TW201839027A - Resin composition - Google Patents

Abstract

Provided is a resin composition having low viscosity, high fluidity, excellent shelf life and low-temperature curability. The cured product of the resin composition has very high moisture permeation resistance. The composition comprises (A) an epoxy resin, (B) a polythiol compound, and (C) a glass in flake form.

Description

Resin composition

In particular, the present invention relates to a resin composition suitable for use as a sealant, a hardened material of the resin composition, and a display device that seals a gap of a peripheral edge portion of a substrate with one of the holding display elements by the hardened material of the resin composition.

In recent years, in the field of various display devices such as organic EL displays and electronic paper, a thin film transistor (TFT) using an organic semiconductor layer has attracted much attention. This thin film transistor is called an organic TFT. The organic TFT can be formed at a low temperature by an evaporation method or the like for forming an inorganic semiconductor layer in a conventional inorganic TFT (thin film transistor using an inorganic semiconductor layer), so it has a low heat resistance. The advantages of substrates such as plastic films can also be installed.

However, a display device generally has a laminated structure in which a display element is held by a pair of substrates. Therefore, there is a gap between the opposing substrates at the peripheral edge portion of the pair of substrates, and the gap is usually sealed with a sealant or the like made of a curable composition. Such a sealant made of a hardening composition must have fluidity that penetrates the gap between the substrates at the peripheral edge of a pair of substrates before hardening, so the viscosity must be sufficiently low. On the other hand, the hardened material after hardening must have High moisture permeability resistance. Moreover, when a display device using an organic TFT as a display element requires low-temperature curability to the composition. As a sealant made of such a hardenable composition, for example, a hardenable composition is proposed in Patent Document 1, which contains (i) an epoxy resin which is liquid at 23 ° C, and (ii) which is 100 parts by mass of solid secondary amines or tertiary amines, or microcapsules containing secondary amines and tertiary amines, and (iii) fillers relative to the total amount of (i) and (ii), (iii) Contains 50 to 300 parts by mass. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2013/108629

[Questions to be Solved by the Invention]

However, the curable composition used in such a sealant is required to be further improved in terms of moisture permeability resistance, low-temperature curability, and storage stability. Therefore, when a high content is blended such as talc to improve the moisture permeability resistance, the viscosity of the composition becomes high, the fluidity is lost, and the workability in the sealing operation tends to be poor. Therefore, these balanced resin compositions are required.

The present invention was made in view of these circumstances, and in order to solve these problems, it is to provide a resin composition with low viscosity, high fluidity, excellent storage stability, and low-temperature hardening, and the cured product has extremely high moisture permeability resistance. Thing. [Means to solve the problem]

As a result of active research by the present inventors in order to solve the above-mentioned problems, they have found that a resin composition containing an epoxy resin, a polythiol compound, and a sheet glass plays an extremely advantageous role in solving the above-mentioned problems, and thus completed the present invention. That is, the present invention is as follows.

[1] A resin composition comprising (A) an epoxy resin, (B) a polythiol compound, and (C) a sheet glass. [2] The resin composition as described in [1] above, in which the viscosity measured at 25 ° C and 20 rpm by an E-type viscometer is 0.1 to 10 Pa. s. [3] The resin composition according to the above [1] or [2], wherein the epoxy resin content in the resin composition is 20 to 60% by mass when the non-volatile content of the resin composition is 100% by mass. [4] The resin composition according to any one of the above [1] to [3], wherein the molar ratio (epoxy group / thiol group) of the epoxy group to the thiol group in the resin composition is 0.9 to 1.5. [5] The resin composition according to any one of the above [1] to [4], wherein the content of the flake glass in the resin composition is 5 to 40 when the non-volatile content of the resin composition is 100% by mass. quality%. [6] The resin composition according to any one of the above [1] to [5], wherein the aspect ratio of the sheet glass is 10 or more and 100 or less. [7] The resin composition according to any one of the above [1] to [6], wherein the 200 μm thick moisture permeability of the cured product after the resin composition is thermally cured at 70 ° C. for 1 hour is 30 (g / m ^2. 24h) or less. [8] The resin composition according to any one of the above [1] to [7], which is a sealant. [9] The resin composition according to any one of the above [1] to [7], which is a sealant for a display device. [10] The resin composition according to the above [9], wherein the display device is an electronic paper. [11] A hardened product, which is a hardened product of the resin composition according to any one of the above [1] to [6], and has a 200 μm thick moisture permeability of 30 (g / m ² .24h) or less. [12] A display device comprising a display element, holding a pair of substrates of the display element, and a hardened material that seals a gap between substrates at the peripheral edge portion of the pair of substrates, as described in any of the above [1] to [7] The cured product of one item or the cured product as described in [11] above. [Inventive effect]

According to the present invention, it is possible to provide a resin composition having sufficiently low viscosity before hardening, excellent fluidity, good storage stability, and extremely hardened moisture permeability.

Since the resin composition of the present invention has the above-mentioned excellent characteristics, it can be used as an adhesive, a sealant, a protective film, and the like in various technical fields. It is particularly useful as a sealant for a display element or a display device. For example, if a sealant is used to seal a gap between substrates in a peripheral portion of a display device having a structure in which a display element is held between a pair of substrates, the display element is extremely unlikely to occur. Performance degradation due to moisture can achieve high-quality display devices.

Hereinafter, the present invention will be described in a preferred embodiment. In addition, the numerical range specified by the symbol "~" in this manual is a value including both ends (upper limit and lower limit) of "~". For example, "0.01 to 5" means 0.01 or more and 5 or less.

The main characteristics of the resin composition of the present invention include at least (A) an epoxy resin (hereinafter sometimes referred to as "(A) component"), (B) a polythiol compound (hereinafter sometimes referred to as "(B) component") And (C) sheet glass (hereinafter sometimes referred to as "(C) component").

<(A) Epoxy resin> The epoxy resin of the present invention is not particularly limited as long as it has two or more epoxy groups per molecule. Examples are, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, biphenylaralkoxy epoxy resin, naphthol epoxy resin. Resins, naphthalene-type epoxy resins, phosphorus-containing epoxy resins, aromatic glycidylamine-type epoxy resins (e.g., tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diamine Glycidyl toluenediamine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, bisphenol A Type novolac epoxy resin, epoxy resin containing polyalkylene glycol skeleton, epoxy resin with butadiene structure, diglycidyl etherate of bisphenol, diglycidyl etherate of naphthalene glycol, phenols Glycidyl etherate of alcohols and diglycidyl etherification of alcohols, and alkyl substituents, halides and hydrides of epoxy resins, etc. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenolic glycidyl etherate (e.g. Resorcinol diglycidyl ether, etc.), alcohol diglycidyl etherate (such as 1,4-cyclohexanedimethanol diglycidyl ether, etc.). The epoxy resin preferably has an epoxy equivalent in the range of 50 to 1500 g / eq, more preferably in the range of 70 to 500 g / eq, and more preferably in the range of 100 to 200 g / eq. The "epoxy equivalent" in the present invention is the number of grams (g / eq) of the resin containing one gram equivalent of epoxy groups, and is measured in accordance with the method prescribed by JIS K 7236. The epoxy resin may be used singly or in combination of two or more kinds.

The resin composition of the present invention is intended as an example of its use, and is intended to be a sealant that seals a gap between substrates in a peripheral portion of a display device having a structure in which a display element is held between a pair of substrates. Therefore, the resin composition before curing must have fluidity that penetrates into the gap between the substrates, and the epoxy resin (the component (A)), which is the main component of the resin composition, must have fluidity. Therefore, although the epoxy resin (component (A)) may include a solid-shaped epoxy resin, 50 to 100% by mass of the entire component (A) is preferably a liquid epoxy resin, and more preferably the entire epoxy component (A). 70 to 100% by mass is a liquid epoxy resin. Here, the solid epoxy resin means an epoxy resin that is solid at 23 ° C, and the liquid epoxy resin means an epoxy resin that is liquid at 23 ° C.

In addition, from the viewpoints of low viscosity and moisture permeability resistance, the epoxy equivalent is preferably 50 g / eq or more, more preferably 70 g / eq or more, and particularly preferably 100 g / eq or more. In addition, from the viewpoint of low viscosity and moisture permeability resistance, the epoxy equivalent is preferably 500 g / eq or less, and more preferably 200 g / eq or less.

The content of the component (A) in the resin composition of the present invention is not particularly limited, but from the viewpoint of the viscosity of the composition, the content of the nonvolatile content in the resin composition is 100 mass%, preferably 60 mass% or less. , More preferably 55 mass% or less, still more preferably 51 mass% or less, and particularly preferably 50 mass% or less. On the other hand, from the viewpoint of the viscosity of the composition, the content of the nonvolatile matter in the resin composition is preferably 100% by mass or more per 100% by mass, more preferably 25% by mass or more, and particularly preferably 30% by mass. the above.

<(B) Polythiol compound> 物 中 In the resin composition of the present invention, by using a polythiol compound as a hardener, the resin composition can be hardened in a low-temperature region, and the viscosity of the resin composition can be reduced. Helpful. The polythiol compound is not particularly limited as long as it is a compound that crosslinks or polymerizes epoxy groups, but it is preferred that the number of thiol groups in one molecule is 2 to 6 (bifunctional to 6functional), and more preferably 3 to 6 (3-functional to 6-functional), such as trimethylolpropane tri (3-mercaptopropionate) (abbreviation: TMPT), pentaerythritol tetra (3-mercaptopropionate) (abbreviation: PEMP), dipentaerythritol hexa (3-mercaptopropionate) (abbreviation: DPMP), tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate (abbreviation: TEMPIC), tris (3-mercaptopropyl) isopropyl Cyanurate (abbreviation: TMPIC), ethylene glycol dithioglycolate (abbreviation: EGTG), trimethylolpropane trithioglycolate (abbreviation: TMPG), pentaerythritol tetrathioglycolate ( Abbreviations: PETG), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tri (mercaptobutyrate) (abbreviation: TPMB), trimethylolethyl Alkane tris (3-mercapto chicken butyrate) (abbreviation: TEMB), 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, 4,4'-isopropylidenebis [(3 -Mercaptopropoxy) benzene] and the like.

These compounds can be synthesized by conventional methods, and commercially available products can be used. For example, tris (3-mercaptopropyl) isocyanurate (abbreviation: TMPIC) or 4,4'-isopropylidenebis [(3-mercaptobutoxy) benzene] can be obtained by, for example, Japanese Patent Application Laid-Open No. 2012-153794 Synthesized by the method described in Japanese Patent Publication No. 2001 or International Publication No. 2001/00698. Examples of commercially available products are PEMP manufactured by SC Organic Chemicals Co., Ltd., OTG, EGTG, TMTG, PETG, 3-MPA, TMTP, PETP manufactured by Yodo Chemical Co., Ltd., and TEMP and PEMP manufactured by Kao Chemical Industry Co., Ltd. , TEMPIC, DPMP, PE-1 (pentaerythritol tetrakis (3-mercaptobutyrate)), BD-1 (1,4-bis (3-mercaptobutyryloxy) butane) manufactured by Showa Denko Corporation, NR-1 (1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione), TPMB TEMB, TS-G (1,3,4,6-tetrakis (2-mercaptoethyl) glycol urea) manufactured by Shikoku Chemical Industry Co., Ltd., etc. The polythiol compound may be used singly or in combination of two or more kinds.

The polythiol compound is based on the viewpoints of low viscosity and low-temperature hardening property of the resin composition, and moisture permeability resistance of the hardened material. The thiol group equivalent is preferably in the range of 50 to 500 g / eq, more preferably 75 to 300. The range of g / eq is more preferably in the range of 100 to 200 g / eq. The so-called "thiol group equivalent" refers to the gram of resin (g / eq) containing 1 gram equivalent of thiol group, and can be measured by a conventional method such as an iodine solution titration method using starch as an indicator.

The content of the component (B) in the resin composition of the present invention is not particularly limited, but it is preferably a molar ratio (epoxy group / thiol group) of an epoxy group to a thiol group in the resin composition, that is, The ratio of the total molar number of epoxy groups (M2) of the (A) component in the resin composition to the total molar number (M1) of thiol groups of the (B) component in the resin composition ( M2 / M1) is a content of 0.9 to 1.5, and more preferably, the ratio (M2 / M1) is a content of 1.0 to 1.2.

From the viewpoint of effectively curing the resin composition at low temperature, when the content of the component (B) in the resin composition is such that the non-volatile content of the resin composition is 100% by mass, it is preferably 10% by mass or more, and more preferably It is 20% by mass or more, more preferably 25% by mass or more, and particularly preferably 30% by mass or more. On the other hand, from the viewpoint of storage stability of the resin composition, when the nonvolatile content of the resin composition is 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, and more It is preferably at most 45% by mass, and particularly preferably at most 40% by mass.

<(C) sheet glass> 含有 The resin composition of the present invention can improve the moisture permeability of the cured product of the resin composition to an extremely high level by containing the sheet glass. The glass composition of the flake glass is various glass compositions such as A glass, C glass, and E glass. Among them, E glass is particularly preferred. In addition, the sheet glass is also generally called a "glass sheet."

The average thickness of the flake glass is preferably 0.1 to 5 μm, and more preferably 1 to 3 μm. This average thickness can be measured by the following method. Using a scanning electron microscope (SEM), the thickness of each of 100 or more glass pieces was measured, and the measured values were averaged to obtain. In this case, a single glass sheet may be observed and measured by a scanning electron microscope, or the glass sheet may be filled with a resin and molded, and the glass sheet may be fractured, and the fractured surface may be measured. In any of the measurement methods, the sample stage of the scanning electron microscope is adjusted by the sample table micro-movement device so that the cross section (thickness surface) of the glass sheet is perpendicular to the irradiation electron beam axis of the scanning electron microscope.

The average particle diameter of the flake glass is preferably 5 μm or more, more preferably 20 μm or more, and particularly preferably 40 μm or more from the viewpoint of moisture permeability resistance. In addition, from the viewpoint of sealing properties such as the gap between substrates in the peripheral portion of the display device, it is preferably 300 μm or less, more preferably 200 μm or less, and particularly preferably 160 μm or less.

The average particle diameter of the flake glass can be measured by laser scattering diffraction method based on Mie scattering theory. Specifically, the particle size distribution of the flake glass can be made on a volume basis by a laser diffraction type particle size distribution measuring device, and the median diameter can be measured as the average particle size. As the measurement sample, a sheet glass is preferably dispersed in water by ultrasonic waves. As a laser diffraction scattering particle size distribution measuring device, LA-500 manufactured by Horiba, Ltd., etc. can be used.

The aspect ratio (average particle diameter / average thickness) of the flake glass is preferably 10 or more, more preferably 13 or more, based on the viewpoint that the cured product exhibits sufficiently high moisture permeability resistance, based on the fluidity of the resin composition. The viewpoint is preferably 100 or less, more preferably 45 or less, and still more preferably 40 or less.

The content of the component (C) in the resin composition of the present invention is not particularly limited, but from the viewpoint of sufficiently improving the moisture permeability of the hardened material of the resin composition, the content is such that the non-volatile content of the resin composition is 100 mass In the case of%, it is preferably 5 mass% or more, more preferably 7 mass% or more, still more preferably 10 mass% or more, and still more preferably 15 mass% or more. On the other hand, from the viewpoint of low viscosity of the resin composition, when the nonvolatile content of the resin composition is 100% by mass, it is preferably 40% by mass or less, more preferably 3% by mass or less, and more It is preferably 30% by mass or less, and even more preferably 25% by mass or less.

<(D) Hardening Accelerator> 树脂 The resin composition of the present invention may further contain (D) a hardening accelerator (hereinafter sometimes simply referred to as "(D) component"), if necessary, to improve low-temperature hardening properties. The hardening accelerator is not particularly limited, but examples thereof include amine-based hardening accelerators, guanamine-based hardening accelerators, imidazole-based hardening accelerators, and fluorene-based hardening accelerators. These can be used singly or in combination of two or more kinds.

The amine-based hardening accelerator is not particularly limited, but examples thereof include trialkylamines such as triethylamine, tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-tris ( Amine compounds such as dimethylaminomethyl) phenol, 1,8-diazabicyclo (5.4.0) -undecene (hereinafter referred to as DBU), organic dihydrazine (AMICURE VDH-J, AMICURE UDH , AMICURE LDH, etc. (both Ajinomoto Precision Technology Co., Ltd.) and so on. Examples of the modified polyamine include a modified polyamine containing a tertiary amine group, a modified polyamine containing a urea bond, and a modified polyamine containing an imidazole. Modified polyamines containing grade 3 amine groups are amine adducts obtained by excessively reacting polyamines with grade 3 skeletons to epoxy resins and / or phenol resins. Examples include EH4380S, EH3616S, and EH5001P made by ADEKA. , EH4375S, etc. Modified polyamines containing imidazole are amine adducts obtained by excessively reacting polyamines with imidazole skeleton to epoxy resins and / or phenol resins. Examples include PN-23, PN made by Ajinomoto Precision Technology Co., Ltd. -H, PN-40, ADEKA (share) EH4346S, T & K TOKA (share) FXR-1121, AIR PRODUCTS JAPAN (share) SUNMIDE LH210, etc. Modified polyamines containing urea bonds are adducts obtained by reacting polyamines in excess with isocyanate compounds, and examples thereof include FXR-1020 and FXR-1081 manufactured by T & K TOKA. An amine hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

The guanamine-based hardening accelerator is not particularly limited, but examples include dicyanobiamine, 1-methylguanamine, 1-ethylguanamine, 1-cyclohexylguanamine, 1-phenylguanamine, 1- (o-tolyl) guanamine, dimethylguanamine, diphenylguanamine, trimethylguanamine, tetramethylguanamine, pentamethylguanamine, 1,5,7-triazine Bicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide Amine, 1-n-butyl biguanide, 1-n-octyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl Biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide and the like. These can be used singly or in combination of two or more kinds.

The imidazole-based hardening accelerator is not particularly limited, but examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl- 4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl 2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamine -6- [2'-methylimidazole- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazole- (1') ] -Ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4-methylimidazole- (1 ')]-ethyl-s-triazine, 2,4 -Diamino-6- [2'-methylimidazole- (1 ')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2 -Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzene Benzimidazole, 1-dodecyl-2-methyl-3-benzimidazolium Imidazole compounds such as chloride, 2-methylimidazoline, 2-phenylimidazoline, 1- (2-hydroxy) -3-phenoxypropyl-2-methylimidazole and the like between imidazole compounds and epoxy resins Adducts, etc. These can be used singly or in combination of two or more kinds.

The fluorene-based hardening accelerator is not particularly limited, but examples include triphenylphosphine, fluorene boronate compounds, tetraphenyl fluorene tetraphenylborate, n-butyl fluorene tetraphenylborate, and tetrabutyl fluorene decanoate , (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. These can be used singly or in combination of two or more kinds.

(D) Among the hardening accelerators, amine-based hardening accelerators are preferred, modified polyamines are more preferred, and modified polyamines containing imidazole groups and modified polyamine hardening accelerators containing urea bonds are particularly preferred.

In the resin composition of the present invention, the content of the (D) component in the resin composition is not particularly limited, but from the viewpoint of improving the storage stability of the resin composition, the content is such that the non-volatile content of the resin composition is 100 mass In the case of%, it is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less. On the other hand, from the viewpoint of efficiently curing the resin composition and improving the low-temperature curability, when the non-volatile content of the resin composition is 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass. The above is more preferably 2% by mass or more.

<(E) Others> The resin composition of the present invention may optionally contain various additives ((E) components) other than the components (A) to (D) as long as the effects of the present invention are not impaired. Examples of the various additives include a storage stabilizer, an organic filler, a tackifier, a leveling agent, an adhesiveness-imparting agent, and an inorganic filler other than sheet glass ((C) component).

Examples of the storage stabilizer include a borate compound, a titanate compound, an aluminate compound, and a zirconate compound.

Representative examples of borate compounds include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, Amyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tri- Dodecyl borates, tris-hexadecyl borates, tris-octadecyl borates, tris (2-ethylhexyloxy) borane, bis (1,4,7,10 -Tetraoxaundecyl) (1,4,7,10,13-pentaoxatetradecanyl) (1,4,7-trioxaundecyl) borane, tribenzylboron Acid esters, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, and the like. Typical examples of the titanate compound include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl titanate, and the like. Representative examples of the aluminate compounds include triethylaluminate, tripropylaluminate, triisopropylaluminate, tributylaluminate, and trioctylaluminate. Typical examples of the zirconate compound include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, tetrabutyl zirconate, and the like. Among these, it is based on widespread use. From the viewpoint of high safety and excellent storage stability, boric acid esters are preferred, and triethyl borate, tri-n-propyl borate, tri-isopropyl borate, and tri-n-butyl borate are more preferred. Esters, particularly preferably triethylborate.

The content of the storage stabilizer in the resin composition is not particularly limited. From the viewpoint of improving the storage stability of the resin composition, it is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, relative to 100 parts by mass of the epoxy resin. And more preferably 0.1% by mass or more. On the other hand, from the viewpoint of not causing a hardening time delay, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 1 part by mass or less with respect to 100 parts by mass of the epoxy resin.

Examples of organic fillers include rubber particles, polysiloxane powder, nylon powder, fluororesin powder, etc., and examples of tackifiers include Orben, Benton, etc .; examples of defoamers or leveling agents, such as silicon, fluorine, etc. For example, as the adhesion-imparting agent, a triazole compound, a thiazole compound, a triazine compound, a porphyrin compound, or the like is used as an adhesion-imparting agent.

Examples of inorganic fillers other than sheet glass include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and boron nitride. , Aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. Generally, silicon oxide is especially used. These can be used singly or in combination of two or more kinds. Examples of commercially available inorganic fillers include hydrophilic fumed silica, such as "200", "200CF", "300", "300CF", "380", etc., manufactured by Japan Aerosil Corporation, or "R-805", "R-812", "RY-200", "RY-300", "RX-200", "RX-300" and other hydrophobic fuming silicas, "SOC2" and "SOC1" made by ADMATECHS Wait.

When an inorganic filler other than sheet glass is included, the content is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass when the non-volatile content of the resin composition is 100 mass%. % Or less, particularly preferably 0.5 mass% or less. When the total content of the sheet glass ((C) component) in the resin composition and the inorganic filler other than the sheet glass is 100% by mass, the resin composition is preferably 40% by mass or less. , More preferably 35 mass% or less, still more preferably 30 mass% or less, and particularly preferably 25 mass% or less.

<Manufacturing method of resin composition> 之 The resin composition of the present invention can be blended by, for example, a blending component containing at least the components (A) to (C) with a three-roller, ball mill, bead mill, sand mill, or the like. , Or mixing means such as super mixer, planetary mixer, etc. The compounding ingredients can be mixed at one time, but from the viewpoint of storage stability of the resin composition, it is preferable to mix the epoxy resin ((A) component) and the sheet glass ((C) component) in order, and then mix the polythiol therein. Compound ((B) component).

In addition, when preparing a resin composition that further contains a hardening accelerator ((D) component), other additives ((E) component), etc., from the viewpoint of dispersibility, inorganic materials other than sheet glass other than (C) component are preferred. The filler is mixed with the sheet glass ((C) component) and the epoxy resin ((A) component). From the viewpoint of storage stability of the resin composition, the hardening accelerator ((D) component) and (E) component The storage stabilizer and the like are preferably mixed with a mixture of an epoxy resin ((A) component) and a sheet glass ((C) component) before using the polythiol compound ((B) component) (using (E) In the case of an inorganic filler other than sheet glass, it is a mixture of epoxy resin ((A) component) and sheet glass ((C) component) and inorganic filler other than sheet glass).

<Resin composition and its use> 树脂 The resin composition of the present invention has extremely high moisture permeability resistance of the cured product after curing. In addition, the evaluation of the moisture permeability resistance of the examples described below is based on the permeability of water vapor (gas). This evaluation also becomes the evaluation of the gas barrier properties of the hardened material. The hardened material of the resin composition of the present invention also shows the gas barrier properties. Excellent sex. Therefore, the resin composition of the present invention can be used as an adhesive, a sealant, a protective film, and the like in various technical fields. For example, it can be used for adhesives in electronic parts, semiconductor devices, optical circuit parts, etc., and sealing of optical semiconductor devices such as solar cells, high-brightness LEDs, LCDs, EL elements, and organic TFTs (coating elements to isolate the elements from the air environment) In addition, it can be used for sealing of HDD (hard disk drive) (sealing agent to prevent gas from escaping when the inside of HDD is filled with a gas such as helium), and an insulating protective film for printed circuit boards.

The resin composition of the present invention has an excellent low-temperature hardening property that it hardens quickly even in a low-temperature region. The hardening temperature is not particularly limited, but is preferably 50 to 120 ° C, more preferably 70 to 100 ° C, and the hardening time is preferably 30. ~ 120 minutes, more preferably 60 ~ 90 minutes. Since it can be cured at a low temperature and for a short time, it is also possible to perform bonding or sealing on an object to be thermally deteriorated or an object to be sealed without causing such thermal degradation. Therefore, for example, a display device (e.g., electronic paper) using an organic TFT for a display element or an organic EL device having an organic EL element can form a desired sealing structure without thermally deteriorating the organic TFT or the organic EL element. The heating method at the time of hardening is not specifically limited, For example, a hot-air circulation type oven, an infrared heater, a heating gun, a high-frequency induction heating device, heating by pressing with a heating tool, or the like can be used.

The resin composition of the present invention is, for example, heat-cured at 70 ° C for 1 hour (60 minutes) at a thickness of 200 μm. The moisture permeability when measured according to the moisture permeability test method (cup method) described in JIS Z0208 shows 30 (g / m ² .24 h) or less (preferably 20 (g / m ² .24 h) or less). If the water vapor transmission rate is low, the lower limit is better, so the lower limit value is not particularly limited. In reality, it is about 3 (g / m ² .24 h) or more, but it is not limited thereto. Therefore, the object to be sealed with the hardened material is extremely unlikely to be deteriorated by moisture. In the present invention, the "hardened material" means that the resin composition before the curing reaction reacts by 90% or more by heating. For example, the total amount of the resin composition before curing is measured by differential scanning calorimetry (DSC). The calorific value (H ₀ ), the residual calorific value (H ₁ ) derived from the hardened material obtained by heating the resin composition at 70 ° C. for 1 hour, and the reaction rate calculated by the following calculation formula shows 90% or more.

Response rate (%) = (H ₀ -H ₁ ) / H ₀ × 100

For example, the higher the Tg of the cured product obtained by thermally curing the resin composition of the present invention at 70 ° C. for 1 hour (60 minutes), the better the moisture permeability resistance. The Tg of the cured product is not particularly limited, but is preferably 30 ° C or higher, more preferably 40 ° C or higher, and particularly preferably 50 ° C or higher.

In addition, the viscosity of the composition of the resin composition of the present invention measured at 25 ° C. and 20 rpm by an E-type viscometer before curing was 15 Pa. s (preferably 0.1 Pa.s or more and 10 Pa.s or less), and the thixotropic index (TI value) shows less than 2.0 (preferably less than 1.5), which is a liquid with low viscosity and low structural viscosity. Shows high fluidity at room temperature. Therefore, the resin composition can be quickly immersed in the narrow recesses or gaps. Therefore, for example, a sufficient amount can be embedded in the gap between the substrates formed at the peripheral edge portion of the display device having a structure in which the display element is held between a pair of substrates without leaving a gap. Resin composition. In a display device (especially an electronic paper) using an organic TFT as a display element, the gap between the substrates of one pair of substrates holding the display element is generally about 100 to 300 μm and is very narrow, but the resin composition according to the present invention can be formed A sealing portion that seals a gap between the substrates formed on the peripheral edge portion of the substrate by one of the electronic papers without leaving a gap. In addition, since the cured product has extremely high moisture permeability resistance, it is extremely difficult for the performance of the display element to deteriorate due to moisture, and a high-quality electronic paper can be obtained.

In addition, the resin composition of the present invention has excellent storage stability and can be directly stored in a low viscosity state without gelation for a long period of time. The so-called "preservation stability" in the present invention means the state of use after production, and furthermore, the stability in the period of use at the place of purchase where the commodity is distributed. When used after circulation or long-term storage, the stability of storage can be extended by keeping the refrigerator and freezer at a lower temperature. Generally based on the viewpoint of withstanding the circulation at an ambient temperature of 20 ° C to 40 ° C, the storage stability is at least 3 hours, preferably 6 hours or more, more preferably 12 hours or more, and more preferably 1 day or more, especially more It is preferably more than 3 days, and particularly preferably more than 7 days. Storage stability The longer the storage period in the low-viscosity state, the better. The upper limit is not particularly limited, but it is preferably 2 weeks, more preferably 3 weeks, more preferably 1 month, and even more preferably 2 months. The best time is 3 months, preferably 6 months. [Example]

The following examples and comparative examples illustrate the present invention more specifically, but the present invention is not limited to the following examples. In addition, "part" in the following description means "mass part."

1. Raw material [(A) component] (A1) "jER807": Mitsubishi Chemical Corporation, bisphenol F-type epoxy resin, epoxy equivalent (EPW) 160-175 g / eq, liquid (A2) " jER828 ": manufactured by Mitsubishi Chemical Corporation, bisphenol A epoxy resin, epoxy equivalent (EPW) 184-194 g / eq, liquid (A3)" EX-201 ": manufactured by NAGASE CHEMTEX, Inc. Resorcinol diglycidyl ether, epoxy equivalent (EPW) 117 g / eq, liquid (A4) "DME-100": manufactured by Shin Nippon Chemical Co., Ltd., 1,4-cyclohexanedimethanol diglycidyl Ether, epoxy equivalent (EPW) 145-170 g / eq, liquid

[(B) component] (B1) PEMP: manufactured by SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate), thiol equivalent 122 g / eq (B2) TMTP: manufactured by Yodo Chemical Industry Co., Ltd., Trimethylolpropane tri (3-mercaptopropionate), thiol equivalent 140 g / eq (B3) DPMP: Dipentaerythritol hexa (3-mercaptopropionate), thiol equivalent 131 g / eq (B4) PE1 : "KARENZ MT" manufactured by Showa Denko Corporation, pentaerythritol tetrakis (3-mercaptobutyrate), thiol equivalent 136 g / eq (B5) TMPIC: tris (3-mercaptopropyl) isocyanurate, sulfur Alcohol equivalent 117 g / eq (B6) TS-G: manufactured by Shikoku Chemical Industry Co., Ltd., 1,3,4,6-tetrakis (2-mercaptoethyl) glycol urea, thiol equivalent 94 g / eq ( B7) 4,4'-isopropylidenebis [(3-mercaptopropoxy) benzene]: thiol equivalent 189 g / eq

[(C) component] (C1) GF750E: GLASS FLAKE LIMITED, flake glass, average particle size 160 μm, average thickness 5 μm, aspect ratio 32 (C2) GF003: GLASS FLAKE LIMITED, flake glass, average Particle size 40 μm, average thickness 3 μm, aspect ratio 13 (C3) GF-001: made by GLASS FLAKE LIMITED, flake glass, average particle size 40 μm, average thickness 1 μm, aspect ratio 40

[(D) Ingredient] (D1) AMICURE PN-23: Made by Ajinomoto Precision Technology Co., Ltd., imidazole group-containing modified polyamine (solid) (D2) FUJICURE FXR-1081: Made by T & K TOKA Co., Ltd., Modified polyamine containing urea bond, solid type (D3) NOVACURE HX-3722: Modified microcapsules containing imidazole, manufactured by Asahi Kasei Corporation

[Other ((E) ingredients)]

(E1) RD-8AL: Longsen Co., Ltd., silica, average particle size 15 μm 15 (E2) Talc MS: Japan Talc Co., Ltd., talc, average particle size 14 μm E (E3) AEROSIL 200: Japan AEROSIL Co., Ltd., fuming silica (E4) TEB: manufactured by Chunzen Chemical Industry Co., Ltd., triethyl borate (E5) HN-2200: manufactured by Hitachi Chemical Co., Ltd., 3 or 4-methyl- 1,2,3,6-tetrahydrophthalic anhydride, molecular weight 166

2. Evaluation test (1) Viscosity Measured at 25 ° C and 20 rpm using an E-type viscometer RE-80 (manufactured by Toki Sangyo Co., Rotor: 3 ° × R9.7).

(2) Thixotropic index (TI value) Using an E-type viscometer RE-80 (manufactured by Toki Sangyo Co., Rotor: 3 ° × R9.7), measure the viscosity at 2 rpm and 20 rpm at 25 ° C. The ratio of the viscosity to the viscosity at 20 rpm (2 rpm / 20 rpm) was used as the thixotropic index (TI value).

<Evaluation Criteria> 〇: Less than 1.5 △: 1.5 or more and less than 2.0 ×: 2.0 or more

(3) Storage stability The composition was stored in a plastic closed container at 25 ° C for 7 days. The E-type viscosity meter RE-80 (manufactured by Toki Sangyo Co., Ltd., rotor: 3 ° × R9.7) was used at 25 ° C. The temperature was measured at 20 ° C and 20 ° C, and the viscosity increase rate from the initial viscosity was calculated from the viscosity / initial viscosity after 7 days. <Evaluation criteria> 〇: 1.2 times or less △: 1.2 or more and 1.5 times or less: 1.5 times or more

(4) Low-temperature hardenability The composition was measured at 70 ° C until it was not drawn by a hot plate gelation tester GT-D (manufactured by Nisshin Scientific Co., Ltd.) in accordance with JIS C6521. Specifically, put about 0.5g of the composition on a heating plate type gelation tester preheated to 70 ° C, start the stopwatch, and repeat the contact circle operation with a scraping blade with a width of 5 mm at the front end, and measure until the gelation time. <Evaluation criteria> 〇: Less than 10 points △: More than 10 points and less than 30 points ×: More than 30 points

(5) Moisture resistance (moisture permeability) 涂布 Coat the composition on the release surface of the release PET film (NS-80A), stretch to a thickness of about 200 μm with a glass rod, and heat in an oven at 70 ° C for 60 minutes To produce a hardened film of the composition. The cured film is a resin composition that constitutes a film before heating in which the reaction is more than 90%. Using the produced hardened film, an aluminum cup was produced in accordance with the method of JIS Z0208. The mass before and after being left in a high-temperature and high-humidity tank at 60 ° C and 80% RH for 24 hours was used to calculate the hardening thickness of 200 μm from the following calculation formula. The material is permeable to humidity.

Moisture permeability (g / m ² ．24h) = [(Mass of aluminum cup after 24 hours (g)-Mass of aluminum cup before placing (g)) / Area of film (m ² )] × (Measured value of film thickness (μm) / 200 (μm))

<Evaluation Criteria> ○: Less than 20 (g / m ² .24h) △: 20 (g / m ² .24h) or more and less than 30 (g / m ² .24h) ×: 30 (g / m ²⁾ . 24h) or more

3. Examples and Comparative Examples The components shown in the upper columns of Tables 1 and 2 below were mixed to prepare resin compositions of Examples 1 to 18, Comparative Examples 1 to 4 and Reference Examples 1 to 2. In the table, (parts) represents parts by mass, and (%) represents mass%.

The resin composition was mixed with the components (A), (C), and (E3) by a three-roller mixer in Examples 1 to 15, and 17, and then added the components (D) and (E4) to the mixture. Mix by machine, add component (B) to it, and fully disperse with a mixer, and then stand and defoam to prepare. The preparation operation was performed at 25 ° C, and the total mixing time was 30 minutes.

In Example 16, (A) component, (B) component, (C) component, and (E3) were mixed with the 3 roll mixer, (D) component, (E4) were added to this, and after fully dispersing, it was left to stand and remove Bubble and modulation. The mixing means, temperature, and total mixing time were the same as those in Examples 1 to 15.

In Example 18, (A) component and (C) component were mixed, (D) component, and (E4) were added, and it fully disperse | distributed, and it stood still and defoamed, and was prepared. The mixing means, temperature, and total mixing time were the same as those in Examples 1 to 15.

In Comparative Example 1, the component (A) and (E1) were mixed, the component (D) was added thereto and mixed, and (E5) was added thereto to disperse sufficiently, and the mixture was allowed to stand and defoam to prepare. The mixing means, temperature and total mixing time are the same as those in Examples 1 to 15.

In Comparative Example 2, the component (A) and (E1) were mixed, the component (D) was added to the mixture, and the component (B) was added to the mixture to disperse the mixture sufficiently. Then, the mixture was left to defoam and prepared. The mixing means, temperature and total mixing time are the same as those in Examples 1 to 15. In Comparative Examples 3 to 4, the components (A), (E2), and (E3) were mixed, the components (C) and (E4) were added to the mixture, and the components (B) were added to the mixture to fully disperse them. And modulation. The mixing means, temperature and total mixing time are the same as those in Examples 1 to 15.

In Reference Example 1, the component (A) and the component (C) were mixed, the component (D) was added thereto and mixed, and (E5) was added thereto to disperse sufficiently, and then the mixture was left to stand and defoam to prepare. The mixing means, temperature and total mixing time are the same as those in Examples 1 to 15. In Reference Example 2, the component (A) and the component (C) were mixed, and the component (D) was added and mixed, and then the mixture was left to stand and defoamed to prepare a mixture. The mixing means, temperature and total mixing time are the same as those in Examples 1 to 15.

The resin compositions of Examples 1 to 18, Comparative Examples 1 to 4, and Reference Examples 1 to 2 were subjected to the aforementioned evaluation tests. The results are shown in the lower columns of Tables 1 and 2. In addition, since Comparative Example 1 and Reference Example 1 were too brittle, the test piece could not be made, and the moisture permeability of the hardened product could not be measured.

As can be seen from Tables 1 and 2, as the results of Examples 1 to 18, the initial viscosity and thixotropic index (TI value) of the resin composition of the present invention are low, the storage stability is also good, and the hardened material shows excellent moisture permeability resistance. . In contrast, the resin composition of Comparative Example 1 has poor storage stability, low-temperature hardenability, and moisture permeability resistance of the cured material, and the resin composition of Comparative Examples 2 and 3 has poor moisture permeability resistance. The initial viscosity and thixotropic index (TI value) of the resin composition are high, and it is understood that the resin composition does not have such high performance as the resin composition of the present invention.

This application is based on Japanese Patent Application No. 2017-037013 filed in Japan, the contents of which are incorporated in this specification in their entirety.

Claims (12)

A resin composition containing (A) an epoxy resin, (B) a polythiol compound, and (C) a sheet glass. For example, the resin composition of claim 1, wherein the viscosity measured at 25 ° C and 20 rpm by an E-type viscometer is 0.1 to 10 Pa. s. For example, the resin composition of claim 1 or 2, wherein the epoxy resin content in the resin composition is such that when the non-volatile content of the resin composition is 100% by mass, it is 20 to 60% by mass. The resin composition according to any one of claims 1 to 3, wherein the molar ratio (epoxy group / thiol group) of the epoxy group to the thiol group in the resin composition is 0.9 to 1.5. For example, the resin composition according to any one of claims 1 to 4, wherein the content of the flake glass in the resin composition is such that when the non-volatile content of the resin composition is 100% by mass, it is 5 to 40% by mass. The resin composition according to any one of claims 1 to 5, wherein the aspect ratio of the flake glass is 10 or more and 100 or less. For example, the resin composition according to any one of claims 1 to 6, wherein the 200 μm-thick moisture permeability of the cured product after the resin composition is thermally cured at 70 ° C. for 1 hour is 30 (g / m ² .24 h) or less. The resin composition according to any one of claims 1 to 7, which is used as a sealant. The resin composition according to any one of claims 1 to 7, which is used as a sealant for a display device. The resin composition according to claim 9, wherein the display device is electronic paper. A hardened product, which is a hardened product of the resin composition according to any one of claims 1 to 6, and has a moisture permeability of 200 μm thickness of 30 (g / m ² .24 h) or less. A display device comprising a display element, a pair of substrates holding one of the display elements, and a hardened material that seals the gap between the substrates at the peripheral edge portion of the pair of substrates, which is the resin composition according to any one of claims 1 to 7. Hardened or hardened as claimed in item 11.