JP6571242B1 - Epoxy resin composition - Google Patents

Abstract

An object of the present invention is to provide a design property so that it is not known whether or not it is fixed with an adhesive, and to fix the cocoon frame material and the cocoon wing, which has a driving resistance enough to prevent the wings from shifting even if they are driven. An epoxy resin composition is provided. SOLUTION: 15 to 25% by weight of bisphenol epoxy resin, 5 to 15% by weight of softening epoxy resin, 10 to 20% of amine curing agent, and calcium carbonate as a whole. It is to obtain an epoxy resin composition containing 40 to 60% by weight and 1 to 10% by weight of the whole aluminum powder obtained by the atomizing method. [Selection figure] None

Description

  The present invention relates to an epoxy resin composition suitable for fixing a cocoon frame material and a wing of a loom.

Patent Document 1 is a loom publication relating to weaving of a three-dimensional fabric. Since the loom weaves the warp and weft yarns, it requires a kite.
Patent Document 2 is a publication relating to a wing material that has wear resistance and corrosion resistance and can be applied to special fiber yarns such as titanium oxide coated fibers for UV cut.

  The kite needs to align the warp yarns at regular intervals, guide the weft yarn conveyance, and drive it in, so it is necessary to arrange the kite wings at equal intervals, and it is necessary to have a driving resistance that does not cause the warp wings to be misaligned. It becomes.

Patent Document 2 does not show a method for fixing a wing feather to a heel frame material, but this fixing may be performed with an adhesive.
As shown in Patent Document 2, if the wing material is a metal and it is fixed with a normal adhesive, that portion becomes conspicuous, which is not preferable in appearance.
In some cases, it is not known whether or not it is fixed with an adhesive, and a fixing method having design properties may be used.

JP 2-191741 A JP2004-225085 JP2005-325149 JP 4-88077 JP2004-99887 JP2000-336333

  Although the compositions of Patent Document 3 and Patent Document 4 show a metallic appearance, they are only suitable for a metallic appearance in order to achieve another purpose, and are not suitable for fixing wings. . Patent Document 5 shows an adhesive composition for fixing an ornamental stone such as a watch to a decorative article base, but it is not suitable for fixing a wing.

  Patent Document 6 is an epoxy resin composition gazette, but there is room for improvement in driving resistance for fixing wings.

  Epoxy that secures the cocoon frame material and the cocoon wings, which has a design so that it does not know whether it is fixed with an adhesive, and has a puncture resistance that does not cause the cocoon wings to slip even if nailed. A resin composition is provided.

  The present inventor contains 15 to 25% by weight of bisphenol-based epoxy resin, 5 to 15% by weight of total flexibility-imparting epoxy resin, 10 to 20% of amine-based curing agent, and contains calcium carbonate as a whole. An epoxy resin composition containing 40 to 60% by weight of aluminum powder obtained by the atomization method and 1 to 10% by weight of the total was obtained.

  The epoxy resin composition of the present invention exhibits a stable adhesion to the frame material and the wings, has an impact resistance, and can have a design so that it is not known whether it is fixed with an adhesive.

  Contains 15 to 25% by weight of bisphenol-based epoxy resin, 5 to 15% by weight of total flexibility epoxy resin, 10 to 20% of amine-based curing agent, and 40 to 60% by weight of calcium carbonate. %, To provide an epoxy resin composition containing 1 to 10% by weight of the aluminum powder obtained by the atomizing method.

The present application and the epoxy resin composition are of a two-component type.
The amount of the bisphenol-based epoxy resin contained in the main agent is 10 to 30% by weight of the whole, and more preferably 15 to 25% by weight of the whole.
Examples of the bisphenol-based epoxy resin include bisphenol A diglycidylate, bisphenol F diglycidylate, bisphenol E diglycidylate, and bisphenol S diglycidylate, and may be a hydrogenated (hydrogenated) type. The molecular weight is 400 or less, and the basic structural formula of bisphenol A type epoxy is shown in Formula (1), but n = 0 isomer.

. . . (1)

... (2)

In addition to the bisphenol-based epoxy resin, the main agent includes a softening epoxy resin. The addition amount is 1 to 20% by weight of the whole, and more preferably 5 to 15% by weight of the whole.
The flexibility-imparting epoxy resin is a compound that lowers the crosslinking point of a cured epoxy composition, that is, an epoxy resin having a large epoxy equivalent.
The epoxy equivalent of bisphenol A diglycidylate is 190, the epoxy equivalent of bisphenol F diglycidylate is 170, and the epoxy equivalent of the softening epoxy resin is 220 or more.
More specifically, the flexibility-imparting epoxy resin is more than 1 in the case of the bisphenol type, as shown in the formula (2), compared to 1 for the bisphenol, epichlorohydrin and bisphenol. Mention may be made of epoxy compounds prepared and prepared. Specific products include Adeka Corporation, product name: Adeka Resin EP-4000 (total of n and m is 2, epoxy equivalent is 320), and the like.
Specific examples of non-bisphenol products include Emerald Performance, trade name: HyPoxRA-840 (bisphenol A diglycidylate adduct of carboxy-modified nitrile rubber, epoxy equivalent is 350), Dow Chemical Co., trade name: Examples thereof include epoxy resins such as DER732 (propylene glycol diglycidylate, epoxy equivalent is 320).

  A diluent can also be added to the main agent. Examples of the diluent include glycidylated aliphatic compounds and glycidylated ether compounds, and the number of glycidylated compounds is arbitrary. Representative examples include Yokkaichi Gosei Co., Ltd., trade name: DY-BP (butyl glycidyl ether), trade name: CY-BP (butyl glycidyl ether), trade name: EPOGOSE EN (C12-13 mixed alcohol glycidyl ether), product Name: Epogosay AN (C12-13 mixed alcohol glycidyl ether), trade name: Epogosay 2EH (2-ethylhexyl glycidyl ether), trade name: Epogosay HD (M) (1,6-hexanediol diglycidyl ether), etc. .

Examples of the curing agent include amine compounds. The addition amount is 5 to 25% by weight of the whole, and more preferably 10 to 20% by weight.
Specific product names of amine-based curing agents include: Evonik Japan Co., Ltd., trade name: Ancamide 260A, trade name: Ancamide 350A, trade name: Ancamide 375A, trade name: Ancamide 910, trade name: Ancamide 2050, Product name: Ancamide 2137, Product name: Ancamide 2353, Product name: Ancamide 2396, Product name: Ancamide 2426, Product name: Ancamide 2445, Product name: Ancamide 910, Product name: Ancamin 1110, Product name: Ancamin 1561, Product name : Ancamine 1618, Product name: Ancamine 1618F, Product name: Ancamine 1693, Product name: Ancamine 1704, Product name: Ancamine 1769, Product name: Ancamine 1884, Product name: Ancamine 1895, Product name: Ancamine 934, product name: Ancamine 2071, product name: Ancamine 2072, product name: Ancamine 2074, product name: Ancamine 2075, product name: Ancamine 2143, product name: Ancamine 2280, product name: Ancamine 2199, product name: Ancamine 2205, Product name: Ancamine 2228, Product name: Ancamine 2368, Product name: Ancamine 2405, Product name: Ancamine 2432, Product name: Ancamine 2422, Product name: Ancamine 2502, Product name: Ancamine 2505, Product name: Ancamine 2609, Product name : Ancamine 1618, Product name: Ancamine 1884, Product name: Ancamine 1934, Product name: Ancamine 2074, Product name: Ancamine 2143, Product name: Ancamine 2280, Product name: Ancamine 2596, Product name: Ann Min 2643, trade name: Ancamine 2644, trade name: Ancamine 2706, trade name: Ancamine 2730, trade name: Ancamine 2049, trade name: Ancamine 2264, trade name: Ancamine K-54, trade name: Ancamine K-61B, Pii・ Product name: Hardener PH-770, Product name: Hardener PH-776P, Product name: Hardener PH777P, Product name: Hardener PH-780, Product name: Hardener PH-781, Product name: Hardener PH782, trade name: Hardener PH785, trade name: Hardener PH-798, trade name: Hardener KA-861, trade name: Hardener KA-935, and the like.

The present application and the epoxy resin composition include calcium carbonate in the main agent and the curing agent for both color adjustment and viscosity adjustment. The amount of calcium carbonate added is 40 to 60% by weight after mixing the two main liquids and the hardener.
Calcium carbonate is commercially available from Nitto Flour Chemical Co., Ltd., Shiraishi Calcium Co., Maruo Calcium Co., Inoue Lime Industry Co., Ltd., Shimizu Kogyo Co., etc.
Examples of the calcium carbonate include heavy calcium carbonate obtained by crushing limestone, light calcium carbonate obtained by reacting carbon dioxide with slaked lime, and the like, and any of them may be used. As for the surface treatment of calcium carbonate, any of untreated products and treated products treated with a silane coupling agent or the like can be used.
In this application, Maruo Calcium Co., Ltd. product name: Snowlight SSS was used.

This application and an epoxy resin composition contain the aluminum powder produced by the atomization method which served as both color adjustment and viscosity adjustment. The addition amount is 0.5 to 15% by weight of the whole, more preferably 1 to 10% by weight of the whole, and it may be added only to either the main agent or the curing agent, or to both. Good.
In this application, the product name: Al-At-200 by Minalco Co., Ltd. was used for the aluminum powder produced by the atomization method.

The present application, epoxy resin composition is calcium carbonate, atomized aluminum powder, as long as the appearance and adhesive strength are not impaired, silica, kaolin, calcined kaolin, clay, calcium silicate, calcium sulfate, aluminum oxide (alumina), water Inorganic fillers such as aluminum oxide, aluminum silicate, titanium oxide, zinc oxide, magnesium carbonate, magnesium silicate, talc, zeolite, glass beads, and shirasu balloon can be added.
Polyethylene, polypropylene, polymethyl methacrylate, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-vinyl acetate copolymer, nylon, polyethylene terephthalate, polybutylene terephthalate, polystyrene Organic fillers such as ABS resin, acrylonitrile-styrene copolymer, and polycarbonate can be added.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and demonstrated in detail about this invention, a specific example is shown and it does not specifically limit to these. All the parts are parts by weight.

Main agent preparation bisphenol A diglycidylate of Example 1 (in Tables 1 to 3, described as BisAEP): 21.2 parts by weight, DER732: 9.9 parts by weight, Snowlite SSS: 29.5 parts by weight, Al-At -200: 5.5 parts by weight were weighed and stirred until uniform to obtain the main agent of Example 1.

Examples 2 to 8 and Comparative Examples 1 to 5 were prepared in the same manner as the preparation of the main agent in Example 1, with the mixing ratios shown in Tables 1, 2 and 3 of Comparative Examples 1 to 5. The main agent of ~ 5 was produced. BisFEP is bisphenol F diglycidylate, No. 600 is a crushed aluminum powder manufactured by Fukuda Metal Foil Powder Industry.

Curing agent preparation of Example 1 Ancamide 375A: 12.9 parts by weight, Hardener PH-770: 2.7 parts by weight, Snowlight SSS: 18.3 parts by weight were weighed and stirred until uniform, Example 1 A curing agent was obtained.

Curing agent preparation of Examples 2 to 8 and Comparative Examples 1 to 5, Examples 2 to 8 and Comparative Example in the same procedure as the curing agent preparation of Example 1 at the mixing ratio ratio shown in Table 1, Table 2 and Table 3 1 to 5 main ingredients were prepared.

Two-component stirring method The main agent and the curing agent were weighed so as to have a weight ratio of 2: 1, stirred slowly so as not to contain bubbles, and stirred until uniform. After checking the appearance using this two-component mixed solution, a shear test piece and a T-shaped peel test piece were prepared.

Appearance confirmation The above-mentioned two-component mixture was applied to an aluminum plate and stored in a 23 ° C. environment for 5 days to confirm the appearance after curing.
The case where the cured product was metallic and synchronized with the aluminum plate was marked with (◯), and the case where it was judged that the resin was clearly applied to the aluminum plate was marked with (x).
In addition, regarding the comparative example 5, since the external appearance was very bad, the shear test and the T-shaped peeling test were not performed.

Shear test The shear test was performed using a commercially available SPCC plate.
Apply the above two-component mixture to one of two SPCC plates with a thickness of 25 mm x 100 mm x 1.6 mm, and stack the other SPCC plate together so that the contact area is 25 mm x 12.5 mm. It was. The two clips were pressed and stored in a 23 ° C. environment for 5 days. The clip was removed and used as a shear specimen, and a shear test was performed.
The shear rate was 5 mm / min, and the adhesive strength measurement environmental temperature was 23 ° C./50% RH.
In the shear test, 13 MPa or more was evaluated as (◯), and the case where it was below 13 MPa was determined as (×).

T-shaped peel test The T-shaped peel test was performed using a commercially available aluminum plate.
Apply the above-mentioned two-component mixture to one of two aluminum plates of 25 mm × 100 mm × 0.5 mm thickness, leaving the end of the aluminum plate, and another piece of aluminum so that the bonding area is 25 mm × about 70 mm. The boards were stacked. The sample was placed on a weight so that a pressure of 0.05 MPa was applied uniformly and stored in a 23 ° C. environment for 5 days. After curing, the unbonded portion of the aluminum plate was bent approximately 90 ° in opposite directions to produce a T-shaped peel test piece, and a T-shaped peel test was performed.
The peeling rate was 50 mm / min, and the adhesive strength measurement environmental temperature was 23 ° C./50% RH.
In the T-peeling test, 0.6 N / mm or more was evaluated as (◯), and the case where it was below 0.6 N / mm was determined as (×).

  15-25% by weight of bisphenol-based epoxy resin, 5-15% by weight of epoxy resin with flexibility, 10-20% of amine-based curing agent, 40-60% by weight of calcium carbonate In Examples 1 to 8 containing 1 to 10% by weight of the aluminum powder obtained by the atomizing method, the appearance, the shear test, and the T-shaped peel test were (◯).

In Comparative Example 1 in which DER732, which is a flexibility-imparting epoxy resin, was more than the bisphenol-based epoxy resin, the shear test was (x).
In addition, Comparative Example 2 in which the amount of DER 732 added is extremely small and Comparative Example 3 in which no modified epoxy resin is added have a shear test and a T-shaped peel test of (×). This indicates that there is a risk of shifting.

No. of aluminum powder produced by the pulverization method, not aluminum powder produced by the atomizing method. The comparative example 4 which added 600 became (*) by the external appearance confirmation. The appearance of Comparative Example 5 to which calcium carbonate was not added was also (x).
It was shown that aluminum powder and calcium carbonate produced by the atomization method are essential components.

Claims (1)

Epoxy compound or emerald performance prepared by adding more than 1 of acrylic hydrin to 1 to 25% by weight of bisphenol epoxy resin, bisphenol and epichlorohydrin and bisphenol Product name: HyPoxRA-840 (bisphenol A diglycidylate adduct of carboxy-modified nitrile rubber, epoxy equivalent is 350), or product name: DER732 (propylene glycol diglycidylate, epoxy equivalent is 320) 5) to 15% by weight of the total amount of the softening epoxy resin selected from the above) , 10 to 20% of the total amount of the amine-based curing agent, and 40 to 60% by weight of the total amount of calcium carbonate. Contains 1 to 10% by weight of aluminum powder Mu epoxy resin composition.