JPS5985058A - Prestressed member and production and use thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a prestressing element coated or coated with two plastic layers.
, especially those in which the concrete layer is a storage-stable moldable and thermosetting composition and the outer layer is a hard radiation-cured plastic layer. The present invention relates to a method for manufacturing and a method for using the same.

A prestressing member with a two-layer plastic coating for concrete supporting structures is disclosed in German Patent Specification 1 “Second,
It has been known since before No. 018,941.

All-plastic coatings serve a variety of functions. The supporting core of the prestressing member must therefore be effectively protected from corrosion, and the plastic layer exhibits a very durable bond or bond (5) to the surrounding bonding material. At the same time, the two frass and tick layers must be firmly bonded together. , "The plastic layer of part A must also act as a protective layer for the inner plastic 741 ring.

In the subsequent processing, it is currently impossible to produce a double layer without the formation of corrodes and defects, which are the cause of corrosion and the formation of liquid in the bond, which is the cause of a decrease in strength. It is known that there is a problem with patrols. moreover,
It is highly desirable for the plastic layer of the exterior 1 to be accessible to the manufacturer as soon as possible, thus simplifying handling, storage and transport, and at the same time having effective protection of the interior. . No satisfactory solution has yet been proposed to overcome the spontaneous reactions that occur in the internal coating when external Kj is applied and cured.

An object of the present invention is to provide a restless component having two layers of blasted rice covering and hobbing (6). Once inserted, the two layers provide an effective line protection against corrosion, and the inner layer of the coated prestressed member is resistant to at least subsequent processing. It is storage stable until it is used. The coated prestressed member provided by the present invention is also easy to handle even immediately after its manufacture, and is also storable, and the outer layer is an effective protector of the inner layer reservoir. The generation of defect areas between those layers and the intermixing of those layers are almost eliminated. Furthermore, it avoids reacting the inner layers at the same time as the outer layers are cured. The outer layer must also have sufficient thermal insulation properties during heating and curing of the inner layer to avoid damage to the surrounding binder material.

The object material of the present invention is a moldable and thermosetting composition whose inner layer is storage stable at room temperature, and whose outer layer is made of a radiation-curable plastic (7) material. In addition, if it is necessary, the middle J
F (and the external frustacle 1).

Fresless members are generally reinforced with bonding agents.
God's thing τ used as U1 (can be completely decorated,
(:d! Can be used in various forms. Appropriate materials) Examples of materials include metal threads, structural materials, and similar materials. must be maintained.

Preferred forms of freeless members such as wires are, for example, rods, strips, l#@% stays, fibers, strands, single and multiple filaments, fabrics, mats.

The internal and IA filaments may be interbedded with interlayers of many types of materials, such as glass or gold, filaments. When the composition of the fresless member is a nonconductor, the intermediate layer may be electrically conductive, e.g. The layers containing or separating conductors are themselves electrical conductors.

For this purpose, in the case of non-conductors, the core of the prestressing element can also be wrapped with an electrical conductor before being coated.

The inner layer is storage stable at room temperature. Otsu means that if the composition is processed a little to avoid premature hardening, @Ushi will react only slightly. Additionally, the inner layer is moldable so that it can be smoothed without causing damage to the inner layer when pressure is applied, such as the occurrence of carcasses.

The inner layer can be in a low viscosity state to a solid state,
It can be thixotropic to avoid running or dripping of the applied material. If the inner layer is solid, its moldability is achieved (by heating and melting);
Depending on the packaging, the curing reaction can then already begin.

(9) The inner layer is thermosetting. In order to obtain non-shrinkage hardenability,
Preference is given to using starting materials which are hardened by polyaddition or polymerization in the form of duroplasts. Suitable starting materials are, for example, those based on unsaturated polyesters, in particular maleic acid, which can be used on their own or in admixture with olefinically unsaturated compounds as reaction diluents. These departures vl
The quality is known to those skilled in the art. Further suitable starting materials are polyesters based on acrylic acid and/or methacrylic acid and polyols, in particular reaction products of these acids with epoxy resins, in which self-reactive diluents as mentioned above can be used. .

Another solution to suitable starting materials is prepared by masked polyurethane, and phenol masked polyurethane.

These materials are also well known to those skilled in the art.

A preferred glue αO) for the strength of the bond obtained is a polyepoxide compound. Suitable such ones are, for example, especially those having on average more than one glycidyl group, such as petro g-< atoms (e.g. sulfur atoms,
a β-methylglycidyl group or a 2,3-epoxycyclopentyl group bonded to an oxygen atom or a nitrogen atom, respectively; as can be produced in particular from bis-(2j3-epoxycyclopentyl) ether, e.g. 1,4-butane diol, or di- or polyglycidyl ethers of polyhydric aliphatic alcohols, such as polyalkylene glycols, or polyalkylene glycols, such as polyalkylene glycols, 2,
Di- or polyglycidyl ethers of cycloaliphatic polyols such as 2-bis-(4-hydroxycyclohexyl)-propane, resorcinol, bis-(p-hydroxyphenyl)-methane, 2.2-bis-(p-hydroxyphenyl) )-propane to dimethane), 2.2-bis-
(4'-Hydroxy-3', 5'-dibromophenyl)α1)-furopane, 1,1,2.2-tetrakis-(p-hydroxyphenyl)-ethane, etc. Polyglycidyl ether or phenol
Condensation products of formaldehyde with phenols obtained under acidic conditions, such as novolacs and cresol novolacs, the above-mentioned polyhydric alcohols or polyphenol 7 or poly-(β-methylglycidyl) ethers;
Polyglycidyl esters of polycarboxylic acids such as phthalic acid, terephthalic acid, Δ-tetrahydrophthalic acid and hexahydrophthalic acid; N,N-diglycidylaniline, N,N-diglycidyltoluidine, N,N,N ',N
'-tetraglycidyl-bis-(p-aminophenyl)
- N-glycidyl derivatives of amines, amides and petrochemical nitrogen bases such as methane; triglycidyl-incyanure): N,N'-diglycidyl-ethyleneurea,
, N'-diglycidyl-5゜5-dimethylhydantoin, N,N'-diglycidyl-5-isopropyl-hydantoin, N,Nα2) -diglycidyl-5,5-dimethyl-6-improvil-5,6-sihydrouracil It is.

Before application, the polyepoxide compounds can optionally be pre-reacted with customary curing agents such as polyamines, polyols and polycarboxylic acids in order to form an isotropic, yet fusible product (B stage). .

If desired, to reduce the viscosity of the polyepoxide, e.g. styrene oxide, butyl glycidyl ether,
inoctyl glycidyl ether, phenyl glycidyl ether, te is cresyl glycidyl ether, or glycidyl esters of synthetic highly branched and mainly tertiary aliphatic monocarboxylic acids [CARDURA (CARD)
An active diluent such as URA)E) can be added. Such diluents are particularly used with solid noephoxide resins.

Preferred among the epoxide compounds are the glycidyl ethers of aromatic polyphenols, such as bisphenols. α3) Especially with an epoxy content of 3 to 8, especially 4 to 6V a
1/Kg% and a viscosity of about 1000 to 20,000, with a range of 1000 to 12,00 t)m/)is. Particularly preferred are glycidyl ethers of bisphenol-A1, bisphenol-F, and epoxide novolaks.

The thermosetting inner layer further incorporates a curing agent when the curing reaction is not initiated spontaneously upon application of heat. If desired, curing accelerators can also be added. A latent curing agent is then added to ensure storage stability. They are those that can be activated by heat.

This thermal activation can be based on physical or chemical mechanisms. Thus, the curable starting material can be a curing agent that is pebble at room temperature, but which decomposes and initiates curing upon heating and melting of the cured layer.

04) Curing agents that become reactive compounds when heated, e.g. radical products for unsaturated polyesters, or organic compounds that eliminate H-acids, such as bisphenols, polyols or polymercaptans for polyurethanes. ,
Alternatively, an organic compound that is completely eliminated or removed for a polyepoxide compound can be used by dissolving it in the starting material. Furthermore, it is also possible to use curing agent systems that react very slowly at room temperature and react very quickly when heated.

Latent hardeners suitable for polyepoxide compounds include:
The polyepoxide used is illegal at room temperature. Examples of these are benzoic acid, phenyl derivatives or
Aromatic carboxylic acids such as ethylene- or propylene diamine, diethylene triamine,
(2) Salts of aliphatic-monocycloaliphatic- and araliphatic polyamines such as 4-diaminocyclohexane or xylene diamine. They are first and second, tertiary polyamines, and preferably those tertiary polyamines containing dimethylamino groups. A group of urgent hardeners are solid mononuclear and polynuclear phenols such as bisphenols and novolacs, mononuclear and polynuclear aromatic polyamines, polycarboxylic acid anhydrides and polycarboxylic acids.

Solid hardeners formed from polyepoxide compounds and polyamines or polycarboxylic anhydrides are also suitable as hardeners. Dicyandiamide with a curing accelerator is also 4-functional. The curing agent is also a urea derivative,
Accelerators such as imidazole or tin salts can be used together.

The inner layer may also consist of a solid B-stage epoxy resin, which may be prepared directly by pre-reaction of the polyepoxide with hardeners such as polyphenols, aromatic polyamines and polycarboxylic anhydrides. It can be manufactured on prestressed parts. When the breathless member is placed under pressure, these B-stage resins can be melted by induction heating, thus ensuring lubrication, and then fully photocured. Pre-reaction methods can be recommended to increase storage stability when the epoxy resin/curing agent system in solution does not have sufficient storage stability.

Suitable radiation-curable starting materials for the outer layer include photopolymerizable, photodimerized, and ethylenically unsaturated monomers, oligomers, and polymeric compounds which give multicylindrical solid products. It is. Especially for this purpose: esters and amides of ethylenically unsaturated carboxylic acids and of polyols or polyepoxides, and polymers with ethylenically unsaturated fatty acids in the main or side chains, For example, unsaturated polyester,
Polyamides and polyurethanes, and their copolymers, polybutadiene and polybutadiene copolymers, polyisoprene and polyisogrene copolymers, polymers and copolymers with side chain maleimidyl groups or acrylic or methacrylic groups, or A saturated epoxy resin, co-6, and also a mixture of one or more such polymers.

Examples of ethylenically unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, or unsaturated fatty acids such as linole M or oleic acid. Acrylic acid and methacrylic acid are preferred.

Suitable polyols for the esters are aromatic and especially aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4-dihydroxyphenylene, bisphenols such as bisphenol-A or -F, and novolacs and resols. Suitable polyepoxides for the ester reservoir are, for example, those based on the polyols mentioned above, especially aromatic polyols and shrimp chlorohydrin. Also suitable as aliphatic polyols are polymers and copolymers having a hydroxyl concentration in the polymer chain or 1 uI group, such as polyvinyl alcohol and copolymers thereof, or For example, it is a polymethacrylic-dispersed hydroxyalkyl ester such as β-hydroxyethyl ester or a copolymer thereof. Also suitable aliphatic polyols are low polymeric esters with hydroxyl end groups.

A preferred group of aliphatic or cycloaliphatic polyols has the general formula Rn (OH)n, where R is n-valent, preferably 2- to 8-valent, % 2- to 6-valent, and , a nitrogen atom, a sulfur atom, and an aliphatic group having 2 to 30 carbon atoms, which may be interrupted by cycloalkylene, or a cycloalkylene having 5 or 6 ring carbon atoms. It is a polyol. Such polyols are preferably fullylene diols having from 2 to 12 carbon atoms, such as ethylene glycol, 1, 2- or 1.3-carbon atoms.
Propanediol, 1.2-11.3- or 1.4-
Butanediol, bentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, 1υ0
Polyethylene glycol, 1.2-11.3- or 1,4-cyclohexanediol, 4-dihydroxymethylcyclohexane, glycol, tris-(β-hydroxyethyl)amine, trimethylolethane, having a molecular weight of 1,500 to 1,500. , trimethylolpropane,
Mention may be made of pentaerythritol, dipentaerythritol and sorbitol.

The polyols can be partially or fully esterified with one or various ethylenically unsaturated carbon moieties; as partial esters, free hydroxy A can be esterified, e.g. It can be esterified with. An example of such an ester is f';
i, trimethylolpropane triacrylate, trino fO-lethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, Tetran 9 ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate , pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate , dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol cyitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentitaconate, dipentaerythritol hexytaconate, t, -), ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol shiitaconate, sorbitol triacrylate, sorbitol hexaacrylate, sorbitol tetramethacrylate acrylate,
Rubitol bentaacrylate, sorbitol hexaacrylate, acrylic low-polymerized ester, methacrylic acid low-polymerized ester, di- and triacrylic glycerol, 1,4-cyclohexane diacrylate, bis-polyethylene glycol with a molecular weight of 100 to 1500
Mention may be made of acrylates and bismethacrylates, or mixtures thereof.

Preferably 2 to 6, especially 2 to 4 amino groups, and 2
aromatic, cycloaliphatic and aliphatic polyamines having a number of carbon atoms of from 30 to 30, in particular from 2 to 18,
Amides of different unsaturated carboxylic acids are also suitable. Examples of amines are ethylenediamine, 1, 2- or 11.
(-propylene diamine, 1.2-11.3- or 1
．． 4-Butylene diamine, 1,5-pentylene diamine, 1,6-hexanediol, octanediol, dodecylene diamine, ■, 4-diaminocyclohexane, isophorone diamine, phenylene diamine, bisphenylene diamine, di-β-7 Minoethyl ether, diethylenetriamine, triethylenetetraamine, di(β-
7minoethoxy)- or di(β-aminopropoxy)
- Ethane is given. Examples of the better amides are methylene-bis-acrylamide, 1,6-hexamethylene-bis-acrylamide, diethylene-triamine-tris-methacrylamide, bis(methacrylamidopropoxy)-ethane, β-methacrylamide-amide. Examples include ethyl methacrylate or N((β-hydroxyethyloxy)-ethylnoacrylamide.Further suitable polyamines include polymers and copolymers with amine groups in their side chains, and low polymerized amides with amine end groups. It is.

Unsaturated polyesters and polyamides are suitable as radiation-curable starting materials, such as those derived from maleic acid and diols or diamines.

Maleic acid can be partially replaced with other dicarboxylic acids. They can be used with ethylenically unsaturated comonomers such as styrene. The polyesters and polyamides may also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially those in ascending order of seven carbon atoms d5 to 20. Examples of polyurethanes are polyurethanes synthesized from saturated or unsaturated olodiisocyanates and unsaturated or saturated diols.

Radiatable polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers for such co-X combinations are, for example, polyolefins such as ethylene, propene, butene, hexene, acrylates and methacrylates, acrylonitrile, styrene or vinyl chloride. A radiation-like curable 1 compound having a maleimidyl group in till is disclosed in the German patent No. 2, for example.
, No. 626,795. Radiation-curing monomers with side chain acrylate and/or methacrylate groups are likewise known. They are, for example, reaction products of epoxy resins based on novolacs with acrylic acid and 7- or methacrylic acid, polyvinyl alcohols esterified with acrylic acid and/or methacrylic acid! 1. These are homo- or copolymers of hydroxyalkyl derivatives thereof, or homo- and copolymers of acrylates or methacrylates having oxyalkyl acrylate or oxoalkyl methacrylate groups.

In the case of radiation-curable, unsaturated epoxy resins, 1 They are mainly -HC=CH-C- or 1 It is a resin containing a -HC=CH-C-CH=CH- group.

Such epoxy resins are described, for example, in German patent application no.
No. 344407.

The radiation-curable starting materials can be used on their own or in certain selected mixtures.

It is advantageous to add esters of unsaturated carboxylic acids, in particular acrylic esters or methacrylic esters of polyols and/or also vinylated compounds such as vinylpyrrolidine or vinylpyrrolidine.

Further suitable radiation-curable starting materials are epoxy resins, in particular epoxy resins based on aromatic polyols, with a hardening effect which can be activated by radiation, for example. Examples of such 1v curing agents are α- and β-acylsulfonyloxy compounds, diazonium fences, Va of the periodic table.
, onium salts of elements of group VIa or Vlla, e.g. chloride\bromide, iodide, especially salts of complex acids such as e.g. - Esters of methylolbenzoin and human tetraxyacrylphenone: o-nitrobenzaldehyde and α-chloro or α-butetramoacylphenone. Among the onium salts, preferred salts are sulfonium salts such as triphenylsulfonium hexafluorophosphate. Suitable grading agents are metallocene salts such as (η6-
Methylnaphthalene)-(η5-cyclopentadienyl)
Iron-U-hexafluorophosphate. Suitable radiation-curable starting materials are also aromatic diazide oligomers and polymers as crosslinking agents.

The outer layer is preferably a radiation-curing epoxy acrylate or epoxy methacrylate, an epoxy resin, an acrylic or methacrylic polyester based on bisphenols (unsaturated polyurethanes or polyesters), or containing maleimide groups, especially dimethylmaleimide groups. Contains polymers with side chains.

The outer layer particularly preferably contains at least one acrylic or methacrylic ester of an aliphatic polyol.
A binder can also be added to the outer layer of the radiation-curable epoxy acrylate or epoxy methacrylate mixed with the outer layer.

It is sometimes advantageous when the radiation-curable starting material is a liquid or viscous material.

Suitable binders include, for example, from about s,ooo to 2,000,0
00.

Preferably, it is a polymer having a molecular weight of 10,000 to 1,000,000. Examples include homo- and copolymers of acrylates and methacrylates, such as copolymers of methine methacrylate/ethyl acrylate/methacrylic acid, poly(methacrylic acid alkyl esters), poly(acrylic acid alkyl esters) (where the alkyl groups (a has 1 to 20 carbon atoms) and p (a) also includes cellulose acetate, cellulose gamma acetate pterate, methyl cellulose, cellulose esters such as ethyl cellulose, and ethyl cellulose, (7) polyvinyl acetate, polyvinyl formal, cyclized rubber. , polyethylene oxide, polyethylene oxide, polyethers such as polytetrahydrofuran: polyesterene, polycarbonate, polyurethane, chlorinated polyolefins, polyvinyl chloride, vinyl chloride/vinylidene chloride copolymers, vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate. Copolymer, polyvinyl acetate.

Polyamides such as copoly(ethylene/vinyl acetate), poly(hexamethylene adipamide) and polyglolactam, polyesters such as poly(ethylene glycol terephthalate) and poly(hexamethylene glycol succinate).

The radiation-curable starting material selected is advantageously such that the outer layer is hydrolytically stable and non-shrinkable. Polyinitiators and sensitizers can be used to increase photosensitivity, such as aromatic ketones such as tetramethylcyanobenzophenone, penzophenono, Michler's ketone [4,4'- Bis-(dimethylamino)
benzophenone), 4,4'-bis(diethylamino)
Penzoquenone, 4-acryloxy-4'-diethylatanobe/siphenon, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquino/, phenanthraquinone, 2,6-butylanthraquinone, ■
, 2-benzanthraquinone, 2,3-benzanthraquinone, 2,3-dichloronaphthoquinone, benzyl dimethyl ketal and the aromatic ketone described in US Pat. No. 52,973: benzoin.

Benzoin ethers such as benzoin methyl ether, benzoin ether ether, benzoin isobutyl ether and benzoin phenyl ether, methylbenzoin, ethylbenzoin and other benzoins, P-maleic acid imidobenzenesulfonic acid azide, thioxanthone derivatives such as thioxanthone, 2-chloro Conjugated with aromatic amines such as thioxanthone, 2-ingrovir thioxanthone, thioxanthone-1-carboxylic acid ethyl ester, P-dimethylaminebenzoic acid ethyl ester, and 4,4′-bis(dimethylamino)-benzophenone. Curing of a radiation-sensitive starting material, which may be 3-methoxy7-1-carboxylic acid ethyl ester, is performed using gamma radiation, X-rays,
The outer layer can be further thermally cured by the same functional groups, such as epoxy groups, in the curable composition of the inner layer. gender is particularly advantageous.

More specifically, the outer layer contains a-functional groups that react simultaneously with the thermal curing of the inner layer. This method provides particularly good adhesion of the layers after curing. Possible functional macrogroups are olefinically unsaturated groups such as allyl or methallyl groups, 0H1S)I, -COOH,
They are an amino group and a urethane group.

The thickness of the internal nozzle is generally 50 to 300 μm, 1%
00 to 300 μm. The thickness of the outer layer is fJ50pm to about 1m, preferably 10(lt
'm to 800μm and 250μm to 50I1m
It is. When the outer layer is free of filler, its thickness may be approximately 400 μm to 4 mm, preferably 600 μm to 2 mm. To obtain good adhesion,
It is possible to enhance the flavor of the material using the appropriate method.

The inner and outer layers contain additives to be phase-degraded, such as tigisotropic agents, fixing agents, and all types of partially divided fillers and other processing aids, as well as additives that improve the final properties. be able to. The external JtJ can be structured by roughening or loading filler to achieve better bonding with the binder. For example, glass beads can be added to the external nozzle to provide thermal insulation.

The prestressing member of the present invention is manufactured by first applying the inner layer to the core of the prestressing member using conventional coating methods such as dipping, flow coating, brushing or spraying, in a manner that is itself official. , and, if desired, apply a separation material to this layer. A satisfactory method is spraying with an annular nozzle. No coating is necessary when applying a solid but still moldable inner layer, such as when applying B one-stage resin. The composition of the inner layer is dissolved in a solvent, applied to the surface, and the solvent is removed. However, direct coating is preferred, which is possible by selecting a composition with a low viscosity. The outer layer is then applied to the inner layer or separation layer, preferably under the UV rays of a mercury vapor lamp.
Advantageously, it is exposed to radiation in a lamp and cures immediately after application.

The subject of the invention is therefore to: a) apply to the prestressing part an inner layer of a room-temperature storage-stable, formable and thermosetting composition and, if necessary, apply this with a separable material; After coating the outer door layer b) with a radiation-curable composition; With such a laborious process, it would be possible to produce two-layer plastic coatings (separated by an intermediate layer if necessary) for prestressing parts, without a single step during a long reaction time and with e.g. It can be stored and transported immediately, without the extra cost of complex holding equipment required for long periods of time, and is still reactively active but sufficiently shelf-stable until further processing! It is possible to obtain a prestressed part with a plastic coating of -, the two plastics j- not only not being mixed during production, which would cause defects, but also remaining separated from each other. .

The prestressing member of the present invention is ideal for manufacturing prestressed support structures. The third subject of the invention is this method of use. For this purpose, the prestressing member is first compressed.

It is then encased in a bonding agent, such as a thermosetting or durable plastic, or a structural material such as concrete, followed by subsequent heating and curing of the interior. ) JD Netsu is the core of prestressed members.

or, in the case of a non-conductor, by an induced conductive current (by applying a voltage to a conductive intermediate layer). A strong bond can be obtained that withstands high loads and has effective corrosion retention of the core of the prestressed member.

A particular use of the prestressed members of the present invention is the manufacture of concrete support structures.

The following examples further illustrate the invention.

Example 1 An internal layer of the following composition is applied to structural steel by spray coating.

Composition: Epoxy t K 45.2 to 5.5 Val 7 M
y and viscosity i9,000 to 12,000 mPa (2
Epoxy m based on bisphenol-A with
100 parts by weight of moonlight, 13 parts by weight of a curing agent consisting of the following composition, 8 parts by weight of dicyandiamine.

Layer thickness using a mixture of 3-(P-ethoxyphenyl)-1,1-dimethylurea 4 parts, 0.3 parts of silicic acid (aerosol) and 0.7 parts by weight of dibutyl 7-talate v' is 1200 to 300 μm. Wrap the band around the layer and add the outer photocurable layer (9350 mm thick)
μm): Composition applied to the band: Epoxy acrylate [acrylic acid and bisphenol]
Reaction product of A-diglycidyl ether, 70% tripropylene glycol diacrylate solution, solution viscosity: 17,000 mPa (25°C)] 660 parts by weight tripropylene glycol diacrylate 22
Electric tM (S5 Trimethylolpropane acrylate xzM
Amount m Benzyl dimethyl ketal 4 parts by weight Triethanolamine 2tJt parts Talc
20 parts by weight and 6 parts by weight of silicic acid (Aerosol 200) The layer is irradiated with UV light from a mercury pressure lamp (80 W/cm) and cured for 4 to 6 seconds. The layer is characterized by good adhesion. The inner layer is storage stable for about 3 weeks at room temperature and can be cured by induction heating at 150°C for 10-15 minutes.

Example 2: The same procedure as in Example 1 is followed except that the following inner layers are used: 85 parts by weight of the epoxy resin described in Example 1, 15 parts by weight of dibutyl phthalate and 42 parts by weight of m-xylene cyabane dibenzoate. .

The internal no is slightly thixotropic.

It is storage stable at room temperature for up to about 3 months. Hardening 6 This is done by heating at 120° C. for 5 to 7 minutes.

Example 3: The same procedure as in Example 1 is followed except that the following internal layers are used.

Epoxy resin as described in Example 1: 92 parts by weight of dibutyl phthalate and 37 parts by weight of ethylenediamine dibenzoate.

The inner layer is chicken rope and is storage stable at room temperature for up to about 3 months. Complete curing at 120°C for 5-7 minutes
This is done by induction heating.

Example 4: The same procedure as Example 1 is followed except that the following internal layers are used and the separating layer is omitted.

100 parts by weight of the epoxy resin described in Example 1
- Curing agent based on aminophenylonmethane
29 parts by weight leveling agent
2 parts by weight methanol 1 part by weight Bentone 27 (montmorillonite) 27 parts by weight Titanium dioxide 1 parts by weight Crotalc 10 parts by weight and 34 parts by weight barite.

The outer layer is applied directly on top of which the B-stage resin is obtained as a solid layer after curing for 10 hours at room temperature. Storage stability at room temperature is approximately 2 months. Curing of the outer layer is done by induction heating at 120° C. for 15-20 minutes.

Example 5: A) Degrease the rod (diameter = 32 tmn) and clean the surface. Thereafter, apply internal nodule dt of the following composition to the surface by brushing.

composition: a) 100 parts by weight of the epoxy resin described in Example 1, b) 8 parts by weight of dibutyl phthanate, and C) Ethylenediamine dibenzoate 400 parts A mixture of.

The thickness of the coating is 200 to 400 μm. Wrap the wet layer with glass filament tape (tape should be 30-50% O-wrapped).

Next, use a brush to apply an external coat of the following mixture: a) Unsaturated polyurethane [Actilane]
Actilane AJ) 18.5NPE) 42
0 parts by weight.

b) 1,6-hexanediol diacrylate 175
Parts by weight, c) l-vinyl-2-pyrrolidone 10505 by weight d) Silicic acid [Aerosil 200.
Degussa #) 7 parts by weight,
e) 262 parts by weight of Merck, and f) 311 parts by weight of benzyl dimethyl ketal.

The thickness of the outer layer is between 400 and 700 μm. The outer layer of Part 9 is cured by irradiation with two UV lamps (2000 W each). The stick applied at that time was 10 crn.
Pass the ring light at a passing speed of 4.5 m/rtk.

B) The same procedure as in A) is carried out, except that before hardening, quartz powder with a particle size of 0°1 to 0.3° is sprinkled onto the outer layer.

C) Follow the same procedure as A) except that the layer consists of the following mixture.

Inner layer: a) Viscosity 1400-2000 mPa (50°C)
, t5.6 to 5.8 Val/”P including epoxide
100 parts by weight of epoxidized novolak.

b) 12 parts by weight of dibutyl phthalate, and C) 44 parts by weight of ethylenediaminedibenzonyh and 12 parts by weight of a) commercially available acrylic suphenol-A-diglycidyl ether mixed with 30% by weight of tripropylene glycol diacrylate. Acid ester [viscosity 60 to 65 Pa
s (25°C)) 452 parts by weight, b) 9 parts of 1,6-hechitinediol diacrylate.

c) 1-vinyl-2-pyrrolidone 97 parts by weight, d) Talc 32222 parts by weight e) Silicic acid [Aerosil 200.
Degu? (Degussa)] 6 parts by weight.

and f) benzyl dimethyl ketal 26 M Jt
D) Same procedure as C) except that quartz powder with a particle size of 0.1 to 0.3 rrtm is sprinkled on the outer layer before hardening.

The rods coated according to A) to D) are wrapped in concrete and the concrete is hardened. By resistive heating, the rod is heated to 120-130° C., and after reaching this temperature the supply of current is stopped.

The inner layer is hardened as a result of the heat capacity of the rod.

Thereafter, a tensile test was conducted on these specimens, and one crack was observed in the concrete. Therefore, the contact strength of the inner layer on the steel material, the outer layer on the inner layer, and the contact strength between the outer layer and the concrete is greater than the fracture strength of the concrete.

Claims (1)

[Scope of Claims] (1) The inner layer is a moldable and thermosetting composition that is shelf-stable at room temperature, and the outer layer is a radiation-cured one lath material. be designed so that, if necessary, they are separated by an intermediate layer,
A fresless member having a circular polymer-forming layer applied to the top surface and an outer solid 1 lath nuck layer. (2) The composition of the inner layer is formed by polyaddition or addition polymerization)
A fresless member according to claim 1, characterized in that it contains a starting material that can be cured into the shape of a Duro 1 last. (3) The restless member according to claim 2, wherein the starting material is an epoxy resin, masked polyurethane, or unsaturated polyester. (4) The prestress member according to claim 2, wherein the inner layer is a solid pre-treated epoxy resin. (5) The prestressing member according to claim 1, wherein the curable composition of the inner layer contains a heat-activatable curing agent, optional additives, and further a curing accelerator. (6) The fresless member according to claim 1, characterized in that the curable composition contains an epoxy resin based on glycidyl ether of polyphenol. (7) The outer layer is further thermosetting. (8) The prestressing member according to claim 1, characterized in that the outer layer is thermosetting due to the presence of an epoxy group. (9) The prestressing member according to claim 1, wherein the outer layer contains a functional group that reacts incidentally upon thermosetting of the inner layer. (10) The outer layer is radiation-cured epoxy acrylate, epoxy methacrylate, epoxy resin,
Claimed part characterized in that it is a polyester acrylate based on bisphenols, a polyester methacrylate, an unsaturated polyurethane, an unsaturated polyester, or a polymer with maleimide side groups. (11) Claims characterized in that the outer layer is a radiation-cured epoxy acrylate or epoxy methacrylate, which is further mixed with at least one acrylic ester or methacrylic ester of an aliphatic polyol. Prestressing member according to item 10. (12) a) Applying to the prestressed part an inner layer of a moldable thermosetting composition that is storage-stable at room temperature, separating this layer if necessary; (3) After applying the substance; b) applying an outer layer of a radiation-curable composition; and C) curing the outer layer with radiation. (13) Method of manufacturing a container for producing compressively stressed support structural members. , the inner layer is a moldable, thermosetting composition that is storage stable at room temperature, and the outer layer is a plastic material that is cured by radiation. (14) Method of using a prestressed member in which an inner coalescing layer and an outer solid plastic layer are applied to the upper surface, if necessary, with a slight separation from the intermediate layer. 14. Use according to claim 13, characterized in that it is used in concrete support structures, such as towers, bridges, wells, or large convener walls and rock bracings.