JPH0517252B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a method of manufacturing a structure using a photocurable epoxy resin used for pipes, hollow tanks, insulating rods, etc. [Conventional technical background and problems thereof] Phenol resins, polyester resins, epoxy resins, etc. are known as synthetic resins generally used for pipes, tanks, rods, etc. Among these, epoxy resins are mainly used because they have a particularly low viscosity, are easy to impregnate, and have good adhesive properties. These resins are usually cured by heating,
Because the heating process takes a long time, manufacturing takes a long time. In addition, when continuously manufacturing pipes, rods, etc., there is a problem that when heated, the initial viscosity decreases and the composition tends to drip, and this problem is especially true when manufacturing long structures. This was remarkable and caused many defective products to be produced. [Objective of the Invention] The present invention solves the above-mentioned problems and manufactures a structure using a light-cured epoxy resin that cures quickly by light, especially ultraviolet irradiation, and does not drip due to viscosity reduction due to heating. The purpose is to [Summary of the invention] The present invention provides roving-like, strand-like, non-woven fabric,
At least one type of film-like base material is impregnated and coated with a composition containing as essential components an epoxy resin, an aluminum compound, and a silicon compound that generates silanol groups when irradiated with light, and the base material is shaped into a desired shape. This is a method for producing a structure using a photocurable epoxy resin, which is characterized in that the composition is cured by light irradiation.
It is characterized by consisting of an epoxy resin; an aluminum compound; and a silicon compound that generates silanol groups upon irradiation with light. First, as the epoxy resin used in the present invention,
Examples include monofunctional epoxy compounds and polyfunctional epoxy compounds. Monofunctional epoxy compounds include ethylene oxide, propylene oxide,
Examples include butylene oxide, styrene oxide, phenyl glycidyl ether, butyl glycidyl ether, and the like. The polyfunctional epoxy compound is not particularly limited, but includes, for example, bisphenol A epoxy resin; bisphenol F epoxy resin; phenol novolak epoxy resin; alicyclic epoxy resin; triglycidyl isocyanate, hydantoin epoxy Heterocyclic epoxy resins such as hydrogenated bisphenol A type epoxy resins; aliphatic epoxy resins such as propylene glycol-dicrycidyl ether and pentaerythritol-boriglycidyl ether; aromatic, aliphatic or alicyclic carboxylic acids Epoxy resin obtained by the reaction of and epichlorohydrin; Spiro ring-containing epoxy resin; Glycidyl ether type epoxy resin which is a reaction product of o-allyl-phenol novolak compound and epichlorohydrin; Each hydrogen group of bisphenol A o-
Examples include glycidyl ether type epoxy resins which are the reaction products of diallybisphenol compounds having an allyl group at the position and epichlorohydrin, and one or more selected from these can be used as desired. . The aluminum compound, which is the second component of the composition used in the present invention, has an alkoxy group, phenoxy group, acyloxy group, β
A complex compound of organoaluminum to which -diketonato group, o-carbonylphenolate group, etc. is bonded is preferable. Here, the alkoxy group preferably has 1 to 10 carbon atoms, such as methoxy, ethoxy, isoproboxy, butoxy, pentoxy, etc., and the phenoxy group includes phenoxy group, o-
Examples include methylphenoxy group, o-methoxyphenoxy group, p-nitrophenoxy group, 2,6-dimethylphenoxy group, and examples of acyloxy group include acetato, propionato, isopropionato, butyrate, stearato, and ethyl acetoacetate. , propyl acetato, butylacetoacetate, diethylmalato, dipivaloylmethanato, and the like; examples of the β-diketonato group include acetylacetonato, trifluoroacetylacetonato, hexafluoroacetylacetonato,

【formula】

【formula】

Examples of the o-carbonylphenolate group include salicylaldehydato. Specific examples of such aluminum compounds include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum, isopropoxydiethoxyaluminum, trisputoxyaluminum, tris Aluminum acetoxy, aluminum trisstearato, aluminum aluminum trisphthylate, aluminum aluminum trisprobionato, aluminum aluminum trisisoprobionato, aluminum aluminum trisacetylacetonato, aluminum aluminum trifluoroacetylacetonato, aluminum aluminum trishexafluoroacetylacetonato, aluminum trisethyl acetoacetate Tatoaluminum, trissalicylaldehydatoaluminum, trisdiethylmalolatoaluminum, trispropylacetoacetatoaluminum, trisbutylacetoacetatoaluminum, trisdibivaloylmethanatoaluminum, diacetylacetonatodibivaloylmethanatoaluminum

[Embodiments of the invention]

Embodiments of the present invention will be described based on the drawings. Examples 1 to 6 The manufacturing equipment used in the examples of the present invention was a roving feeder as shown in FIG. 1 as a top view of a partially cut away main part, and as shown in FIG. 2 as a side view of a partially cut away main part. 1. This is an apparatus consisting of a resin impregnation machine 2, a winding body 3, and an ultraviolet irradiation machine 4. With this manufacturing apparatus, a hollow pipe was manufactured using a mandrel 6 using a glass roving 5 as a base material. The manufacturing conditions are as follows. ERL4221 (product name,
Manufactured by UCC; alicyclic, epoxy equivalent: 145), Epicote 828 (trade name, manufactured by Ciel Chemical Co., Ltd.; bisphenol A type, epoxy equivalent: 190-210), Epicote
1001 (trade name, manufactured by Ciel Chemical Co., Ltd.; bisphenol A type, epoxy equivalent weight 450-525, molecular weight 900), Epicote 1004 (trade name, manufactured by Ciel Chemical Co., Ltd.; bisphenol type A, epoxy equivalent weight 900-1000, molecular weight
1400), and the organoaluminum compounds include trisisopropoxyaluminum (TIPA), trisethylacetoacetatoaluminum (TEAACA), tris-n-butylacetoacetatoaluminum (TBAAA), and trissalicylaldehydatoaluminum (TSAA). ), triphenyl(o-nitrobenzyloxy)silane (TPONS), triphenyl(tert-butylperoxy)silane (TPTBS), and triphenyl(benzoyl)silane (TPBZS) were used as organosilicon compounds, and a sensitizer was used. Benzophenone was used as the The compositions of Examples 1 to 6 were prepared by blending these compounds into the compositions shown in Table 1 (shown in parts by weight). Glass roving 5 is GYR-30FIWE (Nittobo
Co., Ltd.) is set in the roving feeder 1, introduced into the resin impregnation machine 2 through guide rails 7a and 7b, and then passed through the guide rail 7c to the end plate 8 with a pin at one end of the mandrel 6. tied together. The mandrel 6 is made of hollow iron and has dimensions of 137 mmφ x 2100 mm, and an end plate 8 with a pin is provided at its end for hooking the glass roving 5. The winding conditions are 45° helical winding with traverse 9 at 90 revolutions/min and mandrel 6 at 25 revolutions/min, and traverse 9 at 88 revolutions and mandrel 6 at 25 revolutions/min.
Alternating parallel windings of 88° were carried out at a speed of revolutions per minute. Under the above conditions, the compositions of Examples 1 to 6 in Table 1 were put into the resin impregnation machine 2, and impregnated into the glass roving 5 supplied from the roving supply machine 1. Board 8
wrapped around. At this time, the thickness of the mandrel 6 is set in advance.
A pipe wrapped with a 25 μm polyester film (not shown) and then cured is attached to a mandrel 6.
I made it easy to remove. Next, this glass roving 5 was wound around a mandrel 6 and set on it at a distance of about 10 cm.
The tube was irradiated with ultraviolet rays using an ultraviolet irradiator 4 equipped with a high-pressure mercury lamp (not shown) of 80 W/cm, and the pipe was manufactured by winding it in 8 layers while proceeding with curing reaction. Thereafter, the mandrel 6 is removed from the winding machine main body 3, and after cooling in a drying oven (not shown) at 150°C for 1 hour, the end plate 8 with pins is cut off, and the hollow pipe is removed from the mandrel 6. I pulled it out. The obtained pipe was cut to a width of 20 mm, and a tensile test was performed using a jig 10 shown in a front view in FIG. 3 and in a side view in FIG. In addition, a compression test was conducted using the jig 11 shown in a front view in FIG. 5 and in a side view in FIG. Next, a NOL ring test was conducted using the jig 12 shown in the front view in FIG. 7 and in the side view in FIG. Furthermore, a buckling test was conducted on a pipe cut to a width of 200 mm using jig 13 shown in a side view in FIG. The above results are also shown in the table.

【table】

〔Effect of the invention〕

According to the manufacturing method of the present invention, it is possible to manufacture a structure using a photocurable epoxy resin that cures in a short time without dripping due to a decrease in viscosity during the manufacturing process.

[Brief explanation of the drawing]

The drawings show the manufacturing method of the present invention and various strength testing methods for structures manufactured by the manufacturing method. Figure 2 is a partially cutaway side view of the main part, Figure 3 is a front view showing the state of the tensile test, Figure 4 is the side view, Figure 5 is a front view showing the state of the compression test, and Figure 6. is its side view, and Figure 7 is its side view.
FIG. 8 is a front view showing the state of the NOL ring test, FIG. 8 is a side view thereof, and FIG. 9 is a side view showing the state of the buckling test. 1... Roving supply machine, 2... Resin impregnation machine,
3...winding machine body, 4...ultraviolet radiation, 5...glass roving, 6...mandrel.

Claims (1)

[Scope of Claims] 1. A composition containing, as essential components, an epoxy resin, an aluminum compound, and a silicon compound that produces silanol groups when irradiated with light, in at least one base material selected from among roving, twine, nonwoven fabric, and film. A method for producing a structure using a photocurable epoxy resin, which comprises impregnating and coating a base material to form a desired shape, and then curing it by light reflection. 2 The base material is glass, carbon, boron, copper, iron,
2. A method for manufacturing a structure using a photocurable epoxy resin according to claim 1, wherein the photocurable epoxy resin is at least one organic polymer material. 3. A method for producing a structure using a photocurable epoxy resin according to claim 1, wherein the aluminum compound is an organic aluminum compound. 4 The silicon compound has a peroxysilane group, o-
A method for producing a structure using the photocurable epoxy resin according to claim 1, which is a silicon compound having either a nitrobenzyloxy group or an α-ketosilyl group. 5. Using the photocurable epoxy resin according to claim 1, wherein the aluminum compound and the silicon compound are blended in amounts of 0.001 to 10% by weight and 0.1 to 20% by weight, respectively, based on the weight of the epoxy resin. Method of manufacturing the structure.