WO2019198378A1

WO2019198378A1 - Compound and use thereof

Info

Publication number: WO2019198378A1
Application number: PCT/JP2019/008141
Authority: WO
Inventors: 由貴中村
Original assignee: 株式会社Moresco
Priority date: 2018-04-13
Filing date: 2019-03-01
Publication date: 2019-10-17
Also published as: TWI706970B; JP2022159286A; CN111971322B; JP7324346B2; TW201945419A; CN111971322A; JPWO2019198378A1

Abstract

Provided is a compound that has low crystallinity and continues exhibiting excellent properties after being cured. The compound is represented by formula (1) or formula (2). In formula (1) and formula (2), n is an integer of 2 or greater, and R and R' each represent an aliphatic group or an aromatic group.

Description

Compounds and their use

The present invention relates to a compound, a resin composition containing the compound, and a sealant containing the compound or the resin composition.

Epoxy resins are used for sealants, adhesives, coating agents, and the like. Epoxy resins tended to crystallize at room temperature, particularly at low temperatures. In particular, epoxy resins having a large amount of n = 0 (monomer) components such as molecularly distilled epoxy resins are easily crystallized.

As a method for inhibiting crystallization of an epoxy resin, for example, Patent Document 1 is characterized in that an acidic compound is added to an epoxy resin and 5 to 16% of the epoxy groups of the epoxy resin are reacted with the acidic compound to cause ring opening. A method for preventing crystallization of an epoxy resin is disclosed.

Patent Document 2 discloses that an aliphatic monocarboxylic acid having 10 or more carbon atoms is added to an uncured epoxy resin obtained by a reaction between an aromatic dihydroxy compound and an epihalohydrin based on an epoxy group of the epoxy resin. A method for preventing crystallization of an uncured epoxy resin is disclosed, which is characterized in that it is added at a ratio of ˜30 equivalent% and heat-treated.

Japanese Patent Publication “Japanese Patent Laid-Open No. 50-2797” Japanese Patent Publication “JP-A-2-189324”

However, when the above-described conventional method is applied to a resin that is easily crystallized because of a large amount of n = 0 components, such as an epoxy resin that has been molecularly distilled, the modification rate should be set to sufficiently suppress crystallization. Need to increase. As a result, many epoxy groups are consumed, that is, the active site of the curing reaction is consumed, so that there is a problem that the physical properties are lowered, for example, the curing rate of the resin cured product or the glass transition point is lowered.

One embodiment of the present invention has been made in view of the above problems, and an object thereof is to provide a compound having low crystallinity and excellent physical properties even after curing.

In order to solve the above problems, the present inventor has solved the above problems by a compound obtained by subjecting a compound having two or more epoxy groups and a divalent or higher carboxylic acid or a carboxylic acid derivative to a ring-opening addition reaction. The present inventors have found that the problem can be solved and have completed the present invention. That is, the present invention includes the following configurations.

[1] A compound represented by the following formula (1) or formula (2),

In the above formulas (1) and (2), n represents an integer of 2 or more, and R and R ′ represent an aliphatic group or an aromatic group.

[2] The compound according to [1], wherein, in the above formulas (1) and (2), R is a bisphenylene group.

[3] A resin composition comprising the compound according to [1] or [2].

[4] The ratio of the compound represented by the following formula (3) measured by gel permeation chromatography is 90 area% or less with respect to 100 area% of the resin composition,

In said formula (3), said R shows an aliphatic group or an aromatic group, The resin composition as described in [3] characterized by the above-mentioned.

[5] A sealant comprising the compound according to [1] or [2] or the resin composition according to [3] or [4].

[6] The sealant according to [5], further comprising at least one component selected from the group consisting of a polymerization initiator, an inorganic compound, and a silane coupling agent.

[7] The sealing agent according to [6], wherein the polymerization initiator is a photopolymerization initiator.

According to one embodiment of the present invention, a compound having low crystallinity and exhibiting excellent physical properties after curing can be provided.

One embodiment of the present invention will be described below, but the present invention is not limited to this. Unless otherwise specified in this specification, “A to B” indicating a numerical range is intended to be “A or more and B or less”. Also, “mass” and “weight” are considered synonymous.

[1. Compound〕
The compound which concerns on one Embodiment of this invention is a compound represented by following formula (1) or Formula (2),

In the above formulas (1) and (2), n represents an integer of 2 or more, and R and R ′ represent an aliphatic group or an aromatic group. R may be different from each other or the same. R and R ′ may be the same or different.

When the compound is a compound represented by the above formula (1) or (2), the crystallinity is low and excellent physical properties are exhibited after curing (polymerization). Specifically, for example, a compound having a low crystallinity and a water permeability after curing, and a high curing rate and a high glass transition point after curing can be obtained. In this specification, "low crystallinity" intends that a crystal | crystallization does not precipitate for one month or more.

As described later, the above compound can be obtained by subjecting a compound having two or more epoxy groups to a ring-opening addition reaction with a divalent or higher carboxylic acid or carboxylic acid derivative. Depending on the point at which the epoxy group is ring-opened, any of the structures of the above formulas (1) and (2) can be taken.

The aliphatic group may be linear, branched, or cyclic, and may be saturated or unsaturated. Examples of the aliphatic group include an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, and a cycloalkynylene group. Examples of the cycloalkylene group include a decahydronaphthylene group and a tricyclodecanylene group. Examples of the cycloalkynylene group include a dicyclopentadienylene group.

Examples of the aromatic group include a phenylene group, a naphthylene group, a bisphenylene group, an anthrylene group, and a phenanthrenylene group.

In the above formulas (1) and (2), R is preferably an aromatic group, more preferably a bisphenylene group. The bisphenylene group may be F-type or A-type.

Examples of the F-type bisphenylene group include a group represented by the following formula (4).

Both ends of formula (4) represent a bond. That is, Formula (4) represents the following structure.

—CH ₂ —O—Ph—CH ₂ —Ph—O—CH ₂ —
Examples of the A-type bisphenylene group include a group represented by the following formula (5).

Similar to equation (4), both ends of equation (5) also represent a bond. That is, Formula (5) represents the following structure.

—CH ₂ —O—Ph—C (CH ₃ ) ₂ —Ph—O—CH ₂ —
In the above formulas (1) and (2), R preferably has 3 to 200 carbon atoms, more preferably 5 to 100, and still more preferably 5 to 40. Thereby, the said compound can be made into an appropriate viscosity.

In the above formulas (1) and (2), R ′ preferably has 1 to 300 carbon atoms, more preferably 2 to 100, and even more preferably 2 to 20. Thereby, the said compound can be made into an appropriate viscosity.

<Method for producing compound>
The method for producing a compound according to an embodiment of the present invention includes a mixing step of mixing a compound represented by the following formula (3) and a divalent or higher carboxylic acid or carboxylic acid derivative to obtain a mixture, and the above mixture: Heating to obtain a compound by heating

In said formula (3), said R shows an aliphatic group or an aromatic group. Preferably, in the above formula (3), the above R is as described above in the above formula (1) and formula (2). In the compound represented by the above formula (1) or (2), R is a structure derived from the compound represented by the above formula (3), and R ′ is a divalent or higher carboxylic acid or carboxylic acid derivative. It is a derived structure.

In the present specification, a compound represented by the above formula (3), that is, a component that has not reacted with a divalent or higher carboxylic acid or carboxylic acid derivative is also referred to as “n = 0 component”.

(Mixing process)
In the mixing step, the compound represented by the above formula (3) is mixed with a divalent or higher carboxylic acid or carboxylic acid derivative to obtain a mixture. By mixing the compound represented by the above formula (3) with a divalent or higher carboxylic acid or carboxylic acid derivative to make it uniform, the reaction rate in the heating step can be increased.

When the carboxylic acid or carboxylic acid derivative is divalent or higher, two or more compounds represented by the formula (3) can be linked via the carboxylic acid or carboxylic acid derivative. For this reason, the compound represented by the said Formula (1) or Formula (2) whose crystallinity is lower than the compound represented by the said Formula (3) can be manufactured.

The compound represented by the above formula (3) is preferably a bisphenol F type epoxy resin or a bisphenol A type epoxy resin. Examples of the bisphenol F-type epoxy resin include EXA-830CRP manufactured by DIC, EP-4901HF manufactured by ADEKA, Wells Advanced Materials Co., Ltd. FM-880 manufactured by Ltd., YDF-870GS manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the like. Examples of the bisphenol A type epoxy resin include EPICLON EXA850-CRP manufactured by DIC, EP-4100HF manufactured by ADEKA, and YD-825GS manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

The carboxylic acid is not particularly limited as long as it is divalent or higher, but may be a divalent carboxylic acid (dicarboxylic acid), a trivalent carboxylic acid (tricarboxylic acid), or a tetravalent carboxylic acid (tetracarboxylic acid). Preferably, it is a divalent carboxylic acid or a trivalent carboxylic acid. If the carboxylic acid is a divalent carboxylic acid or a trivalent carboxylic acid, the above compound can have an appropriate viscosity. The carboxylic acid has an aliphatic group or an aromatic group, and the aliphatic group may be linear, branched, or cyclic, and may be saturated or unsaturated. Examples of the divalent carboxylic acid include succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, suberic acid, sebacic acid, and long-chain branched divalent carboxylic acid (eg, MMA-10R manufactured by Okamoto Oil Co., Ltd.). Can be mentioned. Examples of the trivalent carboxylic acid include trimellitic acid, citric acid, 3-butene-1,2,3-tricarboxylic acid, and 1,3,5-benzenetricarboxylic acid. Examples of the tetravalent carboxylic acid include meso-butane-1,2,3,4-tetracarboxylic acid, pyromellitic acid and biphenyl-3,3 ', 5', 5-tetracarboxylic acid.

The carboxylic acid derivative is not particularly limited as long as it is a derivative of a divalent or higher carboxylic acid, and examples thereof include carboxylic acid esters, carboxylic acid anhydrides, and carboxylic acid salts. Examples of the carboxylic acid ester include a block carboxylic acid represented by the following formula (6), isononyl adipate, and dimethyl 4,4′-biphenyldicarboxylate.

The carboxylic acid or carboxylic acid derivative preferably has 2 to 500 carbon atoms, more preferably 5 to 300, still more preferably 5 to 100. Thereby, the compound represented by the said Formula (1) or Formula (2) can be made into appropriate viscosity.

The mixing means is not particularly limited, and examples thereof include a flask equipped with a stirring blade, a kneader, a roll, a melting tank, a Banbury mixer, and an extruder.

The proportion of the divalent or higher carboxylic acid or carboxylic acid derivative added is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the compound represented by the above formula (3). The amount is more preferably 01 to 20 parts by weight, and further preferably 0.05 to 10 parts by weight. Thereby, the compound represented by the said Formula (1) or Formula (2) can be manufactured efficiently.

In the mixing step, a reaction accelerator may be mixed in addition to the compound represented by the above formula (3) and the divalent or higher carboxylic acid or carboxylic acid derivative. The reaction accelerator may be a catalyst that can promote a ring-opening addition reaction with a divalent or higher carboxylic acid or carboxylic acid derivative, such as an alkali metal hydroxide, a metal alcoholate, a tertiary amine compound. Quaternary ammonium salts, quaternary phosphonium salts, and tertiary phosphines. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Examples of metal alcoholates include sodium methylate and sodium ethylate. Examples of the tertiary amine compound include triethylamine, triethanolamine, and 2,4,6-tris (dimethylaminomethyl) phenol. Examples of the quaternary ammonium salt include tetramethylammonium chloride and tetrabutylammonium chloride. Examples of the quaternary phosphonium salt include benzyltriphenylphosphonium chloride, tetrabutylphosphonium hydroxide and butyltriphenylphosphonium bromide. Examples of the tertiary phosphine include tributyl phosphine, trioctyl phosphine, triphenyl phosphine, and styryl diphenyl phosphine.

(Heating process)
In the heating step, the mixture is heated to obtain a compound. By heating the above mixture, the compound represented by the above formula (3) and a divalent or higher carboxylic acid or carboxylic acid derivative undergo a ring-opening addition reaction, and the above formula (1) or (2) The compounds represented can be obtained. The heating temperature is preferably 80 to 250 ° C, more preferably 100 to 180 ° C, and further preferably 120 to 150 ° C. Thereby, the efficiency of the ring-opening addition reaction between the compound represented by the above formula (3) and a divalent or higher carboxylic acid or carboxylic acid derivative can be increased. That is, the yield of the compound represented by the above formula (1) or formula (2) can be increased.

The heating means is not particularly limited, and examples thereof include a mantle heater, a throwing heater, a hot plate, and an IH heater.

The mixing step and the heating step may be performed under an inert gas stream or may be performed in an open system. As an inert gas, Ar etc. are mentioned, for example.

[2. Resin composition]
It is preferable that the resin composition which concerns on one Embodiment of this invention contains the compound mentioned above. Thereby, the resin composition has low crystallinity and excellent physical properties even after curing. Specifically, for example, a resin composition having a low crystallinity and a water permeability after curing, and a high curing rate and a glass transition point after curing can be obtained. The resin composition may contain either one of the compound represented by the formula (1) and the compound represented by the formula (2), or both of them. Usually, the mixture of the compound represented by Formula (1) and the compound represented by Formula (2) is obtained by the above-mentioned manufacturing method. Therefore, the said resin composition may contain the mixture of the compound represented by Formula (1), and the compound represented by Formula (2).

In addition, about the said compound, [1. The description overlapping the content described in [Compound] will not be repeated.

The resin composition according to an embodiment of the present invention may further include a compound represented by the following formula (3),

In said formula (3), said R shows an aliphatic group or an aromatic group.

The ratio of the compound represented by the above formula (3) (ratio of n = 0 component) is preferably 90 area% or less and 100 area% or less with respect to 100 area% of the resin composition. Is more preferable, and it is further more preferable that it is 70 area% or less. In the present specification, the “ratio of the compound represented by the formula (3)” means n = 0 component with respect to the entire area of all peaks of the resin composition obtained by GPC (gel permeation chromatography). The ratio of the peak area (unit: area%) is intended. The measuring method by GPC (gel permeation chromatography) will be described in detail in Examples described later. When the ratio of the n = 0 component is 100 area%, crystals are precipitated, whereas the ratio of the n = 0 component is 90 area% or less, so that the precipitation of crystals can be suppressed. . That is, since the ratio of the compound having low crystallinity represented by the formula (1) or the formula (2) in the resin composition can be increased by the configuration, the crystal is precipitated even at a low temperature (10 ° C.). Can be suppressed. The ratio of the compound represented by the above formula (3) is preferably as low as possible and preferably 0 area%, but in reality, the lower limit may be about 30 area%.

<Method for producing resin composition>
The manufacturing method of the resin composition which concerns on one Embodiment of this invention is the same as the manufacturing method of the said compound.

[3. Sealant)
It is preferable that the sealing agent which concerns on one Embodiment of this invention contains the compound mentioned above or the resin composition mentioned above. The sealing agent has low crystallinity and exhibits excellent physical properties even after curing. Specifically, for example, it is possible to obtain a sealant having low crystallinity and moisture permeability after curing, and high curing rate and glass transition point after curing. The said sealing agent may contain any one of the compound represented by Formula (1) and the compound represented by Formula (2) similarly to the said resin composition, and may contain both of them. Good.

In addition, about the said compound and the said resin composition, [1. Compound] and [2. The description overlapping the content described in [Resin composition] will not be repeated.

The sealant according to an embodiment of the present invention preferably further includes at least one component selected from the group consisting of a polymerization initiator, an inorganic compound, and a silane coupling agent. When the sealing agent contains a polymerization initiator, the compound represented by the formula (1) or formula (2) contained in the sealing agent can be polymerized by light irradiation or heating. . When the sealing agent contains an inorganic compound, the moisture permeability after curing can be lowered. When the sealing agent contains a silane coupling agent, the polymer of the compound represented by the formula (1) or the formula (2) can be coupled.

The polymerization initiator is preferably a cationic polymerization initiator. The cationic polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.

The cationic photopolymerization initiator is not particularly limited as long as it can generate cations by light irradiation and initiate the curing reaction of the photocationically polymerizable compound. Examples of the cationic photopolymerization initiator include sulfonium salts such as triarylsulfonium salts and triphenylsulfonium salts, and iodonium salts. Examples of the triarylsulfonium salt include triarylsulfonium borate salt (borate type), triarylsulfonium · SbF ₆ salt (antimony type), triarylsulfonium · PF ₆ salt (phosphorus type), and the like. Examples of the triphenylsulfonium salt include triphenylsulfonium tetrafluoroborate.

Further, the cationic thermal polymerization initiator is not particularly limited as long as it can generate cations by applying heat and can initiate the curing reaction of the thermal cationic polymerizable compound. Examples of the cationic thermal polymerization initiator include quaternary ammonium salts of trifluoro acid, 1-naphthylmethylmethyl p-hydroxyphenylsulfonium = hexafluoroantimonate, (4-acetoxyphenyl) benzyl (methyl) sulfonium = tetrakis ( Pentafluorophenyl) borate and benzylmethyl p-hydroxyphenylsulfonium = hexafluoroantimonate.

Examples of the inorganic compound include mica, talc, alumina, clay, colloidal silica, and titanium oxide.

Examples of the silane coupling agent include 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl). Examples thereof include alkylalkoxysilanes such as ethyltrimethoxysilane.

The sealing agent may further contain additives other than the above-described components, if necessary, as long as the crystallinity is low and physical properties after curing are not impaired. Examples of the additive include stabilizers, antioxidants, compatibilizers, antifoaming agents, adhesion promoters, viscosity modifiers, thixotropic agents, and fillers.

The encapsulant according to one embodiment of the present invention has low crystallinity and excellent physical properties even after curing even when the amount of chlorine contained in the encapsulant is low.

<Method for producing sealant>
The manufacturing method of the sealing agent which concerns on one Embodiment of this invention is a compound manufacturing process, and the compound obtained by the compound manufacturing process is at least selected from the group which consists of a polymerization initiator, an inorganic compound, and a silane coupling agent. A kneading and dispersing step of kneading and dispersing one or more components to obtain a kneaded dispersion; and a filtration step of obtaining a sealant by filtering the kneaded dispersion obtained in the kneading and dispersing step.

The compound production process includes the above-described <compound production method> mixing step and heating step. In the compound production process, the compound represented by the above formula (1) or formula (2) is produced.

In the kneading dispersion step, at least one component selected from the group consisting of a polymerization initiator, an inorganic compound and a silane coupling agent is kneaded and dispersed in the compound obtained in the compound production step to obtain a kneaded dispersion.

The proportion of the polymerization initiator added is preferably 0.2 to 20 parts by weight and preferably 1 to 15 parts by weight with respect to 100 parts by weight of the compound represented by the above formula (3). More preferred is 2 to 10 parts by weight. When the proportion of the polymerization initiator added is 0.2 to 20 parts by weight, the compound represented by the above formula (1) or formula (2) can be efficiently polymerized.

The proportion of the inorganic compound added is preferably 20 to 90 parts by weight, more preferably 30 to 90 parts by weight with respect to 100 parts by weight of the compound represented by the above formula (3). More preferably, it is 40 to 80 parts by weight. When the proportion of the inorganic compound added is 20 parts by weight or more, the moisture permeability after curing can be lowered. When the ratio of adding the inorganic compound is 90 parts by weight or less, it can be adjusted to an appropriate viscosity.

The proportion of the silane coupling agent added is preferably 0.1 to 30 parts by weight, and preferably 1 to 20 parts by weight with respect to 100 parts by weight of the compound represented by the above formula (3). Is more preferably 5 to 10 parts by weight. When the ratio of adding the silane coupling agent is 0.1 parts by weight or more, the polymer of the compound represented by the formula (1) or the formula (2) can be efficiently coupled. When the proportion of the silane coupling agent added is 30 parts by weight or less, appropriate physical properties of the cured product can be maintained.

The kneading and dispersing means is not particularly limited, and examples thereof include a flask equipped with a stirring blade, a kneader, a roll, a melting tank, a Banbury mixer, and an extruder.

In the filtration step, the kneaded dispersion obtained in the kneading and dispersing step is filtered to obtain a sealant. A conventionally known method can be used as the filtering means, and for example, pressure filtration may be used.

[4. Sealant hardened product)
The cured sealant according to one embodiment of the present invention is [1. The compound] preferably contains a compound obtained by polymerizing the above-described compound.

The cured encapsulant according to one embodiment of the present invention is [2. Resin composition] and [3. It is more preferable that each component contained in the resin composition and the sealant described in “Sealant” is included. In addition, in this specification, the sealing agent hardened | cured material which does not contain an inorganic compound and a silane coupling agent is also called "resin hardened | cured material."

The cured sealant according to one embodiment of the present invention preferably has a glass transition point of 100 ° C. or higher, and more preferably 120 ° C. or higher. The glass transition point is a value measured by DSC (differential scanning calorimeter). The measuring method of the glass transition point by DSC (differential scanning calorimeter) will be described in detail in Examples described later. When the glass transition point is within the above range, when used as a sealant for an organic EL display, an organic EL element or the like can be sealed.

In addition, the cured sealant according to an embodiment of the present invention preferably has a moisture permeability of less than 6.5 g / (m ² · day), and less than 4.5 g / (m ² · day). More preferably. The moisture permeability is a value determined by the cup method. The method for measuring the moisture permeability by the cup method will be described in detail in Examples described later. When the moisture permeability is within the above range, an organic EL element or the like can be sealed when used as a sealant for an organic EL display.

An organic EL display including the cured sealant according to an embodiment of the present invention is also included in the present invention.

<Method for producing cured sealant>
The manufacturing method of the sealing agent hardened | cured material which concerns on one Embodiment of this invention is a method of irradiating light to the sealing agent mentioned above or heating the said sealing agent, and obtaining sealing agent hardened | cured material. .

When the sealant contains a photopolymerization initiator, the sealant is irradiated with light. The wavelength for light irradiation is appropriately selected depending on the type of photopolymerization initiator. The amount of light irradiation and the time for light irradiation are appropriately selected depending on the composition of the sealant. Examples of the means for irradiating light include ultraviolet irradiation lamps such as metal halide lamps, mercury lamps, LEDs, halogen lamps, xenon lamps and deuterium lamps.

When the sealant contains a thermal polymerization initiator, the sealant is heated. The heating temperature and time are appropriately selected depending on the type of thermal polymerization initiator and the composition of the sealant.

After the sealant is irradiated with light or the sealant is heated to cure the sealant, a post-curing treatment may be performed in which the cured sealant is heated. The heating temperature and time of the post-curing treatment are appropriately selected depending on the composition of the sealant.

In the manufacturing method of the hardened | cured sealant which concerns on one Embodiment of this invention, it is contained in the said sealing agent before hardening with respect to 100 mol% of moles of the epoxy group contained in the said sealing agent before hardening. The ratio (curing rate) of the difference between the number of moles of the epoxy group and the number of moles of the epoxy group of the cured sealant after curing is preferably 70 mol% or more, and more preferably 90 mol% or more. preferable. Thereby, the water | moisture-content rate of the said sealing agent hardened | cured material can be made low.

The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

[Example 1]
100 parts by weight of EXA-830CRP (bisphenol F type epoxy resin, manufactured by DIC) as an epoxy resin and 4.7 parts by weight of adipic acid (divalent carboxylic acid) as a carboxylic acid were placed in a flask and mixed with a stirring blade. Then, it heated at 150 degreeC with the mantle heater, and obtained the resin composition. Mixing and heating were performed under an Ar stream.

[Example 2]
FM-880 (bisphenol F type epoxy resin, manufactured by Wells Advanced Materials Co., Ltd.) was used instead of EXA-830CRP, and 3.8 parts by weight of MMA-10R (instead of 4.7 parts by weight of adipic acid ( A resin composition was obtained in the same manner as in Example 1 except that long-chain branched divalent carboxylic acid (manufactured by Okamoto Oil Co., Ltd.) was used.

Example 3
Instead of 4.7 parts by weight of adipic acid, 0.075 parts by weight of meso-butane-1,2,3,4-tetracarboxylic acid (tetravalent carboxylic acid) was used, and mixing and heating were performed in an open system. A resin composition was obtained in the same manner as in Example 1 except that.

Example 4
Example 1 was used except that 9.0 parts by weight of Nocure TN-1 (trivalent carboxylic acid derivative (trimellitic acid ester), manufactured by NOF Corporation) was used instead of 4.7 parts by weight of adipic acid. Similarly, a resin composition was obtained.

Example 21
Exa-850CRP (bisphenol A type epoxy resin, manufactured by DIC) was used instead of EXA-830CRP, and 3.9 parts by weight of MMA-10R was used instead of 4.7 parts by weight of adipic acid. A resin composition was obtained in the same manner as in Example 1.

[Comparative Example 1]
A resin composition was obtained in the same manner as in Example 1 except that adipic acid was not added.

[Comparative Example 2]
Instead of 4.7 parts by weight of adipic acid, 2.0 parts by weight of acetic acid (monocarboxylic acid) was used, 0.01 parts by weight of potassium hydroxide was further added as an additive, and mixing and heating were performed in an open system. A resin composition was obtained in the same manner as in Example 1 except that the above was performed.

[Comparative Example 3]
Example 1 was used except that 17.0 parts by weight of oleic acid (monocarboxylic acid) was used instead of 4.7 parts by weight of adipic acid, and 0.05 parts by weight of triphenylphosphine was further added. Thus, a resin composition was obtained.

[Comparative Example 16]
A resin composition was obtained in the same manner as in Example 21 except that MMA-10R was not added.

<Evaluation of properties of resin composition>
(Measurement of n = 0 component amount (GPC (gel permeation chromatography)))
The amount of n = 0 component (carboxylic acid and unreacted epoxy resin) in each resin composition was measured by GPC (gel permeation chromatography). The equipment includes a system controller manufactured by SHIMAZU: SCL-10AVP, a liquid pump: LC-20AD, a degasser: DGU-12A, an autoinjector: SIL-10A, a column oven: CTO-10AVP, a detector: RI-made by shodex. 71 was used. Chloroform was used as the solvent, and the flow rate was 1 mL / min. Three columns of GPC K-805L (8 × 300 mm) manufactured by shodex were connected, and polystyrene was used as a standard substance. The ratio of the area of the peak of the n = 0 component was calculated as an area% ratio with respect to the total area of all peaks integrated in the chromatograph.

(Crystallization test)
20 g of the resin composition was weighed into a glass bottle and left to stand at 60 ° C. for 16 hours. After returning to room temperature, 2 g of calcium carbonate and 2 g of ethanol were added and stirred with a glass rod until uniform. The glass bottle was covered and stored in a refrigerator at 10 ° C. for observation. The fluidity was confirmed once a day, and the number of days required for solidification was confirmed.

Crystal suppression when the number of days required to solidify due to loss of flow is longer than 3 months ◎ Crystal suppression when 1 to 3 months ○ Crystal suppression when 1 to 4 weeks △ When less than 1 week Crystal suppression x.

<Result>
Tables 1 and 2 below show the composition and property evaluation results of the resin compositions prepared in Examples 1 to 4 and 21, and Comparative Examples 1 to 3 and 16.

The resin compositions of Examples 1 to 4 and 21 and Comparative Example 3 were found to have lower crystallinity because no crystals were precipitated for a longer time than the resin compositions of Comparative Examples 1, 2, and 16. Further, it was confirmed that the resin compositions of Example 1 and Comparative Example 3 had lower crystallinity than the resin compositions of Example 2 and Example 3.

Example 5
To the resin composition produced in Example 1, 2.1 parts by weight of CPI-101A (antimony, manufactured by San Apro) as a cationic photopolymerization initiator was further added and mixed to obtain a resin composition. The resin composition was made into a film using a doctor blade YD-3 type manufactured by Yoshimitsu Seiki Co., Ltd. so as to have a thickness of 100 μm. The resin composition in the form of a film was irradiated with 6000 mJ / cm ² ultraviolet rays using a metal halide lamp and subjected to post-curing treatment at 80 ° C. for 1 hour to obtain a cured resin.

Example 6
A cured resin was obtained in the same manner as in Example 5 except that the resin composition prepared in Example 2 was used instead of the resin composition prepared in Example 1.

Example 7
A cured resin was obtained in the same manner as in Example 5 except that the resin composition prepared in Example 3 was used instead of the resin composition prepared in Example 1 and that 2.0 parts by weight of CPI-101A was used. .

Example 8
A cured resin was obtained in the same manner as in Example 5 except that the resin composition prepared in Example 4 was used instead of the resin composition prepared in Example 1 and that CPI-101A was changed to 2.2 parts by weight. .

[Example 22]
A cured resin was obtained in the same manner as in Example 5 except that the resin composition prepared in Example 21 was used instead of the resin composition prepared in Example 1.

[Comparative Example 4]
A cured resin was obtained in the same manner as in Example 5 except that the resin composition prepared in Comparative Example 1 was used instead of the resin composition prepared in Example 1 and that 2.0 parts by weight of CPI-101A was used. .

[Comparative Example 5]
A cured resin was obtained in the same manner as in Example 5 except that the resin composition prepared in Comparative Example 2 was used instead of the resin composition prepared in Example 1 and that 2.0 parts by weight of CPI-101A was used. .

[Comparative Example 6]
A cured resin was obtained in the same manner as in Example 5 except that the resin composition prepared in Comparative Example 3 was used instead of the resin composition prepared in Example 1 and that CPI-101A was changed to 2.3 parts by weight. .

[Comparative Example 17]
A cured resin was obtained in the same manner as in Example 5 except that the resin composition prepared in Comparative Example 16 was used instead of the resin composition prepared in Example 1 and that 2.0 parts by weight of CPI-101A was used. .

<Evaluation of properties of cured resin>
(Measurement of curing rate by FT-IR method)
The epoxy group of the resin composition before curing and the cured resin product after curing was measured by FT-IR (Freee conversion infrared spectroscopy) method. The apparatus used was NICOLET iS10 manufactured by Thermo SCIENTIFIC. The decreasing rate from the height of the epoxy group peak of the resin composition before curing to the peak height of the epoxy group of the cured resin product after curing was calculated as the curing rate. Based on the height of the peak of the benzene ring near the wavelength of 1508 / cm, from the height of the peak of the epoxy group near the wavelength of 914 / cm, standardize the epoxy group of the resin composition before curing and the cured resin after curing The height of the peak was calculated. A curing rate of 90% or more was evaluated as ◎, 70% or more and less than 90% as ○, 50% or more and less than 70% as Δ, and less than 50% as ×.

(Measurement of glass transition point (Tg) (DSC))
A DSC (Differential Scanning Calorimeter ASC7000S, manufactured by Bruker Ax) was used as the apparatus. The sample was a cured resin of 15 mg, and the temperature was measured by repeating heating and cooling twice at 10 ° C./min in the temperature range of −100 to 200 ° C. The inflection point at the second temperature increase was defined as Tg. When Tg was 120 ° C. or higher, ◎, when 100 ° C. or more and less than 120 ° C., ◯, when less than 100 ° C., and when measurement was impossible.

<Result>
Tables 3 and 4 below show the results of composition and property evaluations of the resin compositions prepared in Examples 5 to 8 and 22 and Comparative Examples 4 to 6 and 17.

The cured resins of Examples 5 to 8 and 22 and Comparative Examples 4, 5, and 17 were found to have a higher curing rate and glass transition point than the cured resin of Comparative Example 6. In addition, it was confirmed that the cured sealants of Examples 5 to 8 and 22 and Comparative Examples 4 and 17 had a higher curing rate than the cured sealant of Comparative Example 5. Furthermore, it was recognized that the sealing agent hardened | cured material of Example 6, 8, and 22 and Comparative Examples 4 and 17 had a higher glass transition point compared with the sealing agent hardened | cured material of Example 5 and 7. FIG.

Example 9
Resin composition prepared in Example 1, 5.2 parts by weight of CPI-310B (borate-based, manufactured by San Apro) as a cationic photopolymerization initiator, 57.6 parts by weight of mica as an inorganic compound, and silane coupling As an agent, 5.2 parts by weight of 3-glycidoxypropyltriethoxysilane (epoxy-modified) was kneaded and dispersed with a kneader. Thereafter, pressure filtration was performed to obtain a sealant composition. Thereafter, the sealant composition was formed into a film shape using a doctor blade YD-3 type manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness was 100 μm. The sealant composition formed into a film was irradiated with 6000 mJ / cm ² of ultraviolet rays using a metal halide lamp and subjected to post-curing treatment at 80 ° C. for 1 hour to obtain a cured sealant.

Example 10
Using 9.4 parts by weight of CPI-101A in place of 5.2 parts by weight of CPI-310B, using 52.4 parts by weight of talc instead of 57.6 parts by weight of mica, 3-glycidoxypropyl A cured sealant was obtained in the same manner as in Example 9 except that 9.4 parts by weight of triethoxysilane was used.

Example 11
Instead of 5.2 parts by weight of CPI-310B, 9.4 parts by weight of CPI-200K (phosphorus-based, manufactured by San Apro) was used, and 57.6 parts by weight of mica was replaced by 47.1 parts by weight of alumina. Used in the same manner as in Example 9 except that 3-glycidoxypropylmethyldimethoxysilane was used instead of 3-glycidoxypropyltriethoxysilane and three rolls were used instead of the kneader. Got.

Example 12
Similar to Example 9 except that the resin composition prepared in Example 2 was used instead of the resin composition prepared in Example 1, mica was 57.1 parts by weight, and three rolls were used instead of the kneader. Thus, a cured sealant was obtained.

Example 13
The resin composition prepared in Example 2 was used instead of the resin composition prepared in Example 1, 9.3 parts by weight of CPI-101A was used instead of 5.2 parts by weight of CPI-310B, and 57. Example 9 except that 51.9 parts by weight of talc was used instead of 6 parts by weight of mica, 9.3 parts by weight of 3-glycidoxypropyltriethoxysilane was used, and three rolls were used instead of the kneader. In the same manner as above, a cured sealant was obtained.

Example 14
The resin composition prepared in Example 2 was used in place of the resin composition prepared in Example 1, and 5.0 parts by weight of CPI-200K (phosphorus-based, San-Apro) was used instead of 5.2 parts by weight of CPI-310B. 46.7 parts by weight of alumina instead of 57.6 parts by weight of mica, and 3-glycidoxypropylmethyldimethoxysilane instead of 3-glycidoxypropyltriethoxysilane. Except that, the cured sealant was obtained in the same manner as in Example 9.

Example 15
Instead of the resin composition prepared in Example 1, the resin composition prepared in Example 3 was used, CPI-310B was 5.0 parts by weight, mica was 55.0 parts by weight, and 3-glycidoxypropyl A cured sealant was obtained in the same manner as in Example 9 except that 5.0 parts by weight of triethoxysilane was used.

Example 16
The resin composition prepared in Example 3 was used instead of the resin composition prepared in Example 1, and 9.0 parts by weight of CPI-101A was used instead of 5.2 parts by weight of CPI-310B. A cured sealant was prepared in the same manner as in Example 9 except that 50.0 parts by weight of talc was used instead of 6 parts by weight of mica, and 9.0 parts by weight of 3-glycidoxypropyltriethoxysilane was used. Obtained.

Example 17
The resin composition prepared in Example 3 was used instead of the resin composition prepared in Example 1, 9.0 parts by weight of CPI-200K was used instead of 5.2 parts by weight of CPI-310B, and 57. 45.0 parts by weight of alumina is used instead of 6 parts by weight of mica, and 5.0 parts by weight of 3-glycidoxypropylmethyldimethoxy instead of 5.2 parts by weight of 3-glycidoxypropyltriethoxysilane. A cured sealant was obtained in the same manner as in Example 9 except that silane was used and three rolls were used instead of the kneader.

Example 18
Instead of the resin composition prepared in Example 1, the resin composition prepared in Example 4 was used, CPI-310B was 5.5 parts by weight, mica was 60.0 parts by weight, and 3-glycidoxypropyl A cured sealant was obtained in the same manner as in Example 9 except that 5.5 parts by weight of triethoxysilane was used.

Example 19
The resin composition prepared in Example 4 was used instead of the resin composition prepared in Example 1, and 9.8 parts by weight of CPI-101A was used instead of 5.2 parts by weight of CPI-310B. A cured sealant was prepared in the same manner as in Example 9 except that 54.5 parts by weight of talc was used instead of 6 parts by weight of mica, and 9.8 parts by weight of 3-glycidoxypropyltriethoxysilane was used. Obtained.

Example 20
The resin composition prepared in Example 4 was used instead of the resin composition prepared in Example 1, and 9.8 parts by weight of CPI-200K was used instead of 5.2 parts by weight of CPI-310B. 49.1 parts by weight of alumina is used instead of 6 parts by weight of mica, and 5.5 parts by weight of 3-glycidoxypropylmethyldimethoxy instead of 5.2 parts by weight of 3-glycidoxypropyltriethoxysilane. A cured sealant was obtained in the same manner as in Example 9 except that silane was used and three rolls were used instead of the kneader.

Example 23
Example 9 is the same as Example 9 except that the resin composition prepared in Example 21 was used instead of the resin composition prepared in Example 1, and CPI-310B was changed to 5.2 parts by weight and mica was changed to 57.1 parts by weight. Similarly, a cured sealant was obtained.

Example 24
The resin composition prepared in Example 21 was used instead of the resin composition prepared in Example 1, and 9.4 parts by weight of CPI-101A was used instead of 5.2 parts by weight of CPI-310B. A cured sealant was prepared in the same manner as in Example 9 except that 52.0 parts by weight of talc was used instead of 6 parts by weight of mica, and 9.4 parts by weight of 3-glycidoxypropyltriethoxysilane was used. Obtained.

Example 25
The resin composition prepared in Example 21 was used instead of the resin composition prepared in Example 1, and 9.4 parts by weight of CPI-200K was used instead of 5.2 parts by weight of CPI-310B. 46.8 parts by weight of alumina is used instead of 6 parts by weight of mica, and 5.2 parts by weight of 3-glycidoxypropylmethyldimethoxy instead of 5.2 parts by weight of 3-glycidoxypropyltriethoxysilane. A cured sealant was obtained in the same manner as in Example 9 except that silane was used and three rolls were used instead of the kneader.

[Comparative Example 7]
Instead of the resin composition prepared in Example 1, the resin composition prepared in Comparative Example 1 was used, CPI-310B was 5.0 parts by weight, mica was 55.0 parts by weight, and 3-glycidoxypropyl A cured sealant was obtained in the same manner as in Example 9 except that 5.0 parts by weight of triethoxysilane was used.

[Comparative Example 8]
The resin composition prepared in Comparative Example 1 was used instead of the resin composition prepared in Example 1, 9.0 parts by weight of CPI-101A was used instead of 5.2 parts by weight of CPI-310B, and 57. A cured sealant was prepared in the same manner as in Example 9 except that 50.0 parts by weight of talc was used instead of 6 parts by weight of mica, and 9.0 parts by weight of 3-glycidoxypropyltriethoxysilane was used. Obtained.

[Comparative Example 9]
The resin composition prepared in Comparative Example 1 was used instead of the resin composition prepared in Example 1, 9.0 CPI-200K was used instead of 5.2 parts by weight of CPI-310B, and 57.6 wt. 45.0 parts by weight of alumina is used instead of 5 parts by weight of mica, and 5.0 parts by weight of 3-glycidoxypropylmethyldimethoxysilane is used instead of 5.2 parts by weight of 3-glycidoxypropyltriethoxysilane. A cured sealant was obtained in the same manner as in Example 9 except that three rolls were used instead of the kneader.

[Comparative Example 10]
Instead of the resin composition prepared in Example 1, the resin composition prepared in Comparative Example 2 was used, CPI-310B was 5.1 parts by weight, mica was 56.1 parts by weight, and 3-glycidoxypropyl A cured sealant was obtained in the same manner as in Example 9 except that 5.1 parts by weight of triethoxysilane was used.

[Comparative Example 11]
The resin composition prepared in Comparative Example 2 was used in place of the resin composition prepared in Example 1, 9.2 parts by weight of CPI-101A was used instead of 5.2 parts by weight of CPI-310B, and 57. Example 9 except that 51.0 parts by weight of talc was used instead of 6 parts by weight of mica, 9.2 parts by weight of 3-glycidoxypropyltriethoxysilane was used, and three rolls were used instead of the kneader. In the same manner as above, a cured sealant was obtained.

[Comparative Example 12]
The resin composition prepared in Comparative Example 2 was used in place of the resin composition prepared in Example 1, 9.2 parts by weight of CPI-200K was used instead of 5.2 parts by weight of CPI-310B, and 57. 45.9 parts by weight of alumina is used instead of 6 parts by weight of mica, and 5.1 parts by weight of 3-glycidoxypropylmethyldimethoxy instead of 5.2 parts by weight of 3-glycidoxypropyltriethoxysilane. A cured sealant was obtained in the same manner as in Example 9 except that silane was used.

[Comparative Example 13]
Instead of the resin composition prepared in Example 1, the resin composition prepared in Comparative Example 3 was used, CPI-310B was 5.9 parts by weight, mica was 64.4 parts by weight, and 3-glycidoxypropyl A cured sealant was obtained in the same manner as in Example 9 except that 5.9 parts by weight of triethoxysilane was used and three rolls were used instead of the kneader.

[Comparative Example 14]
The resin composition prepared in Comparative Example 3 was used instead of the resin composition prepared in Example 1, 10.5 parts by weight of CPI-101A was used instead of 5.2 parts by weight of CPI-310B, and 57. A cured sealant was prepared in the same manner as in Example 9 except that 58.5 parts by weight of talc was used instead of 6 parts by weight of mica, and 10.5 parts by weight of 3-glycidoxypropyltriethoxysilane was used. Obtained.

[Comparative Example 15]
The resin composition prepared in Comparative Example 3 was used instead of the resin composition prepared in Example 1, 10.5 parts by weight of CPI-200K was used instead of 5.2 parts by weight of CPI-310B, and 57. 52.7 parts by weight alumina instead of 6 parts by weight mica, and 5.9 parts by weight 3-glycidoxypropylmethyldimethoxy instead of 5.2 parts by weight 3-glycidoxypropyltriethoxysilane A cured sealant was obtained in the same manner as in Example 9 except that silane was used.

[Comparative Example 18]
Instead of the resin composition prepared in Example 1, the resin composition prepared in Comparative Example 16 was used, CPI-310B was 5.0 parts by weight, mica was 55.0 parts by weight, and 3-glycidoxypropyl A cured sealant was obtained in the same manner as in Example 9 except that 5.0 parts by weight of triethoxysilane was used and three rolls were used instead of the kneader.

[Comparative Example 19]
The resin composition prepared in Comparative Example 16 was used instead of the resin composition prepared in Example 1, 9.0 parts by weight of CPI-101A was used instead of 5.2 parts by weight of CPI-310B, and 57. Use 50.0 parts by weight of talc instead of 6 parts by weight of mica, 9.0 parts by weight of 3-glycidoxypropyltrimethoxy instead of 5.2 parts by weight of 3-glycidoxypropyltriethoxysilane A cured sealant was obtained in the same manner as in Example 9 except that silane was used.

[Comparative Example 20]
The resin composition prepared in Comparative Example 16 was used instead of the resin composition prepared in Example 1, 9.0 parts by weight of CPI-200K was used instead of 5.2 parts by weight of CPI-310B, and 57. 45.0 parts by weight of alumina is used instead of 6 parts by weight of mica, and 5.0 parts by weight of 3-glycidoxypropylmethyldimethoxy instead of 5.2 parts by weight of 3-glycidoxypropyltriethoxysilane. A cured sealant was obtained in the same manner as in Example 9 except that silane was used.

<Evaluation of properties of cured sealant>
(Measurement of water permeability (WVTR) by the cup method)
The moisture permeability was measured using a cured sealant having a thickness of 100 μm and a diameter of 6 cm. 7 g of calcium chloride (manufactured by Kishida Chemical Co., Ltd.) was sealed with a hardened sealant and paraffin, and allowed to stand at a temperature of 40 ° C. and a humidity of 90% for 24 hours, and the amount of weight increase was measured. WVTR was calculated by the following formula.

WVTR (g / (m ² · day)) = Increased mass (g) /0.03×0.03×3.14 (m ² ) × 1 (day)
When the WVTR is less than 4.5 g / (m ² · day), ◎, when it is 4.5 g / (m ² · day) or more and less than 6.5 g / (m ² · day), ○, 6.5 g / ( When m ² · day) or more and less than 15.5 g / (m ² · day), Δ, when 15.5 g / (m ² · day) or more, or when measurement is not possible due to poor curing, ×.

<Result>
Tables 5 to 10 below show the composition and property evaluation results of the cured sealants prepared in Examples 9 to 20 and 23 to 25 and Comparative Examples 7 to 15 and 18 to 20, respectively.

It was confirmed that the cured sealants of Examples 9 to 20, 23 to 25 and Comparative Examples 7 to 9 and 18 to 20 had lower moisture permeability than the cured sealants of Comparative Examples 10 to 15. It was. Further, the cured sealants of Examples 9, 10, 13, 15, 16, 18 to 20 and 24 and Comparative Examples 7 to 9, 18, and 19 are examples 11, 12, 14, 17, 23, It was confirmed that the moisture permeability was lower than that of the cured sealant of 25 and Comparative Example 20.

As described above, Examples 1 to 4 and 21 were found to be excellent in crystal suppression. In addition, it was confirmed that the cured sealants of Examples 5 to 8 and 22 using any one of the resin compositions of Examples 1 to 4 and 21 had a high curing rate and glass transition point. Furthermore, the cured sealants of Examples 9 to 20 and 23 to 25 using any of the resin compositions of Examples 1 to 4 and 21 were found to have low moisture permeability. On the other hand, the resin composition of Comparative Example 3 exhibited the same crystal suppression as that of the example. However, the encapsulant cured product of Comparative Example 6 using the resin composition of Comparative Example 3 is inferior in that the curing rate is low and the glass transition point cannot be measured, and the resin composition of Comparative Example 3 is inferior. The cured sealants of Comparative Examples 13 to 15 using the product are inferior in that the moisture permeability is high. Further, the cured sealants of Comparative Examples 4, 5 and 17 showed the same curing rate and glass transition point as those of Examples, and the cured sealants of Comparative Examples 7 to 9 and 18 to 20 were equivalent to Examples. The water permeability was shown. However, the resin compositions of Comparative Examples 1, 2, and 16 used in any of the cured sealants of Comparative Examples 4, 5, 7 to 9, and 17 to 20 are inferior in crystal suppression.

The present invention can be used as a sealant, an adhesive, and a coating agent that are also suitably used in an organic EL display.

Claims

A compound represented by the following formula (1) or formula (2),

In the above formula (1) and formula (2), n represents an integer of 2 or more,
R and R ′ represent an aliphatic group or an aromatic group.
In the above formulas (1) and (2), R is a bisphenylene group.
A resin composition comprising the compound according to claim 1 or 2.
The ratio of the compound represented by the following formula (3) measured by gel permeation chromatography is 90 area% or less with respect to 100 area% of the resin composition,

In said formula (3), said R shows an aliphatic group or an aromatic group, The resin composition of Claim 3 characterized by the above-mentioned.
An encapsulant comprising the compound according to claim 1 or 2, or the resin composition according to claim 3 or 4.
The sealing agent according to claim 5, further comprising at least one component selected from the group consisting of a polymerization initiator, an inorganic compound, and a silane coupling agent.
The sealing agent according to claim 6, wherein the polymerization initiator is a photopolymerization initiator.