JPS5954551A - Adhesive sheet for reinforcing metallic plate - 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 This invention relates to a metal plate-reinforced mutually S-resistant sheet.

Conventionally, in automatic tunnels, various reinforcement measures have been applied to heavy steel plates. For example, roof, fuenta
- Although it has a relatively wide and flat shape like the hood, trunk, rear panel, and door part, it is a plate 1'? H-bow! , for 17-inch outer panels, relative to the external force)
1. Since it is necessary to provide a certain degree of rigidity, the inner plates r and y from the metal reinforcement part are pasted by spot welding or adhesive.
(Method 3 has been adopted. However, 2. This force method-C has a lot of heavy use of metal bending force removal, and it goes against the idea of making the outer panel into a vj board, which was designed to reduce the weight of small bowls.) However, it has disadvantages such as increased use, increased costs, and the process of inspection becomes more complicated.

On the other hand, asphalt]
Rubber, epoxy resin, acrylic resin, phenolic resin,
Polymer interest, such as unsaturated polyester resin, for the outer panel!
, i::, A method is also known in which a considerable amount of surface area is painted on the city side. In this method, an H material with a high tensile bullet 1 survival rate and a large enclosing force is selected as the polymer material, and this is 1'? <11-1> A considerably large reinforcing effect can be obtained for coating misalignment, and this construction method also has the advantage of being lightweight compared to the use of metal reinforcement members.

However, on the other hand, it has no tensile modulus (171), and polymers/materials with high force (generally 5-dimensional) Yes, and according to this resin silk book 1, curing shrinkage etc.! 1℃
This is a fatal problem in that the trapped residual stress after curing causes distortion (dents) in the board, impairs the flushness of the car body, and seriously reduces the product value. Atsupuko.

This invention has been developed to address these circumstances and to use a thermosetting resin which is more advantageous than the metal reinforcing part (1).
7, distortion of the metal plate due to curing shrinkage of this feed 4
This was discovered as a result of intensive research in order to develop a new or useful force-q dog that can suppress and have a sufficiently large reinforcing effect.

That is, in this invention, the elastic modulus of the claw provided on a metal plate and hardened by heating is sufficiently large to improve the rigidity of the metal plate. , or -゛) In the first thermosetting resin composition layer, the resin composition is made such that the glass transition temperature is high when heated (↓),
Is the tensile modulus of elasticity similar to the above example insufficient to increase the rigidity of the metal plate? A sorting body is constructed by laminating a second thermosetting resin composition layer in which the resin is blended so as to have a low AA degree, and at least the second thermosetting resin composition layer is imparted with conductivity. This is related to the metal plate ``1111'' metal plate whose characteristic is ``1111''.

. However, in the thermosetting resin composition of the present invention, the tensile modulus and glass transition temperature after heat curing are determined by the resin composition (i.e., the type and composition of the resin, curing agent, and other components). +12 etc. make a big difference.

This invention was originally designed to improve the tensile modulus of elasticity described above and the rigidity of metal plates such as heavy body skins.
Prepare a thermosetting resin composition ((・↓) with a resin composition that has a high glass transition temperature when cured by heating, When we tried reinforcing the metal plate, we found that the reinforcing effect was satisfactory, but the problem of distortion of the metal plate due to curing shrinkage could not be avoided.Conversely, the above tensile modulus of elasticity A thermosetting resin composition with a 4RI fat composition that has an insufficient size to increase the 17k and has a low glass transition temperature when heated and cured is prepared. In this case, the distortion ZJ of the metal plate due to shrinkage (1J!) almost appeared [7 levers 1. The intended purpose of reinforcement was not achieved at all.

The present invention solves the above contradictory problems by using a first thermosetting tri resin that has a tensile strength of 100% and a high glass transition temperature.
A second resin composition layer having a low tensile modulus and a low glass transition temperature is laminated on the resin composition layer, and the latter layer is brought into contact with the metal plate. fl-,
4"1[, By heating and curing, it is beautifully cured;',
i: It has been served. That is, according to this method, the curing shrinkage of the ml thermosetting resin composition layer is alleviated by the second thermosetting .IIl', tM. On the other hand, a sufficient reinforcing effect of 11M can be obtained mainly by the first thermosetting resin composition layer.

Also, a little 1. By applying electrical conductivity to the second thermosetting resin composition layer, the following various effects may be obtained.

Zunawa 1-1, metal plate reinforcement joint i"1'lll: i・-1・′old is pasted on the steel plate, 10
After that, the same! z1. I'it painted heavy stones on the IN board, c +
(!2. Boundary between the side surface of the adhesive sheet -1. and the steel plate) 11. Paint is difficult to apply. If some parts are not painted like this, they will be exposed to a humid atmosphere for a long time,
This can cause rust. The progression of this rust on the exterior panels of automobiles may lead to dwarf defects.

On the other hand, in the present invention, by making at least the second resin composition layer conductive, adhesive sorting for reinforcing a metal plate can be applied to a steel plate (after applying an electric coating, 1 layer of the second thermosetting resin composition (4 layers) 1)
It is also coated with electrodeposition, so it will not rust even if exposed to a hair 1 (111) atmosphere for a long period of time.

The first thermosetting (δ・■) resin composition layer in the adhesive sheet of this invention has tensile strength i; ii, i
Is the 4NN resin metal assembly fj3: such that ti is necessary and sufficient to improve the rigidity of the metal plate, and the glass transition temperature when heated and hardened is 0. , among which the tensile modulus is generally: 0~500
7/・''TN11 degree 1, glass transition temperature is usually 80
℃ or higher. If this elasticity becomes too strong or the glass transition temperature reaches its limit, the distortion of the metal plate will be prevented despite the presence of the second thermosetting resin composition layer. There is a possibility that it will not be possible.

In addition, this specification N: smell, tensile elasticity・↑・te,
I SOI (ecomm cndaLion R-5
27, using a test piece of ")'T)e1"(7,5peed1').

In the adhesive sorting of the present invention, a) the second thermosetting resin composition layer has a tensile modulus of elasticity after heat curing that is insufficiently thick to improve the rigidity of the metal plate, and is heat-cured. The resin composition is such that the glass transition lrl' is low when the glass transition occurs, and the tensile modulus is generally about 0.1 to 1-5 K7/', and the glass transition IJ
n degree ill: 7 (below 1°C. If this elastic modulus becomes too small or the glass transition 111o'1 degree becomes low, the reinforcing effect of the metal plate will be poor. The first and second thermosetting resin composition layers described in 1-1 are prepared by blending a thermosetting resin with a heat-activated curing agent and adding various additives as necessary. Additives of
7 Semi-cured state (can be formed by two-sort molding (C-). In this sort-molding, by setting the angle of the thermosetting resin seed), curing agent, and other additives as appropriate, Alternatively, by setting the distribution amount of each component, etc., the tensile modulus of elasticity of the first and second heat-curing resin layer after heating curing is 1. L, glass q (k transfer; Ar
3. The thermosetting resin used to form each composition layer is typically Evoquine, and this epoxy resin is old.
Normal glycidyl ester type, glycidyl ester Q9
．． There are various intercalated resins such as , grindylamine type, linear aliphatic epoxide type, and alicyclic epoxide type, and depending on the physical properties of each composition layer, one type can be used in 11 islands or 2 types. The above can be assembled and used by the staff now.

The heat-activated curing agent may be a normal curing agent that exhibits curing action when heated, and generally has a hardening effect of 80 to 20'.
It is sufficient to be active in the 1-degree range of C, for example, dicyandiamide, 4,4'-diaminosifolone, imitazole derivatives such as 2-n-hebutadenimitazole, isophthalic acid dihydrazide, N
, N-sial 4-nylurea derivatives, N,N-dialkylnaourea derivatives; ij'', T form, etc. are used.
-1 is thermosetting resin 100 small i? The ratio may be 15 parts to 15 parts for 1 part to 15 parts.

In addition to the above-mentioned thermosetting resin and curing agent, a composition (which has a cohesive force to the extent that sort molding is possible, and
] To prevent wetting, or by lowering the melt viscosity by 1.
Various kinds of additives are used as necessary, such as for increasing l toward -1.

Even if (1) improves the performance of the sheet, polyvinyl normal, polyamide, boriyamide; Thermal i'iJ plastic resins such as epoxy resins of Polymer A and epichlorohydrin-171, Soil/J Phthadiene-Acrylic 1-1
A nitrile copolymer or a derivative thereof can be blended. , these uses 1,11k, thermosetting resin 100 cities (
6 parts to 7 to 15~i (1('l jr-[j,'
4. Also, for the purpose of preventing sagging of the 11 former compound, it is preferable to fill it with carbonic acid, tar, asbestos, silicic acid), carbon black, + 11 ital silica, etc. I need medication once a month. Formulation 1+;,
i;, 1, thermosetting resin 1.00 tJj -i edition (
Normally 10 to 300 cars for B i6 [about 1 part of J and 1
That's fine.

Furthermore, the purpose of improving wettability by adding 1.0% of iris viscous jO-, reaction + 1.0 diluting agent such as tool 1-lucidyl ether, long-chain alcohol monoglycidyl ether, etc.
Phthalic acid-based Ij such as dioctyl phthalate can be blended with thermosetting resin 100.
For the lesser instep, it is usually about 5 to 30.9j, ii'f, and about 1-.

(The second thermosetting resin composition 1 (-) is the amount of the component described in 10.1 in order to impart conductivity to this second layer.) 7 "External 1j8 month charge is added as an essential ingredient. This material calculation (7.
'Lumini Uno, powder 5, metal powder such as copper powder, carbon powder, 5! ``There are roughite powders, etc. The amount of this material is.

For example, J-pokin resin 100 cars (11 parts to (-7 parts)
25 to 800 middle-aged ('lj degrees and ") - good.
Among the first and second thermosetting resin composition layers formed in this way, the second pre-curing resin composition layer is especially one that has adhesive properties. 3. It is desirable that
This is because temporary adhesion of the j+l thermosetting curve becomes easier. Of course, the first thermosetting resin composition layer may have viscosity as well. In order to make the reinforcing effect W of the metal plate visible, the first thermosetting resin composition layer (
It is also possible to bury reinforcement +4 -C: Kill 3,? : As for the capture and kidnapping of
Inorganic i + Mj #, Ui 4f [cloth, linen, cotton, Ny[J/', poly-1-stell, polypropylene 7 organic material made of 4 fibers, Boris aluminum film, Nitcom film, etc.] From plastic film, paper such as kraft paper, polyester fiber, polypropylene fiber, etc.
Rumiram, iron, copper, 411. There are metal cylinders made of lead, etc.

Reinforcement +" (this is when molding the first thermosetting resin composition layer in a sorted shape j (1,.Reinforcement (・12 not on one side of 1) thermosetting (1?・↑ Do not apply the fat 4n compound 1. Impregnation is good.Regulation reinforcement shrine should be impregnated even on one side ([therefore, it is sufficient to obtain a large reinforcing effect). It is preferable to use inorganic fibers 1. or 31, and it is preferable to use glass fiber non-woven fabrics. The ISJ of the metal plate is different from the god of the metal plate and the degree of reinforcement ((-yotsuY), but generally (or the first
0 thermosetting resin composition layer - r = about 0.01 to 10 mm, (lT - week (this is 0.1 to 5 mm, second thermosetting resin composition layer - (01 to 30 mm culm) , good] 1 mm is O, J ~ 1° open, the whole J'y is usually 0.2 ~ 40 m
The distance is preferably 0.5 to 20 m.

The preferred four shapes of the blue engraving properties of the present invention obtained in step (P) above include the first and second heat rlUJ
The I-forming resin composition layer is usually jMt -fT" The material has flexibility and pliability, so even if it is bent from 250 to 300 years, there will be no damage to it.
The C-shaped gyrus has a n° cylindrical shape. (-Daka-) Te-1 is preferably 5 dry F'#r, because the shape is flexible, the reinforced metal plate to be hit is wavy, 1111: g-shaped, square, curved. Even if it is pasted, 711 is applied, and it is used as a sorting for reinforcement.

The drawing is -1-j! The following is a small example of the metal plate reinforcing adhesive layer 1 of the present invention produced as shown in b. A main body consisting of a curable resin composition layer 11, 2 a conductive layer contained in the second thermosetting resin composition;
゛1.

4. As described in detail, the contact r+ = I/l of this invention is based on the sea 1 body ((7) and the second thermosetting (!1, 1 fat composition layer side) By press-bonding the material to a metal plate and avoiding heat curing, a large reinforcing effect can be obtained without causing distortion of the metal plate, and at least the second thermosetting ((+・↑fat composition layer) To obtain the effects of the gods as described above, !4-1 c': hl-7.

In addition, the contact 4Ixyu...-1 of this invention is
As stated in C..., just like the evening H reaction during T II, there is no problem with the use of III or NISO 0) 11 Q, and each camp's 4'i + 8' mountain air refrigerators should be washed. Metal plates that are generally used as thin sheets, such as the cases of home appliances, etc.

Furthermore, with the configuration of the present invention, the damping effect W can also be achieved for a period of time.

Hereinafter, I will describe the embodiments of the invention and explain them in more detail. ”ru.

Example 1 Shrimp=I-) #828 (Yuka Shell Co., Ltd. Bisnoto Nor A type liquid epoxy resin) 35 parts, -r Pico-1
-# to 02 (manufactured by Yuka Shell Co., Ltd., Hisphenol A type solid Evokin resin) 50 parts, Bi [1 N #500
(15 parts of Polynisdel (6.1 fat) manufactured by Toyobo Co., Ltd., 2 parts of Kyureozol 2MZ-AZINE (latent curing agent for Evokane resin manufactured by Shikoku Kasei Co., Ltd.), 2 parts of dicyandiamide (latent curing agent for Epoquine resin manufactured by Nippon Carbide Co., Ltd.) ) 5 parts, talc 50
An Evogin resin compact consisting of 27 parts of asbestos powder and 11 parts of asbestos powder was kneaded with a conventional mixing roll [7,
The resulting resin mass was blown to a thickness of 0.4 mm using a direct pressure brush.
The first thermosetting resin composition layer and the first thermosetting resin composition layer were formed by laminating a sheet-like C-C glass mat (MC#300 manufactured by Nitto Boseki Co., Ltd.).

This first thermosetting resin composition layer has a tensile + film property of 97 K? after heating and curing. y'-, and the glass transition temperature was 110°C.

Shrimp]-1-#871 (Timer acid-modified Epoquin resin manufactured by Yuka Shell Co., Ltd.) 80 parts, Ebico-+-#10
02 (111J issue) Part 10 and No\Squid-CTIS
10 parts of N1300
-ζ To the 100 copies of the obtained set 1j, send f Z -A I to Cuj'zol 2.

I N I': (output u+) 2 parts, 5 parts of cyannadiamide, Graph j'i 1ne 4ζ (Shin'etsu 1y, C manufactured by Suidogyo Co., Ltd.
I' B-: 3) 200 parts + 1 and 3 parts of asbeth 1- powder were blended. This is for "Hata's Mixing 1-"
] - At Le? ``Y1 Yukito sushi ((-Obtain a resin lump, mold it into a shape of 1 mm using a direct pressure press, and make a second uncured resin with a thickness of 1 mm). A thermosetting resin composition layer was used.The tensile modulus of this layer after heat curing was 28 Kq, i-.The glass transition temperature of this layer after heat curing was 40°C.

Next, the first and second thermosetting resin composition layers were laminated together to form an adhesive sheet for reinforcing a metal plate of the present invention.

At the same time, this metal plate reinforced pressure welding is sorted by 5 (・m1
7] Cut 1υ l-1 into a length of
After applying electric coating
The adhesive sort was cured by heating for minutes.

After hardening, no sink mark phenomenon of the steel plate was observed under visual inspection. In addition, the side surface of the second thermosetting 1 NOF resin composition layer and the boundary between that part and the steel plate are also well maintained.
'-1 It was not painted.

A rust test was conducted on the steel plate reinforced in this manner using a test piece and a salt spray tester (Toyo Rika Kogyo ST-JR Model 1).No rust occurred even after 500 hours had passed. .

Comparative Example 1 Metal plate reinforcing adhesive 17J- , 1-1- was prepared (7) After coating the degreased steel plate with 100% paint, it was coated with electrolyte paint, heated and cured, and then subjected to a salt spray test.As a result, after 500 hours, - Rust occurs from the interface of i11"/-1.
It has been found that when used for the exterior panels of automobiles, there is a sleet that causes a dirt defect.

Example 2 Ebitsu 1'#82B (+ reappearance) 50 parts, Epicote #], o02 (r reappearance) 50 parts, No\squid-#],
072 (B, l=', G4' Nitrirugono, manufactured by Tsudoritsuchi Co., Ltd.) 10 parts, Plaquemid II 103 P (11 Wood Rilsan rL co-cross nylon resin) 40 parts, l) 1.
'/\-2 parts of donor (curing agent manufactured by Maruji Hiokuminonol Co., Ltd.), 5 parts of ginj'indj'mide, 50 parts of talc, and 2 parts of asbestos were placed in a normal mixing roll.
J1j The kneaded and crushed resin mass was molded into a sorted shape with a thickness of 0.3 mm using a direct pressure press (7, laminated with glass cloth (WI et al. 2 (i104) manufactured by Nitto Boseki Co., Ltd.). [7
1. The tensile elasticity of this layer after heat curing t: is 72 parts M
3. Also, is this layer heat-cured iD- glass transition? l+a l scoldi i 05℃tea-].

Tsuki (This, γ Deka EP-4000 (Evokin Shield manufactured by Asahi Denka Co., Ltd. (Kawaj) '75 part, J-Pico-1-# l 0
02 (published by 1llj) Part 15 and Hiker et”3
Mix 10 parts of N 1300 x 8 (+ re-release) with melt ia.
7. To 10 () parts of the stolen composition, 1) 2 parts of ■' hardener (extracted from RJIJ), gin-j' diamide, iron powder (manufactured by Dowa Iron Powder 1) PS-2513400 parts, and 3 parts of asbestos. The white irises are mixed, and after 5 minutes, the mixing glow that is common in the ear, /shiku (2 in i, lt', i to do 1 (from this) (6.1 fat mass to 111, this stroke to the function ceremony) Zo1/s((
A second thermosetting resin composition layer having a thickness of 100 nm was obtained. The tensile strength and 111 ratio of this layer after heat curing were l OKq; In addition, this layer of heating hard fts t's horn last,
The crystallinity is 5jO℃-Ca-). The thermosetting property of fAIJ1 in the thermosetting resin composition layer of B2 is 4δ・1
The resin composition layer is bonded to the U-lever of the present invention for metal + 1 mass strength contact and L7 (l).

Next, the exact same example 1 as real pigeon example 1. ]'; k: Then 1. Note 7゛--Section 1- is removed and 1 finger is crimped to the steel plate 1. j
l', :Q', i Painted ν silently cured 6, 0·Ij (if not observed at all by f-J view, the side of the second thermosetting resin layer (If it is C11 (・=
The boundary between that part and the steel plate was well coated with electricity.Furthermore, a rust test was performed using a salt spray tester C (secondary method). There were no outbreaks.

[Brief explanation of drawings]

1 sea f for reinforcing metal plate of this invention
1 sex no 1-C) - Show an example ・F"'dJF ...Second thermosetting +7i,
Fat #, I-1 product; (I H, ■...2...-1 body,
2...ko L7 electric 11i go 1'j, It,)I')
l:1゜Special, l'l'lN petitioner [1 Tokyo Electric Power Co., Ltd. 11 representatives Patent attorney Nei I11゛O Kunio 1'',
゛、゛・□、゛1 THE 1″、'4、・□

Claims (2)

[Claims] (1) Tensile modulus of elasticity when heat-cured after being applied to a metal plate is large enough to be necessary and sufficient to improve the rigidity of the metal plate, and the glass transition temperature when heat-cured is The first thermosetting resin composition layer, which is blended with a resin so as to have a high tensile modulus of elasticity of -1-1, has a size insufficient to match the stiffness of the metal plate, and is heated and cured. The sheet body is constructed by laminating a thermosetting resin composition layer of FUCO F4S2 which is blended with resin so that the transfer temperature is low, and at least
An adhesive sheet for reinforcing a metal plate, in which a thermosetting resin composition layer has conductivity of τ1j-j. (2) 4' with reinforcement A' embedded in the first thermosetting resin composition layer! f j'l'il'l range number (
Adhesive tar 1-6 for reinforcing metal plates as described in section 1)