JPH04131234A - Resin coated metal - Google Patents

Abstract

PURPOSE:To strengthen the display of a character or figure on the surface of a metal by thermally Welding a fluoroplastic film having a printing layer formed from an ink resin composition to the surface of the metal and adding pearl pigment to the ink resin composition. CONSTITUTION:In a resin coated metal plate, a fluoroplastic film 3 having a printing layer 2 formed from an ink resin composition is thermally welded to the surface of a metal plate 1. As the metal material forming the metal plate 1, aluminum alone, an aluminum alloy of every kind and an aluminum type metal containing a small amount of manganese or magnesium are used. The ink resin composition forming the printing layer 2 contains pearl pigment and is based on a resin binder. As the resin binder, there is a fluoroplastic binder or an acrylic resin binder. As the pearl pigment, inorg. pearl pigment prepared by coating mica with metal oxide such as iron oxide or titanium oxide is used. By this method, a resin coated metal having a beautiful pearl-like hue and having display content of a character or figure strongly formed to the surface thereof in a hardly releasable state is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin-coated metal formed by laminating a fluororesin film on a metal surface by thermal fusion.

[Conventional technology]

Conventional resin-coated metals are made by forming a fluororesin layer on the surface of a metal base material such as aluminum, thereby improving the heat resistance, chemical resistance, electrical properties, mechanical properties, etc. of the fluororesin layer on the metal. It is known to have excellent properties.

[Problem to be solved by the invention]

However, the fluorine-based resin of conventional resin-coated metal,
Although it is possible to color the entire resin the same color by kneading coloring ingredients such as pigments, it is generally extremely difficult to color characters, figures, etc. for decoration or display by printing. There has been a problem in that it is extremely difficult to display figures etc. in color.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a resin-coated metal in which the displayed contents of letters and graphics displayed on the surface of the metal are robust, easy to peel, and do not fade.

[Means to solve the problem]

In the present invention, a fluororesin film that covers a metal surface and prints a printing layer formed of an ink resin composition is heated to
The above-mentioned ink wood composition is applied to the paper.
The above-mentioned IJ objectives have been achieved by providing a resin-coated metal containing a pigment as a main component.

Hereinafter, the invention will be explained in detail with reference to FIG. 1.

FIG. 1 is a partial sectional view schematically showing a resin-coated metal according to an embodiment of the present invention.

The resin-coated metal of this example is a resin-covered metal plate, and a fluorine-based St resin film 3 having a printing layer 2 formed of an ink resin composition is thermally attached to the surface of the metal. be.

↑-Metal metal plate 1 is not limited to a specific material, and can be appropriately selected from the materials described below as necessary. , - It is preferable to use a ram-based alloy. 1, and the printed layer 2 was formed by printing each of the above-mentioned fluorine thread resins. It may be formed on either side of the fluororesin film 3, but
The back side of the l-containing monolithic resin film 3, which is the side that contacts the metal plate 1, is formed (this protects the printed layer 2 from abrasion, etc.). , 1: The thickness of the printed layer 2 is particularly controlled, usually 1
=== 1. OOp m is preferable. Further, the above-mentioned 2゛-based resin film 3 is made of a conventionally known material f, which will be described later.
1 can be selected as needed. Also, the IIX is particularly 11JIJ@F, usually 5-1000μrn.

stomach.

, Next, the metal plate, ink resin composition, and fluororesin film will be described in further detail.

As mentioned above, the metal material forming the metal plate 1 can be made of various metals, including aluminum alone, various aluminum alloys such as duralumin, and aluminum containing a small amount of manganese, magnesium, etc. Preferred are aluminum-based metals such as metals. others,
Iron-based metals, copper-based metals, digital metals, and the like can also be preferably used. The metal plate 1 is subjected to surface cleaning treatment (degreasing, cleaning, etc.) or roughening treatment (sandblasting, chemical etching, etc.) in order to improve its adhesion to the fluororesin film 3. It is preferable to carry out the treatment in advance.

The ink resin composition forming the blended printing layer 2 contains a Burl pigment and has a resin binder as its main component. Examples of resin binders include fluorine-based resin binders, indium resin binders, and acrylic resin binders.
The fluororesin binder is preferable (in addition, the resin binder will be explained about the soil and the thread resin binder), l::, the above ink resin composition is
@jl'f In addition to the binder and Burl pigment, it contains a solvent, a cytosotrophic agent, a pyrolizing agent, pigments other than the Burr pigment (also dyes), and various other additives depending on the required number.

The fluorine-based Ilt resin binder is not particularly restricted, but in 1) the fluorine-based resin binder and [7] are usually difluor A-roethylene-tetone fluoro-cochlene-hexafluoropropylene #, ffi combination 4It.
Preferred are difluoroethylene-tetrafluorocotylene copolymer resins, particularly difluoroethylene-tetrafluorocotylene copolymer resins, and particularly ethylene-hexafluoropropylene copolymer resins. preferable. Other hooks
Thread resin binders and [, generally 1. Those with a fluorine content of 30% by weight or more, particularly 401% or more are preferred, for example, ethylene-tetrafluor A loesalene copolymers. 1. L-fluoroethylene copolymer, hexafluoroethylene copolymer, hexafluoroethylene copolymer, b-fluoro-11alkylvinyl-Y--'J' -tetrafluoroethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, etc. are preferred. Among these, ethylene-tetrafluoroethylene copolymers containing fluoroolefins, cyclohexyl vinyl ethers, alkyl vinyl ethers, and hydroxyalkyl vinyl ethers as essential components. are preferable, and furthermore, fluoroolefins, cyclohexyl vinyl ethers, alkyl vinyl ethers,
The content of units based on hydroxyalkyl vinyl ether and other comonomers is 40-60 mol%, 5-60 mol%, respectively.
45 mol%, 5-45 mol%, 3-15 mol% and 0
~30 mol%, and an intrinsic viscosity of 0.1 to 2.0 measured in tetrahydrofuran at 30°C in the uncured state.
dl/g is preferred. Furthermore, in the above fluorine copolymer, the fluoroolefin is a perhaloolefin such as chlorotrifluoroethylene or tetrafluoroethylene, and the alkyl vinyl ether contains a linear or branched alkyl group having 2 to 8 carbon atoms. More preferably, the hydroxyalkyl vinyl ether is hydroxybutyl vinyl ether.

The above-mentioned Burr pigment is preferably a mica-based pigment, and in particular, an inorganic pearl pigment in which mica is coated with a metal oxide such as iron oxide or titanium oxide is preferable. It is preferable in terms of alkali resistance, heat resistance, coloring power, burl gloss, etc.

Iriodin 500 is a bar pigment coated with iron oxide.
．． 502.504.520.522.524.530(
Iriodin 3 (manufactured by Merck & Co., iron oxide coverage 20-60%)
00.302.303.320.323.351.35
5 (manufactured by Merck & Co., iron oxide coverage 4-40%, titanium oxide coverage 10-50%), and examples of Burl pigments coated with titanium oxide include Iriodin 100.103.1.
11.120.121.131.153.163.17
3 (manufactured by Merck & Co., titanium oxide coverage 10-40%), Iriodin 205.215.217.219.225.2
35 (manufactured by Merck & Co., titanium oxide coverage 40-60%).

The above-mentioned Burr pigment preferably has an average particle size of 5 to 20
0μ, particularly preferably 10 to 100μ, and even more preferably 20 to 50μ. Further, the amount of the Burl pigment is preferably 5 to 100 parts by weight, particularly preferably 10 to 80 parts by weight, based on 100 parts by weight of the ink resin, in order to produce the pearlescent luster and unique color tone unique to Burl pigments.

Further, the crosslinking agent crosslinks the fluororesin binder when heat-sealing the fluororesin film 3 to the metal plate 1, and crosslinks the resin binder to form the printed layer 2. Increase the strength and print layer 2
This makes the printed layer 2 more difficult to peel off from the fluororesin film 3 and the metal plate 1 by making it more robust and increasing the adhesive strength to the fluororesin film 3 and the metal plate 1.

As the crosslinking agent, for example, OH crosslinked polyols, amine crosslinked organic amines, and peroxide crosslinked peroxides are preferably used.

The polyols used in the above-mentioned OH crosslinking type are excellent as crosslinking agents because they do not cause the so-called scorch trouble in which the fluororesin binder hardens during storage, and have a fast crosslinking speed. As the polyol, for example,
Bisphenol, bisphenol AF (hexafluoroisopropylidene bisphenol), and the like are preferably used.

Incidentally, an acid acceptor such as magnesium oxide, zinc oxide, calcium hydroxide or the like is added to the polyols, if necessary, to remove the acid generated during crosslinking.

In addition, the organic amines used in the above amine crosslinked type are:
Although the crosslinking rate is fast, there may be scorch troubles, it is necessary to add a scorch inhibitor, and it is also necessary to add the above-mentioned acid acceptor. As the organic amines, for example, hexamethylenediamine, hexamethylenediamine carbamate (HMDAc), ethylenediamine carbamate, N,N-dicinnamylidene-1,6-hexanedidiamine (DCHDA), etc. are preferably used. It will be done.

Additionally, the peroxides used in the peroxide cross-linked type do not necessarily require an acid acceptor;
Frame ti, +, li, d' SF constant, ', t CL
ui own knee 1 〉7-,. 7 series resin base...
1. .

The varoxides, C, are, for example, penzoylvaroxide, 2.・Cumil per quinide, etc. are preferred I," (Used 3, t-1I3self, g bridge All), ・Element system product 1 fat bar, f
The amount of hardness for the diameter is 100% and the weight is 6(;
λ・t L7'l' 1-2011ii part is good i L
, <, 2-153-Okibe is more Q-P 19. <, 3
-10 parts by weight is most preferred.

In addition, 1-500 is preferable for 1-500'i: L<, 20□・4
oo is more preferable, and 30.about.300 is most preferable. pull)・fu1′? - Inodesox is undesirable because it becomes a groove at the heat fusion stage described later, and the adhesion of metal [1\ is low]. Preferable 1. because the printing will smudge. <No.

Note that the 1″a melt flow index is the same as the above i...
Excluding the dissolved Nj component of the resin composition, the tr circumferential component ζ”
, represents the fluidity of thermoplastic resin during melting t m &
So, for example, use Ryou 1/2 L Torch Star, and
jij no i7300 “C1 load” Ov/ca
t's also 2 to 1, /z +1. ．． Extrude 1 g of sample material from the nozzle between q￥'1+uay-I throat 2, and at that time 1 is ◇ time
'', and the above temperature is the sample resin (fluorine-based St piece □)
Melt-molded cutting blade I]F temperature range (flow start temperature, thermal decomposition start groove) and temperature range between fl')
The humidity level at which the flow starts is y't.

": The above solvent is C1"1, the boiling point is 100 to 2.00
I like it! L<、Example・Ba、10My thing is a woman、■、I.

Jll-7, If force j JS carbon, two bases, Miki Sil Spirit Ara group hydrocarbon, xylene, sulfur naphtha, tetrari, /, dipentene, toluene alcohol, 1-
7", cyclohexyl, cyclohexyl, 2-methyl, chlorhequinyl, cyclohexyl, 7", cyclohexyl, cyclohexyl, 7", cyclohexyl, 7", cyclohexyl, cyclohexyl, 7", cyclohexyl, cyclohegisanone, cyclohexyl, cyclohexane 4゛The, non, dir-cetone alcohol λ1, isopho-D glycols 1. r-glycol, propylene glycol, l-7-glycols, me-delcellosolve (
y-glen glycol 1,000 ml = -pur), cellosolve
-tail), butyl cellosolve, cutbi)-)L Glycol needle ester: cellosorg li acid, butyl cellosolve acetate, carpitol acetate (diezalene glycolmo,), ': 1'7 chill J
-Terua Seven Meal 1.) Amides Class 1 Dimethylformamide, Dimethylacetamide Also, Handbook Thixoto 1.7 Bi-imparting agent and 1. Examples include near-zero idal silica (Ayu, Rosil #400), aluminum alcoholate, organic bentside, aluminum chelate, barium sulfate, etc. Thixotropic index (TI
value) is preferably 2 to 8, and 3 to 7 is more than Δ
Preferably, 4 to 6 are even more preferable. Also, Tl@i! , temperature 25°? ' B J (um: LAN for 'St'
-c~, 7 cy> o-evening-t L for stool, E number 2
Viscosity N2 measured at human, l, F 20 [1] rotation
and N'20, that is, T I ==N2/N20, is 6°.In addition, the soil, pigment, or IJ dye can be selected as appropriate depending on the purpose and use11. It is used as

kl jd 'NI 劃 and 1. J- has inorganic pigments, organic pigments, and constitution Ei thorns, 6, inorganic face with 1 doji ('', butane oxide, carbon black, Bengara, iron black, navy blue, ultramarine,
Preferably used are zinc white, yellow lead, silver, cobalt blue fired green, sulfurized lead, bronze powder, aluminum powder, var pigments, etc. 2. Also, organic pigments, etc. So, insoluble azos, azoregis, now b'criton red, power-min red, watch, /brenod,
Condensed azored, Peri1/Nred, Asisuraquinone,
Disazo Orange, Gee Loary/Orange, γ Setron Orange, Disazo Ivo, Rho, Hansa Yellow, Acetron I]-Rho Chlorinated Notarocyanine, Prillian Ogreen Le 4, Pig 11 Cyanine, Indes 1/
Preferably, use is made of mesalbeimeresoto, fluorescent pigments, phosphorescent pigments, etc., and as extender pigments, precipitated barium sulfate, calcium carbonate, alumina white, clay, etc. are preferably used. used.

In addition, as the above-mentioned dyes, ordinary acid dyes, basic dyes, oil-soluble dyes, and disperse dyes are used, and as the oil-soluble dyes,
Azo type, triarylmethane type, anthraquinone type, and azine type are used.

In addition, other additives include conventionally known gelling agents,
A thickener, an antioxidant, an antifoaming agent, a matting agent, an ultraviolet absorber, and a light stabilizer are used, and if necessary, a curing catalyst such as benzyltriylphosphoonium chloride is used.

The above-mentioned ink resin composition consists of the above-mentioned components, and the preferred blending ratio of each component is 50 to 150 parts by weight of the solvent and 2 to 10 parts by weight of the chicken-tropy imparting agent to 100 parts by weight of the fluororesin binder. Then, add an appropriate amount of pigment or dye (usually 10 to 400 parts by weight) and other additives depending on the purpose and use, and further add 0.1 to 2 parts by weight of a curing catalyst as necessary. I can do that. Further, when blending each component, each component and the amount thereof blended are appropriately selected so that the resulting resin composition has a melt flow index of 1 to 500.

Further, as the fluororesin forming the fluororesin film 3, ethylene-tetrafluoroethylene copolymer,
Trifluoroethylene copolymers, vinylidene fluoride copolymers, vinyl fluoride polymers, fluorinated alkoxyethylene resins, tetrafluoroethylene resins, tetrafluoroethylene-hexafluoropropylene copolymers, etc. are preferred, and further, Ethylene-tetrafluoroethylene copolymers are more preferable, and among them, the molar ratio of tetrafluoroethylene/ethylene is 4.
0/60 to 60/40, and the general formula CH2=CH-C
The content of the perfluoroalkyl vinyl monomer represented by nF2n+1 (where n in the formula is an integer of 2 to 10) is 0.1 to 10 mol%, and the melt flow index is 10 to 500 □ 3/sec is preferred. When the melt flow index is within this range, the adhesion strength of the fluororesin film 3 to the metal plate 1 increases, and a good resin-coated metal that does not peel off can be obtained. Note that the melt flow index is measured in the same manner as in the case of the fluororesin composition.

The method for producing the resin-coated metal is not particularly limited, and any method can be adopted. For example, a fluororesin film 3 on which a printing layer 2 is formed using the ink resin composition is prepared in advance, and the surface of a metal plate l is treated with the fluororesin film with the printing layer 2 inside. The resin-coated metal of the present invention can be manufactured by heat-sealing the resin-coated metal of the present invention. Further, in this case, the fluororesin film may be heat-sealed to the metal plate with the printed layer 2 on the outside. The resin-coated metal of the present invention can also be produced by heat-sealing the fluororesin film onto the surface of the metal plate 1 on which the printed layer 2 has been previously formed using the ink resin composition.

Further, the method of forming the printed layer 2 on the fluororesin film 3 is not particularly limited as long as it is a method capable of closely forming a thin film of the ink resin composition, but the method of forming the printing layer 2 on the fluororesin film 3 is not particularly limited as long as it is a method that can closely form a thin film of the ink resin composition. resin film 3
There are a method of forming the printed layer 2 by printing on the metal plate 1, a method of directly printing the above-mentioned ink resin composition on the metal plate 1, and the like.

A specific method for forming the printed layer 2 on the fluororesin film 3 will be described below.

For example, the fluororesin film 3 has a thickness of 5 to 1
For example, the screen used for screen printing has a mesh size of 100 to 300 μm.
Using a mesh screen, a thin film (printed layer 2) of the ink resin composition with a thickness of 1 to 100 μm is obtained.

In addition, prior to printing the ink resin composition on the fluororesin film 3, the surface of the fluororesin film 3 is subjected to corona discharge treatment, blast treatment, sodium etching treatment, etc., and the wettability index of the surface is However, for example, activating it so that it is 35 dynes or more increases the adhesion] and it is extremely difficult to hang. So, the screen is ``:'' by notification 1.
1 tree, q) i′7shi+S+metal 81, uru[[]88
To obtain 11 layers, ~t=l! +:', (Using 11 blocks, l=, il", Ingi resin point 1 by n method)
jat: material seal III 1 is enough, in that case, 1l1
Ink at the month + t J, i, '(hl's digisoto [7 Bee: 3 When you become a prisoner, go to the version 4. Convenient incident I:, also) 3. There is a possibility that there will be some inconveniences such as a drop in the leveling of cell ``7'' on the first screen.

- Printed layer 2 was formed on one layer as described in 1. Inside III &::
1. , '+Predetermined surface treatment 17]-Metal plate 1
Apply heat to the surface, then heat to 260-360℃
The resin-coated metal of Mokuto [91] is made into L by heat-melting knitting with heat melt knitting.
When the composition contains a predetermined amount of crosslinking agent and the melt index of the solid is adjusted to 1.-500, t=me, upper J. 13 However, the printing butter/shape is eclipsed! I
: Ii' rises 4 to 5', and it is as strong as the 2nd cut with the λ sword [1j printing layer 2 is the surface of metal illumination +,
, :: Thermal melting 4t' 4 , Knee, , Hi 5
, Sub-) i-1 According to the present invention, when the resin film 3 is heat-fused on the surface of the metal shaving 1, 1. ': At the time of cross-linking with 4 fill-All of the fluorine thread resin binder cross-linking in the resin composition 7') The resin-coated metal of the present invention can be obtained by forming a print layer 2 that is hard to peel off. ``Limited,''1; -7) It may be of any form as long as the raw resin film can be heat-sealed.5゜[2 effects] This book The resin-coated metal of the invention (・"j: fluorine thread resin film 75 is firmly fused to the metal and peeled off from the metal.
It is possible to form a beautiful printing layer with a burr-like appearance.

If Example] Next, the present invention will be described in Section 1, Section J based on Examples, and Section 1. I will explain it in terms of light.

Implementation 4 + l11 ma 1'',〉〉゛fu 1 seal ro: I-7 dire・'-atononol iIJ゛''g-b゛ Hegi Lif, 112 o■7
11 on '1 ti = ffi legal i month (kai +
9301 (manufactured by Ai Yuka Co., Ltd.) f Soho 17 and Schiff 11 \ Kata 4') Non-kara na A) Mountain 1. Self-melting da・1
(J to sentence, jt, te 1・1'!
100g (2 pieces,
75 gQ゛, Nku1 phhexanone, 7
Next, 5g of the resin solution was dispersed and mixed in an ink mill with the ingredients adjusted to a ratio of 4 to obtain a pearl-like color. Create things L
7'':.

(a) KYNA-93011long (b) IRIKIJIN 500Wn; 30g (Iron oxide coati 5/Rimica) (0 kIdarushiri force, 10g +a) Sulfuric acid: barium,
5 g (e) Z oxide 1 cum i
5 Bi, A 'Tree JLLI' introduced acidic F -u, so L -TA1 Be Int ', Phantom nano + h m + acid; 1 month, 50 μm] 711
・N-tI・Rahul 11 “1-cho, that]...Common i1i
: )'p resin (no 7, .71.', ', I>・c
op made by Asahi Glass (Ki), film-[ba, 2
25/9, - After screen printing using a human screen, it was dried at 120°C for 60 minutes. . The thickness of the printed layer of the film No. 1 was measured 14, and the thickness was 8 μm. T-luminium cypress (JIS A300) with JV size 2.
The product 1 of the present invention was prepared by heat fusion bonding.

Example 2 In place of 9301 in Example 1, Lakunoso 17'' N50S (Asahi Sen', ... 1, manufactured by Co., Ltd.) was used. Example 3 Inventive product 2 was prepared by using vinylidene fluoride resin (Kynar 301F) in place of Kynar 9301 in Example 1, and methyl ethyl ketone in place of the mixed solvent isophorone-cyclohexanone. Product 3 was produced.

Example 4 Inventive product 4 was produced in the same manner as in Example 1 except that Iriodin 300 Gold Peal (manufactured by Merck & Co., Ltd.) was used instead of Iriodin 500Wn in Example 1.

Example 5 Product 5 of the present invention was prepared in the same manner as in Example 1 except that Iriodin 103 manufactured by Merck & Co., Ltd. was used instead of Iriodin 500Wn in Example 1.

Example 6 Inventive product 6 was produced in the same manner as in Example 1 except that 5 g of phthalocyanine blue was further used.

Tests for taper wear, weather resistance, and bending workability were conducted for each of the products 1 to 6 of the present invention, and each was evaluated according to the following criteria, and the evaluation results are shown in Table 1 below.

As is clear from the results shown in Table 1 below, all of the products 1 to 6 of the present invention were found to be excellent in taper wear, weather resistance, and bending workability.

Table 1 In Table 1, taper wear, weather resistance, and bending workability are evaluated based on the following criteria.

Taper Wear: A wear test was carried out under the conditions of a load of 500 gf and a rotational speed of 1000 revolutions using a weather-resistant bendable parking machine specified in JIS-7204. ◎ is good, △ is slightly poor, and × is poor.

Using WS type sunshine carbon (Suga Test Instruments Department) specified in JIS A1415-1977, an accelerated exposure test was conducted for 5000 hours, and changes in appearance were compared with storage test pieces.

Almost no difference in appearance from the storage test. If not, 01 has changed somewhat. Cases where this is the case are indicated by ○.

Length 10o1, diameter 5o, thickness A diameter of 2H is placed in the center of the two crane test pieces. A steel round bar is arranged and the round bar is supported. Bending at 18o° as a point When doing so, the bending part may be damaged. Check for cracks and peeling. If there are no cracks or peeling ◎ If there is a certain amount, ○ means a lot. Some cases are marked with a △.

〔Effect of the invention〕

The resin-coated metal of the present invention has a beautiful burl color tone, and the display contents such as letters and figures displayed on the surface of the metal are robust and difficult to peel off.

[Brief explanation of drawings]

FIG. 1 is an enlarged partial cross-sectional view of an example of the resin-coated metal of the present invention. 1... Metal plate 2... Print layer 3... Fluorine resin film

Claims (5)

[Claims] (1) A fluororesin film having a printing layer formed of an ink resin composition is heat-sealed to the surface of a metal, and the ink resin composition contains a pearl pigment. resin-coated metal. (2) The resin-coated metal according to claim (1), wherein the printing layer is interposed between the fluororesin film and the surface of the metal. (3) The resin-coated metal according to claim (1) or (2), wherein the ink resin composition has a melt flow index of 1 to 500. (4) The resin-coated metal according to any one of claims (1) to (3), wherein the ink resin composition has a fluororesin composition as a main component. (5) The resin-coated metal according to any one of claims (1) to (4), wherein the metal is aluminum or an aluminum alloy.