JP2014173008A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition excellent in fire resistance and quick curing property.SOLUTION: There is provided a curable resin composition containing (A) an epoxy resin material selected from a mixture of a phosphorus-containing epoxy resin, a mixture of the phosphorus-containing epoxy resin and an epoxy resin having no phosphorus, a mixture of an organic phosphorus compound and the epoxy resin having no phosphorus, and a mixture of the organic phosphorus compound and a phosphorus-containing epoxy resin, (B) a thiol compound having 2 or more thiol groups in a molecule, and (C) a curing accelerator, and having X: the content of a phosphorus atom based on the total mass of (A) to (C) components (mass%) and Y: the content of the sulfur atom based on the total mass of (A) to (C) components (mass%) satisfying the following (I) and (II) formulae: 1≤Y≤14 (I) and 1.056-0.051Y≤X≤2.0 (II).

Description

  The present invention relates to a curable resin composition excellent in flame retardancy and rapid curing. In particular, the present invention relates to a novel epoxy resin composition in which a phosphorus-containing epoxy resin and a thiol compound are combined.

Epoxy resins have been used as curable adhesives by using polymercaptan, polythiol compounds and the like as curing agents. In particular, an epoxy resin composition using a polythiol compound as a curing agent and a reaction product of a compound having an isocyanate group and an amino group as a curing accelerator has good curability and a sufficiently long usable time. It is known to have (Patent Document 1). Furthermore, the epoxy resin composition which improved the low temperature rapid curability and storage stability by adding a boric acid ester compound is also known (patent document 2). Furthermore, the epoxy resin which improved the flame retardance by adding a phosphorus flame retardant is also examined (patent document 3).
However, in order to improve the flame retardancy of epoxy resin, a large amount of phosphorus-based flame retardant is required. On the other hand, epoxy resin containing a large amount of phosphorus-based flame retardant causes a prolonged curing time, and the material There has been a drawback in that the resin fluidity for satisfactorily applying to the substrate is deteriorated.

Japanese Patent Application Laid-Open No. 6-21970 JP-A-11-256013 JP 2012-87226 A

The objective of this invention is providing the curable resin composition excellent in the flame retardance and quick-hardness.
Another object of the present invention is to provide a curable resin composition that does not contain a phosphorus-based flame retardant or has improved flame retardancy while reducing the phosphorus content.
Another object of the present invention is to provide a one-part form containing the curable resin composition in one fraction or a kit containing the curable resin composition in separate fractions, and thermosetting the curable resin composition. It is in providing the epoxy resin hardened | cured material and the electronic component containing the said hardened | cured material, the sealing material containing the said curable resin composition, and an adhesive agent.

The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems. As a result, the epoxy resin material containing phosphorus, a specific thiol compound serving as a curing agent for the epoxy resin material, and curing acceleration for these curings. The present invention was completed by finding that a curable resin composition containing an agent at a specific ratio has immediate curing while maintaining desired flame retardancy.
That is, the present invention can be as follows.
[1] (A) (i) a phosphorus-containing epoxy resin, (ii) a mixture of a phosphorus-containing epoxy resin and a phosphorus-free epoxy resin, (iii) a mixture of an organic phosphorus compound and a phosphorus-free epoxy resin, and (iv) a mixture of an organic phosphorus compound and a phosphorus-containing epoxy resin, an epoxy resin material selected from any one or more of (i) to (iv);
(B) a thiol compound having two or more thiol groups in the molecule, and (C) a curing accelerator, and a phosphorus atom content X (mass%) relative to the total mass of the components (A) to (C); The sulfur atom content Y (% by mass) relative to the total mass of the components (A) to (C) is represented by the following formulas (I) and (II):
1 ≦ Y ≦ 14 (I)
1.056-0.051Y ≦ X ≦ 2.0 (II)
The curable resin composition characterized by satisfy | filling.
[2] The curable resin composition according to [1], wherein the content of phosphorus atoms contained in the component (A) is 0.5 to 40% by mass with respect to the total mass of the component (A).
[3] The (B) thiol compound, -X ₁ -R ⁵ -SH group or
A compound having a group (R ⁵ is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, X ₁ is a divalent group, X ₂ is a trivalent group, -X ₁ -is -O-, One or more selected from —O—CO—, —S—, and —O—Si—,

It is 1 or more types chosen from. Curable resin composition according to [1] or [2].
[4] The (B) thiol compound is
Trimethylolpropane tris (3-mercaptopropionate),
Pentaerythritol tetrakis (3-mercaptopropionate),
Dipentaerythritol hexakis (3-mercaptopropionate),
Pentaerythritol tetrakis (3-mercaptobutyrate),
Trimethylolpropane tris (3-mercaptobutyrate),
Trimethylolethane tris (3-mercaptobutyrate),
Any one of [1] to [3], which is at least one selected from tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and tris (3-mercaptopropyl) isocyanurate Curable resin composition.
[5] Any one of [1] to [4], wherein the component (A) is (i) a phosphorus-containing epoxy resin, or (ii) a mixture of a phosphorus-containing epoxy resin and a phosphorus-free epoxy resin. The curable resin composition according to Item.
[6] The curable resin composition according to any one of [1] to [5], further comprising (D) an inorganic filler.
[7] Further, the following formula (I-2):
2 ≦ Y ≦ 13 (I-2)
The curable resin composition according to any one of [1] to [6], wherein
[8] A kit comprising the curable resin composition according to any one of [1] to [7], wherein the kit comprises a first component containing at least a component (A) and at least (B). And a second component containing the component.
[9] By thermally curing the curable resin composition according to any one of [1] to [7], or by combining the first component and the second component included in the kit according to [8]. Epoxy resin cured product obtained by mixing and thermosetting.
[10] An adhesive comprising the curable resin composition according to any one of [1] to [7] or the kit according to [8].
[11] The adhesive according to [10], which is for electronic parts.
[12] The adhesive according to [10] or [11], wherein the viscosity is 0.1 to 1000 Pa · sec when measured at 25 ° C. using an E-type viscometer.
[13] A sealing material comprising the curable resin composition according to any one of [1] to [7] or the kit according to [8].
[14] The sealing material according to [13], which is for electronic parts.
[15] An electronic component comprising the cured product according to [9].

Further, the present invention may preferably be as follows.
[I] (A) A phosphorus-containing epoxy resin, wherein the phosphorus atom content is 1 to 20% by mass with respect to the total mass of the phosphorus-containing epoxy resin,
(B) Trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) ), Trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, tris (3-mercaptopropyl) One or more selected from isocyanurates,
(C) an imidazole compound or a solid dispersion-type amine adduct-based latent curing accelerator, and (D) spherical silica, and a phosphorus atom content X (mass%) with respect to the total mass of the components (A) to (C) The sulfur atom content Y (% by mass) relative to the total mass of the components (A) to (C) is represented by the following formulas (I-3) and (II-2):
2.5 ≦ Y ≦ 12 (I-3)
1.056-0.051Y ≦ X ≦ 1.8 (II-2)
The curable resin composition characterized by satisfy | filling.

The curable resin composition of the present invention has rapid curing while maintaining desired flame retardancy.
The curable resin composition of the present invention cures in about 30 to 60 minutes at, for example, 120 ° C., and thus has been required to be maintained at a high temperature of about 150 ° C. for 60 minutes or more. It can be cured at a low temperature and in a short time compared to products, for example, as a sealing material for covering or sealing an electronic component that cannot be operated at a high temperature such as a thermistor, or an adhesive for an electronic component Can be used. In addition, when used as an adhesive for bonding electronic components to each other and an electronic component and a substrate, or when used as a liquid sealing material for sealing a substrate on which an electronic component is mounted, the present invention Since the curable resin composition has an appropriate viscosity, it can be favorably applied onto a substrate by a dispensing (coating) process or a printing process. In addition, since the curable resin composition of the present invention is gelled at 120 ° C. in about 10 seconds to 3 minutes, it is appropriately cured, adhered, and sealed without flowing out to an undesired part during heat curing. The surface of the cured resin after curing can be made uniform.

It is a distribution graph of phosphorus atom content (mass%) and sulfur atom content (mass%) with respect to the total mass of the components (A) to (C) of Examples and Comparative Examples. A portion surrounded by the straight lines (1) to (4) is one embodiment of the present invention.

<Curable resin composition>
The curable resin composition according to one embodiment of the present invention includes (A) (i) a phosphorus-containing epoxy resin, (ii) a mixture of a phosphorus-containing epoxy resin and a phosphorus-free epoxy resin, (iii) an organic phosphorus compound, A mixture of an epoxy resin not containing phosphorus, and (iv) a mixture of an organic phosphorus compound and a phosphorus-containing epoxy resin, an epoxy resin material selected from any one or more of (i) to (iv),
(B) a thiol compound having two or more thiol groups in the molecule, and (C) a curing accelerator, and a phosphorus atom content X (mass%) relative to the total mass of the components (A) to (C); The sulfur atom content Y (% by mass) relative to the total mass of the components (A) to (C) is represented by the following formulas (I) and (II):
1 ≦ Y ≦ 14 (I)
1.056-0.051Y ≦ X ≦ 2.0 (II)
It is characterized by satisfying. Hereinafter, it divides into each component and demonstrates in detail.

(A) Epoxy resin material In the epoxy resin material that can be used in the present invention, on average, an epoxy resin having two or more epoxy groups per molecule and a phosphorus-containing component are simultaneously present. Specifically, the epoxy resin material includes (i) a phosphorus-containing epoxy resin, (ii) a mixture of a phosphorus-containing epoxy resin and a phosphorus-free epoxy resin, (iii) an organophosphorus compound and a phosphorus-free epoxy resin; And (iv) a mixture of an organophosphorus compound and a phosphorus-containing epoxy resin, at least one selected from (i) to (iv).

As a phosphorus containing epoxy resin, what has a phosphorus atom in a molecule | numerator and has an average of two or more epoxy groups per molecule may be sufficient, for example.
For example, polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol; polyglycidyl ether obtained by reacting a polyhydric alcohol such as glycerin and polyethylene glycol with epichlorohydrin; p-hydroxybenzoic acid Glycidyl ether ester obtained by reacting a hydroxycarboxylic acid such as β-hydroxynaphthoic acid with epichlorohydrin; obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin Table 1 shows the polyglycidyl ester obtained; and further, epoxidized phenol novolak resin, epoxidized cresol novolak resin, epoxidized polyolefin, cycloaliphatic epoxy resin, other urethane-modified epoxy resin; A compound, can be obtained by reacting in the presence high temperature and catalyst.
In Table 1, as a compound represented by the following formula (1), HCA-HQ (10- (2,5-dihydroxyphenyl) -10-dihydro-9-oxa- represented by the formula (1-1) 10-phosphaphenanthrene-10-oxide), HCA-NQ represented by formula (1-2) (10- (2,7-dihydroxynaphthyl) -10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide), PPQ (Hokuko Chemical Co., Ltd. diphenylphosphinyl hydroquinone), diphenylphosphinylnaphthoquinone, CPHO-HQ (Nippon Chemical Industry Co., Ltd. cyclooctylene phosphinyl-1,4-benzenediol), Cyclooctylenephosphinyl-1,4-naphthalenediol, phosphorus-containing phenol disclosed in JP-A-2002-265562 Le compounds. The compounds shown in Table 1 may be used alone or in combination of two or more. Examples of the resin having 1 to 4 phosphorus atoms per unit structural formula, preferably 1 to 2 phosphorus atoms, are not limited thereto.

Specific examples of phosphorus-containing epoxy resins include FX-289Z-1 and FX-305 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., EP150 and EP200 manufactured by Clariant Co., Ltd., and EXA-9710 manufactured by DIC Corporation. Can be mentioned.
Moreover, the epoxy compound of said formula (2)-(5) and resin obtained by superposing | polymerizing these can be used as (A) component of this invention.

  In the present invention, as the epoxy resin not containing phosphorus that can be used as a part of the epoxy resin material of the component (A), a known epoxy resin not containing phosphorus can be selected. As the said epoxy resin, what has 2 or more epoxy groups per molecule on average may be used, for example. 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 Glycidyl ether ester obtained by reacting a hydroxycarboxylic 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 to, et al.

  As epoxy resin not containing phosphorus, bisphenol A type and F type mixed epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd.), bisphenol A type epoxy resin (“jER828EL” manufactured by Mitsubishi Chemical Corporation), “ YL980 "," jER1009 "), bisphenol F type epoxy resin (" jER806H "," YL983U "manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (" jER152 "" jER154 "manufactured by Mitsubishi Chemical Corporation), DIC ( "N-730", "N-740"), naphthalene type bifunctional epoxy resin ("HP4032," "HP4032D," "HP4032SS," "EXA4032SS"), naphthalene type tetrafunctional epoxy manufactured by DIC Corporation. Resin (“HP4700”, “HP4710” manufactured by DIC Corporation), naphtho Type epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd.), epoxy resin having butadiene structure (“PB-3600” manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having biphenyl structure (Nipponization) “NC3000H”, “NC3000L”, “NC3100” manufactured by Yakuhin Co., Ltd.), xylenol type epoxy resin (“YX4000”, “YX4000H”, “YX4000HK”, “YL6121” manufactured by Mitsubishi Chemical Corporation)), anthracene type epoxy Resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin ("EXA-7310", "EXA-7311", "EXA-7311L", "EXA7311-G3") manufactured by DIC Corporation), Glycidyl ester type epoxy resin (“EX711”, “E” manufactured by Nagase ChemteX Corporation) 721 ”,“ R540 ”manufactured by Printec Co., Ltd.), dicyclopentadiene type epoxy resin (“ HP-7200H ”manufactured by DIC Corporation), xylene type epoxy resin epoxy resin (“ YX7700 ”manufactured by Mitsubishi Chemical Corporation), etc. Is mentioned.

As the organic phosphorus compound, an organic phosphorus compound usually used as an organic phosphorus flame retardant can be used. Specifically, examples of the organic phosphorus compound include aluminum diethylphosphinate (phosphorus atom concentration: 23% by mass), a compound represented by the formula (1) in Table 1, a compound represented by the following formula (6), or a derivative thereof. Can be mentioned.

In the above (6), R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an amino group, or a phenyl group. When both R3 and R4 are hydrogen atoms, it is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA, phosphorus atom concentration 14.3 mass%), and R3 and R4 When either is a substituent other than a hydrogen atom, it is a derivative of HCA.

Examples of other organic phosphorus compounds include, but are not limited to, aluminum polyphosphate (OP-930, OP-935 manufactured by Clariant). The structural formula of OP-930 is as follows.

  When the component (A) is a mixture of (ii) a phosphorus-containing epoxy resin and a phosphorus-free epoxy resin, the mass ratio of the phosphorus-containing epoxy resin to the phosphorus-free epoxy resin is, for example, 40:60 to 95: 5, It is preferably 50:50 to 95: 5, more preferably 60:40 to 95: 5. When the component (A) is a mixture of an organophosphorus compound and an epoxy resin not containing phosphorus, the mass ratio of the organophosphorus compound: phosphorus-free epoxy resin is, for example, 1: 100 to 40: 100, preferably 3: It is appropriate that it is 100-30: 100, more preferably 5: 100-20: 100.

In the epoxy resin material of component (A), for example, the content of phosphorus atoms with respect to the total mass of the epoxy resin material of component (A) is 0.5 to 40 mass%, preferably 0.8 to 30 mass%, more preferably. Is suitably 1.0 to 20% by mass. The component (A) epoxy resin material is preferably at least one selected from (i) a phosphorus-containing epoxy resin, or (ii) a mixture of a phosphorus-containing epoxy resin and a phosphorus-free epoxy resin. That is, it is preferable from the viewpoint of resin fluidity (viscosity) that no organic phosphorus compound is contained.
The content of the epoxy resin material as the component (A) is, for example, 5 to 60% by mass, preferably 10 to 50% by mass, more preferably 15 to 40% when the entire curable resin composition is 100% by mass. It is suitable to contain the mass%.

(B) Thiol Compound As the thiol compound of the present invention, a known thiol compound is used as a curing agent for an epoxy resin as long as it is a thiol compound having two or more thiol groups in the molecule (also referred to as a polythiol compound). be able to. For example, examples of the thiol compound include compounds having two or more thiol groups in the molecule and having at least one hydrogen atom in a carbon atom directly connected to the thiol group.
However, as the thiol compound of the present invention, those having as little basic impurity content as possible are preferable from the viewpoint of storage stability.
As the thiol compound of the present invention, for example, an —X—R ⁵ —SH group or
Compounds having a group are preferred. Here, R ⁵ is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, X ₁ is a divalent group, X ₂ is a trivalent group, -X ₁ -is -O-, One or more selected from —O—CO—, —S—, and —O—Si—.

It is 1 or more types chosen from. The carbon number of R ⁵ is more preferably 1 to 4 carbon atoms, more preferably 3 to 4 carbon atoms, and most preferably 3 carbon atoms. R ⁵ may be, for example, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkenylene group, or a cycloalkynylene group, which may be linear or branched.

As the thiol compound of the present invention, specifically, as an example where —X ₁ — is —O—, as an example where mercaptopropoxyphenylalkane; —X ₁ — is —O—CO— and R ⁵ has 1 carbon. , Trimethylolpropane tristhioglycolate (TMTG), butanediol bisthioglycolate (BDTG), pentaerythritol tetrakisthioglycolate (PETG) ethylene glycol bisthioglycolate (EGTG); -X ₁ -is -O-CO -And R ⁵ having 2 carbon atoms include, for example, 3-mercaptopropionic acid (3-MPA, BMPA), methoxybutyl mercaptopropionate, octyl mercaptopropionate (BMPA-2EH), trimethylolpropane tris (3-mercapto Propionate) (TMTP, sulfur atom concentration 24.1% by mass), pentaerythritol tetrakis (3-mercaptopropionate) ) (PEMP, sulfur atom concentration 26.3% by mass), dipentaerythritol hexakis (3-mercaptopropionate) (DPMP, sulfur atom concentration 24.6% by mass), tris-[(3-mercaptopropionyloxy)- Ethyl] -isocyanurate (TEMPIC, sulfur atom concentration: 18.3 mass%); as an example in which —X ₁ — is —O—CO— and R ⁵ has 3 carbon atoms, pentaerythritol tetrakis (3-mercaptobutyrate) (PE1 , Sulfur atom concentration 23.5% by mass), trimethylolpropane tris (3-mercaptobutyrate) (TPMB, sulfur atom concentration 21.8% by mass), trimethylolethane tris (3-mercaptobutyrate) (TEMB, sulfur atomic concentration of 22.6 wt%); - X ₁ - as examples of -S-, both ends thiolated oligo propylene; -X ₁ - examples of -O-Si-, terminal thiol groups Polysiloxane and silsesquioxane having; (4- (2-mercaptoethyl) phenyl alkanes;

But
Examples of tris (3-mercaptopropyl) isocyanurate (TMPIC, sulfur atom concentration 27.4% by mass);

But
As an example, a compound of the following structure




Etc.

Similarly, 4 to 20 carbon atoms having 2 to 10, preferably 2 to 5 thiol groups in the molecule, such as 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc. Preferably 4 to 10 alkyl polythiol compounds; terminal thiol group-containing polyether; terminal thiol group-containing polythioether; thiol compound obtained by reaction of epoxy compound with hydrogen sulfide; terminal obtained by reaction of polythiol compound and epoxy compound A thiol compound having a thiol group can also be used which uses a basic substance as a reaction catalyst in the production process. For thiol compounds produced using basic substances as these reaction catalysts, thiol compounds having two or more thiol groups in the molecule that have been subjected to dealkalization treatment and whose alkali metal ion concentration is 50 ppm or less are used. it can.
These may be used alone or in combination. Among these compounds, the more preferred structural formulas of thiol compounds in the present invention are as shown in Table 2 below.

  Even more preferred thiol compounds are TMTP, TEMPIC and TMPIC with 3 SH functional groups and PEMP with 4 SH functional groups. DPMP having 6 SH functional groups can also be used, in which case, in combination with another thiol compound having 3 to 4 SH functional groups, 3-6 SH average functional groups, more preferably 3-5, More preferably, it is preferably adjusted to 3 to 4.3. When a mercaptobutyrate-based thiol compound is used, it is preferable to use it in combination with a mercaptopropionate-based thiol compound because sufficient flame retardancy can be realized. In particular, excellent flame retardancy is exhibited when the mass ratio of the mercaptopropionate thiol compound to the mercaptobutyrate thiol compound is in the range of 0.1: 0.9 to 0.7: 0.3.

As a method for dealkalizing a thiol compound produced using a basic substance as a reaction catalyst, for example, the thiol compound to be treated is dissolved in an organic solvent such as acetone or methanol, and an acid such as dilute hydrochloric acid or dilute sulfuric acid is added. Examples of the method include, but are not limited to, a method of desalting by extraction and washing, a method of adsorbing using an ion exchange resin, a method of purification by distillation, and the like.
The component (B) thiol compound has a sulfur atom content of 5 to 50% by mass, preferably 10 to 40% by mass, and more preferably 15 to 30% by mass with respect to the total mass of the thiol compound. It is.
(B) The content of the thiol compound is the equivalent of the SH group with respect to 1 equivalent of the epoxy group contained in the epoxy resin to be used, for example, 0.2 to 1.2 equivalents, preferably 0.3 to 1.1 equivalents. More preferably, it is appropriate to contain 0.4 to 1.0 equivalent.

(C) Curing accelerator As the curing accelerator of the present invention, a known curing accelerator capable of accelerating the curing of the epoxy resin material of the present invention and the thiol compound can be used. As the curing accelerator, a compound other than the thiol compound (B) can be used. For example, the curing accelerator is a compound that is insoluble in an epoxy resin at room temperature (25 ° C.), solubilized by heating, and functions as an accelerator, and is a solid imidazole compound or solid at room temperature (25 ° C.). Dispersed amine adduct system latent curing accelerator, for example, reaction product of amine compound and epoxy compound (amine-epoxy adduct system), reaction product of amine compound and isocyanate compound or urea compound (urea type adduct system) Etc. Ionic liquids can also be used with the curing accelerator of the present invention.

  Examples of the imidazole compound that is solid at room temperature (25 ° C.) used in the present invention 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-methylimi Zole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N- (2-methylimidazolyl-1-ethyl) -urea, N, N ′-(2-methylimidazolyl- (1) -ethyl) -aziboyl Although diamide etc. are mentioned, 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 type latent curing accelerator (amine-epoxy adduct type) used in the present invention include, for example, bisphenol A, bisphenol F, catechol, resorcinol and the like. Polyglycidyl ethers obtained by reacting polyhydric alcohols such as monohydric phenols or glycerin or polyethylene glycol with epichlorohydrin; hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid and epichloro Glycidyl ether ester obtained by reacting with hydrin; polyglycidyl ester obtained by reacting polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin; 4,4′-diaminodiphenylmethane or m- amino Glycidylamine compounds obtained by reacting enols with epichlorohydrin; moreover, polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, epoxidized polyolefins, butyl glycidyl ether, phenyl glycidyl ether Monofunctional epoxy compounds such as glycidyl methacrylate; and the like, but are not limited thereto.

  The amine compound used as another raw material for producing the solid dispersion type amine adduct-based latent curing accelerator used in the present invention has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule. What is necessary is just to have at least one functional group selected from a secondary amino group, secondary amino group and tertiary amino group in the molecule. Examples of such amine compounds are shown below, but are not limited thereto. That is, for example, aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane; 4,4'-diaminodiphenylmethane , Aromatic amine compounds such as 2-methylaniline; heterocycles containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, piperazine Compound; and the like.

  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-ethyl Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as -4-methylimidazole and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol 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- (dimethylaminomethyl) phenol, 2, 4,6-tris (dimethylaminomethyl) phenol, N-β- Hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N, N-dimethylaminobenzoic acid, N, N -Tertiary amino acids in the molecule such as 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 a group, phenols, thiols, carboxylic acids and hydrazides;

  In order to further improve the storage stability of the curable resin composition of the present invention, when the latent curing accelerator used in the present invention is produced by addition reaction of the above-described epoxy compound and amine compound, a molecule is used as a third component. An active hydrogen compound having two or more active hydrogens can be added. Examples of such active hydrogen compounds are shown below, but are not limited thereto. That is, for example, polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, phenol novolac resin, polyhydric alcohols such as trimethylolpropane, polyhydric alcohols such as adipic acid and phthalic acid. Examples thereof include carboxylic acids, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid.

Examples of the isocyanate compound used as another production raw material of the solid dispersion type amine adduct-based latent curing accelerator used in the present invention include, for example, n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, and the like. Functional isocyanate compound; hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, Polyfunctional isocyanate compounds such as bicycloheptane triisocyanate; furthermore, these polyfunctional isocyanate compounds and active hydrogen Obtained by reaction of compound, terminal isocyanate group-containing compounds; and the like can also be used. Examples of such terminal isocyanate group-containing compounds include addition compounds having terminal isocyanate groups obtained by reaction of toluylene diisocyanate and trimethylolpropane, and terminal isocyanate groups obtained by reaction of toluylene diisocyanate and pentaerythritol. However, the present invention is not limited thereto.
Examples of urea compounds include, but are not limited to, urea and thiourea.

  The solid dispersion type latent curing accelerator used in the present invention includes, for example, (a) two components of an epoxy compound and an amine compound, (b) three components of the two components and an active hydrogen compound, or (c) an amine. Each component is mixed and mixed in a combination of two or three components of a compound and an isocyanate compound or / and a urea compound, reacted at a temperature of room temperature (25 ° C.) to 200 ° C., cooled and solidified, and then crushed, Alternatively, it can be easily obtained by reacting in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc., removing the solvent and then pulverizing the solid content.

Although the typical example marketed as said solid dispersion type | mold latent hardening accelerator is shown below, it is not limited to these. That is, for example, as an amine-epoxy adduct system (amine adduct system), “Amicure PN-23” (Ajinomoto Co., Ltd. trade name), “Amicure PN-H” (Ajinomoto Co., Ltd. trade name), “Hardener X” -3661S "(trade name of ARC Corporation)," Hardener X-3670S "(tradename of ARC Corporation)," Novacure HX-3742 "(trade name of Asahi Kasei Corporation), “Novacure HX-3721” (trade name of Asahi Kasei Co., Ltd.) and the like, and examples of urea-type adducts include “Fujicure FXE-1000” (trade name of Fuji Kasei Co., Ltd.), “Fujicure FXR-1030”. (Fuji Kasei Co., Ltd.).
(C) The content of the curing accelerator is, for example, 1 to 30 parts by mass, preferably 2 to 20 parts by mass, more preferably 3 to 15 parts by mass, when the epoxy resin in (A) is 100 parts by mass. It is appropriate to include a part.

In the curable resin composition of the present invention, the phosphorus atom content X (% by mass) relative to the total mass of the components (A) to (C) and the sulfur atom relative to the total mass of the components (A) to (C). Content Y (mass%) is the following formulas (I) and (II):
1 ≦ Y ≦ 14 (I)
1.056-0.051Y ≦ X ≦ 2.0 (II)
Meet. More preferably, the curable resin composition of the present invention has the formulas (I-2) and (II-2) instead of the formulas (I) and (II),
2 ≦ Y ≦ 13 (I-2)
1.056-0.051Y ≦ X ≦ 1.8 (II-2)
Meet. More preferably, the curable resin composition of the present invention has the formulas (I-3) and (II-3) instead of the formulas (I) and (II),
2.5 ≦ Y ≦ 12 (I-3)
1.056-0.051Y ≦ X ≦ 1.8-0.051Y (II-3)
Meet. The above (I) to (I-3) and (II) to (II-3) may be arbitrarily combined. More specifically, the portion surrounded by (1) to (4) in FIG. 1 is a range satisfying the above formulas (I) and (II).
By preparing the curable resin composition of the present invention so as to satisfy such a phosphorus atom content and a sulfur atom content, a curable resin composition having a fast curing property while maintaining a desired flame retardancy. Can be obtained.

Here, the content of phosphorus atoms and sulfur atoms can be measured by a general-purpose method. In general, the measurement is performed using, for example, combustion ion chromatography. For example, an automatic sample combustion device (AQF-100 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and an ion chromatograph (ICS-1500 manufactured by Nippon Dionex Co., Ltd .; column; anion exchange column IonPac AG12A) and an auto suppressor (manufactured by Nippon Dionex Co., Ltd.) ASRS-300), the gas generated by burning the sample at 1000 ° C in a mixed atmosphere of alkone and high-purity oxygen is absorbed in 0.03-0.3% hydrogen peroxide solution and measured. ₄ ^- a, in the case of sulfur atom SO ₄ ^- with a mixed standard solution concentration is known including a calibration curve, the calibration curve PO ₄ was measured using the ^- or SO ₄ ^- content It can be calculated as phosphorus atom or sulfur atom content, respectively.
Further, the total mass of the components (A) to (C) is TG / DTA, heated from 25 ° C. to 800 ° C. in a nitrogen atmosphere at 10 ° C./min, then cooled to 200 ° C., and again in an air atmosphere The heating loss when the temperature is raised again to 800 ° C. is measured, and the weight loss can be calculated as components (A) to (C).

  Furthermore, the curable resin composition of this invention can contain an inorganic filler as (D) component. Examples of the inorganic filler include inorganic compounds known as fillers, for example, sulfates or sulfites such as barium sulfate, calcium sulfate, and calcium sulfite, hydroxides such as aluminum hydroxide, magnesium hydroxide, and zinc hydroxide, and carbonic acid. Carbonates such as calcium and magnesium carbonate, oxides such as magnesium oxide, beryllium oxide, zirconium oxide and titanium oxide, nitrides or carbides such as boron nitride, aluminum nitride, silicon nitride and silicon carbide, aluminum borate, zinc borate Such as borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, potassium titanate, titanate such as bismuth titanate, zinc molybdate, barium zirconate, calcium zirconate, silica, Alumina, talc, clay, mica, Mother powder, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, hydrotalcite, or spherical beads, hollow beads, glass fiber talc, amorphous silica, Silica such as fused silica, crystalline silica and synthetic silica is particularly preferred. One or more inorganic fillers can be used.

Specifically, spherical spherical silica “Admafine Series” (“SO-C2; average particle size 0.5 μm”, “SO-C5; average particle size” manufactured by Admatechs Co., Ltd.) is available as commercially available spherical fused silica. 1.6 μm ”,“ SO-C6; average particle size 2.2 μm ”, etc.),“ Denka fused silica series ”(“ FB-5SDC; average particle size 4.5 μm ”,“ FB− ”manufactured by Denki Kagaku Kogyo Co., Ltd.) 105FD; average particle diameter 11.7 μm ”,“ FB-875FC; average particle diameter 22.7 μm ”, etc.)“ Excelica ”series (“ Excelica 6; average particle diameter 6 μm ”, etc.) manufactured by Tokuyama Co., Ltd. The high-purity spherical silica series made by Tatsumori can be raised. As the fumed silica, “Aerosil A-200”, “RY-200”, “R805” manufactured by Nippon Aerosil Aerosil Co., Ltd. and the like can be used.
The inorganic filler is preferably spherical silica having a shape advantageous for dispersibility in the resin varnish, and the average particle diameter is preferably in the range of 0.01 to 30 μm, and in the range of 0.05 to 15 μm. More preferred.
(D) Content of an inorganic filler is 30-80 mass% when the whole curable resin composition is 100 mass%, for example, Preferably, it is 40-75 mass%, More preferably, it is 45-70 mass%. It is appropriate to include.

[Other ingredients]
In addition to the above components (A) to (D), as other components, resins other than epoxy resins, boric acid ester compounds as storage stabilizers, resin additives, powders, thickeners, You may add a foaming agent or a leveling agent, a coupling agent, an adhesiveness imparting agent, an ion trap agent, a coloring agent, etc.
Here, examples of the resin other than the epoxy resin include butadiene rubber, nitrile rubber, butadiene-styrene rubber, acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber, and ethylene-propylene rubber.
Examples of boric acid ester compounds include trimethyl borate, triethyl borate, 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- Trilbore , Tri ethanol amine borate, and the like.
Examples of the resin additive include, for example, powders such as silicone powder, nylon powder, and fluororesin powder, thickeners such as Orben and Benton, silicone-based, fluorine-based, and polymer-based antifoaming agents or leveling agents, Silane coupling agent, triazole compound, thiazole compound, triazine compound, porphyrin compound and other adhesion imparting agents, hydrotalcite and ion traps such as hydrous oxides of elements selected from magnesium, aluminum, bismuth, titanium and zirconium Agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, azo red, carbon black and other colorants, titanate ester compounds, borate ester compounds, aluminate compounds, zirconate compounds, etc. Agents.
For example, black pigment (carbon black) can be preferably added as a colorant, and triethyl borate (TEB) (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) can be preferably added as a reaction inhibitor.

  There is no particular difficulty in preparing the curable resin composition of the present invention using the above-described components such as the epoxy resin material, thiol compound, and curing accelerator as raw materials, and it is possible to follow a conventionally known method. For example, mixing can be performed with a mixer such as a Henschel mixer, a planetary mixer, or a three-roller. The mixing can also be performed in a solvent such as methyl ethyl ketone or toluene, in a liquid epoxy resin material, or substantially in the absence of a solvent. You may carry out under reduced pressure for the defoaming in or after mixing.

<Form of curable resin composition>
The curable resin composition may be in the form of a mixture containing all components in one fraction or in the form of a kit containing the curable resin composition in separate fractions. When it is in the form of a mixture containing all the components of the curable resin composition in one fraction, it is mixed as described above and accommodated in one container. When the curable resin composition is in a liquid form such as a solution or a suspension, it can exist as a one-component form (such as a one-component composition and a one-component adhesive).
Moreover, when a curable resin composition is a kit, it becomes an aspect which divides | segments and preserve | saves into two or more of a 1st component and a 2nd component at least. The kit has a first component including at least the component (A) and a second component including at least the component (B). That is, the component (A) and the component (B) are stored at least separately in the first component and the second component. For example, the kit is separately housed in a first component including the component (A) and the component (C) and a second component including the component (B). In another aspect, the kit is separately housed in a first component including the component (A) and a second component including the component (B) and the component (C). As long as the component (A) and the component (B) are stored in separate fractions, the number of components and the types of components stored in the components are not limited. In the case where the components (A) to (C) or the component (D) and other components are all liquid or in the form of a suspension dispersed in the liquid, the first component and the second component are respectively stored in the container. The liquid and the second liquid may be used. Furthermore, one or more other components may be present, in which case a third liquid, a fourth liquid, etc. may be present. Here, a container such as a glass container, a plastic container, or a laminate container, which is usually used as an epoxy resin adhesive or a sealing material, can be used. In the case of a kit, tertiary amine and imidazole can be used as the component (C). Specifically, tertiary amines such as triethylamine, tripropylamine, and tributylamine, and imidazoles such as 2E4MZ, 2P4MZ, 1B2MZ, and C11-CN (manufactured by Shikoku Kasei Co., Ltd.) can be used.

<Hardened epoxy resin>
The curable resin composition of the present invention becomes an epoxy resin cured product by thermosetting. Moreover, the epoxy resin hardened | cured material which can be used by this invention can be obtained also by mixing the 1st component and the 2nd component which are contained in the said kit of this invention, and thermosetting. Here, it is appropriate that the heat curing can be performed at a curing time of less than 150 ° C. and 60 minutes or less, more specifically, 80 to 140 ° C. for 10 seconds to 30 minutes, preferably 90 to 130. It is carried out by heating at a temperature of 30 seconds to 15 minutes, more preferably at a temperature of 95 to 110 ° C. for 1 to 5 minutes, and even more preferably at 100 ° C. for 1 to 2 minutes. The first component and the second component are mixed by a conventionally known mixing method, for example, a mixer such as a Henschel mixer or a planetary stirrer.

<Sealing material and adhesive>
The curable resin composition of the present invention can be used as a sealing material or an adhesive for electronic parts. Examples of the electronic component include an electronic substrate, a capacitor, a resistor, an IC, a transistor, a thermistor, and a MEMS sensor. In particular, the curable resin composition of the present invention is particularly used in places where flame retardancy is required, such as a sealing material for battery substrates and a sealing material for thermistors. Examples of the adhesive include a one-component adhesive containing all components in one container, and a two-component adhesive stored separately in the first and second liquids.
Here, the gelation time that can be achieved by the curable resin composition of the present invention is, for example, a gelation time at 120 ° C. on a hot plate measured in accordance with JIS C 6521 of 5 minutes or less, preferably 3 It is appropriate that it is less than or equal to 1 minute, more preferably less than or equal to 1 minute. When measuring at 80 ° C. as described above, the gelation time is 60 minutes or less, preferably 30 minutes or less, more preferably 15 minutes or less.

In addition, it is appropriate to make a V-0 determination in the UL94 vertical (V) flame retardancy test. In addition, UL94 vertical (V) flame retardancy test, "test specimen (125 ± 5 × 13 ± 0.5 × 0.5mm) is attached vertically to the clamp, 10mm indirect flame with 20mm flame is performed twice, the combustion behavior Is a test for making a determination based on the following four criteria.
V-0: The burning time of the test piece is 10 seconds or less, it does not burn to the clamp, and there are no drops
V-1: The burning time of the test piece is 30 seconds or less, it does not burn to the clamp, and there are no drops
V-2: The burning time of the test piece is 30 seconds or less and it does not burn up to the clamp, but there is absorbent cotton ignition by dripping.
Not: Burns to clamp Further, the viscosity of the adhesive is, for example, an E-type viscometer RE-80U (manufactured by Toki Sangyo Co., Ltd.) corn rotor 3 ° × R9.7 calibrated with a standard solution for viscosity calibration JS52000, It can be measured at 25 ° C. and 5 rpm. The viscosity is suitably, for example, 0.1 Pa · second to 1000 Pa · second, more preferably 10 Pa · second to 800 Pa · second, and further preferably 20 Pa · second to 500 Pa · second.

  The present invention can seal and bond portions that require flame retardancy using these sealing materials and adhesives using the curable resin composition of the present invention. The sealing material and adhesive of the present invention are, for example, sealing and bonding of control circuit board components of lithium ion batteries used in mobile phones, digital cameras, game machines, etc., electric wire connectors used in hard disks and sensors, etc. Insulating adhesive sealing, sealing and bonding of lighting components, and coil bonding. Furthermore, this invention can provide the electronic component which contains the hardened | cured material of the resin composition of this invention by the said adhesion | attachment or sealing, ie, the hardened | cured material was formed. In addition, the present invention includes electric products such as computers, mobile phones, digital cameras, televisions and game machines, vehicles such as motorcycles, automobiles, trains, ships, airplanes, etc., lighting equipment, sports Leisure goods can also be provided.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, these do not restrict | limit this invention in any meaning. In the following description, “part” means “part by mass”, and “%” means “mass%”.
<Preparation of resin composition>
The components of Examples and Comparative Examples shown in Table 3 and Table 4 were mixed in the parts by mass shown in the table, kneaded with a three-roll mixer, and defoamed under reduced pressure to obtain a resin composition. It was.
Details of the components used are as follows.
(A) Component “FX-289Z-1”: phosphorus-containing epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. “jER828EL”: bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation
“OP-930”: aluminum polyphosphate, manufactured by Clariant, phosphorus concentration of 23% by mass

“HCA-HQ”: 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, manufactured by Sanko Chemical Co., Ltd., phosphorus concentration 9.6% by mass
“ZX-1542”: trimethylolpropane polyglycidyl ether resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

(B) Component “TMTP”: Trimethylolpropane Tris (3-mercaptopropionate, “PEMP” manufactured by Sakai Chemical Co., Ltd .: Pentaerythritol tris (3-mercaptopropionate), “PE1” manufactured by SC Organic Chemical Co., Ltd .: Penta Erythritol tetrakis (3-mercaptobutyrate), “TEMPIC” manufactured by Showa Denko KK: tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, “DPMP” manufactured by SC Organic Chemical Company: dipentaerythritol hexakis (3 -Mercaptopropionate), “TMPIC” manufactured by SC Organic Chemical Co., Ltd .: Tris (3-mercaptopropyl) isocyanurate, manufactured by Ajinomoto Fine Techno Co., Ltd.

(C) Component “Amicure PN23”: amine adduct-based latent curing accelerator, curing agent “MH-700G” in place of (B) manufactured by Ajinomoto Fine Techno Co., Ltd .: (trade name, manufactured by Nippon Nippon Chemical Co., Ltd./hexahydrophthalic anhydride And methylhexahydrophthalic anhydride)
(D) Component “SO-C6”: spherical amorphous silica particles, manufactured by Admatech, average particle size of 2.0 μm
“A-200”: Fumed silica, manufactured by Nippon Aerosil Co., Ltd. (other components)
“Black pigment”: Carbon black “TEB”: Triethyl borate, Reagent (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Flame retardance test>
The obtained resin composition was poured into a 25 mm × 13 mm × 0.5 mm size mold and heated for 1 hour in a heat circulation oven at 150 ° C. to prepare a test piece, and a flame retardancy test was performed. The results are shown in Tables 3 and 4.
The flame retardancy was evaluated based on the UL94 vertical (V) flame retardancy test. Specifically, the test piece was vertically attached to the clamp, 10-second indirect flame with 20 mm flame was performed twice, and the combustion behavior was evaluated based on the following four criteria.

V-0: The burning time of the test piece is 10 seconds or less, it does not burn to the clamp, and there are no drops
V-1: The burning time of the test piece is 30 seconds or less, it does not burn to the clamp, and there are no drops
V-2: The burning time of the test piece is 30 seconds or less and it does not burn up to the clamp, but there is absorbent cotton ignition by dripping.
Not: Burns to the clamp

<Viscosity>
The viscosity of the obtained resin composition was measured at 25 ° C. and 5 rpm using an E-type viscometer RE-80U (manufactured by Toki Sangyo Co., Ltd.) cone rotor 3 ° × R9.7 calibrated with a viscosity calibration standard solution JS52000. did. The results are shown in Tables 3 and 4.

<Gelification time>
The gelation time of the obtained resin composition was measured at 120 ° C. on a hot plate in accordance with JIS C 6521. Specifically, an appropriate amount of a sample (0.05 to 0.10 g) was taken with a micropartel, and this was placed on a hot plate, and then the stopwatch was quickly activated. While extending the sample thinly with a micropartel, the entire sample was stirred so as to draw a circle within a range of 10 mm in diameter once per second. The sample was lifted with a micropartel, and the stringing state of the sample was observed. When the micropartel was separated from the hot plate by about 3 mm, the point at which the stringing completely disappeared was defined as the gel point. The time from the start of holding to the gel point was recorded as the gel time to the second. The results are shown in Tables 3 and 4.

(B) About the difference of a thiol compound (Examples 1-6)
Examples 1-6 were performed in order to consider the difference of the effect in the case of using a different thiol compound. Specifically, first, TMTP, TEMPIC, and TMPIC were used as mercaptopropionate thiol compounds having 3 SH functional groups in Examples 1, 3, and 4, respectively, as thiol compounds. In Example 2, PEMP was used as a mercaptopropionate thiol compound having 4 SH functional groups. All of Examples 1 to 4 exhibited good flame retardancy (V-0).
Next, when PEMP having 4 SH functional groups and DPMP having 6 SH functional groups were mixed as a thiol compound to produce Example 5 having an SH average functional group number of 4.2, good flame retardancy (V-0) was obtained. Expressed.
Further, as a thiol compound, a mercaptobutyrate-based thiol compound PE1 (SH functional group number is 4) and a mercaptopropionate-based thiol compound DPMP having 6 SH functional groups are expressed in an equivalent ratio based on the number of SH functional groups with PE1: DPMP = When mixed at 0.5: 0.5 (Example 6), good flame retardancy (V-0) was exhibited.

(A) Combination of components (Examples 7 to 8)
Examples 7 to 8 were carried out in order to consider the effects when using phosphorus compound addition. The resin composition of the present invention expressed V-0 with the addition of a small amount of phosphorus compound.

Latent curing agent formulation (Comparative Example 1)
In Comparative Example 1, the thiol compound as the component (B) is not used. ZX-1542 belongs to the component (A), but is a trimethylol skeleton compound like TMTP except that the terminal is not an ester thiol group but a glycidyl group. The flame retardancy of the resin composition of Comparative Example 1 was insufficient.

Acid anhydride curing agent blend (Comparative Examples 2 to 4)
In Comparative Examples 2-4, the thiol compound which is (B) component is not used. Instead, MH-700G is used as an acid anhydride curing agent. Since no thiol compound was present, the flame retardancy of the resin compositions of Comparative Examples 2 to 4 was insufficient.

  Following the examples of Examples 1 to 11 and Comparative Examples 1 to 5, comparative examples and examples having different phosphorus atom contents (X) and sulfur atom contents (Y) were prepared by changing the blending ratio as appropriate. The graph of FIG. 1 was created. As a result of changing the ratio of the phosphorus atom content and the sulfur atom content as shown in FIG. 1, 1 ≦ Y ≦ 14 (I) and 1.056−0.051Y ≦ X ≦ 2.0 (II) It was found that a composition satisfying the above condition exhibits good flame retardancy (V-0).

Claims (15)

(A) (i) a phosphorus-containing epoxy resin, (ii) a mixture of a phosphorus-containing epoxy resin and a phosphorus-free epoxy resin, (iii) a mixture of an organic phosphorus compound and a phosphorus-free epoxy resin, and (iv) An epoxy resin material selected from any one or more of (i) to (iv) of a mixture of an organic phosphorus compound and a phosphorus-containing epoxy resin;
(B) a thiol compound having two or more thiol groups in the molecule, and (C) a curing accelerator,
The phosphorus atom content X (mass%) relative to the total mass of the components (A) to (C) and the sulfur atom content Y (mass%) relative to the total mass of the components (A) to (C) are as follows. Formulas (I) and (II);
1 ≦ Y ≦ 14 (I)
1.056-0.051Y ≦ X ≦ 2.0 (II)
The curable resin composition characterized by satisfy | filling.   2. The curable resin composition according to claim 1, wherein the content of the phosphorus atom contained in the component (A) is 0.5 to 40% by mass with respect to the mass of the whole component (A). Wherein (B) thiol compound, -X ₁ -R ⁵ -SH group or
A compound having a group (R ⁵ is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, X ₁ is a divalent group, X ₂ is a trivalent group, -X ₁ -is -O-, One or more selected from —O—CO—, —S—, and —O—Si—,

It is 1 or more types chosen from. The curable resin composition of Claim 1 or 2 selected from these. The (B) thiol compound is
Trimethylolpropane tris (3-mercaptopropionate),
Pentaerythritol tetrakis (3-mercaptopropionate),
Dipentaerythritol hexakis (3-mercaptopropionate),
Pentaerythritol tetrakis (3-mercaptobutyrate),
Trimethylolpropane tris (3-mercaptobutyrate),
Trimethylolethane tris (3-mercaptobutyrate),
The curing according to any one of claims 1 to 3, which is at least one selected from tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and tris (3-mercaptopropyl) isocyanurate. Resin composition.   The curing according to any one of claims 1 to 4, wherein the component (A) is (i) a phosphorus-containing epoxy resin, or (ii) a mixture of a phosphorus-containing epoxy resin and a phosphorus-free epoxy resin. Resin composition.   Furthermore, (D) Curable resin composition of any one of Claims 1-5 containing an inorganic filler. Furthermore, the following formula (I-2):
2 ≦ Y ≦ 13 (I-2)
The curable resin composition of any one of Claims 1-6 which satisfy | fills.   It is a kit containing the curable resin composition of any one of Claims 1-7, Comprising: This kit contains the 1st component containing at least (A) component, and the 2nd containing at least (B) component. A kit comprising: a component.   Heat curing the curable resin composition according to any one of claims 1 to 7, or mixing the first component and the second component contained in the kit according to claim 8. Epoxy resin cured product obtained by doing.   An adhesive comprising the curable resin composition according to any one of claims 1 to 7 or the kit according to claim 8.   The adhesive according to claim 10, which is used for electronic parts.   The adhesive according to claim 10 or 11, having a viscosity of 0.1 to 1000 Pa · sec when measured at 25 ° C using an E-type viscometer.   The sealing material containing the curable resin composition of any one of Claims 1-7, or the kit of Claim 8.   14. The sealing material according to claim 13, which is used for electronic parts.   An electronic component comprising the cured product according to claim 9.