JP6722451B2 - Phenoxy resin containing bisphenol F skeleton, method for producing the same, and resin composition using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a phenoxy resin containing a bisphenol F skeleton, a method for producing the same, and a resin composition using the same, and particularly, it has excellent low viscosity, low temperature thermocompression bonding property, and transparency, which can be suitably used as an adhesive for display element-related members. The present invention relates to a phenoxy resin containing a bisphenol F skeleton, a resin varnish, and a resin composition using the same.

Conventionally, thermoplastic polyhydroxypolyether resin is generally known as a phenoxy resin, and since it is excellent in flexibility, impact resistance, insulation, adhesion, mechanical properties, etc., in the electric/electronic field, 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, and adhesives and films for circuit boards. And, according to the expansion of applications, it is also applied to an adhesive or the like of a display element-related member such as a liquid crystal display panel.

An adhesive as a member related to a display element may have a use process close to a final process at the time of assembling such as a panel bonding, and therefore, the bonding due to heat is often restricted. This is because the already assembled display element material, its related members, and the housing surrounding the display element are easily damaged by heat.

As an adhesive as a member related to a display element, a photo-curable adhesive has been widely studied so as not to damage the display element, its related members, and the housing. A commonly used material is a liquid acrylic adhesive or an adhesive film in which a base film is coated with an acrylic polymer having tackiness at room temperature. Problems such as poor appearance due to exudation and peeling of the adhesive interface due to curing shrinkage during photocuring occur, and in the case of tacky films that have tackiness at room temperature, there are defects in handling surface due to stickiness and heat resistance test There are problems with peeling, whitening in humidity resistance tests, and electrical reliability.

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

Required properties of dry film type adhesives are transparency sufficient to achieve visibility as a display element, high adhesion to various general-purpose substrates, no tackiness at room temperature, and the dry film itself Therefore, a phenoxy resin having a glass transition temperature of room temperature or higher may be applied in some cases because the film forming property of the above is required.

On the other hand, with the recent development of information equipment, display devices such as smartphones have been diversified. In particular, the touch panel and the cover panel on which the frame printing is performed need to hide the circuit material and the electronic components connected to the touch panel, and the print thickness may increase depending on the decorativeness of the frame printing. For this reason, the dry film type adhesive used for this purpose is required to follow a step of about 100 μm due to frame printing and closely adhere the interface without a gap. At this time, as a dry film type adhesive, the product form has flexibility such that it can be wound in a roll, sufficient light transmittance after adhesion, and no tackiness at room temperature, which damages display element-related members. It is required to be melted by heat that does not give heat, exhibit high fluidity capable of following a step, and have good adhesiveness to an adherend.

As an application of a phenoxy resin as an adhesive to a display element-related member that is weak against heat, an organic EL element laminate sealing film as described in Patent Document 1 and the like can be mentioned. In addition, examples of phenoxy resins having excellent optical properties include phenoxy resins described in Patent Documents 2 and 3.

Patent Document 1 discloses a low-temperature curable organic EL sealing resin composition using a phenoxy resin containing a bisphenol A or bisphenol S skeleton, an epoxy resin, and a blocked isocyanate. However, since the organic EL display element has a thickness on the order of nm, there is no description about lowering the viscosity that requires step followability. A 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. Is unsuitable as The phenoxy resin prepared from an epoxy resin having an alicyclic structure as disclosed in Patent Document 3 is economically disadvantageous because it requires a nuclear hydrogenation reaction using a noble metal catalyst. When alcoholic hydroxyl groups and epichlorohydrin are used as starting materials, a chlorohydrin compound which is an impurity is likely to be generated, and the purity of epoxy at both ends is lowered, so that a polymer chain does not grow to a desired molecular weight during synthesis of a phenoxy resin. Purification such as distillation in order to increase the purity of the terminal group leads to a decrease in economic efficiency. 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 having a thickness of 50 μm. No mention is made of the transparency of the resin alone or the application of the adhesive 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, the phenoxy resin composed only of the bisphenol A skeleton has a glass transition temperature of about 90° C., and has a high flow initiation temperature for use as an adhesive for heat-sensitive display element-related members. Is difficult to apply. In order to improve this drawback, a phenoxy resin having a bisphenol F skeleton having excellent fluidity is also well known. However, generally, a phenoxy resin is a linear polymer synthesized from a resin having a divalent glycidyl group and a divalent phenolic hydroxyl group, and since the number of branches is small, the viscosity is almost unique depending on the target molecular weight. Will be decided. 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 demand for further step followability and the demand for low temperature thermocompression bonding due to changes in members are realized. It will be difficult.

As a method of reducing the viscosity of a phenoxy resin having a bisphenol F skeleton, a method of increasing the degree of branching while making the molecular weights the same and decreasing the radius of gyration of the polymer is also 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 reaction as a reaction point with a glycidyl group is conceivable. However, in these methods, it is difficult to control the degree of branching and the growth reaction of the polymer chain, and it is not possible to easily achieve low viscosity, and the dispersion of the molecular weight often becomes large, resulting in high viscosity and, in some cases, a crosslinked structure. Is locally generated and thus becomes insoluble.

In addition, the phenoxy resin using the bisphenol F skeleton as a divalent phenolic compound as a raw material is likely to be colored due to oxidation during the production of the phenoxy resin. This is because the methylene group connecting the aromatic rings is easily oxidized and carbonylated, or changed to another structure forming a chromophore, and the phenoxide form, which is an intermediate at the time of reaction, is oxidized to take a quinoid structure. It is thought that this is because it is easy.

JP, 2011-84667, A JP, 2013-32549, A International publication WO2007/105795

With the conventional phenoxy resin and its manufacturing method, it is difficult to reduce the viscosity when a divalent phenolic compound is used as a raw material, and the transparency and the low viscosity suitable as a dry film type adhesive for display element members are obtained. A method having properties is desired.

As a result of diligent studies by the present inventors, the above problem was solved by using a bisphenol F skeleton-containing phenoxy resin having a certain amount of epoxy groups left at the terminals, while having a molecular weight equivalent to that of a conventional bisphenol F skeleton-containing phenoxy resin. They have found that they can do so 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 having an epoxy equivalent of 4500 to 7000 g/eq. And the phenolic hydroxyl group equivalent is 8000 to 15000 g/eq. And a bisphenol F skeleton-containing phenoxy resin having a polystyrene-equivalent weight average molecular weight of 30,000 to 80,000 as determined by gel permeation chromatography.

（式中、Ａは２価の有機残基である。Ｙは下記一般式（１ａ）で表される基である。但し、Ｙの８０モル％以上は、ｋ＝０成分である。ｎは１０〜２００の平均繰り返し数である。）

(In the formula, 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. It is an average repeat number of 10 to 200.)

（式中、Ｚは下記一般式（１ｂ）又は（１ｃ）で表される基である。Ｒ₁は炭素数１〜７の１価の炭化水素基であり、それぞれ同一でも異なっていてもよい。ｍは独立に０〜４の数であり、ｍ₁は独立に０〜３の数である。ｋは平均値で０〜４の数である。）

(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 7 carbon atoms, which may be the same or different. . M is independently a number of 0 to 4, m ₁ is independently a number of 0 to 3, and k is an average value of 0 to 4.)

（一般式（１ｂ）、（１ｃ）中、Ａは２価の有機残基である。Ｙは上記一般式（１）のYと同意である。ｎ₁及びｎ₂は０〜２００の平均繰り返し数である。）

(In the general formulas (1b) and (1c), A is a divalent organic residue. Y is synonymous with Y in the above general formula (1). n ₁ and n ₂ are average repetitions of 0 to 200. It is a number.)

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

（式中、Ｘは、単結合、メチレン基、ジメチルメチレン基、又は炭素数１〜４のアルキル置換基を有してもよい１，１−シクロへキシレン基である。Ｒ₂は炭素数１〜７の１価の炭化水素基であり、それぞれ同一でも異なっていてもよい。ｍ₂は独立に０〜４の数である。）

(In the formula, X is 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 is 1 carbon atom To 7 monovalent hydrocarbon groups, which may be the same or different, and m ₂ is independently a number of 0 to 4.)

（式中、Ｒ₂〜Ｒ₅は及びｍ₂〜ｍ₅は、それぞれ一般式（２）のＲ₂及びｍ₂と同意である。） Examples of the divalent aromatic group represented by the general formula (2) include groups represented by the following formulas (2a) to (2d).

(In the formula, R _{2 to} R ₅ and m _{2 to} m ₅ are synonymous with R ₂ and m ₂ of the general formula (2), respectively.)

Furthermore, the present invention uses a divalent epoxy resin represented by the following general formula (3) and a bisphenol F derivative represented by the following general formula (4) as raw materials, and in the presence of an onium salt catalyst, an aromatic system In the solvent, the ratio of the number of moles of the epoxy group in the divalent epoxy resin (E1) to the number of moles of the phenolic hydroxyl group in the bisphenol F derivative (F1) is (E1):(F1)=1.029- A method for producing a phenoxy resin containing a bisphenol F skeleton represented by the general formula (1), characterized in that the reaction is carried out in a range of 1.005:1.

（式中、Ａは２価の有機残基である。）

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

（式中、Ｒ₁は炭素数１〜７の１価の炭化水素基であり、それぞれ同一でも異なっていてもよい。ｍは独立に０〜４の数であり、ｍ₁は独立に０〜３の数である。ｋは平均値で０〜４のであるが、ｋ＝０の成分が８０％（面積％）以上を占める。）

(In the formula, R ₁ is a monovalent hydrocarbon group having 1 to 7 carbon atoms and may be the same or different. m is independently a number of 0 to 4 and m ₁ is independently 0 to 0. It is a number of 3. The average value of k is 0 to 4, but the component of k=0 occupies 80% (area%) or more.)

Further, the present invention is obtained by the method for producing a phenoxy resin containing a bisphenol F skeleton and has an epoxy equivalent of 4500 to 7000 g/eq. And the phenolic hydroxyl group equivalent is 8000 to 15000 g/eq. The bisphenol F skeleton-containing phenoxy resin represented by the above general formula (1) is characterized in that the weight average molecular weight measured by gel permeation chromatography is 30,000 to 80,000 in terms of polystyrene.

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.

（式中、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が、下記（イ）〜（ハ）のいずれか１つの条件を満たす。
（イ）すべてのＲ₇が炭素数１〜１０のアルキル基、
（ロ）すべてのＲ₇が置換基を有してもよいアリール基または置換基を有してもよいアラルキル基、
（ハ）３つのＲ₇が、置換基を有してもよいアリール基であり、１つのＲ₇が炭素数１〜１０のアルキル基。

(In the formula, R ₇ represents a monovalent hydrocarbon group and may be the same or different, but 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 's may have an aryl group which may have a substituent or an aralkyl group which may have a substituent,
(C) Three R ₇ are an aryl group which may have a substituent, and one R ₇ is an alkyl group having 1 to 10 carbon atoms.

（式中、Ｒ₈、Ｒ₉は炭素数１〜４のアルキル基を表し、それぞれ同一でも異なっていてもよい。Ｒ₁₀は炭素数１〜１０のアルキル基を表す。） X ₁ is a halogen atom or _one of the following general formulas (5a) to (5c).

(In the formula, R ₈ and R ₉ 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), it is preferable that the component of k=0 is 96.5 area% or more.

Furthermore, the present invention includes the bisphenol F skeleton-containing phenoxy resin, 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. A resin varnish having a resin concentration of 20 to 80% by mass.

It is preferable that the resin varnish uses toluene as the organic solvent (A) and methyl ethyl ketone as the organic solvent (B) in a mass ratio of (A)/(B)=/4 to 1/9. The viscosity of the resin varnish at 25° C. is preferably 500 to 7,000 mPa·s, and the transmittance at a wavelength of 400 nm using a 10 mm quartz cell is preferably 90% or more.

Further, the present invention is a resin composition containing, as an essential component, the phenoxy resin containing the bisphenol F skeleton or the resin varnish, and a curing agent reactive with the phenoxy resin. 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, coating agent, or display device using the bisphenol F skeleton-containing phenoxy resin, the resin composition, or the resin varnish.

The phenoxy resin containing a bisphenol F skeleton of the present invention is excellent in low viscosity, transparency, adhesiveness, and storage stability, and the composition thereof is useful as an optical material application, a coating material application, and an electronic material application. It can be expected that the dry film type adhesive used for laminating a frame and a frame-printed cover panel will be improved, which is a problem such as step followability.

Hereinafter, embodiments of the present invention will be described in detail. The phenoxy resin containing a bisphenol F skeleton of the present invention is represented by the above general formula (1) and has an epoxy equivalent of 4500 to 7000 g/eq. And the phenolic hydroxyl group equivalent is 8000 to 15000 g/eq. And the weight average molecular weight (Mw) measured by gel permeation chromatography is 30,000 to 80,000 in terms of polystyrene.

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, octylene group, cyclohexylene group, 1,4-dimethylenecyclohexyl group, decahydronaphthylene group. Alicyclic hydrocarbon group such as bicyclohexylene group, 4,4′-dimethylene bicyclohexyl 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 group, but are not limited thereto, and may be the same or different. Further, these divalent organic residues may have a monovalent hydrocarbon group having 1 to 7 carbon atoms as a substituent. Examples of preferable substituents 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 styrenyl 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 economical efficiency when a bisphenol F skeleton-containing phenoxy resin is used. Is.
In the general formulas (1) to (4), common symbols have the same meaning unless otherwise specified.

In the general formula (2), X is a single bond, a methylene group, a dimethylmethylene group, or a 1,1-cyclohexylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent.
R ₂ is independently a monovalent hydrocarbon group having 1 to 7 carbon atoms and may 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 styrenyl group. m ₂ is independently a number from 0 to 4. A preferred embodiment is a structure in which m ₂ is 0 from the viewpoints of availability, low viscosity and transparency.

In the general formula (1), Y is a group represented by the general formula (1a). In the general formula (1a), Z is a group represented by the general formula (1b) or (1c). A and Y in general formulas (1b) and (1c) are synonymous with A and Y in 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 7 carbon atoms, which may 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 styrenyl group. m is any number from 0 to 4. A preferred embodiment is a structure represented by m=0 from the viewpoints of availability, low viscosity and transparency.

In general formula (1), n is the average number of repetitions and is in the range of 10 to 200. Within this range, flexibility as a dry film type adhesive for display members, sufficient light transmittance after adhesion, non-tackiness at room temperature, low heat melting property, low fluidity capable of following a step, It is possible to obtain a phenoxy resin containing a bisphenol skeleton, which exhibits good adhesiveness to a binder. The 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 becomes difficult to wind the roll. When n exceeds 200, the viscosity becomes high because the molecular weight is too large, and it becomes difficult to achieve the step followability. For the same reason, the range of n+n ₁ +n ₂ is preferably 10-200.

The epoxy equivalent (g/eq.) of the phenoxy resin containing a bisphenol F skeleton of the present invention is 4500 to 7000. When the epoxy equivalent is less than 4500, the film forming property when used alone becomes weak. On the other hand, when the epoxy equivalent is more than 7,000, a sufficient effect cannot be obtained even if a curing agent reactive with an epoxy group is used. Within this range, not only the film-forming property when the phenoxy resin of the present invention is used alone, but also a cured product can be prepared by curing with a curing agent having reactivity 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, so even if a curing agent having reactivity with the epoxy group is used, it is not incorporated into the reaction, and it is rather unresolved. Since it remains as a reaction product, the heat resistance tends to deteriorate. Since the phenoxy resin containing a bisphenol F skeleton of the present invention can be made to have a high molecular weight while leaving an epoxy group remaining, it can be designed as a thermosetting film resin composition, and various types can be used depending on the application. A curable film can be obtained. The preferred range of the epoxy equivalent is 5000 to 6900, and the more preferred range is 5500 to 6800.

The bisphenol F skeleton-containing phenoxy resin of the present invention has a Mw of 30,000 to 80,000 in terms of polystyrene. If the Mw is less than 30,000, the flexibility is poor and it becomes difficult to wind the roll. On the other hand, when Mw exceeds 80,000, the molecular weight is too large, resulting in high viscosity, which makes it difficult to achieve the step followability. Within this range, flexibility as a dry film type adhesive for display members, sufficient light transmittance after adhesion, non-tackiness at room temperature, low heat melting property, low fluidity capable of following a step, and adherence It is possible to obtain a phenoxy resin containing a bisphenol skeleton, which exhibits good adhesiveness to a material. The preferable range of Mw is 32,000 to 70,000, and the more preferable range is 35,000 to 60,000. Here, Mw is calculated|required by GPC measurement, and GPC measurement conditions are based on the conditions described in the Example.

The ratio of Mw of the bisphenol F skeleton-containing phenoxy resin of the present invention to the polystyrene-equivalent number average molecular weight (Mn) is not particularly limited, but Mw/Mn=3.5 to 6.5 is preferable and 3.6 to 6 0.0 is more preferable, and 3.8 to 5.5 is more preferable. When Mw/Mn is low, the production may be difficult due to the epoxy equivalent exceeding the range of the present invention in the production method of the present invention. When Mw/Mn is high, the polymer contains a large amount of branched structure generated as a side reaction, and the degree of freedom of the polymer main chain is limited by the branched structure, so that the film becomes brittle. There is a fear. Within the above range, flexibility as a dry film type adhesive for display members, sufficient light transmittance after adhesion, non-tackiness at room temperature, low heat melting property, low fluidity capable of following a step, It is possible to obtain a phenoxy resin containing a bisphenol skeleton, which exhibits better properties such as good adhesiveness with a binder. Here, Mw and Mn are obtained by GPC measurement, and GPC measurement conditions are based on the conditions described in the examples.

The phenolic hydroxyl group equivalent (g/eq.) of the bisphenol F skeleton-containing phenoxy resin of the present invention is 8000 to 15000, preferably 8500 to 13000, and more preferably 9000 to 12000. Within this range, when used as a dry film type adhesive for display element members, more suitable transparency and low viscosity are exhibited. When the phenolic hydroxyl group equivalent is small, the epoxy group is not sufficiently consumed, and there is a possibility that sufficient effect cannot be obtained in terms of storage stability, such as increase in viscosity and molecular weight. 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 and a bifunctional resin and a monomer having reactivity with an epoxy group. Due to the characteristics of the reaction, an epoxy group or a functional group having reactivity with an epoxy group is used. The reaction is completed when almost disappeared. On the other hand, the phenoxy resin containing a bisphenol F skeleton obtained by the production method of the present invention is characterized in that the high molecular weight reaction proceeds while leaving both the epoxy group and the phenolic hydroxyl group, resulting in the coexistence of both functional groups. have.

The reason for this is that, in addition to the reaction between the epoxy resin and the phenolic hydroxyl group present in the bisphenol F derivative compound, addition or condensation reaction between polymer main chains occurs at sites other than the epoxy group and the phenolic hydroxyl group, and It is speculated that the high molecular weight reaction proceeds as a side reaction while the phenolic hydroxyl group remains. For example, hydrogen abstraction occurs on the methylene group in the dihydroxydiphenylmethane moiety or on the secondary carbon formed by the reaction of the epoxy group and the phenolic hydroxyl group, and cation or anion is generated on the benzyl position or the secondary carbon. Therefore, it is assumed that side reactions not involving the epoxy group and the phenolic hydroxyl group occur such as electrophilic addition on the benzene ring and methylene site or secondary carbon, nucleophilic substitution reaction, and dimerization reaction. The present inventors presume that this phenomenon appears by selecting a phenol derivative compound having a bisphenol F skeleton, a specific solvent and a specific catalyst. Therefore, it is considered that even if the molecular weight is the same, the radius of gyration of the molecule is shortened, and as a result, the viscosity is lowered during melting. By using the method of the present invention, it is possible to obtain a phenoxy resin and its varnish that have good storage stability without deterioration of the resin during storage even if functional groups that react with each other coexist.

Next, the method for producing the bisphenol F skeleton-containing phenoxy resin of the present invention will be described.

The method for producing a phenoxy resin containing a bisphenol F skeleton of the present invention comprises a divalent epoxy resin represented by the general formula (3) and a bisphenol F derivative represented by the general formula (4) as an onium salt catalyst. In the presence of, in the aromatic solvent, the ratio of the number of moles of the epoxy group in the divalent epoxy resin (E1) to the number of moles of the phenolic hydroxyl group in the bisphenol F derivative (F1) is (E1):( F1)=1.029 to 1.005:1.

By reacting at this ratio, a bisphenol F skeleton-containing phenoxy resin having low viscosity, transparency, adhesiveness, film property, and storage stability can be obtained. When the ratio exceeds 1.029, it is difficult to control Mw within the range of the present invention, and as a result, it becomes difficult to obtain the effects of the present invention. If the ratio is less than 1.005, it becomes difficult to balance the Mw and the epoxy equivalent, and the storage stability and the like deteriorate, which is not preferable. Also, if the phenolic hydroxyl group equivalent deviates from this ratio, it may deviate from the preferable range. The preferred range of (E1):(F1) is 1.029 to 1.005:1, and the more preferred range is 1.025 to 1.01:1.

As the divalent epoxy resin represented by the general formula (3), various known compounds can be applied. 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; and cycloaliphatic diols such as cyclohexanediol, cyclodecanediol, bicyclohexanediol, decalin diol, cyclohexanedimethanol, or bicyclohexanedimethanol Epoxy resins derived from; epoxy resins derived from polyalkylene ether glycols such as polyethylene ether glycol, polyoxytrimethylene ether glycol, or polypropylene glycol; 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, dimethylbisphenol A, tetramethylbisphenol A, dimethylbisphenol F , Tetramethylbisphenol F, dimethylbisphenol S, tetramethylbisphenol S, tetramethylbisphenol Z, hydroquinone, resorcin, catechol, methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, butylhydroquinone, dibutylhydroquinone, methylresorcin, biphenol, tetramethylbiphenol, Dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydiphenyl ether, dihydroxybenzophenone, dihydroxydiphenyl sulfide, thiodiphenol, brominated bisphenol A, or bisphenols obtained by condensation reaction of a monofunctional phenol with a compound having one aldehyde group, or Examples thereof include, but are not limited to, an aromatic group-containing epoxy resin derived from a bisphenol or the like obtained by a condensation reaction of a functional phenol and a compound having one carbonyl group. A preferable epoxy resin is a divalent epoxy resin derived from bisphenol A, bisphenol F, biphenol, or bisphenol Z from the viewpoints of economical availability, transparency, and low melt viscosity.

In addition, bisphenol F diglycidyl ether [4,4′-methylenebis(glycidyloxybenzene), 2,2′-methylenebis(glycidyloxybenzene) and bisphenol F diglycidyl ether obtained by further distilling an epoxy resin obtained from a bisphenol F derivative and epihalohydrin and 2,4'-methylenebis(glycidyloxybenzene) mixture] content of 98% by mass or more of the epoxy resin or bisphenol F derivative and epihalohydrin of 99% by mass or more of the component of k=0 in the general formula (4) The structure of 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 point of view to use the divalent epoxy resin represented by the general formula (3) and the bisphenol F derivative represented by the general formula (4).

In the bispheno F derivative represented by the general formula (4), R ₁ independently represents a monovalent hydrocarbon group having 1 to 7 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 styrenyl group. m is independently a number from 0 to 4, and m ₁ is independently a number from 0 to 3. A preferred embodiment is a structure represented by m=0 and m ₁ =0 from the viewpoints of availability, low viscosity and transparency. k is an average value of 0 to 4, and the component of k=0 is 80% (area %) or more, preferably 95% or more, and more preferably 96.5% or more. When the content of k=0 is less than 80%, the number of trifunctional or higher functional components increases, so that the number of reaction points increases, and the reaction tends to become insoluble as the reaction proceeds, and the effect of the present invention is difficult to obtain. In addition, a component of k=0 may be expressed as a binuclear body, a component of k=1 may be expressed as a trinuclear body, a component of k=2 may be expressed as a tetranuclear body, and a component of k=3 may be expressed as a pentanuclear body. In addition,% of the component such as k=0 is the area% based on the GPC measurement, and the GPC measurement conditions are the same as the molecular weight measurement conditions described in the examples.

Further, the binuclear body in the bisphenol F derivative used in the present invention has isomers. In the present invention, it is important to control the ratio of three kinds of isomers of 4,4'-form, 2,2'-form and 2,4'-form, and other isomers may be ignored. .. The isomer ratio is an area ratio measured by liquid chromatography (HPLC), and 40% or less of 4,4'-form is preferable, and 29 to 37% is more preferable. 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 the amount of these isomers exceeds the above-mentioned ratio, the above-mentioned reaction becomes difficult to occur, and the bisphenol F skeleton-containing phenoxy resin of the present invention having a high molecular weight cannot be obtained while the epoxy group and the phenolic hydroxyl group remain. 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 derivative is carried out, a divalent phenolic compound can be further used in combination as long as the effect of the present invention is 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 further preferably 25 parts by mass or less, relative to 100 parts by mass of the bisphenol F derivative.

When the divalent phenolic compound is used in combination, the total number of moles of the phenolic hydroxyl group in the bisphenol F derivative and the number of moles of the phenolic hydroxyl group in the divalent phenolic compound is defined as the number of moles (F1). In the range of the molar ratio (E1:F1)=1.029 to 1.005:1 with the number of moles (E1) of the epoxy group in the valent epoxy resin.

Specific examples of the divalent phenolic compound 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, bisphenol. AF, bisphenolfluorene, biscresolfluorene, bisphenol Z, bisphenol TMC, dimethylbisphenol A, tetramethylbisphenol A, dimethylbisphenol S, tetramethylbisphenol S, tetramethylbisphenol Z, hydroquinone, resorcin, catechol, methylhydroquinone, dimethylhydroquinone, Trimethylhydroquinone, butylhydroquinone, dibutylhydroquinone, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydiphenylether, dihydroxybenzophenone, dihydroxydiphenylsulfide, thiodiphenol, brominated bisphenol A, or monofunctional phenols and aldehydes Examples thereof include bisphenols obtained by a condensation reaction with a compound having one group, and bisphenols obtained by a condensation reaction of a monofunctional phenol with a compound having one carbonyl group.

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

In the general formula (5), R ₇ satisfies any one of the following conditions (a) to (c).
(A) All R ₇ are alkyl groups having 1 to 10 carbon atoms.
(B) An aryl group in which all R ₇ 's may have a substituent or an aralkyl group which may have a substituent.
(C) Three R ₇ are an aryl group which may have a substituent, and 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 (a) or (c) above 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, the present invention is not limited to these.

Examples of the aryl group which may have a substituent described in (b) or (c) above include a phenyl group, a toluyl group, a dimethylphenyl group, a tert-butylphenyl group, a methoxyphenyl group, a dimethoxyphenyl group, Alternatively, a tert-butoxyphenyl group and the like can be mentioned, but the present invention is not limited thereto. 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 and 4-isopropylbenzyl group. Not done.

In the general formula (5), X ₁ is a halogen atom, (R ⁸ O) ₂ PO ₂ ^— , (R ⁹ O) ₂ PS ₂ ^— or R ¹⁰ CO ₂ ^— . However, R ⁸ and R ⁹ 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. ^{_{(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. Preferred is a methyl group or an ethyl group. R ₁₀ represents an alkyl group having 1 to ₁₀ carbon atoms, preferably a methyl group.

Examples of the organic phosphonium salts represented by the general formula (5) are as follows when R ₇ satisfies the above (a).
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, trimethylcyclohexylphosphonium bromide, trimethylcyclohexylphosphonium iodide and the like.
When X ₁ is the formula (5a): tetramethylphosphonium dimethylphosphate, tetramethylphosphonium diethylphosphate, tetraethylphosphonium dimethylphosphate, tetraethylphosphonium diethylphosphate, methyltripropylphosphonium dimethylphosphate, methyltripropylphosphonium diethylphosphate, methyltributylphosphoniumdimethyl Phosphate, methyltributylphosphonium diethylphosphate, tetra-n-butylphosphonium dimethylphosphate, tetra-n-butylphosphonium diethylphosphate, tetra-n-hexylphosphonium dimethylphosphate, tetra-n-hexylphosphonium diethylphosphate, methyltrihexylphosphonium dimethylphosphate , Methyltrihexylphosphonium diethylphosphate and the like.
When X ₁ is the formula (5b): tetramethylphosphonium-o,o-dimethylphosphorodithioate, tetramethylphosphonium-o,o-diethylphosphorodithioate, tetraethylphosphonium-o,o-dimethylphosphorodithioate , Tetraethylphosphonium-o,o-diethylphosphorodithioate, tetrapropylphosphonium-o,o-dimethylphosphorodithioate, tetrapropylphosphonium-o,o-diethylphosphorodithioate, methyltributylphosphonium-o,o- Dimethyl phosphorodithioate, methyltributylphosphonium-o,o-diethyl phosphorodithioate, tetra-n-butylphosphonium-o,o-dimethyl phosphorodithioate, tetra-n-butylphosphonium-o,o-diethylphospho Rhodithioate, tetra-n-hexylphosphonium-o,o-dimethyl phosphorodithioate, tetra-n-hexylphosphonium-o,o-diethylphosphorodithioate, methyl tree n-hexylphosphonium-o,o-dimethyl Phosphorodithioate, methyl tri-n-hexylphosphonium-o,o-diethyl phosphorodithioate and the like.
When X ₁ is formula (5c): tetraethylphosphonium acetate, tetraethylphosphonium propionate, tetrabutylphosphonium acetate, tetrabutylphosphonium propionate, tetrabutylphosphonium hexanoate, tetrabutylphosphonium decanoate and the like.

When R ₇ satisfies the above (b), it 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 formula (5a): tetraphenylphosphonium dimethyl phosphate, tetraphenylphosphonium diethyl phosphate, benzyltriphenylphosphonium dimethylphosphate, benzyltriphenylphosphonium diethylphosphate, etc.
When X ₁ is the formula (5b): tetraphenylphosphonium-o,o-dimethylphosphorodithioate, tetraphenylphosphonium-o,o-diethylphosphorodithioate, benzyltriphenylphosphonium-o,o-dimethylphosphoro Dithioate, benzyltriphenylphosphonium-o,o-diethyl phosphorodithioate and the like.
When X ₁ is the 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.

When R ₇ satisfies the above (c), it 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 formula (5a): methyltriphenylphosphonium dimethylphosphate, methyltriphenylphosphonium diethylphosphate, ethyltriphenylphosphonium dimethylphosphate, ethyltriphenylphosphonium diethylphosphate, propyltriphenylphosphonium dimethylphosphate, propyltriphenylphosphonium diethyl Phosphate, butyltriphenylphosphonium dimethylphosphate, butyltriphenylphosphonium diethylphosphate, hexyltriphenylphosphonium dimethylphosphate, hexyltriphenylphosphonium diethylphosphate and the like.
When X ₁ is the formula (5b): methyltriphenylphosphonium-o,o-dimethylphosphorodithioate, methyltriphenylphosphonium-o,o-diethylphosphorodithioate, ethyltriphenylphosphonium-o,o-dimethyl Phosphorodithioate, ethyltriphenylphosphonium-o,o-diethylphosphorodithioate, propyltriphenylphosphonium-o,o-dimethylphosphorodithioate, propyltriphenylphosphonium-o,o-diethylphosphorodithioate, Butyltriphenylphosphonium-o,o-dimethylphosphorodithioate, butyltriphenylphosphonium-o,o-diethylphosphorodithioate, hexyltriphenylphosphonium-o,o-dimethylphosphorodithioate, hexyltriphenylphosphonium- o,o-diethyl phosphorodithioate and the like.
When X ₁ is the formula (5c): methyltriphenylphosphonium acetate, methyltriphenylphosphonium propionate, methyltriphenylphosphonium butanoate, methyltriphenylphosphonium hexanoate, methyltriphenylphosphonium octanoate, methyltriphenyl Phenylphosphonium decanoate, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium propionate, ethyltriphenylphosphonium butanoate, ethyltriphenylphosphonium hexanoate, ethyltriphenylphosphonium octanoate, ethyltriphenylphosphonium decanoate Salt, propyl triphenyl phosphonium acetate, propyl triphenyl phosphonium propionate, propyl triphenyl phosphonium butanoate, propyl triphenyl phosphonium hexanoate, propyl triphenyl phosphonium octanoate, propyl triphenyl phosphonium decanoate, butyl tri Phenylphosphonium acetate, butyltriphenylphosphonium propionate, butyltriphenylphosphonium butanoate, butyltriphenylphosphonium propionate, butyltriphenylphosphonium hexanoate, butyltriphenylphosphonium propionate, butyltriphenylphosphonium octanoic acid Salt, butyltriphenylphosphonium propionate, butyltriphenylphosphonium decanoate, hexyltriphenylphosphonium acetate, hexyltriphenylphosphonium propionate, hexyltriphenylphosphonium butanoate, hexyltriphenylphosphonium propionate, hexyltriphenyl Phenylphosphonium hexanoate, hexyltriphenylphosphonium propionate, hexyltriphenylphosphonium octanoate, hexyltriphenylphosphonium propionate, hexyltriphenylphosphonium decanoate, etc.

The organic phosphonium salt represented by the general formula (5) is 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 satisfy any one of the above (a), (b), and (c). , X ₁ is represented by a halogen atom. More preferable organic phosphonium salts are tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetraphenylphosphonium bromide, methyltriphenylphosphonium bromide and 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 and tetramethyl. Ammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutyl Organic ammonium salts such as ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride; and diphenyliodonium iodide, phenyl(2-methylphenyl)iodonium iodide And organic iodonium salts such as phenyl(4-methylphenyl)iodonium iodide and phenyl(2,5-dimethylphenyl)iodonium iodide; triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide, trimethylsulfonium Chloride, trimethylsulfonium bromide, trimethylsulfonium iodide, dimethylphenylsulfonium chloride, dimethylphenylsulfonium bromide, dimethylphenylsulfonium iodide, 4-tert-butylphenyldiphenylsulfonium bromide, 4-tert-butylphenyldiphenylsulfonium iodide, 4 -Tert-butoxyphenyldiphenylsulfonium bromide, 4-tert-butoxyenyl diphenylsulfonium iodide, tris(4-tert-butylphenyl)sulfonium bromide, tris(4-tert-butylphenyl)sulfonium iodide, tris(4-tert) Examples include organic sulfonium salts such as -butoxyphenyl)sulfonium bromide, tris(4-tert-butoxyphenyl)sulfonium iodide, and p-tolyldiphenylsulfonium bromide.

Further, a catalyst capable of reacting an epoxy group with a phenolic hydroxyl group may be used in combination so long as the scope of the present invention is not impaired. 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 and sodium ethoxide. Alkali metal alkoxides, alkali metal phenoxides, sodium hydride, lithium hydride and other alkali metal halide compounds, sodium acetate, sodium stearate and other organic acid alkali metal salts, tri-n-propylphosphine, tri-n -Organophosphine compounds such as -butylphosphine, triphenylphosphine, tri-p-tolylphosphine, tri-2,5-xylylphosphine, tri-(p-methoxyphenylphosphine), triethylamine, tri-n-propylamine, Tertiary amine compounds such as tri-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. Examples include ring compounds.

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 100000 ppm. If it is 5 ppm or less, the reaction rate is very slow and it is economically disadvantageous. If it exceeds 100,000 ppm, the progress of side reactions cannot be ignored, and the resin becomes insoluble in some cases, which is not preferable.

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

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 a solvent other than this, it may be difficult to control the reaction and it may be difficult to judge the reaction end point. When a solvent other than the aromatic solvent is used in combination, it is preferable to use the aromatic solvent in an amount of 70% by mass or more based on the whole solvent. With this amount, the phenoxy resin containing the bisphenol F skeleton of the present invention can be relatively easily obtained. As the solvent other than the aromatic solvent that can be used together, various known solvents can be applied as long as they do not affect the epoxy group and the phenolic hydroxyl group. For example, hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane and other aliphatic hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, Ketone solvents such as cyclopentanone, dioxane, ethyl phenyl ether, ethyl benzyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ether solvents such as diethylene glycol dimethyl ether, and cellosolve solvents such as methyl cellosolve and ethyl cellosolve, Examples include alkylene glycol monoalkyl ether acetate solvents such as methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate, and various solvents such as dimethylformamide and dimethylsulfoxide, but they are not limited to these, and two or more kinds may be used in combination. May be.

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 uses aromatic hydrocarbons having a boiling point of 80° C. to 145° C. Since it is used, the temperature is 80°C to 160°C. If the reaction temperature is 50° C. or lower, the reaction rate is very slow, which is economically disadvantageous. If the reaction temperature exceeds 230° C., the progress of side reactions cannot be ignored and the resin becomes insoluble in some cases, 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 represented by 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. It is possible to produce a phenoxy resin containing a bisphenol F skeleton that can be expressed to the maximum extent. The inventors consider the reason for this as follows.

It is individually known that an aromatic organic solvent is used as a reaction solvent or an organic phosphonium salt is used as a catalyst when producing a phenoxy resin. There is no. A general phenoxy resin is a relatively highly polar polymer having a secondary alcoholic hydroxyl group in its side chain, and an aromatic solvent having a low polarity has a poor dissolving power for the phenoxy resin. On the other hand, when the bisphenol F structure containing a structural isomer is used as a raw material, the polymer main chain structure becomes randomly asymmetric and the solubility is considered to increase even when a solvent having low polarity is used. In the F skeleton-containing phenoxy resin, no phenomenon was observed that the resin macroscopically aggregated and separated even during the reaction. As described above, the bisphenol F derivative used in the present invention generally has three structural isomers as the binuclear body and has an asymmetric structure to improve the dissolving power, and the aromatic solvent contains the bisphenol F skeleton of the present invention. It is considered that the phenoxy resin behaved like a θ solvent, and it is considered that the aromatic hydrocarbon having a boiling point of 80° C. to 145° C. was 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 in which the organic solvent is incompatible are microscopically separated, and the catalyst used in the production of the phenoxy resin acts as a phase transfer catalyst. It is presumed that the behavior is different from the case of a homogeneous system using a solvent. In the method of the present invention, a solvent having a poor solubility in a phenoxy resin such as an aromatic solvent, a specific quaternary phosphonium salt, and a bisphenol F derivative having a structural isomer are used in the above-mentioned benzyl position or secondary carbon. Generation of cations or anions promotes side reactions not involving the phenolic hydroxyl group and epoxy group such as electrophilic addition, nucleophilic substitution reaction and dimerization reaction on the benzene ring and methylene site or secondary carbon. It is speculated that the bisphenol F skeleton-containing phenoxy resin of the present invention was obtained by the progress of higher molecular weight while the group and the phenolic hydroxyl group coexisted. The bisphenol F skeleton phenoxy resin obtained by the production in the presence of such a θ solvent has an epoxy group and a phenolic hydroxyl group coexisting and is excellent in storage stability. In addition, no reported examples of bisphenol F skeleton phenoxy resin having such properties have been found so far. In the present invention, it is speculated that a specific reaction field is created by using the above-mentioned onium salt and an aromatic catalyst in combination, and the bisphenol F skeleton-containing phenoxy resin of the present invention is obtained. In particular, it is speculated that the most effective bisphenol F skeleton-containing phenoxy resin was obtained by using the above organic phosphonium salts and an aromatic catalyst having a boiling point of 80° C. to 145° C. in combination in an optimum state. There is.

As described above, the phenoxy resin that uses the bisphenol F skeleton as a divalent phenolic compound as a raw material is that the methylene group is oxidized during the reaction and is carbonylated, or is easily changed to another structure that forms a color group by conjugation. The phenoxide compound, which is an intermediate at this time, is easily oxidized to give a quinoid structure and is therefore easily colored. The reason why a resin varnish with less coloring is obtained when using a phonium salt as a catalyst is not known in detail, but when a base such as an alkali metal catalyst or amine is used as a catalyst, the polymerization initiation species is phenoxide. Although it is an ion, the reaction by nucleophilic substitution with the epoxy group begins, but since the conjugated structure extends to the methylene site until the nucleophilic addition reaction begins, a coloring group due to a side reaction is likely to occur, When a phonium salt is used as a catalyst, an onium cation is coordinated with an epoxy group to form a polymerization initiation species, and then the polymerization is initiated by an electrophilic addition reaction with phenol. It is presumed that it was difficult to be formed, and as a result, good transparency was obtained without forming a coloring group.

Next, the divalent epoxy resin represented by the general formula (3) and the bisphenol F derivative represented by the general formula (4) are mixed with each other in an aromatic solvent in the presence of an onium salt catalyst. Of the number of moles of the epoxy group (E1) in the polyvalent epoxy resin and the number of moles of the phenolic hydroxyl group (F1) in the bisphenol F derivative are (E1):(F1)=1.029 to 1.005:1. The epoxy equivalent of 4500 to 7000 g/eq. And the phenolic hydroxyl group equivalent is 8000 to 15000 g/eq. The phenoxy resin (A2) containing a bisphenol F skeleton having a weight average molecular weight of 30,000 to 80,000 in terms of polystyrene measured by gel permeation chromatography will be described.

As the divalent epoxy resin represented by the general formula (3), the bisphenol F derivative represented by the general formula (4), the onium salt catalyst, and the aromatic solvent, those shown in the production method of the present invention are used. And 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 the preferable conditions are also the same. The epoxy equivalent, the phenolic hydroxyl group equivalent, and the 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 applies to the preferable ranges, and it is considered that the main chain has the structure represented by the general formula (1), but has a structural unit that cannot be represented by the 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 bisphenol. The F skeleton-containing phenoxy resin (A1) is used, and the latter is a 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 contains 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. It is% by mass. By using these solvents, it is possible to obtain a resin varnish having good transparency and good viscosity and dryness 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 similarly.

As the organic solvent (A), various known solvents can be applied. For example, benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like can be mentioned, but not limited to these, and two or more kinds may be used. A particularly preferable solvent is toluene from the viewpoint of safety, solubility, and energy and time required for drying.

As the organic solvent (B), various known solvents can be applied. Examples thereof include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 2-methyl-3-pentanone, and tert-butyl methyl ketone, but the present invention is not limited thereto and two or more kinds may be used. .. A particularly preferable solvent is methyl ethyl ketone from the viewpoint of solubility and energy and time required for drying.

The resin concentration of the resin varnish of the present invention is 20 to 80% by mass. If the resin concentration is less than 20% by mass, the high molecular weight component of the phenoxy resin having a bisphenol F skeleton of the present invention is rejected, and it may be difficult to obtain a uniform varnish. If the resin concentration exceeds 80% by mass, the fluidity at room 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. The preferable range of the resin concentration is 25 to 70% by mass, and the more preferable range is 30 to 60% by mass.

The resin varnish of the present invention may have a resin concentration of 20 to 80% by mass using a known organic solvent in addition to the organic solvent (A) and the organic solvent (B), and may be used in combination of two or more kinds. Good. Such an organic solvent can be appropriately selected by those skilled in the art according to its use and purpose, but in view of not impairing the scope of the present invention, the boiling point is 60 to 145° C., and the amount used is based on the whole solvent. It is preferably less than 50% by mass. When an organic solvent having a boiling point of less than 60° C. is also used, the quality of the varnish may change due to skinning and evaporation of the varnish during storage. When an organic solvent having a boiling point of 145° C. or higher is used in combination, the solvent may remain during the production of the film adhesive for display members, which may deteriorate the properties of the adhesive.

The solvent composition of the organic solvent (A) and the organic solvent (B) used in the resin varnish of the present invention is not particularly limited, but is usually (A)/{the total amount of the solvent including (A) and (B) in a mass ratio}. Is less than 0.8. It is preferably less than 0.75, more preferably less than 0.65. Within 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)} in mass ratio exceeds 0.8, it means that the amount of the organic solvent (A) is too large, and the uniformity of the resin varnish of the present invention is high. May not be maintained. In particular, it is preferable to use toluene as the organic solvent (A) and methyl ethyl ketone as the organic solvent (B) in a mass ratio of (A)/(B)=8/2 to 1/9, and (A)/ It is more preferable to use the composition of (B)=6/4 to 1/9. If the proportion of (A) is too large, the mixed solvent may become a poor solvent and the compatibility may deteriorate. On the other hand, if the proportion of (A) is too small, the proportion of (B) which is a good solvent becomes too large and is incorporated between the molecules of the phenoxy resin, thereby increasing the radius of gyration and increasing the viscosity, and the desired effect is obtained. You may not get it.

The method for producing the resin varnish of the present invention is not particularly limited, and it can be carried out in a preferred mode for those skilled in the art. For example, the bisphenol F skeleton-containing phenoxy resin of the present invention obtained by the reaction using any solvent is subjected to solvent recovery under normal pressure or reduced pressure and solidified, and then the above-mentioned boiling point of an aromatic system having a temperature of 80 to 145°C. A process of re-dissolving using an organic solvent (A) and a ketone-based organic solvent (B) having a boiling point of 60 to 120° C., or a raw material of the bisphenol F skeleton-containing phenoxy resin of the present invention, and a boiling point of 80 to 145° C. The process of carrying out the reaction using the aromatic solvent (A) and/or the ketone organic solvent (B) having a boiling point of 60 to 120° C. and diluting it to a predetermined concentration can be used. Preferably, the reaction is performed in advance using an aromatic organic solvent (A) having a boiling point of 80 to 145° C., and particularly preferably as an aromatic organic solvent (A) having a boiling point of 80 to 145° C. This is a method using toluene.

The viscosity of the resin varnish of the present invention at 25° C. is preferably 500 to 7,000 mPa·s, more preferably 1,000 to 4000 mPa·s. When the viscosity is low, the molecular weight of the bisphenol F skeleton-containing phenoxy resin of the present invention has not grown sufficiently or the degree of branching is very high, and there is a possibility that desired flexibility may not be obtained sufficiently. .. When the viscosity is high, when it is used as a dry film type adhesive for a display element member, the melt viscosity becomes high and the step followability may be deteriorated.

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

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

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

The bisphenol F skeleton-containing phenoxy resin of the present invention and the resin varnish thereof are excellent in transparency, flexibility, adhesiveness and the like, and thus can be suitably used as an optical adhesive application material, a coating application, and an electronic material application. it can.

As an optical adhesive application, various known applications can be selected. For example, adhesives for imaging elements of cameras (vehicle-mounted 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, light splitter, adhesive for optical element such as optical fiber, cover glass for display device, resin for display device, substrate for display device, color Examples include filter substrates, touch panel substrates, display protective films, display backlights, light guide plates, optical laminated plates such as antireflection films, and adhesives for laminated films.

As the coating use, various known uses can be selected. For example, for the purpose of protection such as rust prevention and glossing, decoration, insulation, etc., flooring applications, metal primer coating applications, precoat metal applications, glass coating applications, ceramic coating applications, and fibers, tapes, cloths, etc. For example, it may be used for coating a composite material produced by impregnating the composition.

As the electronic material application, various known applications can be selected. For example, circuit board applications, interlayer adhesives that bond circuit boards together, coverlay films, coverlay film adhesives, copper clad film adhesives, electromagnetic wave shielding adhesives, semiconductor encapsulant applications, die attach films, etc. Are listed.

Since the bisphenol F skeleton-containing phenoxy resin of the present invention and the varnish thereof have an epoxy group at the terminal, a curable resin composition can be obtained by blending a compound or resin reactive with the epoxy group. Examples of such compounds or resins include polyhydric phenolic compounds or resins such as novolac type phenolic resins, novolac type naphthol resins, naphthol aralkyl resins, and resole type phenolic resins, and phthalic anhydride, tetrahydrophthalic anhydride, and hexahydroanhydride. Carboxylic acid compounds such as phthalic acid, methylated hexahydrophthalic anhydride, trimellitic acid, nuclear hydrogenated trimellitic acid and anhydride compounds thereof, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, metaxylylenediamine, isophoronediamine, Amine compounds such as triethylenetetramine, diethylenetriamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, dicyandiamide, phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, imidazoles and trimellitic acid, isocyanuric acid, boro Examples thereof include imidazole salts which are salts with acids 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 a cation curability that generates a cation species by light or heat as a curing agent.

As the acid anhydride compound, if it has a monovalent acid anhydride group, it is possible to modify the secondary alcoholic hydroxyl group into a carboxyl group by reacting with the phenoxy resin containing the bispheno F skeleton of the present invention. Become. As a result, the 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 modified with a carboxyl group, various known compounds can be applied. For example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride, nadic acid anhydride, hydrogenated nadic acid anhydride, anhydrous Examples thereof include trimellitic acid, trimellitic anhydride, hydrogenated trimellitic anhydride and the like, and if necessary, two or more kinds may be used in combination.

The amount of monovalent acid anhydride compound used for modification is not particularly limited, but is usually 0.2 to 1.0 mol per 1 mol of the secondary alcoholic hydroxyl group present in the phenoxy resin containing the bisphenol F skeleton of the present invention. Is.

If the acid anhydride compound has a divalent acid anhydride group, a cured product can be obtained by reacting it with the phenoxy resin having a bispheno F skeleton of the present invention. As such a divalent acid anhydride compound, various compounds can be applied as long as they are publicly known. For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride , Pyromellitic dianhydride, 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 acid anhydride and the like can be mentioned, and if necessary, two or more kinds may be used in combination.

The amount of the divalent acid anhydride compound used is not particularly limited, but is usually 0.2 mol to 1.0 mol per 1 mol of the secondary alcoholic hydroxyl group present in the bisphenol F skeleton-containing phenoxy resin of the present invention. .. The curing temperature is not particularly limited, and it can be carried out under the conditions preferable to those skilled in the art, but it is usually 50°C to 200°C. In addition, a compound having a basic property may be used in combination in order to accelerate the 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. Examples thereof include diisocyanate, a mixture of isomers thereof, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like, and polyol modified products thereof, but are not limited to these and may be used in combination of two or more kinds. 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 1 mol of the secondary alcoholic hydroxyl group present in the bisphenol F skeleton-containing phenoxy resin of the present invention. ~1.0 mol. Further, a metal compound such as an imidazole compound, an amine compound or dibutyltin dilaurate may be used in combination in order to accelerate the crosslinking reaction.

The curable resin composition of the present invention can be heat-treated to obtain a cured product. The temperature required for the heat treatment is not particularly limited and may be a temperature preferred by those skilled in the art, but is usually 50 to 230°C. If the temperature is 50°C or lower, the reaction does not proceed and it is not realistic. At 230° C. or higher, the phenoxy resin having a bisphenol F skeleton of the present invention may be decomposed.

As the onium salt having a cation curability that generates a cation species by light or heat, various compounds can be applied as long as they are known substances. For example, cation structures such as aromatic sulfonium cations and aromatic oxosulfonium cations are paired with anion structures such as iodonium anions, tetrafluoroborate anions, hexafluorophosphate anions, hexafluoroantimonate anions and hexafluoroarsenate anions. The following compounds may be mentioned, and if necessary, two or more kinds may be used. Although the amount of the onium salt used is not particularly limited, it 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 the above-mentioned cationic curability can be cured to obtain a cured product. The temperature required for the heat treatment is not particularly limited and may be a temperature preferred by those skilled in the art, but is usually 50 to 230°C. If the temperature is 50°C or lower, the reaction does not proceed and it is not realistic. At 230°C or higher, there is a concern that the phenoxy resin having a bisphenol F skeleton of the present invention may be decomposed.

The curable resin composition of the present invention can obtain a cured product by irradiating with UV light when a photocation generator is used as the curing agent. The necessary irradiation intensity of UV light is not particularly limited and may be carried out in a range preferable to those skilled in the art, but it is usually in the range of 50 to 150 mW/cm ² . If it is less than 50 mW/cm ² , the cationic polymerization may not proceed sufficiently, and if it exceeds 150 mW/cm ² , the bisphenol F skeleton-containing phenoxy resin of the present invention may be decomposed. It is also possible to further crosslink by irradiating with light to crosslink and then performing heat treatment. The temperature required for the heat treatment is not particularly limited and may be a temperature preferable to those skilled in the art, but is usually room temperature to 230°C.

When a compound containing an isocyanate group is used among these curable resin compositions, a cured product which can be cured at a low temperature and is excellent in transparency can be obtained. Therefore, it can be suitably used as a resin composition for optical adhesives.

In addition, the bisphenol F skeleton-containing phenoxy resin of the present invention and the resin varnish thereof may be blended with other thermosetting resin or photocurable resin, if necessary. Examples of such thermosetting resin include epoxy resin, unsaturated polyester resin, acrylic resin, melamine resin, urea resin, urethane resin, and oxetane resin. Further, the composition can be prepared by using it together with a curing agent, an accelerator or an initiator having reactivity with such a resin. It is also possible to use a known organic solvent or water in combination as a composition having a desired viscosity. Such a curable resin composition can be suitably used for optical adhesive applications, coating applications, and electronic material applications.

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

As the thermoplastic resin, polyethylene, polypropylene, polybutadiene, polyisobutylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyamide, polyimide, polyamide imide, polyphenylene ether, polyphenylene sulfide, polyether sulfone, polysulfone, polyether ether Examples thereof include ketones and polyether ether imides, but not limited to these, and two or more kinds may be used in combination. The amount used is not particularly limited, but is usually 5 parts by mass 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 agents, antioxidants, light stabilizers, organic dyes, organic pigments, leveling materials, flame retardants, and the like, but are not limited to these, and two or more kinds may be used in combination. Good. The amount to be 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 known. For example, silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, xonotlite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, Examples thereof include zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, aluminum borate, etc., but are not limited thereto, and if necessary, 2 You may use together 1 or more types. The amount used is not particularly limited and may be appropriately adjusted by those skilled in the art according to the purpose.

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

As the constituent material of the release film, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyurethane film, ethylene-vinyl acetate copolymer A film, a resin film such as a polyethylene terephthalate film, a polyester film, a porous material such as paper, cloth, and a non-woven fabric, a net, a foamed sheet, a metal foil, and a thin leaf body such as a laminated body thereof can be preferably used. Is a resin film treated with a silicone liner from the viewpoint of releasability and surface smoothness.

As a method for forming the resin composition for an optical adhesive material of the present invention into a sheet shape, various known methods can be selected. For example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating and the like, but are not limited thereto. Not done.

The configuration of the display device using the resin composition for an optical adhesive of the present invention is not particularly limited, and various configurations can be applied as long as it has a known configuration. For example, a configuration in which a liquid crystal panel/touch panel, a liquid crystal panel/protection panel, a liquid crystal panel/touch panel/protection panel, a polarizing film/touch panel, a polarizing film/touch panel/protection panel, and the like are bonded, but not limited to these Not done.

In particular, the phenoxy resin containing a bisphenol F skeleton of the present invention is excellent in fluidity when heated, and therefore is excellent in embedding a step due to frame printing applied to the cover panel, and is a resin for optical adhesive between the cover panel and the touch panel. It can be suitably used as a composition.

Next, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, parts represent parts by mass, and% represents% by mass.

The analysis method and measurement method are shown below. The equivalent unit is g/eq. Is.

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

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

Molecular weight (Mw, Mn): determined by GPC measurement. Specifically, a main body (manufactured by Tosoh Corporation, HLC-8320GPC) equipped with a column (manufactured by Tosoh Corporation, TSKgel G4000H _XL , TSKgel G3000H _XL , TSKgel G2000H _XL ) in series is used, and the column temperature is 40. ℃. Further, tetrahydrofuran was used as the eluent, the flow rate was 1 mL/min, and the detector was an RI (differential refractometer) detector. Standard monodisperse polystyrene (Tosoh Corporation, A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40. , F-80, F-128) to calculate the number average molecular weight (Mn) and the weight average molecular weight (Mw). As a measurement sample, 100 μL of a sample obtained by dissolving 0.1 g of the sample in 10 mL of tetrahydrofuran and filtering with a microfilter was used.

Isomer ratio: determined by HPLC measurement. Specifically, a column (Cadennza CD-C18, 4.6 mmφ×150 mmL, manufactured by Intact Co., Ltd.) was used for the main body (Agilent-1100, manufactured by Agilent Technologies), and the column temperature was 40° C. Further, acetonitrile/water=34/66 (volume ratio) was used as the eluent, the flow rate was 1 mL/min, and the UV detector (detection wavelength: 280 n) was used as the detector. The isomer ratio in the binuclear body of the bisphenol F derivative was expressed by the area ratio.

Phenolic hydroxyl group equivalent: Bisphenol F (manufactured by Honshu Chemical Industry Co., Ltd., trade name: BPF-D) was prepared in an amount of 50 mL of a tetrahydrofuran solution containing 5 mg/L, 20 mg/L, or 50 mg/L, and tetrabutylammonium hydroxide 10 % Aqueous solution was added and mixed, UV spectrum was measured, and a calibration curve was prepared from the absorbance at 305 nm. 0.1 g of the samples of Examples and Comparative Examples were weighed, dissolved in 50 mL of tetrahydrofuran (dilution ratio: 500 times), 20 μL of a 10% aqueous solution of tetrabutylammonium hydroxide was added and mixed, and then UV spectrum was measured to obtain 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．）

m: sampling amount (g)
c: calibration curve concentration (mg/L)
d: dilution ratio of the sample solution, 500 (mL)
k: Gram equivalent of bisphenol F, 100 (g/eq.)

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 (V-650, manufactured by JASCO Corporation) and a 10 mm quartz cell, the light transmittance at 400 nm was measured with 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 (Nippon Steel & Sumikin Chemical Co., Ltd., Epotote YD-128, epoxy equivalent=186)
YDF-8170: Bisphenol F type liquid epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd., Epotote YDF-8170, epoxy equivalent=158)
YX-4000: Polycondensation product of tetramethylbiphenol and epichlorohydrin (Mitsubishi Chemical Corporation, YX-4000, epoxy equivalent=183)
BPZ-EP: HYPERLINK "http://www.chemicalbook.com/ChemicalProductProperty#JP#CB0103479.htm" Polycondensation product of 1,1-bis(4-hydroxyphenyl)cyclohexane and epichlorohydrin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epoxy equivalent = 200)

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

[Other]
YP-70: Bisphenol A bisphenol F copolymerized phenoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol F skeleton-containing phenoxy resin, Phenothote YP-70)
YP-50S: Bisphenol A type phenoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd., Phenotote YP-50S)

Example 1
In a reactor equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a cooling tube, 100 parts of BPF-1 as a bisphenol F derivative and 190.7 parts of YD-128 as an epoxy resin (the number of moles of the epoxy group (E1 ) And the number of moles of phenolic hydroxyl group (F1) (E1/F1) = 1.025) and 15 parts of toluene (TL) as a reaction solvent were charged, and the temperature was raised to 100°C under a nitrogen atmosphere. Next, after 0.1 part of TMP was charged as a catalyst, the internal temperature was raised to 140°C. Since the reaction liquid began to thicken as the reaction proceeded, 72 parts of toluene was added appropriately in several times to carry out the reaction for 12 hours while keeping the torque of the stirrer constant. The reaction temperature was 140 to 145° C. when the nonvolatile content was 80% or more, and the reflux temperature was used thereafter. After completion of the reaction, 204 parts of methyl ethyl ketone (MEK) (mass ratio of TL/MEK=3/7) was added to obtain a resin varnish.

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=1.028) of YD-128 was used and the reaction time was 18 hours.

Example 5
A resin varnish was obtained in the same manner as in Example 1 except that 162 parts (E1/F1=1.025) of YDF-8170, 64 parts of additional TL, and 183 parts of MEK were used as the epoxy resin.

Example 6
A resin varnish was obtained in the same manner as in Example 1 except that 187.6 parts (E1/F1=1.025) of YX-4000, 71 parts of additional TL and 202 parts of MEK were used as the epoxy resin.

Example 7
A resin varnish was obtained in the same manner as in Example 1 except that 205 parts (E1/F1=1.025) of BPZ-EP, 77 parts of additional TL and 213 parts of MEK were used as the epoxy resin.

Example 8
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 9
A resin varnish was obtained in the same manner as in Example 1 except that 0.1 part of TPPMI, 101 parts of additional TL and 78 parts of MEK were used as the catalyst.

Example 10
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 11
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 12
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 13
A resin varnish was obtained in the same manner as in Example 1 except that 0.1 part of TPPPB, 101 parts of additional TL and 78 parts of MEK were used as the catalyst.

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

Example 15
A resin varnish was obtained in the same manner as in Example 1 except that 100 parts (E1/F1=1.025) of BPF-2 was used as the bisphenol F derivative.

Example 16
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=1.025) were used as the bisphenol F derivative.

Example 17
A resin varnish was obtained in the same manner as in Example 1 except that 159 parts of additional TL and 117 parts of MEK were used.

Example 18
A resin varnish was obtained in the same manner as in Example 1 except that 36 parts of additional TL and 240 parts of MEK were used.

Example 19
A resin varnish was obtained in the same manner as in Example 1 except that 107 parts of MEK was used.

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 the reaction solvent.

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%.

Comparative example 2
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 35%.

Comparative Example 3
Using the same apparatus as in Example 1, 100 parts of BPF-1 as a bisphenol F derivative, 190.7 parts of YD-128 as an epoxy resin (E1/F1=1.025), and 32 parts of cyclohexanone as a reaction solvent. Part charge was performed and the temperature was raised to 140° C. under a nitrogen atmosphere. Next, 0.02 parts of TPPBB was charged as a catalyst, and then the internal temperature was raised to 155° C. (reflux temperature). The reaction was carried out at the reflux temperature, and the reaction solution started to thicken as the reaction proceeded. After the reaction was carried out for 12 hours by making the torque of the stirrer constant by appropriately adding cyclohexanone, cyclohexanone was further charged while cooling to prepare a 25% solution of cyclohexanone. Then, the mixture was dried at 100° C. under the condition of 0.67 kPa (5 Torr) for 24 hours to distill off cyclohexanone, and after solidification, a mixed solvent of TL/MEK=3/7 (mass ratio) was used to remove the resin. Was diluted to obtain a resin varnish having a nonvolatile content of 50%.

Comparative Example 4
Using the same apparatus as in Example 1, 254 parts of BPF-1 as a bisphenol F derivative, 496 parts of YD-128 as an epoxy resin (E1/F1=1.050), and 250 parts of methyl isobutyl ketone as a reaction solvent. Parts and 1.2 parts of TMAOH as a catalyst were charged, and a polymerization reaction was carried out at 130° C. for 7.5 hours in a nitrogen gas atmosphere. Then, it was dried under conditions of 40° C. and 0.67 kPa (5 Torr) for 48 hours to distill off methyl isobutyl ketone, and after solidification, using a mixed solvent of TL/MEK=3/7 (mass ratio). The resin was diluted to obtain a resin varnish having a nonvolatile content of 50%.

Comparative Example 5
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 6
The same apparatus as in Example 1 was charged with 100 parts of BPF-1, 190.7 parts of YD-128 (E1/F1=1.025), and 15 parts of TL, and heated to 100° C. under a nitrogen atmosphere. It was Next, 0.3 part of TPP was charged as a catalyst, and then the internal temperature was raised to 140°C. After reacting at a reaction temperature of 140 to 145° C. for 10 hours, no increase in the molecular weight was observed. Although 0.3 part of TPP was added and the reaction was continued for another 10 hours, the reaction was interrupted because no increase in the molecular weight was observed. The molecular weights at the time of interruption were Mw=14800 and Mn=5240.

Epoxy equivalents, weight average molecular weights (Mw), number average molecular weights (Mn), nonvolatiles, phenolic hydroxyl group equivalents, varnish viscosity, and light transmittance of the resin varnishes obtained in Examples 1 to 21 and Comparative Examples 1 to 5 Are listed in Table 1.

(Storage stability)
The resin varnishes obtained in Examples 1 to 16 and Comparative Examples 1 to 5 were sealed in 500 mL round cans and stored for 1 month at a temperature of 40°C, and the storage stability was measured by measuring the viscosity at 25°C. The sex was evaluated. The judgment items and explanations are as follows. The results are shown in Table 2.
◯: The viscosity after the test was less than 1.5 times the viscosity before storage.
Δ: The viscosity after the test was 1.5 times or more and less than 2.0 times the viscosity before storage.
X: The viscosity after the test was twice or more than the viscosity before the storage.
(Transmittance after storage)
◯: When the light transmittance is measured using the resin varnish after the storage stability test, the light transmittance is 90%T or more.
Δ: When the light transmittance is measured using the resin varnish after the storage stability test, the light transmittance is 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 property)
The resin varnishes obtained in Examples 1 to 16 and Comparative Examples 1 to 5 were applied to a glass substrate of 100 mm x 100 mm x 0.7 µm using a bar coater so that the dry film thickness was 150 µm, and the temperature was 80°C. The solvent was evaporated under the condition of 30 minutes to form a resin layer on the glass substrate. A 100 mm×100 mm×0.7 mm glass substrate having a white printed layer (step) having a width of 10 mm and a thickness of 100 μm provided on the outer periphery of the resin-coated glass substrate is superposed so as to sandwich the resin layer, and hot pressed. Using a machine, bonding was performed for 1 minute under the conditions of 80° C. and 0.2 MPa. Using this sample, the appearance of the periphery of the printed layer (step) was evaluated with an optical microscope. The explanation of the judgment is as follows. The results are shown in Table 3.
◯: No bubbles or peeling at the step portion.
B: Bubbles or peeling are present only on one side.
X: Bubbles or peeling are present 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 16 and Comparative Examples 1 to 5 to prepare resin compositions. Then, this resin composition was applied onto a PET film which had been subjected to a mold 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. .. Then, a 100 mm×100 mm×0.7 mm glass substrate provided with a white print layer (step) having a thickness of 100 μm was stacked so as to sandwich the resin layer, and a hot press machine was used to apply a pressure of 0.2 MPa at 80° C. Bonding was performed for 1 minute under the conditions. After peeling the release-treated PET film, an ITO film having the PET film as a base material was overlaid so that the metal oxide side was in contact with the resin layer, and the hot press machine was used under the conditions of 80° C. and 0.2 MPa. Bonded for 15 minutes. Then, the ITO film was peeled off so as to leave a width of 1 cm, and a 90-degree peel test was performed. The explanation of the judgment is as follows. The results are shown in Table 3.
◯: 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 ×: Adhesive strength is less than 0.5 N/mm

(Rubbing property)
In 100 parts by mass of the resin varnishes obtained in Examples 1 to 16 and Comparative Examples 1 to 5, 0.84 parts by mass of novolac-type phenol resin (manufactured by Showa Denko KK, BRG-557), 0.005 parts by mass of triphenylphosphine. A part was added and the mixture was stirred until it became uniform to obtain a resin composition. Then, the resin composition was applied to a 100 mm×100 mm×0.7 mm glass substrate using a bar coater. The solvent was dried on this glass substrate at 80° C. for 30 minutes, and then heat treatment was performed at 150° C. for 1 hour to cure the glass substrate. Using a cloth impregnated with methyl ethyl ketone, 30 reciprocating rubbing tests were performed on the cured film under a load of 49N. The description of the determination of curability is as follows. The results are shown in Table 4.
◯: The cured film after the rubbing test is transparent.
B: White turbidity is observed in the cured film after the rubbing test. X: White turbidity or peeling is observed in the cured film after the rubbing test.

Claims (16)

The following general formula (3)

(In the formula, A is a divalent aromatic group represented by the following general formula (2).)

(In the formula, X is 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 is 1 carbon atom. To 7 monovalent hydrocarbon groups, which may be the same or different, and m ₂ is independently a number of 0 to 4.)
A divalent epoxy resin represented by the following general formula (4)

(In the formula, R ₁ is a monovalent hydrocarbon group having 1 to 7 carbon atoms and may be the same or different. m is independently a number of 0 to 4 and m ₁ is independently 0 to 0. It is a number of 3. k is an average value of 0 to 4, but the component of k=0 occupies 80% or more.)
And a bisphenol F derivative represented by the formula (1) in the presence of an onium salt catalyst in an aromatic solvent and the number of moles of epoxy groups (E1) in the divalent epoxy resin and the moles of phenolic hydroxyl groups in the bisphenol F derivative. The number (F1) is obtained by reacting in the range of (E1):(F1)=1.029 to 1.005:1, and the epoxy equivalent is 4500 to 7000 g/eq. And the phenolic hydroxyl group equivalent is 8000 to 15000 g/eq. And a bisphenol F skeleton-containing phenoxy resin whose weight average molecular weight measured by gel permeation chromatography is 30,000 to 80,000 in terms of polystyrene. The bisphenol F skeleton-containing phenoxy resin according to claim 1, 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 and may be the same or different, but 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 's may have an aryl group which may have a substituent or an aralkyl group which may have a substituent,
(C) three R ₇ are an aryl group which may have a substituent, and one R ₇ is an alkyl group having 1 to 10 carbon atoms;
X ₁ is a halogen ^{_{atom, (R 8 O) 2 PO}} 2 -, (R 9 O) 2 PS 2 - or ^R 10 CO ₂ ^- is. However, R ⁸ and R ⁹ 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. ) The phenoxy resin containing a bisphenol F skeleton according to claim 1, wherein the component of k=0 of the bisphenol F derivative is 96.5% or more. A method for producing a phenoxy resin containing a bisphenol F skeleton according to claim 1, comprising the following general formula (3):

(In the formula, A is a divalent aromatic group represented by the following general formula (2).)

(In the formula, X is 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 is 1 carbon atom. To 7 monovalent hydrocarbon groups, which may be the same or different, and m ₂ is independently a number of 0 to 4.)
A divalent epoxy resin represented by the following general formula (4)

(In the formula, R ₁ is a monovalent hydrocarbon group having 1 to 7 carbon atoms and may be the same or different. m is independently a number of 0 to 4 and m ₁ is independently 0 to 0. It is a number of 3. k is an average value of 0 to 4, but the component of k=0 occupies 80% or more.)
And a bisphenol F derivative represented by the formula (1) in the presence of an onium salt catalyst in an aromatic solvent and the number of moles of epoxy groups (E1) in the divalent epoxy resin and the moles of phenolic hydroxyl groups in the bisphenol F derivative. A method for producing a phenoxy resin containing a bisphenol F skeleton, characterized in that the reaction is carried out in a ratio of a number (F1) of (E1):(F1)=1.029 to 1.005:1. The method for producing a phenoxy resin containing a bisphenol F skeleton according to claim 4, 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 and may be the same or different, but 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 's may have an aryl group which may have a substituent or an aralkyl group which may have a substituent,
(C) Three R ₇ are an aryl group which may have a substituent, and one R ₇ is an alkyl group having 1 to 10 carbon atoms.
X ₁ is a halogen ^{_{atom, (R 8 O) 2 PO}} 2 -, (R 9 O) 2 PS 2 - or ^R 10 CO ₂ ^- is. However, R ⁸ and R ⁹ 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. ) The method for producing a phenoxy resin containing a bisphenol F skeleton according to claim 4 or 5, wherein the aromatic solvent has a boiling point of 80 to 145°C under normal pressure. The method for producing a phenoxy resin containing a bisphenol F skeleton according to any one of claims 4 to 6, wherein the bisphenol F derivative has a k=0 component of 96.5% or more. A phenoxy resin containing a bisphenol F skeleton according to any one of claims 1 to 3, an aromatic organic solvent (A) having a boiling point of 80 to 145°C (however, a ketone organic solvent is excluded) , and a boiling point of 60 to. A resin varnish having a 120° C. ketone-based organic solvent (B) as an essential component and a resin concentration of 20 to 80 mass %. The resin according to claim 8, wherein toluene is used as the organic solvent (A) and methyl ethyl ketone is used as the organic solvent (B) at a mass ratio of (A)/(B)=6/4 to 1/9. varnish. The resin varnish according to claim 8 or 9, which has a viscosity at 25°C of 500 to 7,000 mPa·s. The resin varnish according to claim 8, which has a transmittance of 90% or more at a wavelength of 400 nm using a 10 mm quartz cell. A resin composition comprising the phenoxy resin containing a bisphenol F skeleton according to any one of claims 1 to 3 and a curing agent reactive with the phenoxy resin as essential components. An optical adhesive comprising the phenoxy resin containing a bisphenol F skeleton according to claim 1. A coating agent comprising the phenoxy resin containing a bisphenol F skeleton according to claim 1. A cured product obtained by subjecting the resin composition according to claim 12 to light and/or heat treatment. A display device using the phenoxy resin containing a bisphenol F skeleton according to claim 1.