JP6555532B2 - Heat resistant epoxy resin composition - Google Patents

Description

  The present invention relates to a one-component thermosetting resin composition containing tris (3-mercaptopropyl) isocyanurate and a specific epoxy resin. The present invention also relates to an adhesive and a sealing material containing the one-component thermosetting resin composition, and a cured resin obtained by heating the curable resin composition.

Epoxy resins have excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, and adhesive strength, and are therefore used in a wide range of applications such as paints, electrical and electronic insulating materials, and adhesives. I came. Up to now, in addition to the so-called two-component epoxy resin composition in which an epoxy resin and a curing agent are mixed and cured at the time of use, the epoxy resin and the curing agent are mixed in advance and cured by heat or the like. Compositions have been developed. In recent years, a one-pack type epoxy resin composition plays an important role for protecting electronic components in the field of sealing of semiconductor elements and the like, increasing the density of circuits, and improving the reliability of connections. In particular, in recent years, there is an increasing demand for curing at a low temperature in a short time for the purpose of improving productivity and workability.
For example, a low-temperature curable one-component epoxy resin composition using a thiol curing agent is known (Patent Document 1). However, if low temperature curability is pursued too much, the adhesive strength may be inferior, and it is difficult to achieve both low temperature curability and adhesion strength.
Moreover, the curing agent contained in the conventional one-component epoxy resin composition having low temperature curability generally has low moisture resistance (migration resistance) and tends to change the shear adhesive force during long-term storage. was there. On the other hand, in order to improve the moisture resistance, there has been a problem that the glass transition temperature (Tg) is lowered when the formulation is studied.

JP-A-6-211969

An object of the present invention is to provide a one-component thermosetting composition that achieves both low-temperature curability and securing adhesive strength.
Another object of the present invention is to provide a one-pack type thermosetting resin composition having both low temperature curability and moisture resistance.

（式（１）中、Ｒは、互いに同一であっても異なっていてもよく、置換基を有していても有していなくてもよい、炭素数１〜３０の二価の炭化水素基であり、Ｇは、互いに同一であっても異なっていてもよく、水素原子又は以下の式（２）：

で表されるグリシジルオキシ基であり、但し、式（１）中のＧの少なくとも２つは前記式（２）で表されるグリシジルオキシ基であり、ｎは０〜１０の整数である）で表されるナフタレン型エポキシ樹脂を含有する、一液型熱硬化性樹脂組成物。

〔２〕前記式（１）中、Ｒが、互いに同一であっても異なっていてもよく、置換基を有していても有していなくてもよい、炭素数８〜１４のジアルキルフェニレン基又は炭素数１〜１０のアルキレン基である、前記〔１〕に記載の樹脂組成物。
〔３〕さらに、固体分散型潜在性硬化促進剤を含有する、前記〔１〕又は〔２〕のいずれか１項に記載の樹脂組成物。
〔４〕さらに、ボレート化合物、チタネート化合物、アルミネート化合物、ジルコネート化合物、イソシアネート化合物、カルボン酸、酸無水物及びメルカプト有機酸から選択される１以上を含有する、前記〔１〕〜〔３〕のいずれか１項に記載の樹脂組成物。
〔５〕前記一液型熱硬化性樹脂組成物の硬化物をＪＩＳ−Ｋ−７２４４−４に従い測定されたガラス転移温度が４０〜２００℃である、前記〔１〕〜〔４〕のいずれか１項に記載の樹脂組成物。
〔６〕前記一液型熱硬化性樹脂組成物の硬化物を120℃、85%RHの条件下２４時間放置後に、ＪＩＳ−Ｋ−６８５０に従い測定される引っ張りせん断接着強さB（N/mm²）が８以上である前記〔１〕〜〔５〕のいずれか１項に記載の樹脂組成物。
〔７〕前記一液型熱硬化性樹脂組成物の硬化物をＪＩＳ−Ｋ−６８５０に従い測定される引っ張り接着強さA(N/mm²)と、前記一液型熱硬化性樹脂組成物の硬化物を120℃、85%RHの条件下２４時間放置後に、ＪＩＳ−Ｋ−６８５０に従い測定される引っ張りせん断接着強さB(N/mm²)とから算出される、前記一液型熱硬化性樹脂組成物の硬化物の強度保持率（B/A）が０．４より大きい前記〔１〕〜〔６〕のいずれか１項に記載の樹脂組成物。
〔８〕前記〔１〕〜〔７〕のいずれかに記載の樹脂組成物を含有する接着剤。
〔９〕前記〔１〕〜〔７〕のいずれかに記載の樹脂組成物を含有する封止用材料。
〔１０〕前記〔１〕〜〔７〕のいずれかに記載の樹脂組成物を加熱することによって得られる硬化物。
〔１１〕さらに、ビスフェノールＡ型エポキシ樹脂を含む、〔１〕〜〔７〕のいずれか１項に記載の樹脂組成物。
〔１２〕前記ナフタレン型エポキシ樹脂と前記ビスフェノールＡ型エポキシ樹脂との質量比が、［ナフタレン型エポキシ樹脂］：［ビスフェノールＡ型エポキシ樹脂］＝１０：１〜１：１０である、〔１１〕に記載の樹脂組成物。 As a result of intensive studies to solve the above problems, the present inventors have found that a curable resin composition containing tris (3-mercaptopropyl) isocyanurate and an epoxy resin, the curable resin composition The one-pack type thermosetting resin composition in which the glass transition temperature of the cured product is 40 to 200 ° C. solved the above problem.
That is, the present invention can be as follows.
[1] Tris (3-mercaptopropyl) isocyanurate and an epoxy resin are represented by the formula (1):

(In the formula (1), R may be the same or different from each other, and may or may not have a substituent, a divalent hydrocarbon group having 1 to 30 carbon atoms. G may be the same as or different from each other, and may be a hydrogen atom or the following formula (2):

Wherein at least two of G in the formula (1) are glycidyloxy groups represented by the formula (2), and n is an integer of 0 to 10. A one-pack type thermosetting resin composition containing a represented naphthalene type epoxy resin.

[2] In the formula (1), R may be the same or different from each other, and may or may not have a substituent, a dialkylphenylene group having 8 to 14 carbon atoms. Or the resin composition as described in said [1] which is a C1-C10 alkylene group.
[3] The resin composition according to any one of [1] or [2], further comprising a solid dispersion type latent curing accelerator.
[4] The above-mentioned [1] to [3], further comprising one or more selected from a borate compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, a carboxylic acid, an acid anhydride, and a mercapto organic acid. The resin composition according to any one of the above.
[5] Any one of [1] to [4] above, wherein the cured product of the one-component thermosetting resin composition has a glass transition temperature measured according to JIS-K-7244-4 of 40 to 200 ° C. 2. The resin composition according to item 1.
[6] Tensile shear adhesive strength B (N / mm) measured according to JIS-K-6850 after leaving the cured product of the one-component thermosetting resin composition at 120 ° C. and 85% RH for 24 hours. ² ) The resin composition according to any one of [1] to [5], in which 8 or more.
[7] A cured product of the one-component thermosetting resin composition is obtained by using a tensile adhesive strength A (N / mm ² ) measured according to JIS-K-6850, and the one-component thermosetting resin composition. The one-component thermosetting calculated from the tensile shear adhesive strength B (N / mm ² ) measured according to JIS-K-6850 after leaving the cured product at 120 ° C. and 85% RH for 24 hours. The resin composition according to any one of [1] to [6], wherein the strength retention (B / A) of the cured product of the conductive resin composition is greater than 0.4.
[8] An adhesive containing the resin composition according to any one of [1] to [7].
[9] A sealing material containing the resin composition according to any one of [1] to [7].
[10] A cured product obtained by heating the resin composition according to any one of [1] to [7].
[11] The resin composition according to any one of [1] to [7], further comprising a bisphenol A type epoxy resin.
[12] A mass ratio of the naphthalene type epoxy resin and the bisphenol A type epoxy resin is [naphthalene type epoxy resin]: [bisphenol A type epoxy resin] = 10: 1 to 1:10, The resin composition as described.

  The one-component thermosetting resin composition of the present invention is an epoxy resin composition that ensures low temperature curability and high adhesive strength. The curable resin composition of the present invention is also a curable resin composition that achieves both low-temperature curability and moisture resistance. The epoxy resin composition of the present invention is excellent in low-temperature curability and moisture resistance, and has an excellent glass transition temperature of, for example, about 40 to 200 ° C., and therefore can be used for adhesives and sealing materials. Furthermore, it can be used for applications such as die attach materials and underfill materials. Here, the “one-pack type” thermosetting resin composition is a composition in which a curing agent and an epoxy resin are mixed in advance, and a composition having a property of being cured by applying heat to the composition. means.

トリス（３−メルカプトプロピル）イソシアヌレートは、エポキシ樹脂の硬化剤として作用する。
トリス（３−メルカプトプロピル）イソシアヌレートの含有量は、本発明の一液性熱硬化性樹脂組成物に含まれる全エポキシ樹脂を１００質量部とした場合、例えば１０〜１００質量部、好ましくは、２０〜９０質量部、より好ましくは、３０〜８０質量部、さらに好ましくは、４０〜７５質量部である。[Tris (3-mercaptopropyl) isocyanurate (TMPIC)]
Tris (3-mercaptopropyl) isocyanurate contained in the one-component thermosetting resin composition of the present invention is a thiol compound that can be represented by the following structural formula.

Tris (3-mercaptopropyl) isocyanurate acts as a curing agent for epoxy resins.
The content of tris (3-mercaptopropyl) isocyanurate is, for example, 10 to 100 parts by mass when the total epoxy resin contained in the one-part thermosetting resin composition of the present invention is 100 parts by mass, It is 20-90 mass parts, More preferably, it is 30-80 mass parts, More preferably, it is 40-75 mass parts.

[Epoxy resin]
The epoxy equivalent of the epoxy resin contained in the one-component thermosetting resin composition of the present invention is, for example, preferably 150 to 1000, more preferably 200 to 800, and more preferably 300 to 600. If the epoxy equivalent of the epoxy resin is 200 or more, the volatility is low, the viscosity is not low, and the viscosity is easy to handle. Moreover, if the epoxy equivalent of an epoxy resin is 1000 or less, it does not become high viscosity and is suitable in terms of handling. Here, the epoxy equivalent is the mass of an epoxy resin containing one equivalent of an epoxy group, and can be measured according to, for example, JIS K 7236 (2009).

上記エポキシ基（グリシジルオキシ基）は、エポキシ樹脂中に少なくとも２つ、好ましくは、２〜２２、より好ましくは、２〜１２含む。エポキシ基は、エポキシ樹脂のどの部分に結合してもよいが、好ましくは、ナフタレン環に直接又はナフタレン環上の置換基を介して間接的に当該ナフタレン環に結合していることが適当である。 Epoxy resins of the present invention preferably contains a naphthalene-type epoxy resin. More specifically, it is suitable that the epoxy resin contains (1) two or more epoxy groups and (2) one or more naphthalene rings.
(1) The epoxy group referred to as “two or more epoxy groups” is a monovalent group (glycidyloxy group) represented by the following formula.

The epoxy group (glycidyloxy group) contains at least two, preferably 2 to 22, more preferably 2 to 12 in the epoxy resin. The epoxy group may be bonded to any part of the epoxy resin, but is preferably bonded to the naphthalene ring directly or indirectly through a substituent on the naphthalene ring. .

(2) One or more naphthalene rings The said naphthalene ring contains at least 1 in the epoxy resin, Preferably it is 1-11, More preferably, it contains 1-6.
When a plurality of naphthalene rings are present, each naphthalene ring may be bonded by a single bond or a divalent hydrocarbon group. Here, as the divalent hydrocarbon group, for example, an alkylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, an alkynylene group, a cycloalkynylene group, an alkapolyene having 1 to 30 carbon atoms excluding a substituent. Examples include a nylene group, an alkadiinylene group, an alkatriinylene group, a divalent aryl group, a dialkylaryl group, and the like, and an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, and a dialkylphenylene group are preferable. Examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group. , Pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group and the like. Preferred divalent hydrocarbon groups include dialkylphenylene groups having 8 to 14 carbon atoms or alkylene groups having 1 to 10 carbon atoms. More preferred divalent hydrocarbon groups include methylene groups and ethylene. Group, propylene group, phenylene group, dimethylphenylene group, diethylphenylene group and dimethylphenylene group.

The naphthalene ring and the divalent hydrocarbon group may have a substituent.
Examples of the substituent include a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a monovalent heterocyclic group, amino And a group selected from a group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group.
As a halogen atom used as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

  The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-14, still more preferably 1-12, even more preferably 1-6, and particularly preferably 1-3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. And decyl group. As will be described later, the alkyl group used as a substituent may further have a substituent (“secondary substituent”). Examples of such an alkyl group having a secondary substituent include an alkyl group substituted with a halogen atom, specifically, a trifluoromethyl group, a trichloromethyl group, a tetrafluoroethyl group, a tetrachloroethyl group, and the like. Is mentioned.

  The number of carbon atoms of the cycloalkyl group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  The alkoxy group used as a substituent may be either linear or branched, and the number of carbon atoms of the alkoxy group is preferably 1-20, preferably 1-12, more preferably 1-6. is there. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, Examples include octyloxy group, nonyloxy group, and decyloxy group.

  The number of carbon atoms of the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkyloxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

  The aryl group used as a substituent is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms of the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 12. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

  The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 12. Examples of the aryloxy group used as a substituent include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

  The number of carbon atoms of the arylalkyl group used as a substituent is preferably 7 to 25, more preferably 7 to 19, and still more preferably 7 to 13. Examples of the arylalkyl group include a phenyl-C1-C12 alkyl group, a naphthyl-C1-C12 alkyl group, and an anthracenyl-C1-C12 alkyl group.

  The number of carbon atoms of the arylalkoxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, and still more preferably 7 to 13. Examples of the arylalkoxy group include a phenyl-C1 to C12 alkoxy group and a naphthyl-C1 to C12 alkoxy group.

  The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom on a heterocyclic ring from a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3-21, more preferably 3-15, and still more preferably 3-9. The monovalent heterocyclic group includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocyclic ring include thienyl group, pyrrolyl group, furyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group, and isoquinolyl group. .

  The amino group used as a substituent may be linear or branched aliphatic or aromatic. The number of carbon atoms of the amino group is preferably 1-20, preferably 1-12, more preferably 1-6. Examples of the amino group include aminomethyl group, aminoethyl group, aminopropyl group, isopropylamino group, aminobutoxy group, sec-butylamino group, isobutylamino group, tert-butylamino group, aminopentyl group, and aminohexyl. Group, aminoheptyl group, aminooctyl group, aminononyl group, aminodecyl group, aminophenyl group and the like.

  The silyl group used as a substituent may be either linear or branched. The number of carbon atoms of the silyl group is preferably 1-20, preferably 1-12, more preferably 1-6. Examples of the silyl group include methylsilyl group, ethylsilyl group, propylsilyl group, isopropylsilyl group, butoxysilyl group, sec-butylsilyl group, isobutylsilyl group, tert-butylsilyl group, pentylsilyl group, hexylsilyl group, heptylsilyl. Group, octylsilyl group, nonylsilyl group, and decylsilyl group.

  The acyl group used as a substituent refers to a group represented by the formula: —C (═O) —R1 (wherein R1 is an alkyl group or an aryl group). The alkyl group represented by R1 may be either linear or branched. Examples of the aryl group represented by R1 include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms of the acyl group is preferably 2 to 20, more preferably 2 to 13, and further preferably 2 to 7. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group.

  The acyloxy group used as a substituent refers to a group represented by the formula: —O—C (═O) —R 2 (wherein R 2 is an alkyl group or an aryl group). The alkyl group represented by R2 may be either linear or branched. Examples of the aryl group represented by R2 include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms of the acyloxy group is preferably 2 to 20, more preferably 2 to 13, and further preferably 2 to 7. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group.

式（１）中、Ｒは、互いに同一であっても異なっていてもよく、置換基を有していても有していなくてもよい、炭素数１〜３０の二価の炭化水素基であり、ここで炭素数は置換基部分の炭素を除く炭素数を意味する。Ｒは、好ましくは、炭素数１〜２０、より好ましくは１〜１５である二価の炭化水素基である。Ｒが芳香族基を含まない場合、置換基を除く炭素数は１〜１５、好ましくは、１〜１０、より好ましくは１〜５であることが適当である。
ここで、「二価の炭化水素基」は、上述したナフタレン環の二価の炭化水素基として列挙されたものを使用することができる。Ｒとして好ましくは、炭素数が８〜１４のジアルキルフェニレン基又は炭素数１〜１０のアルキレン基であり、より好ましくはメチレン基、エチレン基、プロピレン基、フェニレン基、ジメチルフェニレン基、ジエチルフェニレン基、ジメチルフェニレン基であり、特に好ましくは、メチレン基又はジメチルフェニレン基である。The one-pack type thermosetting resin composition of the present invention preferably contains a naphthalene type epoxy resin represented by the following formula (1) as an epoxy resin.

In formula (1), R may be the same or different from each other, and may be a divalent hydrocarbon group having 1 to 30 carbon atoms that may or may not have a substituent. Yes, where the carbon number means the carbon number excluding the carbon of the substituent portion. R is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms. When R does not contain an aromatic group, the number of carbon atoms excluding the substituent is 1-15, preferably 1-10, more preferably 1-5.
Here, as the “divalent hydrocarbon group”, those listed as the divalent hydrocarbon group of the naphthalene ring described above can be used. R is preferably a dialkylphenylene group having 8 to 14 carbon atoms or an alkylene group having 1 to 10 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, a phenylene group, a dimethylphenylene group, a diethylphenylene group, A dimethylphenylene group, particularly preferably a methylene group or a dimethylphenylene group.

Examples of R include the following structures.

  When several R exists in Formula (1), R may mutually be same or different. R may or may not have a substituent. Here, as the substituent, those listed as the substituents of the naphthalene ring and the hydrocarbon group described above can be used. A substituent for R is preferably a halogen atom, a methyl group, an ethyl group, a propyl group, or a hydroxy group.

で表されるグリシジルオキシ基であり、但し、式（１）中のＧの少なくとも２つは前記式（２）で表されるグリシジルオキシ基である。
式（１）中、ｎは０〜１０、好ましくは０〜７、より好ましくは１〜５の整数である。 In formula (1), G may be the same as or different from each other, and may be a hydrogen atom or the following formula (2):

In a glycidyl group represented, provided that at least two G in formula (1) is a glycidyl group represented by the formula (2).
In formula (1), n is an integer of 0 to 10, preferably 0 to 7, and more preferably 1 to 5.

Particularly preferred naphthalene type epoxy resins are those in which, in the above formula (1), G is a glycidyloxy group represented by the formula (2), R is a methylene group or a dimethylphenylene group, and n is 0-10. It is an epoxy resin.
Specific naphthalene type epoxy resins that can be used in the present invention include, for example, HP-4032D manufactured by DIC Corporation, EXA-4710 manufactured by DIC Corporation, and ESN-475V manufactured by Nippon Steel & Sumikin Co., Ltd.

  The one-component thermosetting resin composition of the present application may be prepared by adding various epoxy resins as long as the glass transition temperature of the resin composition of the resin composition is in the desired range in addition to or instead of the naphthalene-type epoxy resin. Can be used. For example, polyglycidyl ether obtained by reacting polychlorophenol such as bisphenol A, bisphenol F, bisphenol AD, catechol and resorcinol, polyhydric alcohol such as glycerin and polyethylene glycol, and epichlorohydrin; p-hydroxybenzoic acid Polyglycidyl ether ester obtained by reacting a hydroxy acid such as β-hydroxynaphthoic acid with epichlorohydrin; obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin Polyglycidyl esters; epoxidized phenol novolak resins, epoxidized cresol novolac resins, epoxidized polyolefins, cycloaliphatic epoxy resins, and other urethane-modified epoxy resins; The present invention is not limited.

  From the viewpoint of maintaining high heat resistance and low moisture permeability, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, Phenol aralkyl type epoxy resins, aromatic glycidyl amine type epoxy resins, and epoxy resins having a dicyclopentadiene structure are preferred, bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferred, and bisphenol A type epoxy resins are more preferred.

Also these resins is a liquid, it may be a solid. Or it may be a mixture of a liquid resin and solid resin. Here, “liquid” and “solid” refer to the state of the epoxy resin at room temperature (25 ° C.). From the viewpoints of coatability, workability, and adhesiveness, it is preferable that at least 10% by mass or more of the entire epoxy resin used is a liquid epoxy resin.
Specific examples of such resins include bisphenol A type (hereinafter sometimes abbreviated as BPA type) epoxy resins (“JER828EL”, “JER827”, “JER1001” manufactured by Mitsubishi Chemical Corporation), and bisphenol F type epoxy resins (manufactured by Mitsubishi Chemical Corporation). “JER807”), bisphenol AF type epoxy resin (“ZX1059” manufactured by Tohto Kasei Co., Ltd.), cresol novolac type epoxy resin (manufactured by DIC, N-695), hydrogenated epoxy resin (“YX8000 manufactured by Mitsubishi Chemical Corporation”) ”), Dicyclopentadiene type polyfunctional epoxy resin (“ HP7200 ”manufactured by DIC), epoxy resin having butadiene structure (“ PB-3600 ”manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having biphenyl structure (Nippon Kayaku) the company made "NC3000H", "NC3000L", Mitsubishi Gakusha made "YX4000"), and the like. Among them, it is preferable to use a BPA type epoxy resin having high heat resistance and low viscosity. “JER828EL”, “JER827”, “JER1001” and “JER807” manufactured by Mitsubishi Chemical Corporation are preferable, and “JER828EL” is more preferable. .

  When using BPA type epoxy resin in addition to naphthalene type epoxy resin, the mass ratio of naphthalene type epoxy resin and BPA type epoxy resin is, for example, naphthalene type epoxy resin: BPA type epoxy resin = 10: 1 to 1:10, Preferably, it is 10: 1 to 1: 2, more preferably 9: 1 to 1: 1, and still more preferably 8: 1 to 2: 1.

[Other additives]
The curable resin composition of the present invention is optionally a curing agent for epoxy resins other than TMPIC, a curing accelerator, a storage stability improver, a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, and a coupling agent. Various additives such as an antioxidant, a thixotropic agent, and a dispersant can be added.

  Examples of curing agents for epoxy resins other than TMPIC include imidazole curing agents and amine curing agents. Furthermore, thiol compounds other than TMPIC, such as 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 the like by an esterification reaction of a mercapto organic acid The resulting thiol compound can also be used as a curing agent for epoxy resins.

  Examples of the curing accelerator that can be used in the present invention include a solid dispersion type latent curing accelerator. The solid dispersion type latent curing accelerator is a compound that is insoluble in the above-mentioned epoxy resin at room temperature (25 ° C.), solubilized 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 dispersion type amine adduct-based latent curing accelerators include reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems), reaction products of amine compounds and isocyanate compounds or urea compounds (urea type). Adduct system). Among these, a solid dispersion type amine adduct-based latent curing accelerator is preferable.

  Examples of the imidazole compound that is solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 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-trimellitate 1-cyanoethyl-2-phenylimidazole-trimellitate, N- (2-methylimidazolyl-1-ethyl) -urea, N, N ′-(2-methylimidazolyl- (1) -ethyl) -adiboyldiamide and the like However, it is not limited to these.

  Examples of the epoxy compound used as one of the raw materials for producing the solid dispersion type amine adduct-based latent curing accelerator (amine-epoxy adduct system) include polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or A 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 A glycidyl ether ester obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin; and an epic with 4,4′-diaminodiphenylmethane or m-aminophenol. A glycidylamine compound obtained by reacting with rhohydrin; a polyfunctional epoxy compound such as an epoxidized phenol novolak resin, an epoxidized cresol novolak resin, or an epoxidized polyolefin, or a simple substance such as butyl glycidyl ether, phenyl glycidyl ether, or glycidyl methacrylate. Functional epoxy compounds; and the like, but are not limited thereto.

  The amine compound used as a raw material for producing the solid dispersion type amine adduct-based latent curing accelerator has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule, and has a primary amino group and a secondary amino group. And at least one functional group selected from tertiary amino groups in the molecule. 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 and 2-methylaniline; nitrogen such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine and piperazine Examples thereof include, but are not limited to, heterocyclic compounds containing atoms.

  Among them, a compound having a tertiary amino group in the molecule is a raw material that provides a latent curing accelerator having excellent curing acceleration ability. Examples of such a compound include dimethylaminopropyl. Amine compounds such as amine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, 2-methylimidazole, 2-ethylimidazole, 2- Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as ethyl-4-methylimidazole and 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-phenoxy) Propyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methyl Imidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4 , 6-Tris (dimethylaminomethyl) phenol, N-β-hy Droxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N, N-dimethylglycine hydrazide, N, N-dimethylpropionic hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, etc. And alcohols having amino groups, phenols, thiols, carboxylic acids and hydrazides.

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

  Examples of the isocyanate compound used as a raw material for producing the solid dispersion type amine adduct-based latent curing accelerator include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; hexamethylene diisocyanate, Range isocyanate (example: 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1 , 3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate and other polyfunctional isocyanate compounds; Obtained by reaction of these polyfunctional isocyanate compound and active hydrogen compound, terminal isocyanate group-containing compounds; and the like can also be used. 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 trimethylolpropane, and a terminal isocyanate group obtained by the reaction of tolylene diisocyanate and pentaerythritol. However, the present invention is not limited thereto.

  Examples of the urea compound used as a raw material for producing the solid dispersion type amine adduct-based latent curing accelerator include urea and thiourea, but are not limited thereto.

  The solid dispersion type latent curing accelerator may be prepared by, for example, appropriately mixing the above-mentioned production raw materials and reacting at room temperature to 200 ° C. and then cooling and solidifying, or pulverizing, or methyl ethyl ketone, dioxane, tetrahydrofuran It can be easily obtained by pulverizing the solid content after the reaction in a solvent such as

  As a typical example marketed as the above-mentioned solid dispersion type latent curing accelerator, for example, as an amine-epoxy adduct system (amine adduct system), “Amure PN-23”, “Amure Cure” manufactured by Ajinomoto Fine Techno Co., Ltd. PN-H ”,“ Hardner X-3661S ”,“ Hardner X-3670S ”manufactured by ARC,“ Novacure HX-3742 ”,“ Novacure HX-3721 ”manufactured by Asahi Kasei Co., Ltd., and urea Examples of the mold adduct system include “FXE-1000” and “FXR-1030” manufactured by T & K TOKA, but are not limited thereto.

  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 more preferable.

  The storage stability improver that can be used in the present invention may be added in order to realize the excellent storage stability of the curable 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 trimethyl borate, 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, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m- Trilbo Chromatography, tri ethanol amine borate, and the like.

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

  Examples of the aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, and trioctyl aluminate.

  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-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, Examples 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 caprylic acid, unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid and crotonic acid, and monochloro. Halogenated fatty acids such as acetic acid and dichloroacetic acid, monobasic oxyacids such as glycolic acid and lactic acid, aliphatic aldehyde acids such as glyoxalic acid and glucose, ketonic acid, oxalic acid, malonic acid, succinic acid and maleic acid Examples include aliphatic polybasic acids, benzoic acids, halogenated benzoic acids, toluic acid, aromatic monobasic acids such as phenylacetic acid, cinnamic acid, and mandelic acid, and aromatic polybasic acids such as phthalic acid and trimesic acid. .

  Examples of the acid anhydride include aliphatic or aliphatic polysuccinic anhydrides such as succinic anhydride, dodecynyl succinic anhydride, maleic anhydride, an adduct of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Examples include basic acid anhydrides, aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. As a typical example marketed as an acid anhydride, for example, 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, is used. Although it is mentioned, it is not limited to this.

  Examples of the mercapto organic acid include mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, dimercaptosuccinic acid and other mercaptoaliphatic monocarboxylic acids, and esterification reaction of hydroxy organic acid and mercapto organic acid. And mercapto aromatic monocarboxylic acids such as mercapto aliphatic monocarboxylic acid and mercaptobenzoic acid.

  Among these, as the storage stability improver, borate compounds are preferable from the viewpoint of high versatility and safety, and improvement in storage stability. Triethyl borate, tri-n-propyl borate, triisopropyl borate, tri- n-Butyl borate is more preferable, and triethyl borate is more preferable. The content of the storage stability improver is not particularly limited as long as the storage stability of the epoxy resin is increased, but when the total content of the epoxy resin is 100 parts by mass, the content of the storage stability improver is It is preferable that it is 0.001-50 mass parts, It is more preferable that it is 0.05-30 mass parts, It is further more preferable that it is 0.1-10 mass parts.

  The curable resin composition of the present invention can be produced from the above-described tris (3-mercaptopropyl) isocyanurate, epoxy resin, and various additives as optional components. The preparation of the curable resin composition is not particularly difficult and can be performed according to a conventionally known method. For example, each component can be mixed with mixers, such as a Henschel mixer, and the one-component thermosetting epoxy resin composition of this invention can be prepared.

Moreover, the obtained one-component thermosetting resin composition can be cured without any particular difficulty and can also be performed according to a conventionally known method. For example, the obtained curable resin composition can be cured by heating. The heating is, for example, 60 to 150 ° C., preferably 75 to 120 ° C., more preferably 80 to 100 ° C., for example, 1 to 60 minutes, preferably 3 to 30 minutes, more preferably 5 to 15 It is appropriate to do this for minutes. In particular, if it is cured by heating at 80 ° C. or 100 ° C. for 10 minutes or less, it can be judged that there is an appropriate low-temperature fast curing property.
Examples of the thixotropic property-imparting agent include fine powder silica, fatty acid amide, polyolefin polymer and the like. Specifically, fine powder silica “AEROSIL 200” (manufactured by Nippon Aerosil Co., Ltd.), “AEROSIL R805” (manufactured by Nippon Aerosil Co., Ltd.), or the like can be used.

[Characteristics of one-component thermosetting resin composition]
-Glass transition temperature As for the hardened | cured material of the one-pack type thermosetting resin composition of this invention, it is suitable that the glass transition temperature measured by the JIS-K-7244-4 is 40-200 degreeC, for example. . Such a glass transition temperature is preferable because it can protect electronic components from temperature and humidity and mechanical external force. The glass transition temperature of a preferable cured product is, for example, 45 to 180 ° C, and more preferably 50 to 160 ° C. Here, the glass transition temperature of the cured product is a peak temperature of a tan δ curve obtained by measuring a resin composition sample cured under a predetermined condition with DMA.

Tensile shear adhesive strength A (maximum load / adhesive area)
The one-component thermosetting resin composition of the present invention is sometimes referred to as tensile shear adhesive strength (hereinafter referred to as tensile shear adhesive strength A) measured by JIS-K-6850 determined from the maximum load / adhesive area. there), for example 12N / mm ² or more, and preferably be 12.5~50N / mm ^2, more preferably 13~30N / mm ^2, more preferably from 14~20N / mm ^2. Here, the tensile adhesive strength (tensile adhesive strength A) can be measured as follows. First, a test piece of mild steel plate (JISG3141, SPCC) is wiped off with a cloth moistened with acetone, and the surface of the bonded surface of the mild steel plate is polished with an endless belt # 120. The resin composition is uniformly applied to the polished surface of the mild steel sheet with a thickness of about 1 mm, and the coated surface is bonded with two clips with an overlap of about 12.5 mm and pressed. At this time, it is better to immediately wipe off the exuded resin composition with a waste cloth. Align the test pieces evenly in an oven, heat cure at 80 ° C. for 60 minutes, and bond. The tensile strength of the obtained specimen is measured with a Tensilon universal testing machine (UTM-5T manufactured by TOYO BALDWIN) (measuring environment: temperature 25 ° C./humidity 40%, tensile speed: 5 mm / min). For measuring the tensile shear bond strength A, it is appropriate to prepare three test pieces for each of the same resin composition.
Based on the maximum load (N) at which the test piece was broken, the adhesion area (mm ² ) was measured, and the tensile shear bond strength A was calculated from the following formula.
Tensile shear bond strength (N / mm ² ) = Maximum load (N) / bond area (mm ² )

Tensile shear adhesive strength B (high humidity test)
Tensile strength (hereinafter referred to as tensile shear bond strength B) when the test of tensile shear bond strength A measured according to JIS-K-6850 is repeated after standing for a certain period of time under high humidity. ), for example, 8N / mm ² or more, preferably 10 N / mm ² or more, more preferably 11~50N / mm ^2, more preferably it is suitable to be 12~30N / mm ^2. This tensile shear bond strength B is performed in order to evaluate the moisture resistance of the one-pack type thermosetting resin composition. Here, the tensile strength (tensile shear bond strength B) under the high humidity can be measured as follows. That is, three test pieces separately prepared in the same procedure as the adhesive evaluation are prepared. After leaving it in a pressure cooker tester set at 120 ° C and 85% RH for 24 hours, the resulting specimen is tested with Tensilon Universal Tester (UTM-5T manufactured by TOYO BALDWIN) in the same manner as the adhesion test. The tensile bond strength is measured (measuring environment: temperature 25 ° C./humidity 40%, pulling speed: 5 mm / min). Based on the maximum load (N) at which the test piece was broken, the adhesion area (mm ² ) was measured, and the tensile shear bond strength B was calculated in the same manner as the evaluation of adhesion.

Strength retention The strength retention of the one-component thermosetting resin composition of the present invention is
[Strength retention] = [Tensile shear adhesive strength B] / [Tensile shear adhesive strength A]
For example, it is larger than 0.4, preferably 0.5 or more, more preferably 0.6 to 2.0, and still more preferably 0.7 to 1.6. By the strength retention ratio can humidity to evaluate the effect on bond strength. It can be said that the larger the strength retention value, the more resistant the test piece is to high humidity.

[Cured epoxy resin, adhesive, sealing material, etc.]
The epoxy resin cured product obtained by heating the one-component thermosetting resin composition is also included in the present invention, and a functional product containing the epoxy resin cured product is also included. Examples of the functional product include an adhesive, a casting agent, a sealing material, a sealing agent, a fiber-reinforced resin, a coating agent, or a paint.

Especially, this invention relates to the adhesive agent containing the one-component thermosetting resin composition mentioned above. Here the adhesive is an adhesive that can be used in the field of electronic components of the adhesive. The adhesive is preferably a one-component epoxy resin adhesive in which a curing agent and an epoxy resin composition are mixed in advance.
In addition to the one-component thermosetting resin composition of the present invention, the adhesive is optionally a curing agent for epoxy resins other than TMPIC, a curing accelerator, a flame retardant, a storage stability improver, a filler, a diluent, Various additives such as a solvent, a pigment, a flexibility imparting agent, a coupling agent, an antioxidant, a thixotropic property imparting agent, and a dispersant may be included.

The present invention also relates to a sealing material containing the above-described one-component thermosetting resin composition. Here, the sealing material is a sealing material such as an underfill agent or a chip-on-board sealant for flip chip mounting.
In addition to the curable resin composition of the present invention, the sealing material is optionally an epoxy resin curing agent other than TMPIC, a curing accelerator, a flame retardant, a storage stability improver, a filler, a diluent, a solvent, Various additives such as a pigment, a flexibility imparting agent, a coupling agent, an antioxidant, a thixotropic property imparting agent, and a dispersing agent may be included.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to a following example. In the following description, “part” means “part by mass”.

[Preparation of one-component thermosetting resin composition]
Each resin composition of the formulation composition shown in Table 1 were prepared. Weigh out the specified amount of material shown in Table 1 into a dedicated plastic container, and then use a rotating / revolving vacuum mixer Awatori Rentaro (ARE-250) at 2000 rpm at room temperature (25 ° C). And thoroughly defoaming for 1 minute to obtain the desired resin composition.
The details of the materials used are as follows.
HP-4032D: manufactured by DIC Corporation, naphthalene type epoxy resin, epoxy equivalent 172 g / eq

（ＥＸＡ４７１０）EXA4710: manufactured by DIC Corporation, naphthalene type novolac epoxy resin, epoxy equivalent of 171 g / eq

(EXA4710)

（ＥＳＮ−４７５V）ESN-475V manufactured by Nippon Steel & Sumikin Co., Ltd., naphthalene type novolac epoxy resin, epoxy equivalent 190 g / eq

(ESN-475V)

Ｎ−６９５：ＤＩＣ社製、クレゾールノボラック型エポキシ樹脂

ＴＭＰＩＣ：味の素ファインテクノ社製、トリス(3-メルカプトプロピル)イソシアヌレート、チオール基合計当量１１７ｇ／ｅｑ
ＴＭＴＰ：淀化学社製、トリメチロールプロパン トリス（３−メルカプトプロピオネート、チオール基合計当量１３３ｇ／ｅｑ
ＰＮ−２３：味の素ファインテクノ社製、アミンエポキシアダクト系硬化剤
ＦＸＲ−１０８１：Ｔ＆Ｋ ＴＯＫＡ社製、変性ポリアミン系潜在性硬化剤
ＡＥＲＯＳＩＬ ２００：日本アエロジル社製、微粒シリカ
ＴＥＢ：純正化学工業社製、トリエチルボレート
ＨＮ−２２００：日立化成工業社製、3又は4-メチル-1,2,3,6-テトラヒドロ無水フタル酸（チオール基合計当量＝１当量のチオール基を含むチオール基含有化合物の質量）JER828EL: Mitsubishi Chemical Corporation, bisphenol A type (BPA type) epoxy resin, epoxy equivalent of 190 g / eq

N-695: manufactured by DIC, cresol novolac type epoxy resin

TMPIC: Ajinomoto Fine Techno Co., Ltd., tris (3-mercaptopropyl) isocyanurate, total thiol group equivalent weight 117 g / eq
TMTP: manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate, thiol group total equivalent 133 g / eq
PN-23: manufactured by Ajinomoto Fine Techno Co., Ltd., amine epoxy adduct curing agent FXR-1081: manufactured by T & K TOKA, modified polyamine latent curing agent AEROSIL 200: manufactured by Nippon Aerosil Co., Ltd., fine silica TEB: manufactured by Pure Chemical Industries, Triethylborate HN-2200: manufactured by Hitachi Chemical Co., Ltd., 3 or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride (total thiol group equivalent = mass of thiol group-containing compound containing 1 equivalent of thiol group)

[Thiol / epoxy equivalent ratio]
The “thiol / epoxy equivalent ratio” in Table 1 was determined from the following formula.
“Thiol / epoxy equivalent ratio” = (thiol mass ÷ thiol group total equivalent) ÷ (epoxy resin mass ÷ epoxy equivalent)
[Measurement of viscosity]
A cone rotor (rotor code No. 6, 3 ° x R9.7) is attached to a RE80 viscometer (manufactured by Toki Sangyo Co., Ltd.), and 0.2 to 0.3 ml of the resin composition to be measured is syringed into the measurement chamber. Weighed in. During measurement, the temperature of the viscometer measurement chamber was controlled at 25.0 ° C. in an external circulation thermostat. The rotation speed of the rotor was set to 0.5, 10, 20, and 100 rpm, and the viscosity after 120 seconds at each rotation speed was measured (unit: Pa · s).

[Measurement of glass transition temperature]
Using each resin composition obtained in Examples and Comparative Examples, a test piece of 7 mm × 30 mm was prepared and pulled using a DMA measuring apparatus (Seiko Instruments Inc., DMS6100) based on JIS-K-7244-4. Tan δ was measured under the conditions of a method, a frequency of 1 Hz, a heating rate of 2 ° C./min, and a measurement temperature range of 0 ° C. to 300 ° C. The temperature at which a peak appears in the obtained tan δ curve was defined as the glass transition temperature. The unit is ° C.
[Evaluation of low-temperature curability]
The low temperature curability of the resin composition of the present invention was evaluated by measuring the gel time (gelation time) according to JISC6521.
Specifically, first, the time when the resin compositions of each Example and Comparative Example did not draw the yarn at 60 ° C. and 80 ° C. with a hot plate type gelation tester (GT-D: manufactured by Nisshin Kagaku Co., Ltd.). Was measured. Specifically, about 0.5 g of a sample (resin composition) is placed on a hot plate type gelation tester and the starting point is 60 ° C. (60 ° C. gel time) or 80 ° C. (80 ° C. gel time). In order for the resin composition to fall within the range of 25 mm in diameter on the hot plate, the contact composition is repeatedly moved with a spatula having a tip width of 5 mm (one rotation per second), and the resin composition is placed on the hot plate. The measurement was performed by taking the time from the start point to the end point as the time until gelation, with the end point being the time when the thread-like material was cut by 30 mm vertically from the end point. The spatula was not lifted while the resin viscosity was low. When the viscosity increased, the spatula was sometimes lifted about 30 mm vertically from the hot plate, and this vertical movement was repeated until the thread-like material was cut. The measurement was repeated three times and the average value was used.

[Evaluation of adhesive strength]
Tensile Shear Test A test piece of mild steel plate (JISG3141, SPCC) was wiped off with a cloth moistened with acetone. Furthermore, the surface of the bonded surface of the mild steel plate was polished with an endless belt # 120. The resin composition was uniformly applied to the polished surface of the mild steel plate with a thickness of about 1 mm. The coated surface was bonded with two clips with an overlap of about 12 mm and pressed. At this time, the exuded resin composition was immediately wiped off with a waste cloth. The test pieces were evenly arranged in an oven and heat-cured at 80 ° C. for 60 minutes for adhesion. Three test pieces were prepared for the same resin. Tensilen universal testing machine (UTM-5T manufactured by TOYO BALDWIN) was used to measure the tensile shear bond strength of the obtained specimen in accordance with JIS-K-6850 (measuring environment; temperature 25 ° C./humidity 40%). , Pulling speed: 5mm / min).
Based on the maximum load (N) at which the test piece was broken, the adhesion area (mm ² ) was measured, and the tensile shear bond strength A was calculated from the following formula.
Tensile shear bond strength (N / mm ² ) = Maximum load (N) / bond area (mm ² )
[Evaluation of moisture resistance]
Three test pieces prepared separately by the same procedure as the evaluation of adhesiveness were prepared. After leaving it in a pressure cooker tester set at 120 ° C and 85% RH for 24 hours, the resulting specimen is tested with Tensilon Universal Tester (UTM-5T manufactured by TOYO BALDWIN) in the same manner as the adhesion test. The tensile shear bond strength was measured according to JIS-K-6850 (measuring environment: temperature 25 ° C./humidity 40%, pulling speed: 5 mm / min). Based on the maximum load (N) at which the test piece was broken, the adhesion area (mm ² ) was measured, and the tensile shear bond strength B was calculated in the same manner as the evaluation of adhesion.

[Strength retention]
Since humidity to evaluate the effect on the adhesion strength was calculated strength retention rate. The strength retention was calculated from the values of the tensile shear bond strength A and the tensile shear bond strength B as follows.
[Strength retention] = [Tensile shear bond strength B] / [Tensile shear bond strength A]
It can be said that the larger the strength retention value, the more resistant the test piece is to high humidity.
[Consideration of evaluation results]
Table 1 shows the results of the above evaluations. As shown in Table 1, the one-component thermosetting resin compositions of Examples 1 to 9 have better low-temperature curability and better moisture resistance than the resin compositions of Comparative Examples. all right.

（式（１）中、Ｒは、互いに同一であっても異なっていてもよく、置換基を有していても有していなくてもよい、炭素数１〜３０の二価の炭化水素基であり、Ｇは、互いに同一であっても異なっていてもよく、水素原子又は以下の式（２）：

で表されるグリシジルオキシ基であり、但し、式（１）中のＧの少なくとも２つは前記式（２）で表されるグリシジルオキシ基であり、ｎは０〜１０の整数である）で表されるナフタレン型エポキシ樹脂を含有する、［１］〜［３］のいずれか１項に記載の樹脂組成物。
［５］
前記式（１）中、Ｒが、互いに同一であっても異なっていてもよく、置換基を有していても有していなくてもよい、炭素数８〜１４のジアルキルフェニレン基又は炭素数１〜１０のアルキレン基である、［４］に記載の樹脂組成物。
［６］
さらに、固体分散型潜在性硬化促進剤を含有する、［１］〜［５］のいずれか１項に記載の樹脂組成物。
［７］
さらに、ボレート化合物、チタネート化合物、アルミネート化合物、ジルコネート化合物、イソシアネート化合物、カルボン酸、酸無水物及びメルカプト有機酸から選択される１以上を含有する、［１］〜［６］のいずれか１項に記載の樹脂組成物。
［８］
［１］〜［７］のいずれかに記載の樹脂組成物を含有する接着剤。
［９］
［１］〜［７］のいずれかに記載の樹脂組成物を含有する封止用材料。
［１０］
［１］〜［７］のいずれかに記載の樹脂組成物を加熱することによって得られる硬化物。 In Table 1, Examples 1 and 4 to 8 are reference examples outside the scope of the present invention.
The present invention may also be the following aspects.
[1]
A one-component thermosetting resin composition containing tris (3-mercaptopropyl) isocyanurate and an epoxy resin, wherein the glass transition temperature of the resin composition is 40 to 200 ° C. Curable resin composition.
[2]
Resin composition as described in [1] whose epoxy equivalent of the said epoxy resin is 150-1000.
[3]
The resin composition according to [1] or [2], wherein the epoxy resin contains a naphthalene type epoxy resin.
[4]
The epoxy resin has the formula (1):

(In the formula (1), R may be the same or different from each other, and may or may not have a substituent, a divalent hydrocarbon group having 1 to 30 carbon atoms. G may be the same as or different from each other, and may be a hydrogen atom or the following formula (2):

In a glycidyl group represented, provided that at least two G in formula (1) is a glycidyl group represented by the formula (2), n is an integer of 0) The resin composition according to any one of [1] to [3], which contains a represented naphthalene type epoxy resin.
[5]
In the formula (1), Rs may be the same as or different from each other, and may or may not have a substituent, a dialkylphenylene group having 8 to 14 carbon atoms or a carbon number from 1 to 10 alkylene group, the resin composition according to [4].
[6]
Furthermore, the resin composition of any one of [1]-[5] containing a solid dispersion type latent hardening accelerator.
[7]
Furthermore, any 1 item | term of [1]-[6] containing 1 or more selected from a borate compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, carboxylic acid, an acid anhydride, and a mercapto organic acid. The resin composition described in 1.
[8]
An adhesive containing the resin composition according to any one of [1] to [7].
[9]
The sealing material containing the resin composition in any one of [1]-[7].
[10]
Hardened | cured material obtained by heating the resin composition in any one of [1]-[7].

Claims (11)

Tris (3-mercaptopropyl) isocyanurate and an epoxy resin are represented by the formula (1):

(In the formula (1), R may be the same or different from each other, and may or may not have a substituent, a dialkylphenylene group having 8 to 14 carbon atoms or a carbon number. 1 to 10 alkylene groups, G may be the same as or different from each other, and may be a hydrogen atom or the following formula (2):

Wherein at least two of G in the formula (1) are glycidyloxy groups represented by the formula (2), and n is an integer of 1 to 10. A one-component thermosetting resin composition containing a represented naphthalene-type epoxy resin , wherein the cured product of the one-component thermosetting resin composition is measured according to JIS-K-7244-4 A one-component thermosetting resin composition having a transition temperature of 40 to 200 ° C. In the formula (1), Rs may be the same as or different from each other, and may be a dimethylphenylene group or a methylene group, which may or may not have a substituent. The resin composition described in 1. Furthermore, the resin composition of any one of Claim 1 or 2 containing a solid dispersion type | mold latent hardening accelerator. Furthermore, 1 or more selected from a borate compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, carboxylic acid, an acid anhydride, and a mercapto organic acid is contained, The any one of Claims 1-3. Resin composition. The cured product of the one-component thermosetting resin composition is allowed to stand for 24 hours under conditions of 120 ° C. and 85% RH, and has a tensile shear bond strength B (N / mm ² ) measured according to JIS-K-6850. the resin composition according to any one of claims 1-4 8 or more. A cured product of the one-component thermosetting resin composition is a tensile adhesive strength A (N / mm ² ) measured according to JIS-K-6850, and a cured product of the one-component thermosetting resin composition. The one-component thermosetting resin composition calculated from the tensile shear bond strength B (N / mm ² ) measured in accordance with JIS-K-6850 after standing at 120 ° C. and 85% RH for 24 hours. The resin composition according to any one of claims 1 to 5 , wherein the strength retention (B / A) of the cured product is greater than 0.4. Adhesive containing the resin composition according to any one of claims 1-6. The sealing material containing the resin composition in any one of Claims 1-6 . Hardened | cured material obtained by heating the resin composition in any one of Claims 1-6 . Furthermore, the resin composition in any one of Claims 1-6 containing a bisphenol A type epoxy resin. Weight ratio of the bisphenol A type epoxy resin and the naphthalene type epoxy resin, [naphthalene type epoxy resin: [bisphenol A epoxy resin] = 10: 1 to 1: 10, the resin of claim 10 Composition.