TWI309670B - Process for filling a three-dimensional cavity using an insert - Google Patents

Description

1309670 Δ7 _____B7 _ ____ V. Description of Invention (I) (Please read the note on the back and then fill out this page) The present invention relates to a cemented insert, especially for filling a three-dimensional cavity 'more special' A cavity in the core of a sandwich composite, a method of making the insert, and a method of using the insert to fill a three-dimensional cavity. Solid-adhesive inserts are known for the use of three-dimensional space cavities. Known inserts are, for example, cylindrical and composed of a split plastic material, such as a cured epoxy material. "Syntactic" is understood to mean a material consisting of hollow microspheres, and thus has a relatively low density but good mechanical properties. These inserts are particularly useful for reinforcing sandwich panels such as honeycomb composites. The reinforcement method using these cylindrical inserts involves removing the core of the portion of the panel to be strengthened by a circular section. The intumescent adhesive tape is then cut to the desired size and the insert is wrapped. After the tape removes the release film, the insert is installed into the cavity of the honeycomb plate. Finally, the core material, the insert, the adhesive tape, and the 'optionally, the outer cover of the core material are additionally attached. The assembly of the surface material or the like is co-cured at a suitable temperature to form a strengthened composite structure. The object of the present invention is to assist the application of the solid insert. In this respect, it has been found that if a special solid embedding is used. In the case of the article, it is possible to avoid the use of additional adhesive means for adhering the insert to the surrounding panel, such as the aforementioned adhesive tape. One subject of the invention is a cementitious insert, in particular for filling a three-dimensional cavity, more particularly a cavity in the core of a sandwich composite, the insert being solid at ambient temperature And its characteristic is that its paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ~~------ 1309670 A7 _______B7__ V. Invention description (y) is solid curable a composition comprising a swellable and adhesively bondable upon heat curing. For the purposes of the present application, "circumferential temperature" means preferably a temperature of less than 35 ° C, for example 1 Torr to 30 ° C., 'coherent' means that the insert is a solid monolithic article at ambient temperature, rather than a powder. The insert of the present invention is preferably solid. It is composed of an expandable curable epoxy composition. The solid curable epoxy composition is particularly composed of the following composition: (A) epoxy resin or epoxy group-containing compound and (B) solidification Amine system which reacts with (A) to give a product, preferably at 55 The melting point of Kofler Heaat Bank between 120 ° C and its content is not sufficient to allow or contribute to chemical gelation under the reaction conditions selected for (A) and (B) and to remove all epoxy groups contained therein. The hydrogen group is substantially stopped before or after being consumed by the epoxy group, (C) - a hardener for the reaction product of (A) and (A) and (B), which is different from (B) And it substantially maintains f substantially unreacted under the reaction conditions selected for (A) and (B), I (D) - expansion agent, which is selected for the reaction conditions of (A) and (B) I have low reactivity or preferably no reactivity, and, if necessary, (E) conventional additives, the composition is substantially not (A) via (A) and (B) The reaction is carried out under the conditions in which the reaction products of (A) and (B) are reacted to be solidified. 4 The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back and fill out this page) F---- 1309670 A7 __ B7_ _ V. Invention description (4 Their compositions are described, for example, in more detail in WO-A-97/19124. Before the composition is solidified by the reaction of (A) and (B), the points (A), (B), (C), (D) and (E) are in any convenient batch or continuous The operations are blended together in such a manner as to at least make (A) and (B) uniform. The reaction of (A) with (B) can be carried out at any suitable temperature and condition, but the limitation itself and the exothermic heat of reaction generated by it cannot be caused (C) or (D) Substantially reacts. The epoxy resin or the epoxy group-containing compound (A) may be a glycidyl ether, a glycidylamine, a glycidyl ester, or a cycloaliphatic compound or a combination thereof, and includes a _ Form. Preferred epoxy resins and blends are those which are suitably liquid at a suitable temperature, typically below 12 ° C, to be smoothly mixed with the other ingredients. Epoxy resins or epoxy-containing compounds or blends thereof which are liquid at room temperature are most convenient. The preferred solidification system (B) used for the conversion of the liquid to the lipid is primarily a compound or a mixture of compounds having the first or second amine which is most reactive with respect to the epoxy species employed. The third amine group having epoxy group reactivity under the reaction conditions selected for (A) and (B) is not accepted by the present invention. For the component (B), it is particularly useful as aromatic and cycloaliphatic a blend of the first and second amines and theirs. The main advantages of these amines, especially aromatic amines, are the low reaction rates plus the extremely long service life of their reaction products with the resin at normal ambient temperatures. When using most of the compounds from their amines, their reaction products with the resin have a lifetime that exceeds that of the resin and 5 rm. Read the back of the back. I want to fill in this page. I n >1 Nt-n_一-OJI n . This paper size applies to China National Standard (CNS) A4 specification (210 297 297 mm) 1309670 A7 ___B7__ V. Invention description (k) The reaction product of their main hardener (c) With a long life. Certain alicyclic, heterocyclic, and aliphatic amines can also be effectively used as advancing agents and will stop treating when their amine-based hydrogen atoms are consumed by the epoxy resin. Part of the invention. In all cases, it is necessary that the third amine produced in the solidification reaction has very low reactivity to the epoxy group under the selected reaction conditions for (A) and (B) and subsequent storage. These solidified amines are generally and mostly bifunctional and/or polyfunctional for the epoxy compound (A), but monofunctional amines can also be used if they are useful for a particular composition. To some extent. The difunctional amines can be used in any desired ratio with the difunctional epoxy resin, but the ratio of the difunctional amines is greater than the level at which the gelation reaction does not occur. The solidification system may contain various other groups which, under the reaction of (A) and (B), may only have very low or no reactivity with respect to the epoxy groups involved. The most useful solidification system can gradually react to substantially complete conditions at room temperature for about 2-14 days. The content of the solidification system must be such that when all of the amine-based hydrogen atoms are reacted with the epoxy substance (Α) under the conditions set for the reaction of (Α) and (Β), the product It also does not chemically gel and has a melting point preferably above 55 ° C and below 12 ° C. The hardener system (C) used for the epoxy compound (A) and the reaction product between (A) and (B), in addition to the acid anhydride which preferentially reacts with the upgrading agent (B), can be widely used. Selected among those well known in the field of epoxy chemistry. Typical but non-exhaustive examples of useful hardeners are aromatic amines such as diaminodiphenyl maple' boron trifluoride monoamine complex, latent imidazole (Latent 6 paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the phonetic on the back? Please fill out this page again) %Binding ---------' 1309670 V. Inventions (<) imidazoles), Carboxylic Acids, Biguanides , hydrazines, dicyandiamide, latent epoxy amine adducts, and substituted ureas. As already explained, one of the main requirements for hardeners is that they should not react substantially when (A) and (B) are reacting. One or several hardeners may be used together. Some of them may accelerate the curing reaction of others, provided that they are subject to the requirements mentioned above. The expansion agent (D) may be any as long as it does not adversely interfere with the production of the solid epoxy composition or its satisfactory curing ability. The resulting swelling effect may be derived from a chemical reaction or a physical reaction or both. An important feature is that the blowing agent should not cause substantial foaming reaction in the manufacture of the solid epoxy composition or in its storage in any form at normal workplace temperatures or lower. . All significant expansion should be achieved during the actual curing cycle. Examples of suitable bulking agents include azodicarbonamide, azobisisobutyronitrile, benzenesulfonamide, dinitrosopentamethylenetetramine, oxybisbenzenesulfonate, p-toluenesulfonyl Tantalum and expandable plastics are for example sold under the trade name Expancel. Most of them are spherical shells with a variable composition, such as polyvinylidene chloride and/or polyacrylonitrile plus other copolymerized additives, and are internally filled with or without isopentane. Other additives which may be used to modify the physical properties of the cured or uncured composition include, but are not limited to, accelerators, shakers, oximes, humectants, surfactants, used for the hardener (C), Fiber materials, dyes, pigments 'flame retardants, aerosol presses, coupling agents, glidants, soluble glass and stabilizers. There is another important class of additives that can be used for a wide variety of purposes. The paper size is applicable to China National Standard (CNS) A4 specification X 297 public interest) (please read the notes on the back and fill out this page)

1309670 A7 ________B7 V. Description of the Invention (L) Dilution, which may be used singly or in the form of a mixture of two or more different tanning materials. Although generally, any dip material can be used in the present invention, and suitable dip materials include, in particular, hollow microspheres, such as those made of glass, carbon, niobate or various plastic materials. A common feature of their microspheres is their low density, which also gives low density to the paste and is the primary reason for their use. Another consideration is that they give the relative ease of sanding or smoothing the cured composition. Another type of dip that is specifically mentioned here is a conductive crucible. The presence of such materials may facilitate the inductive heating of the adhesive insert of the present invention or when using a ready-to-use insert to fill a cavity as described below, for example by means of a sensing wire Curable Compositions ^ The epoxy compositions mentioned above may be prepared to have a low or high melt viscosity by careful selection of (A) and (B). According to (C), they can be cured at 100 to 15 (TC, for example, at about 120 ° C for 30 minutes to several hours, or at 180 ° C to 260 ° C for several times. A wide range of desirable mechanical and thermal properties can be obtained by careful selection of (A), (B) and (C), and smooth modification of physical and mechanical properties can also be achieved by introducing the additive (E). Preferably, the insert has a storage stability at ambient temperature. More particularly, it can be stably stored at a peripheral temperature for three months and longer, especially longer than six months. The insert of the present invention can, For example, it is manufactured by the following procedure: an example of an intumescent curable composition which is solid at ambient temperature (please read the back note first and then fill out this page)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1309670 A7 B7 V. Invention Description (q) If the corresponding epoxy composition does not substantially expand or gel Or a desired shape is formed under curing conditions. This method is another object of the invention. For this purpose, the solid expandable curable composition can be applied, for example, to melt under sufficiently mild conditions so as not to substantially swell or gel or even solidify, and then poured into a desirable physics Form, for example using a mold. In another particular embodiment of the method described above, a liquid, solidizable composition is solidified to form an expandable curable composition that is solid at ambient temperature. If the insert of the invention is produced using, for example, the compositions described in WO-A-97/19124 and the above-mentioned compositions, it can be allowed to stand at ambient temperature for a period of hours to days (for example 5 The solidification of the liquid starting composition was carried out for a period of from hour to 14 days. If it is necessary to accelerate the solidification, it can be heated to reach the temperature, but the limitation is that the temperature used does not promote the reaction of (C) with (A) or with the reaction products of (A) and (B). The heat generated by the completion of the reaction by direct heating or (A) and (B), or the addition of an accelerator, for example, a carboxylic acid which does not adversely affect the stability of the softening point. The solidification of the liquid composition can of course also be carried out in the same day as the formation of the charge. Another aspect of the invention is a method for filling a three-dimensional space cavity in a first material, such as a honeycomb material, wherein the insert of the present invention is placed in the cavity to be heated, preferably. Under pressure, the curable composition contained in the insert is melted, expanded and solidified. (Please read the back note first and then fill out this page)

H 1« nnn ·*-0, n ϋ n I n I Wood paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1309670 Α7 Β7 V. Invention description ($ Substantially fully charged in this a cavity in the first material. In the specific example, the method is covered with a suitable covering material on at least the side of the cavity before heating, and then the covering material is adhered by twisting. Bonding to the first material. The tumbling insert is well suited to provide support for a load bearing element such as a bribe or a screw, such as a honeycomb material, which is generally not capable of obtaining such support. A particular embodiment of the method of cavities in a material comprises the procedural step of securing a load bearing element to the insert. As mentioned above, the heating can be performed via, for example, induction. Of course, the embedding is apparently The material must include sufficient electrically inductive material to be inductively heated. Such an electrically inductive material can be incorporated into the insert as a particulate material such as a conductive crucible or a conductive compact object. ' For example, metal nails or screws.

J Example 1: Preparation of self-adhesive expandable insert of the present invention Araldite GY 260 (bisphenolphthalein epoxy resin from Ciba SC) l〇〇pbw dicyanamide $4.3 pbw 2.2 pbw 10.6 pbw 6.0 Pbw 50 pbw 1.5 pbw (please read the notes on the back and fill out this page). Line.

Chlorotoluron 3,3'-monomethyl 4,4'-diaminodicyclohexylmethane cyclohexylamine

Eccospheres IG 10 (hollow microspheres)

Expancel 551 Du (unexpanded thermoplastic microspheres) 乍This paper scale applies to Chinese National Standard (CyS) A4 specification (210 x 297 mm) 1309670 A7 B7 V. Description of invention (1) Use all the ingredients of the above formula using machinery The mixer was thoroughly mixed together under vacuum for 5 minutes. The mixture was transferred to a cylindrical mold having a size of 25.4 mm and a diameter of 12.7 mm. The mixture was allowed to stand at room temperature for about 17 hours and then heated at 60 ° C for 2 hours. The sample was then cooled to 23 ° C and the sample became a solid. Example 2: A solid cylindrical block made according to Example 1 was held in a mold but the upper surface was opened. The sample and mold were placed in a 12 ° C oven for 60 minutes. The mold and sample were then removed and allowed to cool back to room temperature. The volume of the sample can be seen as the sample is removed from the oven. The sample density before curing was 0.66 g/cm 3 and the density of the sample after curing was 0.52 g/cm 3 . The compressive properties of the samples were measured according to inspection specification ASTM D695. The following results were obtained: i 23 ° C compressive strength 37.5 MPa 23 ° C compression modulus 1182 MPa 177 ° C compressive strength 7.7 MPa 177 ° C compression modulus 127 MPa Example 3 : For the composition in Table 1 and Table 2 The materials 3/1 to 3/9 were treated in a manner similar to that of Example 1. Detailed processing conditions are also listed in the tables, as well as the properties obtained from the samples after processing according to Example 2. 11 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) · nn I ί I I-OJ· nmni I n I . Wisdom material smasher 31^费乂0咋: 1309670

7 7 AB V. INSTRUCTIONS (U) TABLE 1 COMPOSITION 3/1 3/2 3/3 3/4 3/5 Araldite GY260 100 100 100 100 100 Dicyanamide 4.3 4.3 4.3 4.3 Chlorotoluron 2.2 2.2 2.2 2.2 HY2954 10.6 10.6 10.6 10.6 10 Cyclohexylamine 6.0 6.0 6.0 6.0 Eccospheres IG 101 50.0 50.0 50 50 20 Expancel 551 DU 1.5 1.5 - - 0,5 AffiN - - - 0.2 Metalinks - - Diaminodiphenyl 18 Phoschek P30 25 Paraloid EXL 2600 10.0 Upgrade schedule at 23t for 16 hours + at 60 ° (: 2 hours at 23 ° C for 16 hours + at 60 ° (: 2 hours at 23 °. Under 16 hours + at 60 ° (: for 2 hours at 16 hours at 23 ° C + 2 hours at 60 ° 0: 16 hours at 23 ° C + at 60 ° 2 hours under the curing schedule at 120 ° C for 1 hour at 120 ° C for 1 hour at 120 ° C 1 hour at 120 ° C for 1 hour at 177 ° C for 3 hours density gram / cubic centimeter (after upgrade) J 0.66 0.69 0.68 0.62 density gram / cubic centimeter (after curing) 0.52 0.59 0.61 0.46 0.90 compressive strength (MPa) 23 °C 37.49 50.93 64.16 27.3 80.5 Compression modulus (MPa) 23 °C 1182 1448 1939 1315 2024.7 Strong compression Degree (MPa) 177〇C 7.7 11.1 Compression Modulus (MPa) 177〇C 127 99.2 Aluminum Cover Sheet Shear Strength (MPa) 12.9 15.0 13 This paper scale applies to China National Standard (CNS) A4 specification (210 x 297 mm) (Please read the notes on the back and fill out this page) 1309670 A7 B7 V. INSTRUCTIONS Qx) Table 2 Composition 3/6 3/7 3/8 3/9 Araldite GY260 100 100 100 100 Dicyanamide - - 4.3 - Chlorotoluron - - 2.2 - HY2954 10 - 10.6 10.6 Cyclohexylamine - 10 6.0 6.0 Eccospheres IG 101 20 20 - 10 Expancel 551 DU 0.5 0.5 1.5 1.5 AIBN - - - - Metalinks - - - 48.0 Diaminodiphenyl 18 34.5 - - Phoschek P30 25 25 - - BFr-ethylamine 0.6 1.0 - - Upgrade schedule at 23 °C for 16 hours + at 60 °C for 2 hours at 23 °C for 16 hours + at 60 °C for 2 hours at 16 hours at 23 °C + 2 hours at 60 °C at 16 °C for 16 hours + at 60 °C for 2 hours Curing schedule at 177 °C for 3 hours at 177 °C for 3 hours at 120 °C 1 hour at 120 ° C 1 hour density / cubic centimeter (after upgrade) 1.3 1.0 density / cubic centimeter (after curing) 0.91 0.90 1.3 0.9 pressure Strength (MPa) 23 ° C 64.0 68.1 117.5 49.1 Compression modulus (MPa) 23. . 1475.8 1718 2027 1823 Compressive strength (MPa) 177°C 14.3 33.9 Compressive modulus (MPa) 177°C 325.9 926.6 Aluminum cover sheet shear strength (MPa) 39.8 4.1 (Please read the back note before completing this page) - -------定·-------- 堡声耶^曰逢[-时έ n57iu-yzr iRir乍· 14 This paper scale applies to China National Standard (CNS) A4 specification (210 χ 297 MM)

Claims (1)

6. Patent application scope 1. A method for filling a three-dimensional space cavity in a first material A cohesive insert of solid curable composition is placed in the cavity and heated: (A) epoxy or epoxy-containing compound and (B) solidified amine system, which reacts with (A) A product is obtained which is not present in an amount sufficient to permit or cause chemical gelation under the reaction conditions selected for (A) and (B) and which is included in all of the active epoxy-addition hydrogen groups contained therein. The curing is substantially stopped before or at the time of consumption of the oxy group, (C) a hardening agent for the reaction product of (A) and (A) and (B), which is different from (B) and which is (A) And substantially no reaction with (B) the selected reaction conditions, (D) a type of expansion agent' which has low reactivity under the reaction conditions selected for (A) and (B), and Requires (E) a conventional additive, which has been produced by (A) and (B) in (C) substantially not with the reaction products of (A) and (A) and (B) The reaction conditions should be solidified; is the inner of the insert may be contained in the curable composition is melted, expanded and cured, thereby completely filling a cavity, Chen within the first material. 2. The method of claim 1, wherein the covering material is covered with a covering material on at least one side of the cavity prior to heating, and the covering material is adhesively bonded to the first material by heating. 3. The method of claim 1 or 2, wherein the adhesive insert is heated under pressure. 1 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back to write this page) Binding 1309670 1 C8 D8 VI. Patent application scope 4. If the patent application scope is 1 Or the method of item 2, wherein the heating is performed inductively. 5. The method of claim 1 or 2, wherein a load bearing member is attached to the insert before or after the heating. 6. The method of claim 1 or 2, wherein the first material is a honeycomb material. The method of claim 1 or 2, wherein the insert is composed of a solid expandable curable epoxy composition. 8. The method of claim 7, wherein the curable epoxy composition has storage stability at ambient temperature. 9. The method of claim 1, wherein the product obtained by the reaction of the solidified amine system (Β) with (Α) has a Kofler Heat Bank melting point between 55 and 120 °C. 10. The method of claim 1, wherein the expansion agent (D) is non-reactive under the reaction conditions selected for (A) and (B). The method of claim 1, wherein the conventional additive (E) comprises a dip. 12. The method of claim 11, wherein the dip consists of hollow microspheres. The method of claim 11 or 12, wherein the material comprises a conductive material. The method according to claim 1 or 2, wherein the insert has formed a desired shape under conditions in which it does not substantially swell or gel or solidify. 2 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 metric) (please read the notes on the back, write this page): _ _ 1309670 ABC3 VI. Patent application scope 15. If you apply for a patent The method of claim 14, wherein the insert has been formed from a liquid solidizable composition that has been solidified to form a swellable curable composition that is solid at ambient temperature Things. 16. The method of claim 15 wherein the solidification of the liquid composition is carried out while the insert is being formed. (Please read the note on the back to write this page.) Binding the Chinese National Standard (CNS) A4 size (210 X 297 mm)