JP5630182B2 - Epoxy resin composition and epoxy resin / polyethersulfone composite - Google Patents

Description

  The present invention relates to an epoxy resin composition and an epoxy resin / polyethersulfone composite formed by curing the epoxy resin composition.

  Epoxy resins are widely used as resins having excellent adhesiveness, heat resistance, and mechanical strength. However, with epoxy resins alone, the cured product is hard and brittle, so that toughening has been an issue.

  Therefore, conventionally, super engineering plastic polyethersulfone (hereinafter referred to as PES) is alloyed into an epoxy resin, thereby toughening the epoxy resin (for example, see Patent Documents 1-3). .

  The method of alloying PES with this epoxy resin is to prepare a melt of epoxy resin and PES by stirring or kneading the epoxy resin and PES while heating, and then adding a curing agent to the melt. Thus, an epoxy resin composition is prepared, and the epoxy resin composition is heated and cured to obtain a toughened cured product (see, for example, paragraph 0028 of Patent Document 3). In this hardened | cured material, the effect of toughening becomes high, so that there are many ratios of PES with respect to an epoxy resin.

Japanese Patent No. 3142425 Japanese Patent No. 4172220 Japanese Patent No. 4428978

  By the way, the cured product of an epoxy resin alloyed with PES takes a phase structure of a matrix domain in which domains are dispersed in a matrix (so-called sea-island structure) (see, for example, Patent Documents 1 to 3). For toughening, it is desired that tough PES be a matrix and epoxy resin be a domain.

  Moreover, when using an epoxy resin as an adhesive agent, it is calculated | required that it is a liquid which has fluidity | liquidity in the temperature at the time of adhesion | attachment work, ie, normal temperature, from a viewpoint of adhesion workability (handleability).

  However, the conventional epoxy resin composition obtained by blending the cured product after dissolving the epoxy resin and PES has a problem that the adhesive workability is poor because it becomes a viscous or solid material having low fluidity. .

  In view of the above points, the present invention provides an epoxy resin composition having improved adhesion workability as compared with a conventional epoxy resin composition having the same ratio of PES to the epoxy resin, while toughening the cured product. For the purpose.

In order to achieve the above object, in the invention according to claim 1, in an epoxy resin composition comprising an epoxy resin, a curing agent and polyethersulfone,
The mass ratio of the epoxy resin to the polyether sulfone is 80:20 to 40:60, and is a solid particulate form with respect to a mixture of the liquid epoxy resin (2) and diethyltoluenediamine as a curing agent at room temperature. A liquid composition (1) in which the polyethersulfone (3) is dispersed,
When the liquid composition is cured, the cured product (10) has a matrix domain phase structure in which polyethersulfone is used as the matrix (11) and the epoxy resin domains (12) are dispersed in the matrix (11). It is characterized by taking.

Thus, at room temperature, solid particulate polyethersulfone is dispersed in a mixture of liquid epoxy resin and diethyltoluenediamine as a curing agent, and the mass ratio of epoxy resin to PES is 80. : The phase structure of the cured product of the epoxy resin composition can be made to be a matrix-domain structure in which the domains of the epoxy resin are dispersed in the matrix of the PES by increasing the proportion of PES than in the case of 20. For this reason, compared with the case of an epoxy resin alone, toughening of hardened | cured material is attained.

And the conventional epoxy resin composition whose ratio of PES with respect to an epoxy resin is the same by setting it as the structure by which solid particulate PES was disperse | distributed with respect to the mixture of a liquid epoxy resin and diethyl toluenediamine as a hardening | curing agent. An epoxy resin composition having improved adhesion workability can be provided as compared with a product.

  Moreover, according to this invention, the ratio of PES with respect to an epoxy resin is large, and the epoxy resin composition with favorable adhesive workability | operativity at normal temperature can be provided. However, the proportion of PES is made smaller than when the mass ratio of epoxy resin to PES is 40:60. This is because if the proportion of PES is larger than that at this time, the bonding workability is deteriorated.

  In particular, as described in claim 2, even if the blending ratio of the epoxy resin and the PES is a range in which a liquid epoxy resin composition cannot be obtained conventionally (epoxy resin: PES = 60: 40 to 40:60) An epoxy resin composition that is liquid at room temperature can be provided.

  Moreover, in invention of Claim 1, 2, as described in Claim 3, solid particle-like polyethersulfone (3) disperse | distributed to a liquid epoxy resin (2) has an average particle diameter. It is preferable that it is 1 mm or less. By doing in this way, an epoxy resin and PES can be dissolved uniformly at the time of heating for hardening.

  Moreover, in invention of Claims 1-3, as described in Claim 4, it is preferable that the average particle diameter of the domain (12) in hardened | cured material (10) is 1 micrometer or more and 10 micrometers or less.

  The invention described in claim 5 is an epoxy resin / polyethersulfone composite formed by curing the epoxy resin composition (1) according to any one of claims 1 to 4.

  In addition, the code | symbol in the bracket | parenthesis of each means described in this column and the claim shows the correspondence with the specific means as described in embodiment mentioned later.

It is a schematic diagram which shows the epoxy resin composition and its hardened | cured material in this invention. 4 is a SEM photograph of the cured product of Example 4.

  FIG. 1 is a schematic diagram showing an epoxy resin composition 1 and a cured product 10 thereof according to the present invention. The epoxy resin composition 1 contains an epoxy resin, a curing agent, and PES. As shown in FIG. 1A, a liquid composition in which solid particulate PES 3 is dispersed in a liquid epoxy resin 2. The liquid epoxy resin 2 contains a curing agent.

  The epoxy resin composition 1 is suitable for an adhesive between plastics and ceramics, for example, an adhesive between a main body and a lid of a resin (or ceramics) package that houses electronic parts such as various sensors. The bonding operation is usually performed at room temperature (room temperature). Since the epoxy resin composition 1 is in a liquid state at room temperature, it is easy to handle and facilitates the bonding operation.

  Then, as shown in FIG. 1 (c), the cured product 10 obtained by heating the epoxy resin composition 1 under predetermined curing conditions and then cooling it has PES as a matrix 11, and the epoxy resin is contained in the matrix. The domain structure of the matrix domain is dispersed.

  More specifically, the epoxy resin composition 1 shown in FIG. 1A is obtained by stirring and mixing a liquid epoxy resin 2, a powdery PES 3 and a curing agent at room temperature. This normal temperature means a normal temperature (room temperature) that is not heated. Thus, since PES is not dissolved in the epoxy resin, it can be made liquid at room temperature, and the viscosity can be lowered as compared with the case where PES is dissolved in the epoxy resin as in the prior art.

  Examples of the epoxy resin used at this time include bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, resorcinol, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoroacetone. Glycidyl ether type obtained by reaction of polychlorophenol such as tetramethylbisphenol F, bixylenol, dihydroxynaphthalene and epichlorohydrin, or alicyclic glycidyl ether type by hydrogenation thereof; glycerin, neopentyl glycol, ethylene Glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polyethylene Polyglycidyl ether type obtained by reaction of an aliphatic polyhydric alcohol such as propylene glycol and epichlorohydrin; glycidyl ester type obtained by reaction of a hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid and epichlorohydrin; Derived from polycarboxylic acids such as phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endmethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acid, etc. Polyglycidyl ester type; glycidylaminoglycidyl ether type derived from aminophenol, aminoalkylphenol, etc .; glycidylaminoglycidyl ester derived from aminobenzoic acid ; More backbone polyether, polyurethane, polycarbonate, polyester, polyacrylate, and the like flexibility epoxy resin is a silicone. These epoxy resins may be used alone or in combination of two or more. In particular, a bisphenol type epoxy resin is suitably used as an epoxy resin having excellent physical properties and adhesiveness.

  Moreover, the hardening | curing agent used at this time will not be specifically limited if it is a hardening | curing agent which can be used with respect to an epoxy resin. Examples thereof include amine-based curing agents, acid or acid anhydride-based curing agents, basic active hydrogen compounds, imidazoles, polymercaptan-based curing agents, phenol resins, urea resins, melamine resins, and isocyanate-based curing agents. A hardening | curing agent can be used individually or in combination of 2 or more types, respectively.

  Examples of the amine curing agent include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis (hexamethylene) triamine, and 1,3,6-trisaminomethylhexane. Polyamines; polymethylenediamines such as trimethylhexamethylenediamine, polyetherdiamine, diethylaminopropylamine; mensendiamine (MDA), isophoronediamine (IPDA), bis (4-amino-3-methylcyclohexyl) methane, diamino Dicyclohexylmethane, bisaminomethylcyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, manufactured by Mitsui Chemicals, Inc. Cycloaliphatic polyamines such as norbornane skeleton diamines typified by NBDA; aliphatic polyamines containing aromatic rings such as metaxylylenediamine (MXDA); metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane Aromatic polyamines such as these, and derivatives thereof.

  Other amine curing agents include, for example, Mannich-modified diamine obtained by reacting polyamine with aldehyde and / or phenol; amine adduct (polyamine epoxy resin adduct), polyamine-ethylene oxide adduct, polyamine-propylene oxide adduct, cyanoethyl Polyamine, ketimine which is a reaction product of aliphatic polyamine and ketone; tetramethylguanidine, triethanolamine, piperidine, pyridine, benzyldimethylamine, picoline, 2- (dimethylaminomethyl) phenol, dimethylcyclohexylamine, dimethylbenzylamine , Dimethylhexylamine, dimethylaminophenol, dimethylamino-p-cresol, N, N'-dimethylpiperazine, 1,4-diazadisi B Secondary amines such as [2.2.2] octane, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] -7-undecene or Tertiary amines; liquid polyamides obtained by reacting dimer acids with polyamines such as diethylenetriamine and triethylenetetramine.

  Examples of the acid or acid anhydride curing agent include polycarboxylic acids such as adipic acid, azelaic acid and decanedicarboxylic acid; phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol Aromatic acid anhydrides such as tris (andro trimellitate), pyromellitic anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid anhydride; maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, methylnadic anhydride, alkenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic anhydride, methylhymic anhydride, trialkyltetrahydrophthalic anhydride, Poly (phenylhexadecane Cyclic aliphatic acid anhydrides such as acid) anhydrides; aliphatic acids such as polyadipic acid anhydrides, polyazeline acid anhydrides, polysebacic acid anhydrides, dodecenyl succinic anhydride, poly (ethyloctadecanedioic acid) anhydrides Anhydrides: Halogenated acid anhydrides such as chlorendic anhydride, tetrabromophthalic anhydride, and het anhydride.

  Examples of the basic active hydrogen compound include dicyandiamide and organic acid dihydrazide.

  Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl. 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-methylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazoline- (1)]-ethyl-S- Triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazoline- (1)]-ethyl-S-triazine.

  Examples of polymercaptan curing agents include, for example, partial epoxy adducts of 2,2′-bismercaptoethyl ether; pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate, trimethylolpropane dorithioglycolate, etc. An ester of thioglycolic acid; a compound containing a mercapto group such as a polysulfide rubber having a mercapto group at the terminal.

  Examples of isocyanate curing agents include isocyanate compounds such as toluene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate; blocked isocyanate compounds formed by reacting an isocyanate group with a blocking agent such as phenol, alcohol, and caprolactam. Is mentioned.

  As shown in FIG. 1 (b), when the epoxy resin composition 1 is heated under predetermined curing conditions, the solid particles of PES are completely dissolved in the epoxy resin to become a transparent resin. At this time, it is preferable that the average particle diameter of PES3 in the epoxy resin composition 1 shown in FIG. 1A is 1 mm or less so that PES is uniformly dissolved in the epoxy resin. This is because stirring is not performed during heating for curing. Therefore, if the average particle size is larger than 1 mm, even if PES is dissolved during heating, the portion where the PES particles existed is an area of only PES. This is because PES cannot be uniformly dissolved in the resin.

  When the epoxy resin composition 1 is heated under predetermined curing conditions and then cooled, a cured product having a matrix-domain dispersion structure shown in FIG. 1C is obtained. This is because the molecular weight of the epoxy resin is small before the reaction between the epoxy resin and the curing agent, so that the compatibility with PES is high, whereas the molecular weight of the epoxy resin after the reaction between the epoxy resin and the curing agent is high. This is because the compatibility with PES becomes low. This cured product is an epoxy resin / polyethersulfone composite.

  Incidentally, in the dispersed structure of the matrix domain of the cured product 10, the average particle diameter of the domain 12 of the epoxy resin is 1 μm or more and 10 μm or less. Further, the PES matrix 11 may contain a slight amount of epoxy resin, and the epoxy resin domain 12 may contain a slight amount of PES.

  Moreover, the epoxy resin composition 1 of this invention is a thing with the compounding ratio of the liquid epoxy resin 2 and solid particulate PES3 in the range of 80: 20-40: 60 by mass ratio.

  The ratio of PES is larger than when the mass ratio of the epoxy resin and PES is 80:20. The phase structure of the cured product 10 is epoxy in the matrix 11 of PES as shown in the examples described later. This is because the resin can have a matrix domain structure in which the resin domains 12 are dispersed. Thereby, tough PES becomes a matrix, and the epoxy resin becomes a domain. Therefore, according to the epoxy resin composition 1 of the present invention, the toughened (bending strength, Bending strain can be improved) and adhesive strength can be improved.

  Moreover, if the mass ratio of an epoxy resin and PES is 40:60, the ratio of PES is made smaller if the ratio of PES is smaller than that at this time, as shown in Examples described later. This is because the product 1 becomes liquid and good adhesion workability is obtained when used as an adhesive.

  Tables 1 and 2 show the blending ratios of the epoxy resin compositions and the evaluation results of the cured products in Examples and Comparative Examples of the present invention.

In Examples 1 to 5 and Comparative Examples 1 to 3, liquid epoxy resins, powdered PES, and aromatic polyamines as curing agents were blended simultaneously at the blending ratio (mass ratio) shown in Table 1, at room temperature. The epoxy resin composition was prepared by stirring at In Comparative Example 1, it was produced in the same manner as in Examples 1 to 5 except that PES was omitted.

  On the other hand, in Comparative Examples 4-8, after melt | dissolving an epoxy resin and PES with the mixing ratio shown in Table 2, the aromatic polyamine as a hardening | curing agent was mix | blended and the epoxy resin composition was produced. In Comparative Examples 4 to 8, the heating temperature was 100 ° C.

  And the hardened | cured material obtained by hardening | curing the epoxy resin composition produced in each Example and each comparative example was evaluated.

The epoxy resin, PES and aromatic polyamine, curing conditions, and evaluation methods used in each example and each comparative example are as follows.
[material]
・ Epoxy resin: Bisphenol A diglycidyl ether (Product name DER331J, manufactured by Dow Chemical Company)
・ PES: Product name Sumika Excel 5003PS, Sumika Chemtex Co., Ltd. ground to 100 μm or less ・ Aromatic polyamine: Diethyltoluenediamine (Product name: JER Cure W, Mitsubishi Chemical)
[Curing conditions]
100 ° C., 2 hours + 180 ° C., 3 hours [Evaluation of cured product]
The average particle size was calculated by measuring a plurality of domain particle sizes from SEM observation.
A bending test was performed at room temperature in accordance with JIS K 7171, and bending strength and bending strain were measured.

Specimen size: length 80mm x thickness 4mm x width 10mm
Test speed: 2 mm / min
In Tables 1 and 2, “> numerical value” indicates that the numerical value was a measurement limit value. This is because the specimen was not bent any further and could not be measured until the specimen was broken. In practice, this means that a higher numerical value is obtained as a result.
A shear adhesion test was performed at room temperature in accordance with JIS K 6850, and the adhesive strength was measured.

Substrate size: length 100mm x thickness 3mm x width 20mm
Overlap width: 10mm
Test speed: 5mm / min
As shown in Table 1, in Comparative Examples 1 and 2 in which the blending ratio of PES was 0 and 10, the phase structure of the cured product was a matrix-domain structure in which the matrix was an epoxy resin and the domain was PES. .

  In contrast, in Examples 1 to 5 in which the blending ratio of PES was 20 to 60, the phase structure of the cured product was a matrix-domain structure in which the matrix was PES and the domain was an epoxy resin. As an example of this matrix domain structure, FIG. 2 shows an SEM photograph of the cured product of Example 4. As shown in FIG. 2, spherical domain particles made of an epoxy resin are dispersed in a matrix made of PES, and the same structure is confirmed in other examples. Incidentally, as shown in Table 1, the average particle diameter of the domains made of the epoxy resin in Examples 1 to 5 was 2 to 6 μm.

  As can be seen from the results shown in Table 1, the bending strength, bending strain and adhesive strength of the cured products in Examples 1 to 5 are improved as compared with Comparative Example 1.

  Moreover, the epoxy resin compositions of Examples 1 to 5 are liquid at 25 ° C., and it can be said that the adhesion workability (handleability) at room temperature is good. Incidentally, among Examples 1-5, Examples 1 and 2 have the lowest viscosity, and it can be said that the adhesion workability (handleability) is the best.

  On the other hand, it can be said that the epoxy resin composition of Comparative Example 3 having a PES blending ratio of 70 is powdery at 25 ° C. and has poor adhesion workability (handleability) at room temperature.

  Therefore, from these results, it can be seen that the blending ratio of the epoxy resin and PES is preferably in the range of 80:20 to 40:60 in terms of mass ratio.

  Moreover, as shown in Table 2, the epoxy resin compositions of Comparative Examples 4 to 8 have the same blending ratios of the epoxy resin compositions of Examples 1 to 5 and the epoxy resin and PES, respectively. Compared with the examples of the blending ratio, the adhesion workability (handleability) was poor. That is, the properties of the epoxy resin composition at 25 ° C. are Comparative Examples 4 and 5, which are viscous liquids having higher viscosity and lower fluidity than those of Examples 1 and 2, respectively. It was a semi-solid with little property, and Comparative Examples 7 and 8 were solid.

  Therefore, as can be seen by comparing the properties of the epoxy resin compositions of Examples 1 to 5 and Comparative Examples 4 to 8, when the compounding ratio of the epoxy resin and PES is the same, the configuration of the epoxy resin composition is As in 1-5, by setting the solid particulate PES to the liquid epoxy resin, the cured product is dissolved after the epoxy resin and PES are dissolved, as in Comparative Examples 4-8. It can be said that the adhesion workability at room temperature can be improved as compared with a conventional epoxy resin composition obtained by blending.

  Further, as described above, the epoxy resin compositions of Comparative Examples 6, 7, and 8 were not liquid at 25 ° C., whereas the epoxy resin compositions of Examples 3, 4, and 5 were liquid at 25 ° C. .

  From this, according to the present invention, the compounding ratio of the epoxy resin and PES is within a range in which a liquid epoxy resin composition cannot be obtained conventionally (epoxy resin: PES = 60: 40 to 40:60). It can be said that an epoxy resin composition which is liquid at room temperature can be obtained. Incidentally, when the compounding ratios of Examples 3, 4, and 5 are converted, Examples 3, 4, and 5 are 67 parts by mass, 100 parts by mass, and 150 parts by mass, respectively, with respect to 100 parts by mass of the epoxy resin. .

DESCRIPTION OF SYMBOLS 1 Epoxy resin composition 2 Liquid epoxy resin 3 Solid particulate PES
10 Cured product of epoxy resin composition 11 Matrix (= PES)
12 domains (= epoxy resin)

Claims (5)

In an epoxy resin composition comprising an epoxy resin, a curing agent and polyethersulfone,
The mass ratio of the epoxy resin to the polyethersulfone is 80:20 to 40:60, and at room temperature, the liquid epoxy resin (2) and the mixture of diethyltoluenediamine as the curing agent A liquid composition (1) in which the polyethersulfone (3) in the form of solid particles is dispersed,
The cured product (10) obtained by curing the liquid composition has a matrix domain in which the polyethersulfone is used as the matrix (11) and the epoxy resin domains (12) are dispersed in the matrix (11). An epoxy resin composition having a phase structure.   The epoxy resin composition according to claim 1, wherein a mass ratio of the epoxy resin to the polyethersulfone is 60:40 to 40:60.   3. The epoxy resin composition according to claim 1, wherein the polyethersulfone (3) in the form of solid particles has an average particle diameter of 1 mm or less.   The epoxy resin composition according to any one of claims 1 to 3, wherein an average particle diameter of the domain (12) in the cured product (10) is 1 µm or more and 10 µm or less.   An epoxy resin / polyethersulfone composite obtained by curing the epoxy resin composition (1) according to any one of claims 1 to 4.