a curable resin composition can be obtained by blending a compound or resin having reactivity with the epoxy group. Examples of such compounds or resins include polyphenolic compounds or resins such as novolak-type phenol resins, novolak-type naphthol resins, naphthol-aralkyl resins, and resol-type phenol resins, phthalic anhydride, tetrahydrophthalic anhydride, hexahydroanhydride Carboxylic acid compounds such as phthalic acid, methylated hexahydrophthalic anhydride, trimellitic acid, nuclear hydrogenated trimellitic acid and their anhydride compounds, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, metaxylylenediamine, isophoronediamine, Amine compounds such as triethylenetetramine, diethylenetriamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, dicyandiamide, Phosphine compounds such as fins, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole And the like, and imidazole salts that are salts of imidazoles with trimellitic acid, isocyanuric acid, boric acid and the like, but are not limited thereto, and two or more kinds may be used in combination as necessary. .

  The bisphenol F skeleton-containing phenoxy resin of the present invention contains a secondary alcoholic hydroxyl group in the side chain. Therefore, a curable resin composition can also be obtained by using an acid anhydride compound, an isocyanate group-containing compound, or an onium salt having cationic curability that generates cationic species by light or heat as a curing agent.

  Any acid anhydride compound having a monovalent acid anhydride group can be modified with a bisphenol F skeleton-containing phenoxy resin of the present invention to modify a secondary alcoholic hydroxyl group to a carboxyl group. Become. As a result, dispersibility in water is improved, and a cured product can be obtained by reacting with a resin having reactivity with a carboxyl group, for example, an epoxy resin.

  As the monovalent acid anhydride compound that is modified to a carboxyl group, various compounds can be applied as long as they are known ones. For example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride, nadic acid anhydride, hydrogenated nadic anhydride, anhydrous Examples include trimellitic acid, trimellitic anhydride, hydrogenated trimellitic anhydride, and the like. Two or more kinds may be used in combination as necessary.

  The amount of the monovalent acid anhydride compound used for modification is not particularly limited, but is usually 0.2 to 1.0 mol per mol of the secondary alcoholic hydroxyl group present in the bisphenol F skeleton-containing phenoxy resin of the present invention. It is.

  If it has a bivalent acid anhydride group as an acid anhydride compound, hardened | cured material can be obtained by making it react with the bispheno F frame | skeleton containing phenoxy resin of this invention. As such a divalent acid anhydride compound, various compounds can be applied as long as they are known. For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride Pyromellitic anhydride, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3 -Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the like may be mentioned, and two or more may be used in combination as necessary.

  Although the usage-amount of a bivalent acid anhydride compound is not specifically limited, It is 0.2 mol-1.0 mol normally with respect to 1 mol of secondary alcoholic hydroxyl groups which exist in the bisphenol F frame | skeleton containing phenoxy resin of this invention. . The curing temperature is not particularly limited and can be carried out under conditions preferable for those skilled in the art, but is usually 50 ° C to 200 ° C. Moreover, you may use together the compound which has basicity in order to accelerate | stimulate a crosslinking reaction.

  As the compound containing an isocyanate group, a known compound can be used as long as it contains two or more isocyanate groups in one molecule. For example, 2,4′-methylenebis (phenylisocyanate) and 4,4′-methylenebis (phenylisocyanate), isomer mixtures thereof, and polyfunctional homologues thereof, 2,4-toluene diisocyanate, 2,6-toluene Diisocyanate, its isomer mixture, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like and these modified polyols are not limited to these, and two or more kinds may be used in combination. Good.

  The amount of the compound containing two or more isocyanate groups in one molecule is not particularly limited, but is usually 0.2 per mole of the secondary alcoholic hydroxyl group present in the bisphenol F skeleton-containing phenoxy resin of the present invention. -1.0 mol. Moreover, in order to promote a crosslinking reaction, you may use together metal compounds, such as an imidazole compound, an amine compound, and dibutyltin dilaurate.

  The curable resin composition of this invention can obtain hardened | cured material by heat-processing. The temperature required for the heat treatment is not particularly limited and can be carried out at a temperature preferable for those skilled in the art, but is usually 50 to 230 ° C. Below 50 ° C, the reaction does not proceed and is not realistic. If it is 230 ° C. or higher, the phenphenol resin containing the bisphenol F skeleton of the present invention may be decomposed.

  Various compounds can be applied as the onium salts having cationic curability that generate cationic species by light or heat as long as they are known. For example, an anion structure such as an iodonium anion, a tetrafluoroborate anion, a hexafluorophosphate anion, a hexafluoroantimonate anion, a hexafluoroarsenate anion is paired with a cation structure such as an aromatic sulfonium cation or an aromatic oxosulfonium cation. And two or more compounds may be used as necessary. The amount of onium salt used is not particularly limited, but is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the bisphenol F skeleton-containing phenoxy resin of the present invention.

  The curable resin composition having cationic curable properties can be cured by heat treatment. The temperature required for the heat treatment is not particularly limited and can be carried out at a temperature preferable for those skilled in the art, but is usually 50 to 230 ° C. Below 50 ° C, the reaction does not proceed and is not realistic. If it is 230 degreeC or more, there exists a concern of decomposition | disassembly of the bisphenol F frame containing phenoxy resin of this invention.

The curable resin composition of this invention can obtain hardened | cured material by irradiating UV light, when a photocation generator is used as a hardening | curing agent. The necessary light irradiation intensity of UV light is not particularly limited and may be carried out within a range preferable to those skilled in the art, but is usually within a range of 50 to 150 mW / cm ² . If it is less than 50 mW / cm ² , cationic polymerization may not proceed sufficiently, and if it exceeds 150 mW / cm ² , decomposition of the bisphenol F skeleton-containing phenoxy resin of the present invention may occur. In addition, after carrying out light irradiation and bridge | crosslinking, bridge | crosslinking can also be advanced by performing heat processing succeedingly. The temperature required for the heat treatment is not particularly limited and can be carried out at a temperature preferable for those skilled in the art, but is usually room temperature to 230 ° C.

  Among these curable resin compositions, when a compound containing an isocyanate group is used, a cured product that can be cured at a low temperature and is excellent in transparency can be obtained. For this reason, it can be used suitably especially as a resin composition for optical adhesives.

  The bisphenol F skeleton-containing phenoxy resin and the resin varnish of the present invention can be blended with other thermosetting resins or photocurable resins as necessary. Examples of such thermosetting resins include epoxy resins, unsaturated polyester resins, acrylic resins, melamine resins, urea resins, urethane resins, and oxetane resins. Moreover, it can also be set as a composition by using with the hardening | curing agent, accelerator, or initiator which has reactivity with such resin. Moreover, it can also be used as a composition having a desired viscosity by using a known organic solvent or water in combination. Such a curable resin composition can be suitably used for optical adhesives, coatings, and electronic materials.

  The resin composition listed above may be used in combination with other thermoplastic resins, additives, and fillers.

  As thermoplastic resins, polyethylene, polypropylene, polybutadiene, polyisobutylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polyethersulfone, polysulfone, polyetherether Although ketone, polyether ether imide, etc. are mentioned, it is not limited to these, You may use 2 or more types together. The amount to be used is not particularly limited, but is usually 5 to 95 parts by mass with respect to 100 parts by mass of the bisphenol F skeleton-containing phenoxy resin of the present invention.

  Examples of the additive include known silane coupling materials, antioxidants, light stabilizers, organic dyes, organic pigments, leveling materials, flame retardants and the like, but are not limited to these, and two or more types may be used in combination. Good. The amount used is not particularly limited and may be appropriately adjusted by those skilled in the art according to the purpose.

  The filler is not particularly limited as long as it is a known one. For example, silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, zonolite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, Examples include, but are not limited to, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, aluminum borate and the like. More than one species may be used in combination. The amount used is not particularly limited and may be appropriately adjusted by those skilled in the art according to the purpose.

  The bisphenol F skeleton-containing phenoxy resin and resin varnish of the present invention can be used as an optical adhesive to form a display device. More specifically, the optical adhesive of the present invention is formed into a single layer or a multilayer sheet on a release film or the like, and if necessary, the solvent is dried and removed, and a personal computer, a mobile terminal, a game machine, It can be obtained by bonding to a display device constituent member such as a cover panel of an image display device such as a television, a car navigation system, a touch panel, a pen tablet, a liquid crystal display, a plasma display, or an electroluminescence (EL) display.

  Examples of the constituent material of the release film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyurethane film, and ethylene-vinyl acetate copolymer. Examples include films, resin films such as polyethylene terephthalate films and polyester films, porous materials such as paper, cloth, and nonwoven fabrics, nets, foam sheets, metal foils, and thin leaves such as laminates thereof. Is a resin film treated with a silicone liner from the viewpoint of releasability and surface smoothness.

  As a method for forming the optical adhesive of the present invention into a sheet, various methods can be selected as long as they are known. For example, methods such as roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, etc. Not.

  The configuration of the display device using the optical adhesive of the present invention is not particularly limited, and can be applied to various configurations as long as it is a known configuration. For example, a configuration in which a liquid crystal panel / touch panel, a liquid crystal panel / protective panel, a liquid crystal panel / touch panel / protective panel, a polarizing film / touch panel, a polarizing film / touch panel / protective panel, and the like are included is limited thereto. Not.

  In particular, since the bisphenol F skeleton-containing phenoxy resin of the present invention is excellent in fluidity during heating, it is excellent in embedding of a step resulting from frame printing applied to a cover panel, and is a resin for an optical adhesive between a cover panel and a touch panel. It can be suitably used as a composition.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited to a following example, unless the summary is exceeded. Unless otherwise specified, “parts” represents parts by mass, and “%” represents mass%.

  The analysis method and measurement method are shown below. In addition, the unit of equivalent is g / eq. It is.

  Epoxy equivalent: Measured by the method described in JIS K-7236 standard, and a numerical value as a solid content converted value was calculated from the nonvolatile content.

  Nonvolatile content: Measured by the method described in JIS K-7235 standard. The drying temperature was 200 ° C. and the drying time was 60 minutes.

Molecular weight (Mw, Mn, M _RI ): determined by GPC measurement. Specifically, a main body (manufactured by Tosoh Corporation, HLC-8320GPC) and a column (manufactured by Tosoh Corporation, TSKgel G4000H _XL , TSKgel G3000H _XL , TSKgel G2000H _XL ) in series are used, and the column temperature is 40 C. Tetrahydrofuran was used as the eluent, the flow rate was 1 mL / min, and a RI (differential refractometer) detector was used as the detector. As a measurement sample, 100 μL of 0.1 g of sample dissolved in 10 mL of tetrahydrofuran and filtered through a microfilter was used. Standard monodispersed polystyrene (A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40, manufactured by Tosoh Corporation) , F-80, F-128), the number average molecular weight (Mn) and the weight average molecular weight (Mw) were obtained by conversion from a calibration curve obtained from F.128. Further, the weight average molecular weight at which the intensity of the molecular weight distribution becomes the maximum intensity was defined as “M _RI ”.

Absolute molecular weight by static light scattering method: A main body (manufactured by Tosoh Corporation, HLC-8320GPC) equipped with two columns (Showa Denko Corporation, Shodex KF-806M) in series is used, and the column temperature is 40 ° C. I made it. Tetrahydrofuran was used as the eluent, and the flow rate was 1 mL / min. As a measurement sample, 500 μL of 0.01 g of sample dissolved in 10 mL of tetrahydrofuran and filtered through a microfilter was used. As the multi-angle light scattering detector, DAWN HELEOS 8+ (detection angle number: 8) manufactured by Wyatt Technology was used. The refractive index concentration increment (dn / dc) necessary for calculating the absolute molecular weight is a differential refractive index detector (Optylab T-rEX, manufactured by Wyatt Technology), and a tetrahydrofuran solution having a resin concentration of 200 ppm, 600 ppm, or 1000 ppm is used. The differential refractive index was measured, and the refractive index concentration increment was calculated. For the analysis of the absolute molecular weight, Astra ver 6.1.2.84 manufactured by Wyatt Technology was used and analyzed and calculated by a Debye plot consisting of 8 scattering intensities and scattering angles. At that time, the absolute molecular weight at which the intensity of the molecular weight distribution becomes the maximum intensity was defined as “M _LS ”.

  50 mL of a tetrahydrofuran solution containing 5 mg / L, 20 mg / L, or 50 mg / L of phenolic hydroxyl group equivalent: bisphenol F (manufactured by Honshu Chemical Industry Co., Ltd., trade name: BPF-D) was prepared, and tetrabutylammonium hydroxide 10 After adding 20 μL of% aqueous solution and mixing, the UV spectrum was measured, and a calibration curve was prepared based on the absorbance at 305 nm. 0.1 g of the samples of Examples and Comparative Examples were weighed and dissolved in 50 mL of tetrahydrofuran (dilution ratio: 500 times), 20 μL of 10% aqueous solution of tetrabutylammonium hydroxide was added and mixed, and then the UV spectrum was measured at 305 nm. The phenolic hydroxyl group equivalent (POHE) derived from bisphenol F was calculated from the absorbance of the following formula.

ｍ：試料採取量（ｇ）
ｃ：検量線濃度（ｍｇ／Ｌ）
ｄ：試料溶液の希釈倍率、５００（ｍＬ）
ｋ：ビスフェノールＦのグラム当量、１００（ｇ／ｅｑ．）
0

m: Sample collection amount (g)
c: Calibration curve concentration (mg / L)
d: Sample solution dilution factor, 500 (mL)
k: Gram equivalent of bisphenol F, 100 (g / eq.)
0

  Varnish viscosity: Measured by JIS K-7233, single cylinder rotational viscosity method. Specifically, the viscosity at 25 ° C. was measured using a B-type viscometer (TVB10H manufactured by Toyo Seiki Co., Ltd.).

  Light transmittance: Using a UV spectrophotometer (manufactured by JASCO Corporation, V-650) and a 10 mm quartz cell, the light transmittance at 400 nm was measured using the solvent composition used in the preparation of the resin varnish as a reference.

  The abbreviations used in Examples and Comparative Examples are as follows.

[Epoxy resin]
YD-128: bisphenol A type liquid epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epototo YD-128, epoxy equivalent = 186)
YDF-8170: Bisphenol F-type liquid epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epototo YDF-8170, epoxy equivalent = 158)
YX-4000: polycondensate of tetramethylbiphenol and epichlorohydrin (Mitsubishi Chemical Corporation, YX-4000, epoxy equivalent = 183)
BPZ-EP: polycondensate of 1,1-bis (4-hydroxyphenyl) cyclohexane and epichlorohydrin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent = 200)

[Bisphenol F compound]
BFF-1: Distilled bisphenol F (manufactured by Honshu Chemical Industry Co., Ltd., BPF-D, dinuclear compound = 99.2 area%, trinuclear compound = 0.8 area%, isomer ratio (4,4′-isomer: 2,4′-isomer: 2,2′-isomer = 33: 50: 17), phenolic hydroxyl group equivalent = 100)
BPF-2: Bisphenol F (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 2 nuclei = 97 area%, 3 nuclei = 3 area%, k average value = 0.03, isomer ratio (4,4′-form: 2,4′-isomer: 2,2′-isomer = 36: 49: 15), phenolic hydroxyl group equivalent = 100)
BPF-3: Phenol novolac resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 2 nuclei = 10 area%, 3 nuclei = 46 area%, 5 nuclei or more = 21 area%, k average value = 1.7, isomerism Body ratio (4,4′-form: 2,4′-form: 2,2′-form = 60: 35: 5), phenolic hydroxyl group equivalent = 105)

[catalyst]
TMP: Methyltriphenylphosphonium bromide (reagent)
TPPMI: Methyltriphenylphosphonium iodide (reagent)
PX4MP: Methyltributylphosphonium dimethyl phosphate (reagent)
PX4ET: Tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (reagent)
TPPPB: Tetra-phenylphosphonium bromide (reagent)
TBPDA: tetra-n-butylphosphonium decanoate (reagent)
TPPBB: Tetra-n-butylphosphonium bromide (reagent)
TMAOH: 29% tetramethylammonium hydroxide (reagent)
TPP: Triphenylphosphine (reagent)

[Others]
YP-70: bisphenol A bisphenol F copolymerized phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol F skeleton-containing phenoxy resin, phenototo YP-70)
YP-50S: bisphenol A type phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., phenototo YP-50S)

Example 1
In a reactor equipped with a stirrer, thermometer, nitrogen blowing tube, and cooling tube, 100 parts of BPF-1 as the bisphenol F compound and 190.7 parts of YD-128 as the epoxy resin (number of moles of epoxy group (E1 ) And the molar ratio of phenolic hydroxyl group (F1) (E1 / F1) = 1.025), 15 parts of toluene (TL) was charged as a reaction solvent, and the temperature was raised to 100 ° C. in a nitrogen atmosphere. Next, 0.1 parts of TMP was charged as a catalyst, and then the internal temperature was raised to 140 ° C. As the reaction proceeded, the reaction solution began to thicken, so 72 parts of toluene was added in several portions, and the reaction was performed for 12 hours while keeping the torque of the stirrer constant. The reaction temperature was 140 to 145 ° C. when the non-volatile content was 80% or more, and the subsequent reaction temperature was reflux temperature. After completion of the reaction, 204 parts of methyl ethyl ketone (MEK) (TL / MEK mass ratio = 3/7) was added to obtain a resin varnish.
A GPC measurement chart indicated by the relative refractive index difference is shown in FIG. The left vertical axis shows signal intensity, and the right vertical axis shows weight average molecular weight in common logarithm. The outflow curve is shown as a solid line. A calibration curve obtained from the measured value of the weight average molecular weight of the standard substance used is indicated by a dotted line.
A GPC measurement chart indicated by the light scattering intensity is shown in FIG. The vertical axis shows the absolute molecular weight in common logarithm. The outflow curve is shown as a solid line and the absolute molecular weight is shown as a dotted line.

Example 2
A resin varnish was obtained in the same manner as in Example 1 except that 189.8 parts of YD-128 (E1 / F1 = 1.020) and 203 parts of MEK were used.

Example 3
A resin varnish was obtained in the same manner as in Example 1 except that 187.9 parts of YD-128 (E1 / F1 = 1.010), 71 parts of additional TL, and 202 parts of MEK were used.

Example 4
A resin varnish was obtained in the same manner as in Example 1 except that 191.2 parts (E1 / F1 = 1.026) of YD-128 was used.

Example 5
A resin varnish was obtained in the same manner as in Example 1 except that 191.2 parts of YD-128 (E1 / F1 = 1.028) was used and the reaction time was 18 hours.

Example 6
A resin varnish was obtained in the same manner as in Example 1 except that 192.3 parts (E1 / F1 = 1.034) of YD-128, 205 parts of MEK were used, and the reaction time was 8 hours.

Example 7
A resin varnish was obtained in the same manner as in Example 1 except that 192.3 parts (E1 / F1 = 1.034) of YD-128 and 205 parts of MEK were used.

Example 8
A resin varnish was obtained in the same manner as in Example 1 except that 192.3 parts (E1 / F1 = 1.034) of YD-128, 205 parts of MEK were used, and the reaction time was 18 hours.

Example 9
A resin varnish was obtained in the same manner as in Example 1 except that 162 parts of YDF-8170 (E1 / F1 = 1.025), 64 parts of additional TL, and 183 parts of MEK were used as the epoxy resin.

Example 10
A resin varnish was obtained in the same manner as in Example 1 except that 187.6 parts of YX-4000 (E1 / F1 = 1.025), 71 parts of additional TL, and 202 parts of MEK were used as the epoxy resin.

Example 11
A resin varnish was obtained in the same manner as in Example 1 except that 188.5 parts (E1 / F1 = 1.030) of YX-4000, 71 parts of additional TL, and 202 parts of MEK were used as the epoxy resin.

Example 12
A resin varnish was obtained in the same manner as in Example 1 except that 205 parts of BPZ-EP (E1 / F1 = 1.005), 77 parts of additional TL, and 213 parts of MEK were used as the epoxy resin.

Example 13
A resin varnish was obtained in the same manner as in Example 1 except that 0.1 part of TPPMI was used as a catalyst.

Example 14
A resin varnish was obtained in the same manner as in Example 1 except that 0.1 part of PX4MP was used as a catalyst.

Example 15
A resin varnish was obtained in the same manner as in Example 1 except that 0.1 part of PX4ET was used as a catalyst.

Example 16
A resin varnish was obtained in the same manner as in Example 1 except that 0.1 part of TPPPB was used as a catalyst.

Example 17
A resin varnish was obtained in the same manner as in Example 1 except that 0.1 part of TBPDA was used as a catalyst.

Example 18
A resin varnish was obtained in the same manner as in Example 1 except that 100 parts (E1 / F1 = 1.005) of BPF-2 was used as the bisphenol F compound.

Example 19
A resin varnish was obtained in the same manner as in Example 1 except that 80 parts of BPF-1 and 21 parts of BPF-3 (E1 / F1 = 1.005) were used as the bisphenol F compound.

Example 20
A resin varnish was obtained in the same manner as in Example 1 except that 15 parts of xylene and 72 parts of additional TL were used as the reaction solvent.

Example 21
A resin varnish was obtained in the same manner as in Example 1 except that 15 parts of ethylene glycol dimethyl ether, 15 parts of TL, and 57 parts of additional TL were used as a reaction solvent.

Example 22
Resin in the same manner as in Example 1 except that 187.9 parts of YD-128 (E1 / F1 = 1.010), 0.1 part of TPPMI, 71 parts of additional TL, and 202 parts of MEK were used. A varnish was obtained.

Example 23
A resin varnish was obtained in the same manner as in Example 1 except that 191.2 parts of YD-128 (E1 / F1 = 1.028) and 0.1 part of TPPMI were used as a catalyst.

Example 24
A resin varnish was obtained in the same manner as in Example 1 except that 192.3 parts of YD-128 (E1 / F1 = 1.034), 0.1 part of TPPMI and 205 parts of MEK were used.

Comparative Example 1
YP-70 was diluted with a mixed solvent of TL / MEK = 3/7 (mass ratio) to obtain a resin varnish having a nonvolatile content of 50%.
A GPC measurement chart indicated by the relative refractive index difference is shown in FIG. The left vertical axis shows signal intensity, and the right vertical axis shows weight average molecular weight in common logarithm. The outflow curve is shown as a solid line. A calibration curve obtained from the measured value of the weight average molecular weight of the standard substance used is indicated by a dotted line.
A GPC measurement chart indicated by the light scattering intensity is shown in FIG. The vertical axis shows the absolute molecular weight in common logarithm. The outflow curve is shown as a solid line and the absolute molecular weight is shown as a dotted line.

Comparative Example 2
The resin varnish was used in the same manner as in Example 1 except that 192.9 parts of YD-128 (E1 / F1 = 1.037), 73 parts of additional TL, 205 parts of MEK were used, and the reaction time was 18 hours. Obtained.

Comparative Example 3
A resin varnish was obtained in the same manner as in Example 1 except that 186.6 parts of YD-128 (E1 / F1 = 1.003), 71 parts of additional TL, and 201 parts of MEK were used.

Comparative Example 4
Using the same apparatus as in Example 1, 100 parts of BPF-1 as the bisphenol F compound, 190.7 parts of YD-128 as the epoxy resin (E1 / F1 = 1.005), and 32 of cyclohexanone as the reaction solvent The temperature was raised to 140 ° C. under a nitrogen atmosphere. Next, 0.02 part of TPPBB was charged as a catalyst, and then the internal temperature was raised to 155 ° C. (reflux temperature). The reaction was performed at the reflux temperature, and the reaction solution started to thicken as the reaction proceeded. The reaction was carried out for 12 hours by adding the cyclohexanone appropriately to keep the torque of the stirrer constant, and then cyclohexanone was added while cooling to prepare a 25% solution of cyclohexanone. Next, drying was performed for 24 hours under the conditions of 100 ° C. and 0.67 kPa (5 Torr) to distill off cyclohexanone. After solidification, the resin was mixed using a mixed solvent of TL / MEK = 3/7 (mass ratio). Was diluted to obtain a resin varnish having a nonvolatile content of 50%.

Comparative Example 5
Using the same apparatus as in Example 1, 254 parts of BPF-1 as the bisphenol F compound, 496 parts of YD-128 as the epoxy resin (E1 / F1 = 1.050), and 250 methylisobutylketone as the reaction solvent. 1.2 parts of TMAOH was charged as a catalyst, and a polymerization reaction was performed at 130 ° C. for 7.5 hours in a nitrogen gas atmosphere. Next, drying is performed for 48 hours under the conditions of 40 ° C. and 0.67 kPa (5 Torr) to distill off methyl isobutyl ketone. After solidification, a mixed solvent of TL / MEK = 3/7 (mass ratio) is used. The resin was diluted to obtain a resin varnish having a nonvolatile content of 50%.

Comparative Example 6
YP-50S was diluted with a mixed solvent of TL / MEK = 3/7 (mass ratio) to obtain a resin varnish having a nonvolatile content of 50%.

Comparative Example 7
In the same apparatus as in Example 1, 100 parts of BPF-1 and 190.7 parts of YD-128 (E1 / F1 = 1.005) and 15 parts of TL were charged, and the temperature was raised to 100 ° C. in a nitrogen atmosphere. It was. Next, 0.3 parts of TPP was charged as a catalyst, and then the internal temperature was raised to 140 ° C. The reaction was conducted at a reaction temperature of 140 to 145 ° C. for 10 hours, but no increase in molecular weight was observed. 0.3 parts of TPP was added and the reaction was continued for another 10 hours. However, since no increase in molecular weight was observed, the reaction was interrupted. The molecular weight at the time of interruption was Mw = 14800 and Mn = 5240.

Epoxy equivalents, Mw, Mw / Mn, strength ratio (M _LS / M _RI ), phenolic hydroxyl group equivalent, varnish viscosity, and light transmittance of the resin varnishes obtained in Examples 1 to 24 and Comparative Examples 1 to 7, respectively. Table 1 shows the results of the examples and Table 2 shows the results of the comparative examples.

(Storage stability)
The resin varnishes obtained in Examples 1 to 24 and Comparative Examples 1 to 6 were sealed in a 500 mL round can, stored at a temperature of 40 ° C. for 1 month, and measured for viscosity at 25 ° C. for storage stability. Sex was evaluated. The items and explanation of the determination are as follows. Table 3 shows the results of the examples and Table 4 shows the results of the comparative examples.
○: The viscosity after the test was less than 1.5 times the viscosity before storage.
(Triangle | delta): The viscosity after a test was 1.5 times or more and less than 2.0 times the viscosity before storage.
X: The viscosity after the test was at least twice the viscosity before storage.
(Transmittance after storage)
○: When the light transmittance is measured using the resin varnish after the storage stability test, it has a transmittance of 90% T or more.
(Triangle | delta): When light transmittance is measured using the resin varnish after a storage stability test, it has the transmittance | permeability of 80% T or more and less than 90% T.
X: When the light transmittance is measured using the resin varnish after the storage stability test, it has a transmittance of less than 80% T.

(Step embedding)
The resin varnishes obtained in Examples 1 to 24 and Comparative Examples 1 to 6 were applied to a glass substrate of 100 mm × 100 mm × 0.7 μm using a bar coater so that the dry film thickness was 150 μm, and 80 ° C. The solvent was evaporated under the conditions of 30 minutes to form a resin layer on the glass substrate. A 100 mm × 100 mm × 0.7 mm glass substrate provided with a white printed layer (step) having a width of 10 mm and a thickness of 100 μm on the outer peripheral portion is laminated on the resin-coated glass substrate so as to sandwich the resin layer, and hot pressing is performed. Bonding was performed for 1 minute at 80 ° C. and 0.2 MPa using a machine. Using this sample, the appearance of the periphery of the printed layer (step) was evaluated with an optical microscope. The description of the determination is as follows. Table 3 shows the results of the examples and Table 4 shows the results of the comparative examples.
◯: There are no bubbles and peeling at the stepped portion.
Δ: There are bubbles or peeling on only one side.
X: There are bubbles or peeling on two or more sides.

(ITO adhesion)
11 parts by mass of diphenylmethane diisocyanate and 0.01 parts by mass of dibutyltin dilaurate were added to 100 parts by mass of the resin varnishes obtained in Examples 1 to 24 and Comparative Examples 1 to 6 to prepare a resin composition. Next, this resin composition was applied onto a PET film subjected to a release treatment using a bar coater so that the dry film thickness was 150 μm, and the solvent was distilled off under vacuum at 40 ° C. for 1 hour. . Thereafter, a glass substrate of 100 mm × 100 mm × 0.7 mm provided with a white printing layer (step) having a thickness of 100 μm is stacked so as to sandwich the resin layer, and is heated at 80 ° C. and 0.2 MPa using a hot press machine. Bonding was performed for 1 minute under the conditions. After peeling off the release-treated PET film, the ITO film based on the PET film is stacked so that the metal oxide side is in contact with the resin layer, and using a hot press machine at 80 ° C. and 0.2 MPa. Bonded for 15 minutes. Thereafter, the ITO film was peeled off so as to leave a width of 1 cm, and a 90 degree peel test was performed. The description of the determination is as follows. Table 3 shows the results of the examples and Table 4 shows the results of the comparative examples.
○: Adhesive strength is 0.7 N / mm or more Δ: Adhesive strength is 0.5 N / mm or more and less than 0.7 N / mm ×: Adhesion strength is less than 0.5 N / mm

(Solvent resistance)
To 100 parts by mass of the resin varnishes obtained in Examples 1 to 24 and Comparative Examples 1 to 6, 0.84 parts by mass of novolac-type phenol resin (BRG-557, manufactured by Showa Denko KK), 0.005 parts by mass of triphenylphosphine A part was added and stirred until uniform to obtain a resin composition. Next, the resin composition was applied to a 100 mm × 100 mm × 0.7 mm glass substrate using a bar coater. The glass substrate was dried at 80 ° C. for 30 minutes, and then cured by heat treatment at 150 ° C. for 1 hour. The cured film was subjected to 30 reciprocating rubbing tests with a load impregnated with methyl ethyl ketone at a load of 49 N. The explanation of the determination of curability is as follows. Table 3 shows the results of the examples and Table 4 shows the results of the comparative examples.
○: The cured film after the rubbing test is transparent.
Δ: White turbidity is observed in the cured film after the rubbing test. ×: The entire cured film after the rubbing test is white turbid or peeled.

Claims (17)

It is a bisphenol F skeleton containing phenoxy resin having a structure represented by the following general formula (1) in the main chain, and the weight average molecular weight (Mw) by gel permeation chromatography measurement is 30000 to 60000 in terms of polystyrene, The ratio (Mw / Mn) between Mw and the number average molecular weight (Mn) in terms of polystyrene is 3.5 to 6.5, and the intensity of the molecular weight distribution indicated by the light scattering intensity by the static polygonal light scattering method is maximum. The ratio (M _LS / M _RI ) between the absolute molecular weight (M _LS ) that is the strength and the weight average molecular weight (M _RI ) in terms of polystyrene, where the strength of the molecular weight distribution indicated by the relative refractive index based on tetrahydrofuran is the maximum strength. Is a phenoxy resin containing a bisphenol F skeleton, wherein the phenoxy resin is 3.0 to 15.

(In the formula, A is a divalent organic residue, and Y is a group represented by the following general formula (1a). However, 80 mol% or more of Y is a k = 0 component. (The average number of repetitions is 10 to 200.)

(In the formula, Z is a group represented by the following general formula (1b) or (1c). R ₁ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different. M is independently a number from 0 to 4, m ₁ is independently a number from 0 to 3. k is an average value from 0 to 0.6.)

(In the formula, A and Y are the same as A and Y in the general formula (1). N ₁ and n ₂ are average repeating numbers of 0 to 200.) The bisphenol F skeleton-containing phenoxy resin according to claim 1, wherein A in the general formula (1) is a divalent aromatic group represented by the following general formula (2).

(In the formula, X represents a single bond, a methylene group, a dimethylmethylene group, or a 1,1-cyclohexylene group which may have an alkyl substituent having 1 to 4 carbon atoms. R ₂ represents 1 carbon atom. -8 monovalent hydrocarbon groups, which may be the same or different, and m ₂ is independently a number from 0 to 4.) The following general formula (3)

(In the general formula, A is a divalent organic residue.)
And a divalent epoxy resin represented by the following general formula (4)

(In the general formula, R ₁ is a monovalent hydrocarbon group having 1 to 8 carbon atoms and may be the same or different. M is independently a number from 0 to 4, and m ₁ is independently 0. (The number k is an average value of 0 to 0.6, but the component of k = 0 occupies 80% or more.)
In the presence of an onium salt catalyst in an aromatic solvent, the number of moles of an epoxy group (E1) in a divalent epoxy resin and the mole of a phenolic hydroxyl group in the bisphenol F compound. The ratio (E1 / F1) of the number (F1) is obtained by reacting in the range of 1.035 to 1.005, the weight average molecular weight by gel permeation chromatography measurement is 30000 to 60000 in terms of polystyrene, Mw (Mw / Mn) between the number average molecular weight (Mn) in terms of polystyrene and polystyrene is 3.5 to 6.5, and the intensity of the molecular weight distribution indicated by the light scattering intensity by the static polygonal light scattering method is the maximum intensity. The absolute molecular weight (M _LS ) and the molecular weight distribution indicated by the relative refractive index based on tetrahydrofuran are the maximum weight in terms of polystyrene. A bisphenol F skeleton-containing phenoxy resin having a ratio (M _LS / M _RI ) to the weight average molecular weight (M _RI ) of 3.0 to 15.   Epoxy equivalent is 4000-8500 g / eq. The bisphenol F skeleton-containing phenoxy resin according to any one of claims 1 to 3.   The phenolic hydroxyl group equivalent is 7000 to 17000 g / eq. The bisphenol F skeleton-containing phenoxy resin according to any one of claims 1 to 4. It is a manufacturing method of the bisphenol F frame | skeleton containing phenoxy resin of Claim 1, Comprising: The following general formula (3)

(In the general formula, A is a divalent organic residue.)
And a divalent epoxy resin represented by the following general formula (4)

(In the general formula, R ₁ is a monovalent hydrocarbon group having 1 to 8 carbon atoms and may be the same or different. M is independently a number from 0 to 4, and m ₁ is independently 0. (The number k is an average value of 0 to 0.6, but the component of k = 0 occupies 80% or more.)
In the presence of an onium salt catalyst in an aromatic solvent, the number of moles of an epoxy group (E1) in a divalent epoxy resin and the mole of a phenolic hydroxyl group in the bisphenol F compound. The method for producing a bisphenol F skeleton-containing phenoxy resin, wherein the ratio of the number (F1) is in the range of (E1) :( F1) = 1.35 to 1.005: 1. The method for producing a bisphenol F skeleton-containing phenoxy resin according to claim 6, wherein the onium salt catalyst is an organic phosphonium salt represented by the following general formula (5).

(In the formula, R ₇ represents a monovalent hydrocarbon group, which may be the same or different. X ₁ is an atom or atomic group forming a monovalent anion.)   The method for producing a bisphenol F skeleton-containing phenoxy resin according to claim 6 or 7, wherein the aromatic solvent has a boiling point of 80 to 145 ° C under normal pressure.   The manufacturing method of the bisphenol F frame | skeleton containing phenoxy resin in any one of Claims 6-8 whose component of k = 0 in the bisphenol F compound represented by General formula (4) is 96.5% or more.   The bisphenol F skeleton-containing phenoxy resin varnish, wherein the bisphenol F skeleton-containing phenoxy resin according to any one of claims 1 to 5 is dissolved in an organic solvent to adjust the resin concentration to 15 to 90% by mass. .   A resin composition comprising, as an essential component, the bisphenol F skeleton-containing phenoxy resin according to any one of claims 1 to 5 and a curing agent having reactivity with the phenoxy resin.   A resin composition comprising the bisphenol F skeleton-containing phenoxy resin according to any one of claims 1 to 5 and a curable resin as essential components.   An optical adhesive using the bisphenol F skeleton-containing phenoxy resin according to any one of claims 1 to 5.   A coating agent comprising the bisphenol F skeleton-containing phenoxy resin according to any one of claims 1 to 5.   A cured product obtained by subjecting the resin composition according to claim 11 to light and / or heat treatment.   A display device comprising the optical adhesive according to claim 13.   A display device comprising the coating agent according to claim 14.

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