JP2020164562A - One-component resin composition - Google Patents

Abstract

To provide a one-component resin composition that is excellent in low-temperature quick curability.SOLUTION: As a curing agent of epoxy resin, used is a thiol compound that has three or more thiol groups in the molecule and does not have a ring skeleton, an ether skeleton or an ester skeleton in the molecule.SELECTED DRAWING: None

Description

The present invention relates to a one-component resin composition containing an epoxy resin and a thiol compound having a specific structure.

Thermosetting resin compositions using epoxy resins have excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesive strength, etc., and therefore, paints, electrical and electronic insulating materials, and It has been used in a wide range of applications such as adhesives. As such a resin composition, a two-component resin composition and a one-component resin composition have been developed. In the two-component resin composition, the epoxy resin and the curing agent are mixed at the time of use, and the epoxy resin is cured. On the other hand, in the one-component resin composition, the epoxy resin and the curing agent are mixed in advance and are cured by heat or the like at the time of use.

In recent years, one-component resin compositions have played an important role in protecting electronic components in the field of encapsulation of semiconductor devices and the like, increasing the density of circuits, and improving the reliability of connections. In particular, for the purpose of improving productivity and workability, there is an increasing demand for curing at low temperature in a short time. In addition, as electronic components have become smaller and various devices have become more mobile and wearable, electronic devices are increasingly used in more diverse environments than before. As a result, the resin composition is also required to have higher reliability than before in terms of drop impact resistance and high temperature and high humidity resistance.

In relation to the above, for example, Patent Documents 1 and 2 describe one-component epoxy resin compositions, respectively, and describe that a thiol compound having a rigid ring skeleton is used as a curing agent for an epoxy resin. There is.

International Publication No. 2015/060440 International Publication No. 2015/060439

However, since a thiol compound having a ring skeleton generally has a rigid structure, there is a drawback that the curing rate is slow.

An object of the present invention is to provide a one-component resin composition having excellent low-temperature quick-curing properties.

As a result of diligent studies to solve the above problems, the present inventors have a ring skeleton, an ether skeleton and an ester skeleton in the molecule and have three or more thiol groups in the molecule as a curing agent for the epoxy resin. It has been found that a one-component resin composition having excellent low-temperature quick-curing property can be obtained by using a thiol compound which does not have, and the present invention has been completed. That is, the present invention includes the following aspects.

[1] The following components A and B A: Epoxy resin B: A one-component type containing a thiol compound having three or more thiol groups in the molecule and having no ring skeleton, ether skeleton or ester skeleton in the molecule. Resin composition.
[2] The one-component resin composition according to the above [1], wherein the molecular weight of the component B is in the range of 150 to 500.
[3] The B component has the following structure
(X _{1 to} X ₄ are all -SH, or three of X _{1 to} X ₄ are -SH and the remaining one is -H, -OH or -CH ₃ )
The one-component resin composition according to the above [1] or [2].
[4] The following C component C: Any one of the above [1] to [3], further containing a thiol compound having three or more thiol groups in the molecule and having a ring skeleton in the molecule. The one-component resin composition described in 1.
[5] The one-component resin composition according to the above [4], wherein the C component is a thiol compound having no ether skeleton in the molecule.
[6] The one-component resin composition according to the above [4] or [5], wherein the C component is a thiol compound having no ester skeleton in the molecule.
[7] The one-component resin composition according to any one of the above [4] to [6], wherein the functional group equivalent amount of the thiol in the C component is 100 g / eq to 200 g / eq.
[8] Ratio of the number of thiol groups (b) of the B component to the total of the number of thiol groups (b) of the B component and the number of thiol groups (c) of the C component (b / (b + c)) The one-component resin composition according to any one of the above [4] to [7], wherein the amount is 0.2 to 0.9.
[9] The one-component resin composition according to any one of the above [1] to [8], further comprising the following component D: latent curing accelerator.
[10] An adhesive containing the one-component resin composition according to any one of the above [1] to [9].
[11] A sealing material containing the one-component resin composition according to any one of the above [1] to [9].
[12] A cured product obtained by thermally curing the one-component resin composition according to any one of the above [1] to [9].
[13] An electronic component containing the cured product according to the above [12].

The one-component resin composition of the present invention is excellent in low-temperature quick-curing property. Here, the "one-component" resin composition means a composition in which a curing agent and an epoxy resin are mixed in advance and has a property of being cured by applying heat or the like to the composition. ..

[Epoxy resin]
The one-component resin composition of the present invention contains an epoxy resin (component A).

The epoxy resin used in the present invention is not particularly limited, but one having an average of two or more epoxy groups per molecule is preferable. For example, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy. Resins, aromatic glycidyl amine type epoxy resins (for example, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resins, aliphatic chain epoxy resins, phenol novolac Type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin having a butadiene structure, epoxy resin having a dicyclopentadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalene diol, phenols Examples thereof include glycidyl etherified products of the above, diglycidyl etherified products of alcohols, alkyl substituents, halides and hydrogenated products of these epoxy resins. These may be used alone or in combination of two or more.

Among these, the epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a naphthalene type epoxy from the viewpoint of maintaining high heat resistance and low moisture permeability of the resin composition of the present invention. Resins, biphenyl aralkyl type epoxy resins, phenol aralkyl type epoxy resins, aromatic glycidylamine type epoxy resins, epoxy resins having a dicyclopentadiene structure and the like are preferable, and bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferable.

Further, the epoxy resin may be in a liquid state, a solid state, or both a liquid state and a solid state. Here, "liquid" and "solid" are states of the epoxy resin at room temperature (25 ° C.). From the viewpoint of coatability, processability, and adhesiveness, it is preferable that at least 10% by weight or more of the entire epoxy resin used is liquid. Specific examples of such liquid epoxy resin include liquid bisphenol A type epoxy resin (“jER 828EL” and “jER 827” manufactured by Mitsubishi Chemical Co., Ltd.), liquid bisphenol F type epoxy resin (“jER 807” manufactured by Mitsubishi Chemical Co., Ltd.), and phenol. Novolak type epoxy resin (Mitsubishi Chemical's "jER152"), naphthalene type bifunctional epoxy resin (DIC's "HP4032", "HP4032D]), naphthalene type epoxy resin (DIC's" HP-4032SS "), liquid bisphenol AF type epoxy resin (Nippon Steel & Sumitomo Metal Chemical Co., Ltd. "ZX1059"), bisphenol A type epoxy resin (Kaneka Co., Ltd. "MX-135"), hydrogenated structure epoxy resin (Mitsubishi Chemical Co., Ltd. "jER YX8000") ). Specific examples of the solid epoxy resin include a naphthalene type tetrafunctional epoxy resin (DIC Corporation "HP4700"), a dicyclopentadiene type polyfunctional epoxy resin (DIC Corporation "HP7200"), and a naphthol type epoxy resin (Nippon Steel). "ESN-475V" manufactured by Sumikin Chemical Co., Ltd.), epoxy resin having a butadiene structure ("PB-3600" manufactured by DIC CORPORATION), epoxy resin having a biphenyl structure ("NC3000H", "NC3000L" manufactured by Nippon Kayaku Co., Ltd.), "YX4000" manufactured by Mitsubishi Chemical Corporation) and the like.

The epoxy equivalent of the epoxy resin of component A is preferably 100 to 300 g / eq, more preferably 120 to 280 g / eq, and even more preferably 140 to 260 g / eq. Epoxy equivalent means the mass of an epoxy group-containing compound containing 1 equivalent of an epoxy group. Epoxy equivalents can be calculated by dividing the molecular weight of the compound by the number of epoxy groups in the compound.

In the resin composition of the present invention, the content of the epoxy resin is preferably 20% by weight or more, more preferably 40% by weight or more, further preferably 60% by weight or more, based on 100% by weight of the non-volatile content in the resin composition. Preferably, 70% by weight or more is even more preferable, 80% by weight or more is particularly preferable, and 90% by weight or more is particularly preferable. Further, 99.0% by weight or less is preferable, 98.5% by weight or less is more preferable, 98.0% by weight or less is further preferable, 97.5% by weight or less is further preferable, and 97.0% by weight or less is particularly preferable. It is preferably 96.5% by weight or less, and particularly preferably 96.5% by weight or less.

[Thiol compound]
The one-component resin composition of the present invention is a thiol compound (B) that has three or more thiol groups in the molecule and does not have a ring skeleton, an ether skeleton, or an ester skeleton in the molecule as a curing agent for an epoxy resin. Ingredient) is included. By using the thiol compound of the B component as the curing agent, the low-temperature quick-curing property of the one-component resin composition is improved. Further, the thiol compound of the component B containing no ester skeleton is superior in hydrolysis resistance to the thiol compound containing an ester skeleton. Further, since the thiol compound of the B component does not contain an ether skeleton, the one-component resin composition of the present invention has excellent storage stability.

The molecular weight of the thiol compound of the component B is, for example, 150 to 500, preferably 155 to 400, more preferably 160 to 300, and even more preferably 168 to 250.

The functional group equivalent of the thiol in the thiol compound of the component B is preferably 20 to 100 g / eq, more preferably 30 to 80 g / eq, and even more preferably 40 to 60 g / eq. The functional group equivalent of thiol means the mass of a thiol group-containing compound containing 1 equivalent of a thiol group. The functional group equivalent of a thiol can be calculated by dividing the molecular weight of the compound by the number of thiol groups in the compound.

The thiol compound of the B component preferably has the following structure.
(X _{1 to} X ₄ are all -SH, or three of X _{1 to} X ₄ are -SH and the remaining one is -H, -OH or -CH ₃ )
Have.

Thiol compounds having the above structure are available on the market, and for example, 2,2-bis (mercaptomethyl) -1,3-propanedithiol (TMPE) (X _{1 to} X ₄ ) manufactured by Asahi Chemical Industry Co., Ltd. are all available. -SH), three of the 3-mercapto-2,2-bis (mercaptomethyl) -1-propanol (X ₁ to X ₄ is one 1 -SH, remaining but -OH), 2-ethyl-2- ( three of the mercaptomethyl) -1,3-propanedithiol (X ₁ to X ₄ is -SH, remaining one include -CH ₃₎ or the like.

The content of the thiol compound of the component B is, for example, 3 to 50 parts by mass, preferably 5 to 40 parts by mass, more preferably when the total epoxy resin contained in the one-component resin composition of the present invention is 100 parts by mass. Is 7 to 30 parts by mass.

The component B thiol compound does not have a ring skeleton in the molecule, and therefore does not contain a component C thiol compound having a ring skeleton in the molecule described later. Further, the thiol compound of the B component does not contain an ester skeleton, and for example, trimethylolpropane tris (3-mercaptopropionate) (TMTP):
It does not contain thiol compounds obtained by the esterification reaction of polyol and mercapto organic acid such as. Further, the thiol compound of the B component does not contain an ether skeleton, for example, pentaerythritol tripropanethiol (PEPT):.

It does not contain thiol compounds having an ether skeleton such as.

The one-component resin composition of the present invention preferably contains a thiol compound (C component) having three or more thiol groups in the molecule and having a ring skeleton together with the thiol compound of the B component. By using the thiol compound of the C component in combination with the thiol compound of the B component as a curing agent for the epoxy resin, the extensibility of the cured product of the one-component resin composition is maintained while maintaining the low-temperature rapid curing property of the B component. Can be improved. The thiol compound of the C component preferably does not have an ether skeleton from the viewpoint of storage stability. That is, as the thiol compound of the C component, a thiol compound having three or more thiol groups in the molecule, having a ring skeleton in the molecule, and not having an ether skeleton is preferable. Further, the thiol compound of the C component preferably does not have an ester skeleton from the viewpoint of hydrolysis resistance. That is, as the thiol compound of the C component, a thiol compound having three or more thiol groups in the molecule, having a ring skeleton in the molecule, and not having an ester skeleton is more preferable. From these viewpoints, the C component thiol compound is particularly a thiol compound having three or more thiol groups in the molecule, having a ring skeleton in the molecule, and not having an ether skeleton and an ester skeleton. Is preferable.

The functional group equivalent of the thiol in the C component is preferably 100 to 200 g / eq, more preferably 110 to 190 g / eq.

The C component thiol compound is available on the market, and examples thereof include the following products.

TMPI C: Ajinomoto Fine-Techno, Tris (3-mercaptopropyl) isocyanurate, thiol functional group equivalent 117 g / eq

TS-G: Shikoku Kasei Co., Ltd., 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, thiol functional group equivalent 103 g / eq

NR-1: 1,3,5-Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, thiol manufactured by Showa Denko KK Functional group equivalent of 189 g / eq

The content of the thiol compound of the C component is, for example, 3 to 80 parts by mass, preferably 5 to 70 parts by mass, more preferably, when the total epoxy resin contained in the one-component resin composition of the present invention is 100 parts by mass. Is 7 to 60 parts by mass.

In the one-component resin composition of the present invention, the ratio of the number of thiol groups (b) of the component B to the total number of thiol groups (b) of the component B and the number of thiol groups (c) of the component C (b). / (B + c)) is, for example, 0.2 to 0.9, preferably 0.3 to 0.9, more preferably 0.4 to 0.9, and even more preferably 0.5 to 0.8. When the ratio of the number of thiol groups of the component B is within the above range, the effects of low-temperature quick-curing property and extensibility of the cured product can be exhibited in a well-balanced manner.

In the one-component resin composition of the present invention, the ratio (a) of the number of epoxy groups (a) of component A to the total number of thiol groups (b) of component B and the number of thiol groups (c) of component C (a). It is preferable that the components A to C are contained in an amount such that / (b + c)) is 1.

[Latent curing accelerator]
The one-component resin composition of the present invention may optionally contain a latent curing accelerator (component D). Examples of the latent curing accelerator that can be used in the present invention include a solid-dispersed latent curing accelerator. The solid-dispersed latent curing accelerator is a compound that is insoluble in the above-mentioned epoxy resin at room temperature (25 ° C.), solubilizes by heating, and functions as a curing accelerator for the epoxy resin. Examples include, but are not limited to, solid imidazole compounds and solid-dispersed amine adduct-based latent curing accelerators. Examples of solid-dispersed amine adduct-based latent curing accelerators include reaction products of amine compounds and epoxy compounds (amine-epoxy adduct-based), and reaction products of amine compounds and isocyanate compounds or urea compounds (urea type). Adduct system) and the like. Of these, a solid-dispersed amine adduct-based latent curing accelerator is preferable.

Examples of the imidazole compound solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like. 2-Phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2-methylimidazolyl- (1))-ethyl-S-triazine, 2,4-diamino-6- (2') -Methylimidazolyl- (1)')-Ethyl-S-triazine isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-Cyanoethyl-2-methylimidazole-trimeritate, 1-cyanoethyl-2-phenylimidazole-trimeritate, N- (2-methylimidazolyl-1-ethyl) -urea, N, N'-(2-methylimidazolyl- (1) )-Ethyl) -aziboyldiamide and the like, but are not limited thereto.

Examples of the epoxy compound used as one of the raw materials for producing the solid-dispersed amine adduct-based latent curing accelerator (amine-epoxy adduct-based) include polyvalent phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or Polyglycidyl ether obtained by reacting a polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin; reacting a hydroxy acid such as p-hydroxybenzoic acid or β-hydroxynaphthoic acid with epichlorohydrin. Glycidyl ether ester obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; and epic with 4,4'-diaminodiphenylmethane and m-aminophenol. Glycidylamine compounds obtained by reacting with chlorohydrin; further, polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin, and epoxidized polyolefin, butyl glycidyl ether, phenylglycidyl ether, glycidyl methacrylate, etc. Monofunctional epoxy compound; etc., but is not limited thereto.

The amine compound used as a raw material for producing the solid-dispersed amine adduct-based latent curing accelerator has one or more active hydrogens in the molecule capable of performing an addition reaction with an epoxy group, and has a primary amino group and a secondary amino group. Any one having at least one functional group selected from the tertiary amino groups in the molecule may be used. Examples of such amine compounds include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; Aromatic amine compounds such as 4,4'-diaminodiphenylmethane, 2-methylaniline; nitrogen such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, piperazine Examples include, but are not limited to, heterocyclic compounds containing atoms;

Further, among these, a compound having a tertiary amino group in the molecule is a raw material for giving a latent curing accelerator having an excellent curing promoting ability, and examples of such a compound include, for example, dimethylaminopropyl. Amines such as amines, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazin, 2-methylimidazole, 2-ethylimidazole, 2- Primary or secondary amines with tertiary amino groups in the molecule, such as imidazole compounds such as ethyl-4-methylimidazole, 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylamino Ethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1-( 2-Hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl)- 2-Ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylamino) Methyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzoimidazole, 2-mercaptobenzoimidazole, 2 -Mercaptobenzothiazole, 4-mercaptopyridine, N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotic acid, picolinic acid, N, N-dimethylglycine hydrazide, N, N-dimethylpropion Examples thereof include alcohols, phenols, thiols, carboxylic acids and hydrazides having a tertiary amino group in the molecule, such as acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide and the like.

When the above epoxy compound and amine compound are subjected to an addition reaction to produce a latent curing accelerator, an active hydrogen compound having two or more active hydrogens in the molecule can be further added. Examples of such active hydrogen compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resin, polyhydric alcohols such as trimethylolpropane, and adipic acid. , Polyhydric carboxylic acids such as phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, lactic acid and the like. It is not limited.

Examples of the isocyanate compound used as a raw material for producing the solid-dispersed amine adduct-based latent curing accelerator include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; hexamethylene diisocyanate and triisocyanate. Range isocyanate (eg 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalenedisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylenedi isocyanate, 1 , 3,6-Hexamethylene triisocyanate, bicycloheptane triisocyanate and other polyfunctional isocyanate compounds; Furthermore, terminal isocyanate group-containing compounds obtained by the reaction of these polyfunctional isocyanate compounds with active hydrogen compounds; etc. are also used. Can be done. Examples of such a terminal isocyanate group-containing compound include an addition compound having a terminal isocyanate group obtained by the reaction of tolylene diisocyanate and trimethylol propane, and a terminal isocyanate group obtained by the reaction of tolylene diisocyanate and pentaerythritol. Examples thereof include, but are not limited to, additional compounds having.

Further, examples of the urea compound used as a raw material for producing the solid-dispersed amine adduct-based latent curing accelerator include, but are not limited to, urea and thiourea.

For the solid dispersion type latent curing accelerator, for example, the above production raw materials are appropriately mixed, reacted at a temperature of room temperature to 200 ° C., then cooled and solidified, and then pulverized, or methyl ethyl ketone, dioxane, tetrahydrofuran. It can be easily obtained by reacting in a solvent such as the above, removing the solvent, and then pulverizing the solid content.

As typical examples commercially available as the solid dispersion type latent curing accelerator, for example, as an amine-epoxy adduct system (amine adduct system), Ajinomoto Fine-Techno Co., Ltd. "Amicure PN-23" and "Amicure" "PN-H", "Hardener X-3661S" manufactured by ACR, "Hardener X-3670S", "Novacure HX-3742" manufactured by Asahi Kasei, "Novacure HX-3721", etc. Examples of the type adduct system include, but are not limited to, "FXE-1000" and "FXR-1030" manufactured by T & K TOKA.

When the content of the epoxy resin is 100 parts by mass, the content of the curing accelerator is preferably 0.1 to 100 parts by mass, more preferably 1 to 60 parts by mass, and 5 to 30 parts by mass. Is even more preferable.

[Other additives]
The one-component resin composition of the present invention optionally includes a curing agent for epoxy resins other than the B component and the C component, a storage stability improver, a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, and the like. Various additives such as a coupling agent, an antioxidant, an antioxidant, and a dispersant can be added.

Examples of the curing agent for epoxy resins other than the B component and the C component include an imidazole-based curing agent and an amine-based curing agent. Further, for example, trimethylolpropane tris (3-mercaptopropionate) (TMTP), trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris ( β-thiopropionate), pentaerythritol tetrakis (β-thiopropionate), dipentaerythritol poly (β-thiopropionate) and other polyols and thiol compounds obtained by esterification of mercapto organic acids are also epoxy. It can be used as a resin curing agent.

The storage stability improver that can be used in the present invention may be added in order to further improve the storage stability of the resin composition of the present invention. Examples of the storage stability improver include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides and mercapto organic acids.

Examples of the borate compound include trimethylborate, triethyl borate (TEB), tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, and tricyclohexyl borate. , Trioctyl Borate, Trinonyl Borate, Tridecyl Borate, Tridodecyl Borate, Trihexadecyl Borate, Trioctadecyl Borate, Tris (2-ethylhexyloxy) Borane, Bis (1,4,7,10-Tetraoxaundecyl) ) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7-trioxaundecyl) borane, tribenzylborate, triphenylborate, tri-o-tolylborate, tri-m- Examples thereof include trillborate and triethanolamine borate.

Examples of the titanate compound include tetraethyl titanate, tetrapropyl titanate, tetraisoproprutitanate, tetrabutyl titanate, and tetraoctyl titanate.

Examples of the aluminate compound include triethylaluminate, tripropylaluminate, triisopropylaluminate, tributylaluminate, and trioctylaluminate.

Examples of the zirconate compound include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

Examples of the isocyanate compound include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, and 2,6-dimethylphenyl isocyanate. , Tolylene diisocyanate (eg 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalenedi isocyanate, diphenylmethane-4,4'-diisocyanate, trizine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, Examples thereof include paraphenylene diisocyanate and bicycloheptane triisocyanate.

Examples of the carboxylic acid include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid and capric acid, unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid and crotonic acid, and monochloro acid. Halogenized fatty acids such as acetic acid and dichloroacetic acid, monobasic oxyacids such as glycolic acid and lactic acid, aliphatic aldehyde acids such as glyoxal acid and grape acid, and ketone acids, oxalic acids, malonic acids, succinic acids, maleic acids and the like. Examples thereof include aromatic monobasic acids such as aliphatic polybasic acid, benzoic acid, halogenated benzoic acid, toluic acid, phenylacetic acid, cinnamic acid and mandelic acid, and aromatic polybasic acids such as phthalic acid and trimesic acid. ..

Examples of the acid anhydride include succinic anhydride, dodecynyl succinic anhydride, maleic anhydride, additions of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and other aliphatic or aliphatic polyusides. Examples thereof include aromatic polybasic anhydrides such as phthalic anhydride, trimellitic anhydride and pyrolimellitic anhydride such as basic acid anhydride. A typical example commercially available as an acid anhydride is HN-2200 (manufactured by Hitachi Chemical Co., Ltd., molecular weight = 166), which is methyltetrahydrophthalic anhydride that can also be used as a curing agent for epoxy resins. However, it is not limited to this.

The mercapto organic acid is obtained by, for example, an esterification reaction between a mercapto aliphatic monocarboxylic acid such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, and dimercaptosuccinic acid, a hydroxyorganic acid and a mercaptoorganic acid. Examples thereof include mercapto aliphatic monocarboxylic acids and mercapto aromatic monocarboxylic acids such as mercaptobenzoic acid.

Among these, as the storage stability improver, a borate compound is preferable from the viewpoint of high versatility and safety and improvement of storage stability, and triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri- n-Butyl borate is more preferred, and triethyl borate is even more preferred. The content of the storage stability improver is not particularly limited as long as the storage stability of the epoxy resin is enhanced, but when the total content of the epoxy resin is 100 parts by mass, the content of the storage stability improver is high. It is preferably 0.001 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, and even more preferably 0.1 to 10 parts by mass.

Examples of the anti-settlement agent include fine powder silica, fatty acid amide, and polyolefin-based polymers. Specifically, fine powder silica "AEROSIL 200" (manufactured by Nippon Aerosil Co., Ltd.), "AEROSIL R805" (manufactured by Nippon Aerosil Co., Ltd.) and the like can be used.

The one-component resin composition of the present invention can be produced from the above-mentioned epoxy resin of component A, thiol compound of component B, and optional components C, D and various other additives as raw materials. The preparation of the resin composition is not particularly difficult and can be carried out according to a conventionally known method. For example, the one-component resin composition of the present invention can be prepared by mixing each component with a mixer such as a Henschel mixer.

Further, the obtained one-component resin composition can be cured according to a conventionally known method without any particular difficulty. For example, the obtained resin composition can be cured by heating. The heating is carried out at a temperature of, for example, 60 to 150 ° C., preferably 75 to 120 ° C., more preferably 80 to 100 ° C., for example, 1 to 120 minutes, preferably 3 to 100 minutes, more preferably 5 to 80 minutes. It is appropriate to do.

[Low temperature fast curing property of resin composition]
The one-component resin composition of the present invention has excellent low-temperature quick-curing properties. The low-temperature fast-curing property can be evaluated based on the presence or absence of a heat generation peak and the peak top time in the differential scanning calorimetry (DSC7000X, manufactured by Hitachi High-Tech Science Corporation) of the resin composition under predetermined conditions. In particular, when a sample (resin composition) of about 10 mg is heated at 75 ° C. for 30 minutes and an exothermic peak is observed within 25 minutes, it can be judged that the sample (resin composition) is excellent in low-temperature quick-curing property. The better the low-temperature quick-curing property, the shorter the heat generation peak top is observed.

[Epoxy resin cured product, adhesive, encapsulant, etc.]
The present invention also relates to an adhesive containing the above-mentioned one-component resin composition. Here, the adhesive is preferably an adhesive that can be used in the field of adhesives for electronic components. In addition to the one-component resin composition of the present invention, the above-mentioned adhesive is optionally a curing agent for epoxy resins other than the B component and the C component, a curing accelerator, a flame retardant, a storage stability improver, a filler, and a diluent. , Solvents, pigments, flexibility-imparting agents, coupling agents, antioxidants, antisettling agents, dispersants and the like.

The present invention also relates to a sealing material containing the above-mentioned one-component resin composition. Here, the sealing material is a sealing material such as an underfilling agent for mounting a flip chip and a sealing agent for chip-on-board. In addition to the one-component resin composition of the present invention, the encapsulant can optionally be a curing agent for epoxy resins other than the B component and the C component, a curing accelerator, a flame retardant, a storage stability improver, a filler, and a diluent. It may contain various additives such as an agent, a solvent, a pigment, a flexibility-imparting agent, a coupling agent, an antioxidant, an antioxidant, and a dispersant.

The present invention also relates to an epoxy resin cured product obtained by curing the above-mentioned one-component resin composition and an electronic component containing the cured product.

[Extensibility of cured product]
The cured product of the resin composition of the present invention has improved extensibility by containing the thiol compound of the C component. The extensibility is based on the elongation value of a test piece of a cured product obtained by curing a resin composition under a predetermined condition in a tensile test using a Tensilon universal tester (RTM-500, manufactured by Orientec) under a predetermined condition. Can be evaluated.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the following Examples.

[Preparation of one-component resin composition]
Each component was mixed with the compounding composition shown in Table 1 to prepare the resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 3. In Table 1, the blending amount of each component means a mass part. Further, as shown in Table 1, in each Example and Comparative Example, the ratio (a / (b + c)) of the number of epoxy groups (a) to the number of thiol groups (b + c) in the resin composition is approximately It is 1.
Specifically, the amounts of materials shown in Tables 1 and 2 were weighed into a dedicated plastic container. Then, using a rotating / revolving vacuum mixer Awatori Rentaro (manufactured by Shinky Co., Ltd .; ARE-310), the mixture was sufficiently mixed at room temperature at 2000 rpm and defoamed for another 1 minute to obtain the desired resin composition.
The details of the materials used are as follows.

[Epoxy resin]
ZX-1059: Manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type (BPA type) / bisphenol F type (BPF type) epoxy resin, epoxy equivalent 165 g / eq
jER152: Phenolic novolac type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 177 g / eq
HP-4032SS: Naphthalene type epoxy resin manufactured by DIC, epoxy equivalent 144 g / eq
MX-135: Kaneka Corporation, bisphenol A type epoxy resin (25% dispersion of core-shell rubber particles), epoxy equivalent 223 g / eq

[B component thiol]
TMPE: Asahi Kagaku Kogyo Co., Ltd., 2,2 bis (mercaptomethyl) -1,3-propanedithiol, thiol functional group equivalent 50 g / eq

[C component thiol]
TMPI C: Ajinomoto Fine-Techno, Tris (3-mercaptopropyl) isocyanurate, thiol functional group equivalent 117 g / eq
NR-1: 1,3,5-Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, thiol manufactured by Showa Denko KK Functional group equivalent of 189 g / eq
[Other thiols]
PEPT: SC Organic Co., Ltd., pentaerythritol tripropanethiol, thiol functional group equivalent 119 g / eq

[Latent curing accelerator]
PN-23: Ajinomoto Fine Techno Co., Ltd., amine epoxy adduct-based curing agent [storage stability improver]
TEB: Triethyl borate [precipitation inhibitor] manufactured by Tokyo Kasei Co., Ltd.
AEROSIL200: Fumed silica manufactured by Nippon Aerosil

[Evaluation of low temperature fast curing]
For each Example and Comparative Example, the low-temperature fast-curing property was evaluated by measuring the presence or absence of an exothermic peak and the peak top time in differential scanning calorimetry (DSC7000X, manufactured by Hitachi High-Tech Science Corporation). Specifically, about 10 mg of a sample (resin composition) was heated at 75 ° C. for 30 minutes, and the presence or absence of heat generation and the position of the heat generation peak top of the resin compositions of each Example and Comparative Example were measured.

[Evaluation of elongation]
Each resin composition was applied on a release PET film (NS-80A: manufactured by Toray Industries, Inc.) using a bar coat, and heated at 90 ° C. for 60 minutes to cure to obtain a cured product. The obtained cured product having a thickness of 100 μm was punched with a dumbbell (trade name “Super Dumbbell Cutter (Model: SDKM-5889-01)”, manufactured by Dumbbell Co., Ltd.) to prepare a test piece for measuring tensile strength. The PET film was peeled off from the test piece. A tensile test was performed using a Tensilon universal tester (RTM-500, manufactured by Orientec) under the conditions of a temperature of 25 ° C., a humidity of 60%, and a tensile speed of 50 mm / min. The elongation value (6.3 mm) of the test piece of the resin composition of Example 1 was set to 100%, and the elongation values of each Example and Comparative Example with respect to the elongation value of Example 1 were obtained in% to evaluate the extensibility. ..

[Evaluation of storage stability]
The initial viscosity (Pa · s) of each resin composition was measured at 2 rpm and 25 ° C. using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd .: RE-85U, rotor name: 1 ° 34'x R24). did. Next, the resin composition was placed in a closed container and stored under the conditions of 25 ° C. and 60% Rh. Then, this was taken out every other day, and the viscosity of the resin composition at 2 rpm and 25 ° C. was measured by using an E-type viscometer. When the initial viscosity was 100%, the number of days until it reached 200% was defined as storage stability.

[Discussion of evaluation results]
The results of each of the above evaluations are shown in Table 1. It was found that the resin compositions of Examples 1 to 7 were superior in curability at low temperatures as compared with the resin compositions of Comparative Examples 1 and 2.
In detail, when Examples 1 to 7 in Table 1 and Comparative Example 1 are compared, an exothermic peak was confirmed in Comparative Example 1 in which only TMPIC (component C) having a ring skeleton in the molecule was used as a curing agent. However, curing at 75 ° C. did not proceed. In Comparative Example 2 in which only NR-1 (C component) having a ring skeleton and an ester skeleton in the molecule was used as a curing agent, an exothermic peak was observed, but an exothermic peak top appeared in 28 minutes. It was found that it was slower than the case where the curing rate was inferior to that in the case where the B component was present. In each of Examples 1 to 7, an exothermic peak was confirmed within 20 minutes, and improvement in low-temperature rapid curing property was observed due to the B component.
Next, paying attention to the extensibility of Examples 2 to 7 and Example 1 in Table 1, TMPE (B component) and TMPIC or NR-1 (Compared to Example 1 containing only TMPE (B component) as a curing agent, In Examples 2 to 7 including the combination of C component), improvement in extensibility was observed.
Further, in Comparative Example 3 in which PEPT having an ether skeleton in the molecule was used instead of the B component, the storage stability was extremely poor, curing proceeded at room temperature, and the curing rate and extensibility could not be evaluated. The resin composition of Comparative Example 3 in which curing proceeds at room temperature is not suitable for a one-component resin composition.

The one-component resin composition of the present invention can be suitably used for an adhesive or a sealing material, and the cured product thereof can be used as an electronic component.

Claims (13)

The following A and B components A: Epoxy resin B: A one-component resin composition containing a thiol compound having three or more thiol groups in the molecule and having no ring skeleton, ether skeleton or ester skeleton in the molecule. .. The one-component resin composition according to claim 1, wherein the molecular weight of the component B is in the range of 150 to 500. The B component has the following structure
(X _{1 to} X ₄ are all -SH, or three of X _{1 to} X ₄ are -SH and the remaining one is -H, -OH or -CH ₃ )
The one-component resin composition according to claim 1 or 2. The one-component type according to any one of claims 1 to 3, further comprising the following C component C: a thiol compound having three or more thiol groups in the molecule and having a ring skeleton in the molecule. Resin composition. The one-component resin composition according to claim 4, wherein the C component is a thiol compound having no ether skeleton in the molecule. The one-component resin composition according to claim 4 or 5, wherein the C component is a thiol compound having no ester skeleton in the molecule. The one-component resin composition according to any one of claims 4 to 6, wherein the functional group equivalent amount of the thiol in the C component is 100 g / eq to 200 g / eq. The ratio (b / (b + c)) of the number of thiol groups (b) of the B component to the total of the number of thiol groups (b) of the B component and the number of thiol groups (c) of the C component is 0. The one-component resin composition according to any one of claims 4 to 7, which is 2 to 0.9. The one-component resin composition according to any one of claims 1 to 8, further comprising the following component D: a latent curing accelerator. An adhesive comprising the one-component resin composition according to any one of claims 1 to 9. A sealing material containing the one-component resin composition according to any one of claims 1 to 9. A cured product obtained by thermosetting the one-component resin composition according to any one of claims 1 to 9. An electronic component comprising the cured product according to claim 12.