CN100393840C - Heat-resistant label applicable at high temperature - Google Patents
Heat-resistant label applicable at high temperature Download PDFInfo
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- CN100393840C CN100393840C CNB2004800249625A CN200480024962A CN100393840C CN 100393840 C CN100393840 C CN 100393840C CN B2004800249625 A CNB2004800249625 A CN B2004800249625A CN 200480024962 A CN200480024962 A CN 200480024962A CN 100393840 C CN100393840 C CN 100393840C
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Abstract
A composition for heat-resistant labels applicable under the high-temperature conditions of 300 to 1,100 DEG C; a heat-resistant label; a product bearing the label; and a process for producing the label. As heat-resistant label adhesive layer, adhesive is possible under high-temperature conditions by a semicured (hardened) coating film comprising (A) a silicone resin and (B) at least one member selected from the group consisting of a polymetallocarbosilane resin, zinc powder, tin powder, and aluminum powder.
Description
Technical field
The present invention relates to the heat-resisting label that on the heat product of 300 ℃ or higher temperature, can paste with composition, heat-resisting label, be pasted with the manufacture method of goods and this label of this label.
Background technology
In wide industrial fields such as food, machinery, chemistry, pasting the label that is printed with mark, literal, pattern etc. on product or its packing is that pattern forms label, thereby is used in the supervision of construction.Its representation example is to utilize the management system of bar code.In this bar code management system, by by the bar code machine read out goods Manufacturing Status, make information such as responsible official, manufacturing process's time, shipment place, price, thereby realize making, sell, the management of circulation.
But, make label with the low resin of thermotolerance, paper etc., and paste to pay the bar code of the present widespread use of the tackiness agent that contains acrylic resin etc. thereon, under the hot conditions of 300 ℃ or higher temperature, label itself and tackiness agent decomposition evaporation together fall, thereby can not be used for the industrial circle etc. that ceramic industry, metal industry etc. need the pyroprocessing operation.In addition, in No. the 2614022nd, the Japanese patent gazette heat-resisting label is disclosed, but and it is unexposed about the stickup under hot conditions.And then open the spy and to disclose the print label that utilizes aluminum coil to add hot procedure in 2003-126911 number, but show in the comparative example 3 in its specification sheets: if the temperature when pasting not at 150 ℃ or low temperature more, it is unintelligible that its information just becomes.
Therefore, in metal mining industry field, metal melting is formed after, metal products be cooled to can the temperature range (being mostly) of adhesive label about room temperature after, paste the label that artefact management is used.It also is same needing in the field of pyroprocessing at ceramic industry and glass industry etc.
Summary of the invention
Yet, if can be on heat product adhesive label, just can earlier carry out artefact management.
Therefore, the purpose of this invention is to provide the heat-resisting label that on heat product, can paste.
In addition, the purpose of this invention is to provide the heat-resisting label composition that is used to make this heat-resisting label.
And then, the purpose of this invention is to provide the goods that are pasted with this label.
The inventor is in view of the problem of above-mentioned conventional art, study intensively repeatedly, found that: semi-harden (hardened) with composition film (remove desolvate film) can paste on the heat product of 300 ℃ or higher temperature as the heat-resisting label of adhesive coating, wherein, described composition contains (A) silicone resin, (B) and is selected from poly-metal carbon silane (Port リ メ ロ カ Le ボ シ ラ Application) resin, zinc powder, tin powder and the aluminium powder form at least a kind and (C) solvent.And then, the inventor also finds: the heat-resisting label that has aluminium foil or tinfoil paper layer on a side (adhesive side) of ultrahigh-temperature heat resistant support body (for example stainless steel supports, copper supporter), under 670 ℃～1100 ℃, 300 ℃～1100 ℃, can paste respectively, thereby finish the present invention.
That is, the present invention relates to following composition, heat-resisting label, goods and manufacture method.
1. heat-resisting label composition is characterized by, and contains following substances and makes: (A) silicone resin (B) is selected from poly-metal carbon silane resin, zinc powder, tin powder and the aluminium powder form at least a kind and (C) solvent.
2. as 1 described heat-resisting label composition, it is characterized by, contain (A) silicone resin and (B-1) poly-metal carbon silane resin and (C) solvent.
3. as 1 or 2 described heat-resisting label compositions, it is characterized by, (A) silicone resin is about 1 with the mixing ratio by weight that (B-1) gathers metal carbon silane resin: about 9～about 9: about 1.
4. as 1～3 each described heat-resisting label composition, it is characterized by, (A) silicone resin is about 7 with the mixing ratio by weight that (B-1) gathers metal carbon silane resin: about 3～about 2: about 8.
5. as 1～4 each described heat-resisting label composition, it is characterized by, (A) weight average molecular weight of silicone resin is about 1000～about 5000000.
6. as 1～5 each described heat-resisting label composition, it is characterized by, further contain (D) inorganic filling material.
7. as 1 described heat-resisting label composition, it is characterized by, contain (A) silicone resin and at least a kind the high temperature tackiness inorganic powder and (C) solvent that (B-2) are selected from zinc powder, tin powder and the aluminium powder form.
8. as 1 or 7 described heat-resisting label compositions, it is characterized by, (A) silicone resin is about 1 with the mixing ratio by weight that (B-2) is selected from least a kind high temperature tackiness inorganic powder in zinc powder, tin powder and the aluminium powder form: about 5～about 10: about 1.
9. as 1 described heat-resisting label composition, it is characterized by, contain following substances and make: (A) silicone resin, (B-1) poly-metal carbon silane resin, (B-2) be selected from least a kind high temperature tackiness inorganic powder and (C) solvent in zinc powder, tin powder and the aluminium powder form.
10. as 1～6 or 9 each described heat-resisting label compositions, it is characterized by, (B-1) poly-metal carbon silane resin is at least a kind that is selected from poly-titanium carbon silane resin and the poly-zirconium carbon silane resin.
11. as 1～6,9 or 10 each described heat-resisting label compositions, it is characterized by, (B-1) weight average molecular weight of poly-metal carbon silane resin is about 500～about 10000.
12. heat-resisting label is characterized by, and has in the adhesion side of supporter and contains semi-harden adhesive coating of filming, described semi-harden filming contained (A) silicone resin and (B) is selected from poly-metal carbon silane resin, zinc powder, tin powder and the aluminium powder form at least a kind.
13. as 12 described heat-resisting labels, it is characterized by, semi-harden film be with as 1～11 each described composition is coated on the supporter and solvent seasoning is removed and filming of obtaining.
14. as 12 described heat-resisting labels, it is characterized by, semi-harden filming contained (A) silicone resin and (B-1) gathered metal carbon silane resin.
15. as 12 described heat-resisting labels, it is characterized by, semi-harden filming contained (A) silicone resin and at least a kind the high temperature tackiness inorganic powder that (B-2) is selected from zinc powder, tin powder and the aluminium powder form.
16. as 12 described heat-resisting labels, it is characterized by, semi-harden filming contained (A) silicone resin, (B-1) poly-metal carbon silane resin and at least a kind the high temperature tackiness inorganic powder that (B-2) is selected from zinc powder, tin powder and the aluminium powder form.
17. as 12～16 described heat-resisting labels, it is characterized by, the thickness of described adhesive coating is about 5～about 100 μ m.
18. as 12～17 each described heat-resisting labels, it is characterized by, the thickness of described supporter is about 5～about 100 μ m.
19. as 12～18 each described heat-resisting labels, it is characterized by, described supporter is aluminium foil, stainless steel foil or Copper Foil.
20. as 12～19 each described heat-resisting labels, it is characterized by, on the demonstration side of supporter, have stable on heating label substrate layer.
21. as 20 described heat-resisting labels, it is characterized by, described label substrate layer be contain (A) silicone resin and (B-1) sclerosis (cured) of poly-metal carbon silane resin film.
22. as 20 or 21 described heat-resisting labels, it is characterized by, described label substrate layer be with as 2～6 each described compositions coat on the supporter and heat said composition and the sclerosis (cured) that obtains is filmed.
23. as 20～22 each described heat-resisting labels, it is characterized by, the thickness of described label substrate layer is about 0.5～about 100 μ m.
24. as 20～23 each described heat-resisting labels, it is characterized by, on described label substrate layer, have identification division.
25. goods is characterized in that, are pasted with as 12～24 each described heat-resisting labels by the sclerosis adhesive coating.
26. the manufacture method of heat-resisting label is characterized by, and has the operation of coating the adhesion side of supporter as 1～11 each described composition is made semi-harden operation of filming with dry this coating thing.
27. as 26 described manufacture method, it is characterized by, the temperature of dry described coating thing is about 50～about 240 ℃.
28. as 26 or 27 described manufacture method, it is characterized by, before the operation of the adhesion side that will coat supporter as 1～11 each described composition, has the operation of making hardened coating film at the demonstration side of supporter coating thermotolerance label substrate layer with the operation of composition and this coating thing of drying.
29. as 28 described manufacture method, it is characterized by, described label substrate layer composition is as 2～6 each described compositions.
30. have the manufacture method of the goods of heat-resisting label, it is characterized by, on about 300～about 670 ℃ goods, paste as 12～24 each described heat-resisting labels.
31. heat-resisting label is characterized by, supporter and be selected from least a kind metal foil layer laminated forming in aluminium foil, alloy foil, tinfoil paper and the tin alloy foil on the adhesive side of this supporter.
32. as 31 described heat-resisting labels, it is characterized by, described metal foil layer is bonding by bonding coat and described supporter.
33. as 31 or 32 described heat-resisting labels, it is characterized by, the thickness of described metal foil layer is 5～100 μ m.
34. as 31～33 each described heat-resisting labels, it is characterized by, described supporter is stainless steel foil, Copper Foil or iron foil.
35. as 31～34 each described heat-resisting labels, it is characterized by, on the demonstration side of described supporter, have stable on heating label substrate layer.
36. as 35 described heat-resisting labels, it is characterized by, the thickness of described label substrate layer is about 0.5～about 100 μ m.
37. as 35 or 36 described heat-resisting labels, it is characterized by, described label substrate layer is that the sclerosis (cured) that obtains as the resin crosslinks in 2～6 each described compositions is filmed.
38. as 35～37 each described heat-resisting labels, it is characterized by, on described label substrate layer, have identification division.
39. be pasted with goods as 31～37 each described heat-resisting labels.
40. have the manufacture method of heat-resisting label goods, it is characterized by, on about 670～about 1100 ℃ goods, paste as 31～39 each described heat-resisting labels.
Heat-resisting label of the present invention contains (A) silicone resin with composition, (B) is selected from poly-metal carbon silane resin, zinc powder, tin powder and the aluminium powder form at least a kind and (C) solvent.
The present invention has cooperated (B) to be selected from poly-metal carbon silane resin, zinc powder, tin powder and the aluminium powder form at least a kind and (C) composition of solvent in (A) silicone resin by adopting, and makes the instantaneous stickup to heat product become possibility.
In the present invention, (A) silicone resin is the compound that has the poly organo alkyl structure at intramolecularly.As silicone resin, can use any one of straight type (straight) silicone resin, modified organic silicone resin, organosilicon tackiness agent, also can make up two or more and use.As gathering (A) silicone resin of metal carbon silane resin and usefulness with (B-1), preferred straight type silicone resin.In addition, as being selected from least a kind high temperature tackiness inorganic powder (following (B-2) high temperature tackiness inorganic powder that is called sometimes) in zinc powder, tin powder, aluminium powder form and the magnesium dust and (A) silicone resin of usefulness with (B-2), preferred organosilicon tackiness agent.
In addition, the painting process to supporter during from the manufacturing label is easy to angle, and these resins preferably use as the resin liquid that is dissolved in the solvent.
That the weight average molecular weight of such silicone resin is generally is about 1000～and about 5000000, be preferably about 3000～about 1000000.
Straight type silicone resin is meant with the organopolysiloxane of alkyl as main organic group also can have hydroxyl.Comprise aliphatic alkyl and aromatic hydrocarbyl at above-mentioned alkyl, wherein preferred carbon number is that 1～5 aliphatic alkyl and carbon number are 6～12 aromatic hydrocarbyl.These alkyl can be a kind, also can be two or more.
As carbon number is 1～5 aliphatic alkyl, and methyl, ethyl, propyl group, butyl, amyl group, vinyl, allyl group, propenyl, butenyl, pentenyl etc. are for example arranged.As carbon number is 6～12 aromatic hydrocarbyl, and phenyl, aminomethyl phenyl, ethylphenyl, butyl phenyl, t-butyl-phenyl, naphthyl, styryl, allyl phenyl, propenyl phenyl etc. are for example arranged.
Straight type silicone resin obtains in the following way, the silane compound that for example will contain in the chlorosilane cpd of above-mentioned aliphatic alkyl or aromatic hydrocarbyl and the alkoxysilane compound containing trialkylsilyl group in molecular structure a kind or two or more is hydrolyzed and makes its condensation, or the mixture that will be added with tetrachloro silicane or tetraalkoxysilane in above-mentioned silane compound is hydrolyzed and makes its cocondensation.
As above-mentioned chlorosilane cpd, for example can enumerate METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), trimethylchlorosilane, methylethyl dichlorosilane, vinyl dimethyl dichlorosilane (DMCS), vinyl trichloro silane, phenyl-trichloro-silicane, diphenyl dichlorosilane, dichloromethyl phenylsilane, ethenylphenyl dichlorosilane etc.
In addition, as alkoxysilane compound containing trialkylsilyl group in molecular structure, can enumerate methyltrimethoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylammonium methoxy silane, vinyl methyl methoxy base silane, vinyl three butoxy silanes, phenyl triethoxysilane, dimethoxydiphenylsilane, aminomethyl phenyl dipropoxy silane, ethenylphenyl dimethoxy silane etc.
Modified organic silicone resin is meant the organopolysiloxane that contains alkyl organic group in addition, and the silicone resin that contains methoxyl group, the silicone resin that contains oxyethyl group, the silicone resin that contains epoxy group(ing), Synolac modified organic silicone resin, acrylic resin modified organic silicone resin, vibrin modified organic silicone resin, epoxy resin modified organosilicon resin etc. are for example arranged.
These modified organic silicone resins can obtain by the following method, for example make the hydroxyl that in straight type silicone resin, contains and can with the method for the organic compound reaction with functional groups such as carboxyl, anhydride group, hydroxyl, aldehyde radical, epoxy group(ing), chloros of this hydroxyl reaction; Make straight type silicone resin and have the method for the compound copolymerization of unsaturated double-bond with unsaturated alkyls such as vinyl; The modified silane compound that makes above-mentioned silane compound and other organic compound reactions and obtain is carried out the method for condensation or cocondensation etc. by hydrolysis.The organic compound that reacts can be a low molecular compound, also can be the macromolecular compound as resin.
There is no particular limitation about the organosilicon tackiness agent, for example, contains main chain and contain the straight chain organopolysiloxane of RSiO unit (D unit) and contain R
3SiO
0.5Unit (M unit) and SiO
2The organopolysiloxane of the three-dimensional structure of unit (Q unit) uses benzoyl peroxide etc. as stiffening agent.In addition, can also illustration go out to use the addition reaction sclerotic type organosilicon tackiness agent of platinum catalyst, it contains the main chain with vinyl and contains R
2The unitary straight chain organopolysiloxane of SiO, contain R
3SiO
0.5Unit and SiO
2The hardening catalyst of the organopolysiloxane of unitary three-dimensional structure, poly-organic hydroxyl siloxanes, reaction control agent etc., platinic compound.At this, R is the organic group of 1 valency.
In addition, even the organosilicon tackiness agent also has tackiness at 0 ℃, therefore contain as (A) even the present composition of the organosilicon tackiness agent of composition also has tackiness under the temperature about 0 ℃.Therefore, though semi-harden label of filming that adhesive coating has used said composition not only under the hot conditions about 0 ℃～also can paste pasting on the object under about 300 ℃ the temperature.Therefore, if will contain semi-harden the filming of organosilicon tackiness agent uses as adhesive coating, even then adhesive coating is also brought into play tackiness in the normal temperature scope, thereby stripping film preferably is set on adhesive coating, can prevent that label adhesive coating when not using is attached on the object that is attached beyond the body.
As the concrete compound of (A) silicone resin, can enumerate dimethyl polysiloxane, methyl phenyl silicone, polydimethylsiloxane, polydimethyl diphenyl siloxane, diphenyl methyl phenyl silicone resin etc.
(B-1) poly-metal carbon silane resin for example makes the alkoxide reaction of Polycarbosilane and metal and the resin with crosslinking structure that obtains.As above-mentioned metal, use titanium, zirconium, molybdenum, chromium etc. usually, wherein, preferably use titanium, zirconium.As the concrete compound title of preferred poly-metal carbon silane resin, can enumerate poly-titanium carbon silane resin, poly-zirconium carbon silane resin etc.In order to improve the coating of poly-metal carbon silane resin, preferably with toluene, dimethylbenzene equal solvent and usefulness.As the mixture that contains poly-titanium carbon silane resin, for example can use TYRANNO COATVS-100, the TYRANNO COAT VN-100 etc. of emerging product society of space portion system.The weight average molecular weight of poly-metal carbon silane resin is preferably about 500～about 10000, more preferably about 700～about 3000.
In composition of the present invention, (B-1) use level of poly-metal carbon silane resin has no particular limits, the mixing ratio by weight example of preferred silicone resin and poly-metal carbon silane resin becomes about 1: about 9～about amount of 9～about 1 more preferably becomes about 7: about 3～about 2: about 8 amount.The cooperation ratio of two kinds of resins is in above-mentioned scope the time, and is favourable to the stickup under the hot conditions.
Employed in the composition of the present invention (B-2) is selected from that being shaped as of at least a kind high temperature tackiness inorganic powder in zinc powder, tin powder and the aluminium powder form is spherical, fibrous, flakey etc., has no particular limits.Therefore, the bigger material of length-to-diameter ratio that in (B-2) high temperature tackiness inorganic powder, also comprises monocrystalline inorganic fibres such as whisker etc.(B-2) median size of high temperature tackiness inorganic powder is generally 0.05～100 μ m, is preferably 1.0～10 μ m, more preferably 1～5 μ m.
(B-2) use level of high temperature tackiness inorganic powder has no particular limits, and with respect to resinous principle 100 weight parts, is generally 10～500 weight parts, preferred 150～400 weight parts, the more preferably amount of 200～350 weight parts.Therefore, when only containing (A) silicone resin as resinous principle in composition, with respect to (A) silicone resin 100 weight parts, (B-2) use level of high temperature tackiness inorganic powder is the amount of above-mentioned scope; When containing (A) silicone resin and (B-1) gathering metal carbon silane resin, with respect to (A) silicone resin and total 100 weight parts that (B-1) gather metal carbon silane resin, (B-2) use level of high temperature tackiness inorganic powder is the amount of above-mentioned scope.
In the present invention, (C) solvent has the composition in dissolving or the dispersive composition, the effect of adjustment composition viscosity.As solvent, can use for example toluene, dimethylbenzene, cellosolve acetate, ethyl acetate, diethylene glycol monobutyl ether, MEK (methyl ethyl ketone), MIBK (methyl iso-butyl ketone (MIBK)) etc.Be preferably dimethylbenzene, toluene.(C) use level of solvent just has no particular limits as long as use composition of the present invention can make heat-resisting label.Therefore, (C) use level of solvent can suitably be adjusted, be formed on composition of the present invention coat supporter, favourable viscosity when dry.
Although (C) use level of solvent has no particular limits, with respect to resinous principle 100 weight parts, be generally 40～900 weight parts, preferred 200～400 weight parts, more preferably 230～350 weight parts.Therefore, when only containing (A) silicone resin as resinous principle in composition, with respect to (A) silicone resin 100 weight parts, (C) use level of solvent is the amount of above-mentioned scope; When containing (A) silicone resin and (B-1) gathering metal carbon silane resin, with respect to (A) silicone resin and total 100 weight parts that (B-1) gather metal carbon silane resin, (C) use level of solvent is the amount of above-mentioned scope.
In composition of the present invention, can cooperate (D) inorganic filling material as any composition.Because (D) inorganic filling material has relaxed the expansion and the contraction of the heat-resisting label that causes because of thermal conductance, the thermotolerance of heat-resisting label is improved.Therefore, in the composition of the present invention that contains (B-1) poly-metal carbon silane resin, uses as the label substrate layer, preferred (D) inorganic filling material that cooperates is considered the contrast with identification division, further (D) inorganic filling material of preferred white.In addition, if in (D) inorganic filling material, use tinting pigment, then can on the label substrate layer, pay color.(D) inorganic filling material can use a kind separately, perhaps makes up two or more and uses.In addition, the preferably about 0.01～about 200 μ m of median size, more preferably from about 0.1～about 100 μ m.(D) shape of inorganic filling material is not particularly limited, and comprises spherical, fibrous, flakey etc.In (D) inorganic filling material, also comprise for example big material of length-to-diameter ratio of monocrystalline inorganic fibre such as potassium titanate crystal whisker etc.
Although (D) use level of inorganic filling material is not particularly limited, with respect to resinous principle 100 weight parts, be generally 10～500 weight parts, be preferably 150～400 weight parts, more preferably the amount of 200～350 weight parts.Therefore, when only containing (A) silicone resin as resinous principle in composition, with respect to (A) silicone resin 100 weight parts, (D) use level of inorganic filling material is the amount of above-mentioned scope; When containing (A) silicone resin and (B-1) gathering metal carbon silane resin, with respect to (A) silicone resin and total 100 weight parts that (B-1) gather metal carbon silane resin, (D) use level of inorganic filling material is the amount of above-mentioned scope.In addition, when in composition, containing (B-2) high temperature tackiness inorganic powder, (D) use level of inorganic filling material be (B-2) high temperature tackiness inorganic powder and (D) the total amount of inorganic filling material be the amount of above-mentioned scope.In addition, (D) inorganic filling material with (B-2) and the time spent, use level (D) is preferably 0.05: 1 with the weight ratio of use level (B-2)～1: 1, more preferably 0.1: 1～1: 1.
As inorganic filling material, can preferably use mineral dye.For example can enumerate the white thing of silicon-dioxide, titanium dioxide, aluminum oxide, zirconium white, mica, calcium oxide, zinc sulphide barium sulfate (lithopone), talcum, clay, kaolin, lime carbonate etc.In addition, also can enumerate when making heat-resisting label by heating the metallic compound of the oxidized carbonate that becomes white thing, nitrate, vitriol etc.In addition, following substances also can be used as the use of (D) inorganic fine particles: the sorrel thing (for example zinc oxide ferric oxide chromic oxide, manganese oxide aluminum oxide, chromic oxide stannic oxide, ferric oxide etc.) that contains metal ions such as iron, copper, gold, chromium, selenium, zinc, manganese, aluminium, tin; The blue thing (for example cobalt oxide aluminum oxide, cobalt oxide aluminum oxide chromic oxide, cobalt oxide, zirconium white oxidation vanadium, chromic oxide Vanadium Pentoxide in FLAKES etc.) that contains metal ions such as manganese, chromium, aluminium, cobalt, copper, iron, zirconium, vanadium; The black thing (for example cupric oxide chromic oxide manganese oxide, chromic oxide manganese oxide ferric oxide, chromic oxide cobalt oxide ferric oxide manganese oxide, chromic salt, permanganate etc.) that contains metal ions such as iron, copper, manganese, chromium, cobalt, aluminium; The yellow (for example titanium oxide weisspiessglanz nickel oxide, titanium oxide weisspiessglanz chromic oxide, zinc oxide ferric oxide, zirconium silicon praseodymium, vanadium tin, chromium titanium antimony etc.) that contains metal ions such as vanadium, zinc, tin, zirconium, chromium, titanium, antimony, nickel, praseodymium, vanadium; The green thing (for example titanium oxide zinc oxide cobalt oxide nickel oxide, cobalt oxide aluminum oxide chromic oxide titanium oxide, chromic oxide, cobalt chromium, aluminum oxide chromium etc.) that contains metal ions such as chromium, aluminium, cobalt, calcium, nickel, zinc; The pink thing (for example aluminium manganese, iron silicon zirconium etc.) that contains metal ions such as iron, silicon, zirconium, aluminium, manganese.Preferably talcum, clay, kaolin, titanium dioxide, aluminum oxide, zinc oxide ferric oxide chromic oxide, titanium oxide weisspiessglanz nickel oxide, titanium oxide weisspiessglanz chromic oxide, zinc oxide, ferric oxide, zinc oxide ferric oxide chromic oxide, titanium oxide zinc oxide cobalt oxide nickel oxide, cobalt oxide aluminum oxide chromic oxide, cobalt oxide aluminum oxide, cobalt oxide aluminum oxide chromic oxide, cupric oxide chromic oxide molybdenum oxide, cupric oxide chromic oxide manganese oxide, cupric oxide manganese oxide ferric oxide.Use kaolinic label, even contact with the fiber of label applicator head when pasting, the identification division that prints on the label substrate layer also is difficult to take off, thereby more preferably.
In addition, in heat-resisting label usefulness composition of the present invention, preferably cooperate (E) dispersion agent.Because improved rate of dispersion by cooperation (E) dispersion agent, and made the modulation of composition become easy.As (E) dispersion agent, can use amine salt, the polyether phosphate of amine salt, the polyether phosphate of long-chain amine salt, the polyether ester acid of amine salt, the poly carboxylic acid of aliphatics polycarboxylic acid, polyester acid, acid amides amine salt of polyester acid etc.Reach (D) 100 weight parts of inorganic filling material with respect to (B-2) high temperature tackiness inorganic powder, (E) dispersion agent uses about 0.01～about 5 weight parts, preferably uses about 0.1～2 weight part.Therefore, in composition, only contain (B-2) high temperature tackiness inorganic powder and (D) during the either party in the inorganic filling material, with respect to (B-2) high temperature tackiness inorganic powder and (D) either party in the inorganic filling material, (E) use level of dispersion agent is the amount of above-mentioned scope; In composition, contain (B-2) high temperature tackiness inorganic powder and (D) inorganic filling material both the time, with respect to (B-2) high temperature tackiness inorganic powder and (D) gross weight of inorganic filling material, (E) use level of dispersion agent is the amount of above-mentioned scope.
In addition, use in the composition at heat-resisting label of the present invention, be selected from poly-metal carbon silane resin, zinc powder, tin powder, aluminium powder form and the magnesium dust at least a kind, (C) solvent, (D) inorganic fine particles, (E) dispersion agent except adding (A) silicone resin, (B), in not damaging effective scope of the present invention, can add the additive of linking agent, softening agent etc. as required.
As linking agent, boronic acid compounds, organometallic compound etc. are arranged.Wherein, boronic acid compounds is the compound that intramolecularly contains the boric acid residue, and boric acid, borate, boric acid ester etc. are for example arranged.As boric acid, ortho-boric acid, metaboric acid, boron trioxide etc. are arranged; As borate, Sodium Tetraborate, potassium borate, magnesium borate, lime borate, zinc borate, aluminum borate etc. are arranged; As boric acid ester, methyl-borate, ethyl-borate, butyl borate, boric acid monooctyl ester, boric acid dodecane ester etc. are arranged.In these boronic acid compounds, preferred especially ortho-boric acid.
In addition, as organometallic compound, organic nickel compound, organoiron compound, organic cobalt compound, organo-manganese compound, organo-tin compound, organo-lead compound, organic zinc compound, organo-aluminium compound, organic titanic compound etc. are arranged, wherein, preferred chelate compound.With respect to (A) resin and (B) total 100 weight parts of resin, the amount of the metal in the linking agent is about 0.05～about 10 weight parts, preferably becomes about 0.1～about 5 weight parts and cooperates.
As softening agent, aliphatic ester, aromatic ester, phosphoric acid ester etc. are arranged.Laurate methyl, butyl oleate, Diethylene Glycol dilaurate, hexanodioic acid two (2-ethyl butoxyethyl group) etc. are arranged in aliphatic ester; As aromatic ester, rutgers, dioctyl phthalate, phthalic acid two (2-ethylhexyl) ester, phthalic acid two lauryls, M-nitro benzoic acid grease, oleic acid phenyl ester etc. are arranged; As phosphoric acid ester, Tritolyl Phosphate, trioctyl phosphate etc. are arranged.By adding these softening agent, can further improve the flexibility of label substrate layer.
Composition of the present invention can be by mixing and disperseing mentioned component to modulate.As dispersing method, can enumerate with the particle shredder, disperse the dispersion machine of the grinding dispersion machine etc. of ball mill, sand mill, roller mill etc. to come the dispersive method.The fineness of dispersion of dispersion machine is preferably about 0.01～about 200 μ m, 0.1～about 20 μ m more preferably from about.
Composition of the present invention can be used as that to form be that the raw material of adhesive coating of the heat-resisting label of the present invention that uses under 300 ℃ or the higher temperature uses when being adapted at pasting.That is, go up coating composition of the present invention, be dried to the degree that the solvent in the said composition is removed, film and form adhesive coating by making said composition form semi-harden (hardened) in the one side (adhesion side) of supporter.Containing (A) silicone resin can also use as the raw material of the label substrate layer that forms the heat-resisting label of the present invention with the present composition that (B-1) gathers metal carbon silane resin.That is, coating composition of the present invention on the one side of supporter, the resin in said composition takes place to carry out drying under the crosslinked temperature, forms the label substrate layer by making said composition form hardened coating film.
In this manual, semi-harden filming is meant the material that composition dries of the present invention is removed basically to the solvent in the said composition at least, can have the material as the function of adhesive coating under the hot conditions of 300 ℃ or higher temperature.That is, semi-harden filming is to have adhesive filming (the high temperature tackiness is filmed) under the hot conditions of 300 ℃ or higher temperature.Therefore, in the scope that has as the function of adhesive coating, also can carry out the crosslinked of resin.If remaining solvent in filming then has danger on fire under hot conditions.Therefore, the remaining quantity of the solvent in semi-harden the filming is generally about 0.1 weight % or lower, is preferably 0.0001 weight % or lower.In removing the drying process of desolvating, can carry out resin crosslinked in the above-mentioned composition, if but crosslinked carrying out excessively then can harden (cure), lose the adhesion function under hot conditions, therefore when forming semi-harden filming, except that desolvating, carry out under the crosslinked situation, is important as drying conditions to form crosslinked in the scope of the adhesion function under keeping hot conditions.
The hardened coating film that contains the present composition of (B-1) poly-metal carbon silane resin is useful as the label substrate layer of heat-resisting label.For example, can be used as the label substrate layer of the heat-resisting label of the present invention described later and use.In addition, also knownly pasting on the object label of pasting supporters such as stainless steel foil by welding (spot weld etc.), above-mentioned hardened coating film also can be used as with the substrate layer that welds the label of pasting and uses.
In addition, in this manual, hardened coating film is meant composition dries of the present invention to the material that the solvent in the said composition is removed basically, is meant not to be attached to the material that hardens to the degree that keeps this identification division on the stickers machine, when using as having the label substrate layer of identification division when pasting under the hot conditions of 300 ℃ or higher temperature.That is, hardened coating film is not have adhesive filming (the high temperature Abherent is filmed) under the hot conditions of 300 ℃ or higher temperature.To film non-cohesively on stickers machine in order allowing, to be necessary to make the sclerosis of filming, thereby when hardened coating film forms, must be than must form semi-harden filming the time stricter heating condition.At this,, thereby preferably be unworthy of being incorporated in the label substrate layer because high temperature tackiness metal-powder (tin, zinc, aluminium) has the high temperature tackiness.
Being characterized as of heat-resisting label of the present invention, be suitable for when pasting about 300 ℃ or higher (preferred 350 ℃ or higher, more preferably 400 ℃ or higher) stickup of the stickup object of temperature, have in the adhesion side of supporter and to contain semi-harden adhesive coating of filming, described semi-harden filming contained (A) silicone resin and (B) is selected from poly-metal carbon silane resin, zinc powder, tin powder and the aluminium powder form at least a kind.In addition, heat-resisting label of the present invention roughly is divided into and is suitable for being generally the heat-resisting label that uses under the high temperature (about 300 ℃～about 670 ℃) in the temperature of pasting object, with the heat-resisting label (can be described as super heat-resisting label) that is suitable for using down in ultrahigh-temperature (about 670～about 1100 ℃), in this manual the former is called heat-resisting label 1, the latter is called heat-resisting label 2.
The heat-resisting label 1-1 of the present invention is characterized as, and (adhesion side) has and contain the adhesive coating that semi-harden (hardened) films on the one side of supporter, and described semi-harden filming contained (A) silicone resin and (B) poly-metal carbon silane resin.Such label is to have semi-harden filming as the label of adhesive coating, described semi-harden filming is for example to be coated with the present composition that contains (A) silicone resin and (B-1) gather metal carbon silane resin on the adhesion side of supporter, and solvent dry removing from said composition obtained.The adhesive coating of the heat-resisting label 1-1 of the present invention can further contain at least a kind that is selected from zinc powder, tin powder and the aluminium powder form, also can further contain inorganic filling material.
The heat-resisting label 1-2 of the present invention is characterized as, have on the adhesion side of supporter and contain the adhesive coating that semi-harden (hardened) films, described semi-harden filming contained (A) silicone resin and at least a kind the high temperature tackiness inorganic powder that (B-2) is selected from zinc powder, tin powder and the aluminium powder form.Such label is to have semi-harden filming as the label of adhesive coating, described semi-harden filming is for example to be coated with to contain (A) silicone resin and (B-2) present composition of high temperature tackiness inorganic powder on the adhesion side of supporter, and solvent dry removing from said composition obtained.
In heat-resisting label 1-1 and 1-2, can also on the face (demonstration side) relative of supporter, stable on heating label substrate layer be set with having the adhesive coating one side.When the label substrate layer is not set, identification divisions such as direct bar code can be set on supporter.
In heat-resisting label 1 of the present invention, supporter use film like, have stable on heating material, preferably use tinsel.Also small hole can be set on supporter.By the hole is set, removes the gas that produces when the resin that contains in the adhesive coating of lamination on supporter and the label substrate layer at high temperature decomposes easily, thereby can suppress the expansion of label substrate layer.In addition, if the material of supporter be and become the identical material of goods that label is pasted object, then become the label that better patience is arranged for the expansion due to heat and contraction, under hot conditions, can suppress peeling off of label.For example, when the stickup object was aluminium, preferred supporter was an aluminium foil.As tinsel, can aluminium foil, stainless steel foil, Copper Foil, iron foil etc. be shown example.The thickness of supporter is generally about 5～about 100 μ m, is preferably about 10～about 70 μ m, more preferably about 10～about 60 μ m.If supporter in above-mentioned scope, then suppresses the respond well of thermal expansion or thermal contraction, thereby can suppress the disintegration of label and have flexibility, therefore when pasting, conform to the shape of pasting object.
As aluminium foil, can use JIS alloy 1N30,1085,1N90,1N99,3003,3004,5052,8079,8021 etc., preferred 1N30.
As stainless steel foil, can use Martin's system (SUS410, SUS440), ferritic series (SUS430, SUS444), austenite (SUS304, SUS316), two phase system (SUS329J1, SUS329J4L), SUS630, SUS631 etc.
As other metals, can use JIS specification SPHC, SPCC, SECC, SGCC, SZACC, SA1C etc., the material of preferred SPHC, SPCC specification.
As above-mentioned supporter, can use the commercially available tinsel of being generally of easy acquisition.
In heat-resisting label 1 of the present invention, adhesive coating is meant above-mentioned semi-harden filming.That is, be meant composition dries of the present invention is removed basically to the solvent in the said composition at least, to have material as the function of adhesive coating even also not on fire under the hot conditions of 300 ℃ or higher temperature.
The temperature and time of the dry present composition in order to form adhesive coating, so long as composition of the present invention is dried, can use as adhesive coating under hot conditions, just have no particular limits, being coated with the thickness of filming of the present composition and solvent can be according to the material of supporter and thickness and appropriate change.For example use the heated air circulation type baking oven, drying is about 1 minute～about 60 minutes under about 50～240 ℃, preferred about 80～about 200 ℃, preferred dry about 1 minute～about 20 minutes.In addition, can suitably regulate according to the air quantity of hot blast time of drying.
Thickness during adhesive coating drying (semi-harden) is generally about 5～about 100 μ m, is preferably about 10～about 60 μ m.If desciccator diaphragm thickness is in this scope, then with the binding property excellence of adherend, the cohesion that suppresses adhesive coating destroys.
Heat-resisting label 1 of the present invention has adhesive coating on the adhesion side of supporter, promptly show at the opposite side of supporter stable on heating label substrate layer also can be set on the side.The label substrate layer be so long as can tolerate the material of the hot conditions of 300 ℃ or higher temperature, just can use by drying used in the past or the label substrate reported form usefulness, filming etc. of for example containing that the composition of silicone resin, inorganic powder and organic solvent obtains.In addition, also can use the heating present composition and the hardened coating film that obtains as the label substrate layer.This label substrate layer can form by the following method: coating composition of the present invention on the demonstration side of supporter, solvent in the said composition is removed basically, and the resin in said composition takes place to carry out drying under the crosslinked temperature, thereby makes said composition become hardened coating film.
When using composition of the present invention to form the label substrate layer, the temperature and time of the sclerosis present composition, so long as can be used as the label substrate layer under hot conditions through sclerosis, uses composition of the present invention, just have no particular limits, be coated with the thickness of filming and the solvent of the present composition, can be according to the material and the thickness appropriate change of supporter.For example, use the heated air circulation type baking oven, drying is about 1 minute～about 40 minutes under about 245～500 ℃, preferred about 250～about 400 ℃, preferred dry about 2 minutes～about 20 minutes.At this, can suitably regulate time of drying according to the air quantity of hot blast.Thickness when the label substrate layer is dry is generally about 0.5～about 100 μ m, is preferably about 1～about 60 μ m.
In addition, when manufacturing has the heat-resisting label 1 of label substrate layer that the present composition hardened, at first, on the demonstration side of supporter, form the label substrate layer, then on the adhesion side of supporter, form adhesive coating.This is because the also strictness of drying conditions of employed curing condition forms than adhesive coating when the label substrate layer forms time use, if after forming adhesive coating, form the label substrate layer, the then two-layer hardened coating film that all becomes, the stickup of the heat-resisting label under hot conditions becomes impossible.When use label substrate formation in the past forms the label substrate layer with composition, consider drying conditions that is applicable to said composition and the drying conditions that is applicable to adhesive coating, can suitably set the order that layer forms.
The manufacture method of heat-resisting label 1 of the present invention has coats operation on the supporter one side with composition of the present invention, and dry this coating thing becomes semi-harden operation of filming.
As the adhesion side of composition of the present invention being coated supporter or show the operation of side, can carry out with the following method: for example with the mode of printing of silk screen printing etc., roll coating model, photogravure roll coating model, scraper mode, bar coating method etc. in the adhesion side of supporter or show the method that is coated with the present composition on the side.As coating process, preferred silk screen printing, photogravure roller coat mode, bar coating method.Composition of the present invention is applied behind supporter, is dried and forms semi-harden filming (adhesive coating), and drying conditions is identical with the drying conditions of above-mentioned adhesive coating.
In addition, manufacturing has the method for heat-resisting label 1 of label substrate layer of the hardened coating film of the present composition, before the operation of the present composition in the above-mentioned manufacture method being coated supporter adhesion side, have with stable on heating label substrate layer coat with composition supporter the demonstration side operation and heat this coating thing and become the operation that sclerosis (cured) is filmed.
When using composition of the present invention to use composition as stable on heating label substrate layer, be coated with the operation of stable on heating label substrate layer with composition, can carry out in the same manner with the operation of coating the invention described above composition.In addition, dry this coating thing makes the operation of said composition sclerosis (cured), is identical with the curing condition of above-mentioned label substrate layer formation.
When use label substrate formation is in the past used composition with composition as stable on heating label substrate layer, also can carry out in the same manner with the operation of the composition of the invention described above being coated the demonstration side of supporter.Make its hardened operation, can select the drying conditions that suits according to the composition that uses.
Heat-resisting label 2 of the present invention contains supporter and metal foil layer, on the one side side (adhesive side) of supporter, have tinsel (following meeting the is called the adhesion metal paper tinsel) layer that is selected from aluminium foil, alloy foil, tinfoil paper and the tin alloy foil at least a kind, be adapted at about 670～about 1100 ℃, preferred about 700～about 1000 ℃ and use down.At this, when heat-resisting label 2 uses tinfoil paper or tin alloy foil, not only can use down at about 670～1100 ℃, also can use down at about 300～670 ℃.Between supporter and adhesion metal paper tinsel layer, can be provided for the bonding coat of bonding adhesion metal paper tinsel layer.Fusion at high temperature takes place by the adhesion metal paper tinsel and is pasted on the stickup object in heat-resisting label 2.In addition, spray paint aluminium when aluminium lamination is set on supporting body surface by flame plating, fusion does not take place in it under the temperature of pasting object, pastes on the object thereby can not paste.This is considered to: the surface-area of the layer that is formed by flame plating is very big, and its surface is oxidized, and causes melt temperature to rise.
In heat-resisting label 2, supporter uses the material that fused, film like do not take place in the employed temperature range of the label of hope, be preferably tinsel.If the material of supporter is identical with the material of pasting object, then become for expansion that causes because of thermal conductance and the more indefatigable label of contraction.As tinsel, can stainless steel foil, Copper Foil, iron foil etc. be shown example, be preferably stainless steel foil.The thickness of supporter is generally about 5～about 100 μ m, preferred about 10～about 50 μ m, more preferably from about 10～about 40 μ m.If supporter in above-mentioned scope, then suppresses the respond well of thermal expansion or thermal contraction, so the disintegration of label is suppressed, and has flexibility, thereby can conform to the shape of pasting object when pasting.The object lesson of stainless steel foil is identical with the situation of the supporter of heat-resisting label 1.In addition, also the situation with the supporter of heat-resisting label 1 is identical for the object lesson of other tinsels.
In heat-resisting label 2, fusion at high temperature takes place by adhesion metal paper tinsel layer, make the stickup of label become possibility.Thereby adhesion metal paper tinsel layer only is arranged on the adhesive side of supporter.The thickness of adhesion metal paper tinsel layer is generally about 1～about 300 μ m, is preferably about 10～about 100 μ m.Preferred adhesion metal paper tinsel layer is an aluminium foil layer.As aluminium foil, can use JIS alloy 1N30,1085,1N90,1N99,3003,3004,5052,8079,8021 etc., be preferably 1N30.In alloy foil, the proportion of composing that Aluminum in Alloy is occupied is generally 50～99 weight %, is preferably 70～99 weight %.In addition, the situation of tin alloy foil also is the same, and the proportion of composing that tin occupies in the alloy is generally 50～99 weight %, is preferably 70～99 weight %.As aluminium alloy, so long as the alloy of aluminium and other metals and the fused material takes place under the temperature that heat-resisting label 2 is stuck get final product.The situation of tin alloy also is the same, so long as the alloy of tin and other metals and the fused material takes place under the temperature that heat-resisting label 2 is stuck get final product.In addition, can adjust melt temperature by alloying.As Alloy Foil, for example be aluminium and the alloy that is selected from least a kind of metal in zinc, tin, indium, copper, nickel, the silver, be preferably the alloy of alloy, aluminium and the tin of aluminium and zinc.
Adhesion metal paper tinsel layer can be by for example coming the method for bonding supporter and adhesion metal paper tinsel layer by the bonding coat that constitutes by resin etc. lamination on supporter.Be bonded in the area of the adhesion metal paper tinsel layer on the supporter, paste on the object as long as supporter is pasted on, just there is no particular limitation.The area of adhesion metal paper tinsel layer is 10～100% with respect to the area of supporter, is preferably 20～100%.In addition, the shape of adhesion metal paper tinsel layer is pasted on the object as long as supporter pastes, and just there is no particular limitation.For example, perhaps can come lamination adhesion metal paper tinsel layer by the mode of the whole faces that cover supporter, the adhesion metal paper tinsel layer that perhaps can be equivalent to the shape such as circle, rectangle of the area of supporter area about 50% at supporter central part lamination, supporter is when quadrangle, can be on 4 angles of supporter respectively lamination be equivalent to the adhesion metal paper tinsel layer of the shapes such as circle, rectangle of the area of supporter area about 10%.
Bonding coat is bonding with supporter and adhesion metal paper tinsel layer.Bonding coat so long as up to the fusion of adhesion metal paper tinsel and with bonding supporter and paste object till bonding during can bonding supporter and the material of adhesion metal paper tinsel, just there is no particular limitation.Tackiness agent as constituting bonding coat can be illustrated as polyolefin-based resins such as polyethylene (comprising new LDPE (film grade), high density polyethylene(HDPE)), polypropylene, polybutene, polyisobutene, iso-butylene copolymer-maleic anhydride, polyvinyl acetate, polychlorostyrene propylene, polychlorostyrene propylene, polyvinylidene chloride, polyvinyl ether usually; Acrylic ester resins such as polymethylmethacrylate, polyacrylic acid, polymethyl acrylate, polyacrylamide; Polyethylene terephthalate, polybutylene terephthalate, PEN, poly terephthalic acid hexanaphthene are to polyester based resins such as diformazan alcohol esters; Petroleum line resins such as polycyclopentadiene; Silicon-type resins such as straight type silicone resin, silicone adhesive, modified organic silicone resin; Phenolic aldehyde such as 100% resol, lacquer resins, solvable type resol are resin; Modified alkyd resins such as rosin modified alkyd resin, phenol-modified alkyd resin, strenated alkyd resins, silicone alkyd etc., these materials can use a kind or make up two or more and use separately.These resins dissolve in solvent as required or disperse to use.In addition, not only can use these resin, can also use low-melting other tinsels.Constitute the tackiness agent of bonding coat, preferably near the resin that tinsel is attached to the temperature of supporter, evaporates or decompose because of heat.In addition, in resin glue, except cooperating these tackiness agents, can also cooperate suitable additive etc.
Bonding coat is as long as keep the not binding property of extent of exfoliation of supporter and adhesion metal paper tinsel.For resin glue, the thickness that removes after desolvating is generally about 0.1～about 50 μ m, preferred about 2～about 10 μ m.The thin side of bondline thickness is to the evaporation of resin glue and decompose favourable.
In addition, the area of binder resin layer as mentioned above, so long as keep supporter and adhesion metal paper tinsel not the binding property of extent of exfoliation get final product, with respect to the area of adhesion metal paper tinsel, it is preferably 1～100%, more preferably 1～80%.If there is the part of adhesive-free between supporter and the adhesion metal paper tinsel layer, then the adhesion metal paper tinsel directly contacts supporter in this part, adhesion metal paper tinsel generation fusion under ultra-high temperature condition and become easily bonding with supporter, thereby label can be pasted on securely on the stickup object.For example, binder layer is made spirrillum, then can make and be pasted on the label of pasting on the object securely.
When using bonding supporter of resin glue and adhesion metal paper tinsel, after above-mentioned tackiness agent (can add solvent as required) can being coated supporter, make its bonding adhesion metal paper tinsel in dry back, also can behind coating adhesive on the adhesion metal paper tinsel, make its bonding supporter in dry back.These methods are all easily removed solvent in the tackiness agent by drying, thereby are preferred.In addition, can behind bonding tackiness agent on the supporter adhesion metal paper tinsel being bonded on this tackiness agent, carrying out drying then, also can be behind bonding tackiness agent on the adhesion metal paper tinsel, and supporter is adhered on this tackiness agent, carries out drying then.Can also between supporter and adhesion metal paper tinsel, accompany resin film, the method that resin is heated, is rolled under the fusible temperature of performance.
There is no particular limitation with the method for adhesive coated on supporter, adhesion metal paper tinsel, uses mode of printing, roll coating model, photogravure roll coating model, scraper mode, bar coating method of silk screen printing etc. etc. usually.Till the drying of tackiness agent proceeded to solvent and is removed basically, drying temperature, time of drying etc. can suitably be set according to tackiness agent.
When being used as low-melting other tinsels in the tackiness agent, should be metal foil laminated between supporter and adhesion metal paper tinsel, can be bonding by heating under folded metal generation fused temperature.
Heat-resisting label 2 of the present invention has adhesion metal paper tinsel layer on the adhesive side of supporter, but on opposite side (demonstration side) stable on heating label substrate layer can be set also.At this, the label substrate layer be so long as can tolerate the material of the temperature condition (about 670 ℃～about 1100 ℃) that heat-resisting label 2 is used, and just can use by drying and use or the label substrate reported forms that the composition that for example contains inorganic filling material and organic solvent of usefulness obtains films etc. in the past.In addition, so dry the composition of the present invention and hardened coating film that obtains can tolerate the use under 1100 ℃ is preferably as the label substrate layer.In this case, can form the label substrate layer by the following method, promptly on the demonstration side of supporter, be coated with composition of the present invention, solvent in the said composition is removed in fact, and the resin in said composition takes place to carry out drying under the crosslinked temperature, makes said composition become hardened coating film.The label substrate layer is coated the method for supporter, identical with the situation of heat-resisting label 1.
After composition of the present invention coated supporter, carry out drying for making composition sclerosis of the present invention.The exsiccant temperature and time is so long as the solvent in the composition of the present invention just is removed basically has no particular limits, and is coated with the coating thickness of the present composition and solvent material and the thickness appropriate change according to supporter.For example, use the heated air circulation type baking oven, under about 245～about 500 ℃, preferred about 250～about 400 ℃, carried out drying about 1 minute～about 40 minutes, preferred dry about 2 minutes～about 20 minutes.At this, can suitably regulate time of drying according to the temperature and the air quantity of hot blast.Thickness when the label substrate layer is dry is generally about 0.5～about 100 μ m, is preferably about 1～about 60 μ m.
The formation of label substrate layer can not carried out under the state of lamination binder layer, adhesion metal paper tinsel layer at supporter, also can supporter by with the state of binder layer and adhesion metal paper tinsel laminated layer under carry out.
Describe with regard to heat-resisting label 1 of the present invention and 2 common items.Carry out the requirement of artefact management as long as fully satisfy with color classification,, can realize artefact management, thereby also identification division can be set by using painted (for example containing the Bepaint inorganic powder) label substrate layer.But,, then preferably on the label substrate layer, identification division is set if carry out more detailed artefact management.By identification division is set, heat-resisting label is used as data carrier becomes possibility.Therefore, be pasted on the goods, can give these goods various information by the label that will be provided with identification division.When heat-resisting label 1 or 2 does not have the label substrate layer, it can be arranged on the demonstration side of supporter.
Identification division also forms with pattern and image headed by literal and the mark (bar code etc.) by printing on the label substrate layer with known thermotolerance printing ink usually.By such identification division is set, can be used as with the bar code label is that the data carrier of representative is used.Example as identification division, can enumerate the UPC sign indicating number, JAN/EAN sign indicating number (JIS-X-0501, ISO/IEC15420), CODE39 (JIS-X-0503, ISO/IEC15388), CODE128 (JIS-X-0504, ISO/IEC15417), ITF (Interleaved 2of5) (JIS-X-0502, ISO/IEC15390), NW-7 (Codabar) (JIS-X-0503), the one dimension bar code of RSS 14 (UCC/EAN) sample, QR sign indicating number (JIS-X-0510, ISO/IEC18004), Micro QR sign indicating number, PDF417 (ISO/IEC15438), DataMatrix (ISO/IEC16022), MaxiCode (ISO/IEC16023), AztecCode (ISS1997), UCC/EAN matrix material (UCC/EAN, ITS1999) identify code arbitrarily such as two-dimensional code of sample, literal.Preferred identification division is one dimension bar code, two-dimentional bar code.
As above-mentioned thermotolerance printing ink, adopt to tolerate the printing ink that the temperature of carrying out the pyroprocessing operation is 300 ℃ or higher temperature, particularly preferably be the thermotolerance printing ink that contains carbon, metal oxide etc. as tinting pigment.As the metal oxide that in this thermotolerance printing ink, uses, be a kind in the oxide compound of metals such as iron, cobalt, nickel, chromium, copper, manganese, titanium, aluminium or mix the material of two or more, these metal oxides are supplied to as powder, and its median size is generally about 0.01～about 50 μ m, is preferably about 0.1～about 10 μ m.
The thermotolerance printing ink that contains this tinting pigment can be made with the following method: for example with respect to tinting pigment 100 weight parts, about 1～about 1000 weight parts of mixed glue, preferred about 10～about 200 weight parts, add solvent as required, and disperse or mix with the dispersion machine of dispersion machine, ball mill, roller mill, sand mill etc., make the method for aqueous or pulpous state.The tackiness agent that use this moment can be enumerated resin, wax, grease, low melting glass (frits of pyrex, soda glass etc.) etc.The thermotolerance printing ink that preferably contains tinting pigment, frit and organic adhesion agent.
Can enumerate silicone resin as resin, hydrocarbon resin, ethenoid resin, Derlin, inferior amide resins, amide resins, acrylic resin, vibrin, urethane resin, Synolac, protein resin, celluosic resin etc., for example can enumerate organopolysiloxane, poly-metal carbon silane, polystyrene, polyethylene, polypropylene, polyvinyl acetate, polyvinyl butyral acetal, polyvinyl formal, pi, polymeric amide, poly-(methyl) acrylate, gelatin, derivatived cellulose, polyvinyl alcohol, in the polyvinylpyrrolidone etc. a kind, perhaps mixture of two or more or multipolymer.
Can enumerate paraffin, natural wax, higher alcohols wax, senior amide waxe, higher fatty acid, ester type waxes etc. as wax, for example paraffin, polyethylene wax, beeswax, carnauba wax, stearyl alcohol, palmityl alcohol, oleyl alcohol, stearic amide, amine hydroxybenzene, palmitic amide, ethene are for two stearylamides, stearic acid, oleic acid, palmitinic acid, tetradecanoic acid, Stearic ethyl stearate, butyl palmitate, stearic acid cetyl ester, stearic acid stearyl etc.
As grease, can enumerate Viscotrol C, soybean oil, Toenol 1140, sweet oil, butter, lard, mineral wet goods.In addition, as low melting glass, it is 70 ℃ or lower glass or the glass that dissolves in solvent that fusing point is arranged, for example can enumerate be fusing point be 700 ℃ or lower frit, median size is the material of about 0.1～about 100 μ m, preferred about 0.2～about 50 μ m and water glass etc.
As at the solvent that disperses or use when mixing, aliphatic hydrocarbons such as hexane, octane, decane, hexanaphthene are for example arranged, aromatic hydrocarbonss such as benzene,toluene,xylene, isopropyl benzene, naphthalene, ketones such as acetone, ethyl methyl ketone, pimelinketone, alcohol such as methyl alcohol, ethanol, 2-Ethylhexyl Alcohol, ethers such as ethylene glycol-methyl ether, dibutyl ethylene glycol ether, ester classes such as methyl acetate, ethyl formate, methyl aceto acetate, petroleum distillation compositions such as gasoline, lam-oil, light oil, water etc.Measure 100 weight parts with respect to the total of tinting pigment and tackiness agent, the solvent that is used to dilute these materials is about 500 weight parts or still less, preferably uses about 200 weight parts or still less.
Heat-resisting label of the present invention uses the thermotolerance printing ink that contains this constituent material, in forming pattern, by known printing process and laser marking etc., as long as form with the arbitrary graphic pattern headed by the marks such as literal and bar code.As printing process, for example can enumerate intaglio plate lithography, dull and stereotyped lithography, letterpress, intaglio printing, silk screen printing, ink jet printing, ribbon screen printing (ribbon printing) etc.These printing processes and laser marking not only go for being provided with the situation of identification division on the label substrate layer, also be applicable to the situation of directly giving identifier on supporter.
The shape of the heat-resisting label of the present invention has no particular limits, owing to use labelling machine when high temperature is pasted, is preferably the exercisable shape of labelling machine.Heat-resisting label of the present invention can be made by on the supporter of the shape that is processed to be suitable for goods are pasted other integrants (label substrate layer, adhesive coating, bonding coat, adhesion metal paper tinsel layer, identification part grade) being set; Can also on making big supporter, be provided with after the sheet material of other integrants, make by being processed into the shape that is suitable for goods are pasted.Have no particular limits as working method, the method for slit processing, punching processing etc. can illustration be arranged.
The employed labelling machine of the stickup of the heat-resisting label of the present invention just has no particular limits so long as can tolerate the material that uses under the high temperature.The few fabric of deformation at high temperature (fabric that preferred solid inweaves) is used at the position that the labelling machine head contacts with label usually.Usually the fiber that uses in fabric can be illustrated as TYRANNO fiber, carbon fiber, glass fibre, aluminum oxide silica fiber etc., and these materials can use separately, perhaps mix two or more and use.Wherein, preferred TYRANNO fiber.
When the big part of concave-convex surface is pasted, in the labelling machine head the fabric that uses become very important for concavo-convex following.That is, if fabric is good for concavo-convex following, then the contact part of label on adhesive portion increases, and its result can become the very strong label of tack.The TYRANNO fabric makes elastic performance become big, following to become good by thickening the invagination amplitude.Therefore, the TYRANNO fabric that invagination amplitude is thick helps the tack of label.
In addition, the applicant has carried out the heat-resisting pressurized circulation test of TYRANNO fabric under the following conditions, also has excellent thermotolerance and anti-pressurization even confirmed the stickup at high temperature of TYRANNO fabric.
Heat-resisting pressurized circulation test
The TYRANNO fiber that solid is inweaved is (vertical * horizontal stroke * height: 80mm * 180mm * as 8mm) to be placed in 600 ℃ the electric furnace, with pressurization (10 seconds, 100g/cm with cubes
2), then do not pressurize (6 second), 9000 circulations repeatedly as 1 circulation.The TYRANNO fiber does not have deterioration in appearance, and paste functionality is also fine.
Goods of the present invention with that describe.Goods of the present invention can be the materials that is pasted with heat-resisting label 1 of the present invention or 2, can be intermediates, also can be end articles.Heat-resisting label 1 of the present invention is just can paste on the thermotolerance goods about 300 ℃～about 670 ℃ following short period of time of scope pasting the object temperature of articles.The stickup time be generally about 1 the second～about 2 minutes, be preferably about 1 the second～about 1 minute, more preferably about 1 the second～about 30 seconds.As goods, so long as can paste heat-resisting label of the present invention, and temperature of articles is that about 300～about 1100 ℃ material gets final product in the production process of goods.The goods that are suitable for pasting heat-resisting label 1 are about 300～about 670 ℃ goods, and the goods that are suitable for pasting heat-resisting label 2 are about 670～about 1100 ℃, be preferably about 700～about 1000 ℃ goods.Goods of the present invention are generally metal products, ceramic industry goods, glasswork etc.The object lesson of metal products is metal embryos such as iron and steel embryo, aluminium embryo, stainless steel embryo, copper embryo, once-forming goods such as chunk, coil, H stainless steel, pipe, bar, sheet material, post forming goods that these once-forming goods are obtained with manufacturing process such as extrusion molding, cast forms etc.
Embodiment
Below, the present invention will be described in more detail with embodiment, but the present invention is not limited to these embodiment.The material that uses in present embodiment and the comparative example is as follows.
＜supporter 〉
Aluminium foil:
Japan's foliation (strain) system " 1N-30-H-40RT "
Thickness is 40 μ m
Stainless steel foil:
Nippon Steel (strain) system " SUS304H-TA/MW "
Thickness is 20 μ m
＜poly-metal carbon silane resin 〉
The emerging product of space portion (strain) system " TYRANNO COAT VS-100 "
(containing the poly-about 49 weight % of metal carbon silane resin)
“TYRANNO COAT VN-100”
(containing poly-metal carbon silane resin and the about 50 weight % of silicone resin)
＜silicone resin 〉
SHIN-ETSU HANTOTAI's chemical industry (strain) system " KR255 "
(containing the about 50 weight % of straight type silicone resin)
Toshiba's silicone (strain) system " TSR116 "
(containing the about 50 weight % of straight type silicone resin)
SHIN-ETSU HANTOTAI's chemical industry (strain) system " KR3701 "
(containing the about 60 weight % of organosilicon tackiness agent)
SHIN-ETSU HANTOTAI's chemical industry (strain) system " ES-1002T "
(containing the about 50 weight % of epoxy modified silicone resin)
＜inorganic powder 〉
TITAN industry (strain) system " KR-380 "
(Titanium Dioxide (Rutile) Top grade)
Big day (strain) system " TRNS OXIDE RED AA2005 " of refining
(Fe
2O
3)
Ball tail calcium (strain) system " BIKaolin " (kaolin)
Three Tianjin pool pharmaceutical chemicalss (strain) system zinc powder (zinc)
Mountain stone metal (strain) system " AT-Sn.No.600 " (tin)
Japan's aluminium (strain) system " AC-2500 " (aluminium)
Other inorganic powder uses commercially available product
＜dispersion agent 〉
Nanmu originally changes into (strain) system " DISPARLON DA705 "
＜thermotolerance printing ink 〉
GENERAL (strain) makes " HP-350A "
＜aluminium foil layer 〉
Aluminium foil
Japan's foliation (strain) system " 1N-30-H-40RT "
Thickness is 40 μ m
＜bonding coat 〉
The polyisobutene resin
Nippon Oil(Nippon Mitsubishi Oil) (strain) system " TETRAX 4T "
＜exfoliated sheet material 〉
NIPPA (strain) makes " PET-50 * 1SS-4B " (fluorine film)
In addition, rub(bing)test is performed as follows: use to contain 3～5 gauzes that are soaked with dimethylbenzene, with 0.5～1kg/cm
2Pressure friction adhesive coating or label substrate layer.At this, in rub(bing)test, carry out 5～6 frictions, be coated with rete and dissolve and be attached on the gauze, this situation is semi-harden state; Be coated with rete 15 times even rub and also do not peel off, adhering to the situation that is coated with rete on gauze hardly is hardening state.
Embodiment 1 (heat-resisting label 1-1)
Get 20 weight parts as the TYRANNO COAT VS-100 of poly-metal carbon silane resin, 60 weight parts as the KR-380 of inorganic powder, 0.5 weight part as the DISPARLONDA705 of dispersion agent and 5 weight parts dimethylbenzene as organic solvent, carry out mixing after, using particle to grind dispersion machine (ASHIZAWA society system " LMZ-2 ") disperseed 1 hour under 3000rpm, and measure meter with grinding and confirm that median size is 5 μ m or lower, promptly get and disperse abrasive M-1.
In 85.5g dispersion grinding material M-1, add the KR255 of 20g as silicone resin, then add 5g dimethylbenzene, carry out mixing, further append dimethylbenzene and adjust viscosity, make to adopt the viscosity of the viscometer determining of IHS flow cup (rock field flow cup society system) become 25～30 seconds/25 ℃, promptly get coating fluid.Then, be on the one side of aluminium foil of 40 μ m with bar coating machine coating coating fluid at thickness, make dried coating thickness become 15 μ m, drying is after 10 minutes down at 250 ℃ to use heated air circulation type baking oven (ASSF-114S, Isuzu Motors are made made), and room temperature is placed.Confirm to film to be hardening state with rub(bing)test, obtain having the supporter of label substrate layer.
Then, opposition side (adhesive coating side) at this supporter upward is coated with above-mentioned coating fluid with the bar coating machine, make dried coating thickness become 40 μ m, drying is after 5 minutes down at 200 ℃ to use heated air circulation type baking oven (ASSF-114S, Isuzu Motors are made made), and room temperature is placed.Confirm to film to be semi-harden state with rub(bing)test, and be cut into the size of 5cm * 3cm, obtain heat-resisting label.
Embodiment 2～14 (heat-resisting label 1-1)
Under the composition and drying conditions shown in table 1～3, experimentize in the same manner with embodiment 1, promptly get heat-resisting label.In addition, in embodiment 10～12, the dispersion of grinding dispersion machine based on particle is to carry out under 3000rpm 3 hours, rather than 1 hour.In addition, in embodiment 13, semi-harden filming (adhesive coating) only is set, hardened coating film (label substrate layer) is not set in the one side of supporter.
Comparative example 1～3
Under composition and drying conditions as shown in table 4, experimentize in the same manner with embodiment 1, promptly get label with adhesive coating.
Table 1
Table 2
Table 3
Table 4
Test example 1
The label that use obtains in the foregoing description 1～14 and comparative example 1～3 carries out test as follows.Test-results is shown in table 5 and 6.And if print bar code on the label substrate layer of embodiment 14, then bar code printing clearly becomes possibility.In addition, the above-mentioned label that is printed with bar code pasting with pasting under test 1,2 and 3 the same terms, is observed the state of bar code, the result is clear, and the bar code that does not have due to the labelling machine peels off, and is also fine with reading of bar code reading machine.
High temperature is pasted test 1:
Using manual labelling machine, is on 500 ℃ the side of aluminium embryo, with 50g/cm in surface temperature
25 seconds of pressure calendering label, then with aluminium embryo cool to room temperature, observe the outward appearance of adhering to situation, label and the scuff resistance of label.In addition, because the label of embodiment 13 does not have the label substrate layer, so do not carry out the evaluation of outward appearance and scuff resistance.Show the result in the table 5.
About tack, be shown " A " with what label did not peel off, be shown " C " with what label peeled off.
About outward appearance, the state that the label substrate layer is peeled off from a supporter part is shown " C ", will not have the big state that changes to be shown " A " on the label.
About scuff resistance, on one side in the loading about load 500g on the coin, one side abrades label substrate layer 2～3 times with the speed of 5cm/ second, the state that the label substrate layer is peeled off from the supporter one after another is shown " C ", does not have the state of the part shortcoming degree of injured or this laminar surface to be shown " A " fully on the label substrate layer.
High temperature is pasted test 2:
Except the surface temperature of pasting object (aluminium embryo) is 600 ℃, pastes test 1 with high temperature and similarly test.Show the result in the table 5.
High temperature is pasted test 3:
Except the surface temperature of pasting object (iron embryo) is 660 ℃, pastes test 1 with high temperature and similarly test.Show the result in the table 6.
Table 5
Table 6
Embodiment 15 (heat-resisting label 2)
Get 20 weight parts as the TYRANNO COAT VS-100 of poly-metal carbon silane resin, 60 weight parts as the KR-380 of inorganic powder, 0.5 weight part as the DISPARLONDA705 of dispersion agent and 5 weight parts dimethylbenzene as organic solvent, carry out mixing after, using particle to grind dispersion machine (ASHIZAWA society system " LMZ-2 ") disperseed 1 hour under 3000rpm, and measure meter with grinding and confirm that median size is 5 μ m or lower, obtain dispersion grinding material M-1.
In 85.5g dispersion grinding material M-1, add the KR255 of 20g as silicone resin, then add 5g dimethylbenzene, carry out mixing, further append dimethylbenzene and adjust viscosity, make to adopt the viscosity of the viscometer determining of IHS flow cup (rock field flow cup society system) become 25～30 seconds/25 ℃, promptly get coating fluid.Then, be on the one side of stainless steel foil of 20 μ m with bar coating machine coating coating fluid at thickness, make dried coating thickness become 15 μ m, drying is after 10 minutes down at 250 ℃ to use heated air circulation type baking oven (ASSF-114S, Isuzu Motors are made made), and room temperature is placed.Confirm to film to be hardening state with rub(bing)test, obtain having the supporter of label substrate layer.
Then, be on the whole one side of aluminium foil of 40 μ m with the TETRAX 4T of bar coating machine coating at thickness as tackiness agent, make dried coating thickness become 8 μ m, use heated air circulation type baking oven (ASSF-114S, Isuzu Motors are made made) after under 100 ℃ dry 5 minutes, room temperature is placed, and promptly gets the aluminium foil with bonding coat.
The supporter with label substrate layer that obtains is bonding with the aluminium foil with bonding coat.The lamination sheet material that obtains is cut into the size of 5cm * 3cm, obtains heat-resisting label.
Embodiment 16～27 (heat-resisting label 2)
Under the composition and drying conditions shown in table 7～9, experimentize in the same manner with embodiment 15, obtain heat-resisting label.In addition, in embodiment 24～26, the dispersion of grinding dispersion machine based on particle is to carry out under 3000rpm 3 hours, rather than 1 hour.In addition, in embodiment 27, on the one side of supporter, only form aluminium foil, and hardened coating film (label substrate layer) is not set by bonding coat.
Table 7
Table 8
Table 9
Embodiment 28～39 (heat-resisting label 2)
Under the composition and drying conditions shown in table 10～12, except striated ground coating adhesive on the one side of aluminium foil, experimentize in the same manner with embodiment 15, promptly get heat-resisting label.The coating process of tackiness agent is as follows.
Use the bar coating machine, it is the adhesive coated scope of 5mm and the non-coating scope of tackiness agent that fabric width is 10mm that fabric width alternately is set on the one side of aluminium foil, with 45 ℃ angle spiral way striated ground coating adhesive.
In embodiment 36～38, the dispersion of grinding dispersion machine based on particle is to carry out under 3000rpm 3 hours, rather than 1 hour.In addition, in embodiment 39, only form aluminium foil in the one side of supporter by bonding coat, and hardened coating film (label substrate layer) is not set.
Table 10
Table 11
Table 12
Test example 2
Use the foregoing description 1 and 15～39 and comparative example 1～3 in the label that obtains carry out experiment shown below.
High temperature is pasted test 4:
Except the surface temperature of pasting object (iron embryo) is 680 ℃, pastes test 1 with high temperature and test in the same manner.About outward appearance, slight fissured as " B " on label, to occur.Show the result in the table 13.
High temperature is pasted test 5:
Except the surface temperature of pasting object (iron embryo) is 700 ℃, pastes test 1 with high temperature and test in the same manner.The label of embodiment 1 is set as outside the object of this test.Show the result in the table 13.
High temperature is pasted test 6:
Except the surface temperature of pasting object (iron embryo) is 1000 ℃, pastes test 1 with high temperature and test in the same manner.The label of embodiment 1 is set as outside the object of this test.Show the result in the table 14.
Table 13
Table 14
Embodiment 40 and 41 (heat-resisting label 1-1) and comparative example 4 and 5
In the embodiment of the present application 1, bonding coat dried coating thickness is made as 30 μ m, drying conditions is set at following 10 minutes (comparative example 4), 100 ℃ following 5 minutes (embodiment 40) of room temperature, 200 ℃ following 5 minutes (embodiment 41) or 300 ℃ following 5 minutes (comparative example 5), makes heat-resisting label similarly to Example 1.
It is above 500 ℃ the aluminium embryo that the label that obtains is placed surface temperature, rolls for 5 seconds with the pressure of 50g/cm2.With aluminium embryo cool to room temperature, observe burning, the outward appearance of label and the tack of label of label after the calendering.
About the burning of label, with label not on fire be evaluated as A, with label on fire be evaluated as C.About the outward appearance of label, be A with there not being empyreumatic state evaluation in the label, be C with empyreumatic state evaluation is arranged in the label.About the tack of label, it is A that label is attached to the state evaluation that does not float on the embryo, will float the C that is evaluated as that peels off from embryo.Show the result in the table 15.
Table 15
| Drying conditions | Coating thickness | Burning | Outward appearance | Tack | |
| Comparative example 4 | Following 10 minutes of room temperature | 30μm | C | C | A |
| Embodiment 40 | 100 ℃ following 5 minutes | 30μm | A | A | A |
| Embodiment 41 | 200 ℃ following 5 minutes | 30μm | A | A | A |
| Comparative example 5 | 300 ℃ following 5 minutes | 30μm | A | A | C |
The label of the comparative example 4 that solvent is many 500 ℃ on fire down, adhesive coating is non-cohesive by the semi-harden label that proceeds to the comparative example 5 that hardened films.
Embodiment 42 (heat-resisting label 1-2)
Similarly to Example 1, on being the one side of aluminium foil of 40 μ m, thickness forms the label substrate layer.
Then, get 20 weight parts as the KR3701 of silicone resin, 36 weight parts as the zinc powder of inorganic powder, 0.3 weight part as the DISPARLON DA705 of dispersion agent, 20 weight parts dimethylbenzene as organic solvent, carry out mixing after, using above-mentioned particle to grind dispersion machine disperseed 1 hour under 3000rpm, confirm that with grinding to measure to count median size is 5 μ m or lower, obtain dispersion grinding material M-2.Add 4g KR3701 in the 76.3g dispersion grinding material M-2, then add 10g dimethylbenzene, carry out mixingly, further append dimethylbenzene and adjust viscosity, make that the viscosity of the viscometer determining that adopts the IHS flow cup becomes 55～60 seconds/25 ℃, obtain coating fluid.Then, opposite side (adhesive coating side) at this supporter upward is coated with this coating fluid with the bar coating machine, make dried coating thickness become 40 μ m, use heated air circulation type baking oven (ASSF-114S, Isuzu Motors are made made) following dry 5 minutes at 200 ℃, after removing the solvent in filming, room temperature is placed.Obtaining on the adhesion aspect of sheet material being cut into 5cm * 3cm size behind the exfoliated sheet material of lamination fluorine, obtain heat-resisting label.This label being pasted on when being attached thing, peel exfoliated sheet material off, the adhesion aspect is pasted be attached on the thing.
Embodiment 43～47 (heat-resisting label 1-2)
Composition shown in table 16 experimentizes in the same manner with embodiment 42, obtains heat-resisting label.
Table 16
Embodiment 48～53 (heat-resisting label 1-2)
Silicone resin is changed into KR255, and composition shown in table 17 experimentizes in the same manner with embodiment 42, obtains heat-resisting label.Do not use it owing to do not need exfoliated sheet material.
Table 17
Embodiment 54～59 (heat-resisting label 1-2)
Silicone resin is changed into ES-1002, and composition shown in table 18 experimentizes in the same manner with embodiment 42, obtains heat-resisting label.Do not use it owing to do not need exfoliated sheet material.
Table 18
Comparative example 6～8
Do not use inorganic powder, composition shown in table 19 experimentizes in the same manner with embodiment 42, obtains heat-resisting label.Exfoliated sheet material is to use in the label of comparative example 6 of KR3701 having used the organosilicon tackiness agent only.
Table 19
Comparative example 9～17
Use zinc, tin, aluminium inorganic powder in addition, the composition shown in table 20 and 21 experimentizes in the same manner with embodiment 42, obtains heat-resisting label.
Table 20
Table 21
Test example 3
The label that use obtains in the foregoing description 42～59 and comparative example 6～17 is placed 4 hours under temperature identical when pasting behind adhesive label, carries out high temperature in the same manner with test example 1 and pastes test 1～3.Show the result in table 22 and 23.
Table 22
Table 23
The possibility of industrial utilization
Heat-resistant label of the present invention is because having heat resistance, thus can be in high-temperature process operation way or after this operation at once the heat resistance goods of the condition of high temperature paste. Therefore, make the management by heat resistance goods such as bar codes begin to become possibility from more early stage. In addition, can cut down the temperature that makes the heat-resisting goods such as metallic article necessary time, energy, cooling place when waiting for the in the past adhesive label be down near room temperature. For example, in the production of stainless steel embryo, making at about 1100 ℃ stainless steel embryo stickup heat-resistant label 2 becomes possibility. In addition, in the production of aluminium embryo, make just making and paste at once heat-resistant label 1 on the aluminium embryo about 650 ℃ after finishing and become possibility.
In addition, then identical with in the past bar code label etc. if after pasting label of the present invention, do not peel off, can circulate, sales management. In the present invention, so-called goods not only comprise the material that circulates after the manufacturing process, also comprise raw material in the manufacturing process, intermediate material etc.
Claims (22)
1. heat-resisting label, it is by the heat-resisting label of the metal adhesion of the sequential cascade of label substrate layer, supporter, adhesive coating, it is characterized by,
(1) the label substrate layer is the stable on heating label substrate layer that contains hardened coating film, described hardened coating film is to coat the label substrate layer on the demonstration side of supporter with composition, and the heating said composition obtains, described label substrate layer contains following substances with composition: (A) the poly-metal carbon silane resin of reactive silicone resin, (B-1) and (C) solvent, and (A) reactive silicone resin and (B-1) mixing ratio by weight of poly-metal carbon silane resin be 1: 9～9: 1;
(2) supporter is a tinsel;
(3) adhesive coating contains semi-harden filming, and described semi-harden filming contained (A) reactive silicone resin and (B) be selected from least a kind that gathers in metal carbon silane resin, zinc powder, tin powder and the aluminium powder form.
2. heat-resisting label as claimed in claim 1 is characterized by, and the label substrate layer is 7: 3～2: 8 with (A) the reactive silicone resin in the composition with the mixing ratio by weight that (B-1) gathers metal carbon silane resin.
3. heat-resisting label as claimed in claim 1 or 2 is characterized by, and the label substrate layer further contains (D) inorganic filling material with composition.
4. heat-resisting label as claimed in claim 1 or 2 is characterized by, and the label substrate layer is with in the composition, and (B-1) poly-metal carbon silane resin is at least a kind that is selected from poly-titanium carbon silane resin and the poly-zirconium carbon silane resin.
5. heat-resisting label as claimed in claim 1 or 2, it is characterized by, adhesive coating is that following obtain semi-harden filmed: adhesive coating is coated on the supporter with composition, and from said composition, make solvent seasoning and get, described adhesive coating contains following substances with composition: (A) reactive silicone resin, (B) are selected from poly-metal carbon silane resin, zinc powder, tin powder and the aluminium powder form at least a kind and (C) solvent.
6. heat-resisting label as claimed in claim 5 is characterized by, and adhesive coating further contains (D) inorganic filling material with composition.
7. heat-resisting label as claimed in claim 5 is characterized by, and with in the composition, poly-metal carbon silane resin is at least a kind that is selected from poly-titanium carbon silane resin and the poly-zirconium carbon silane resin at adhesive coating.
8. heat-resisting label as claimed in claim 5 is characterized by, and adhesive coating contains (A) reactive silicone resin, (B-2) with composition and is selected from least a kind high temperature tackiness inorganic powder and (C) solvent in zinc powder, tin powder and the aluminium powder form.
9. heat-resisting label as claimed in claim 1, it is characterized by, semi-harden film contain be selected from the poly-metal carbon silane resin of (A) reactive silicone resin, (B-1), (B-2) is selected from least a kind high temperature tackiness inorganic powder in zinc powder, tin powder and the aluminium powder form.
10. heat-resisting label as claimed in claim 1 or 2 is characterized by, and the thickness of supporter is 5～100 μ m.
11. heat-resisting label as claimed in claim 1 or 2 is characterized by, tinsel is aluminium foil, stainless steel foil or Copper Foil.
12. heat-resisting label as claimed in claim 1 or 2 is characterized by, and has identification division on described label substrate layer.
13. heat-resisting label as claimed in claim 1 or 2 is characterized by, and is to be to paste usefulness under 300 ℃ or the higher temperature when pasting.
14. the manufacture method of heat-resisting label, it is by the metal adhesion of the sequential cascade of label substrate layer, supporter, the adhesive coating manufacture method with heat-resisting label, it is characterized by, and has following operation:
To contain the poly-metal carbon silane resin of (A) reactive silicone resin, (B-1) and (C) the label substrate layer of solvent coat the operation of the demonstration side of supporter with composition, the label substrate layer of coating is made the operation of hardened coating film with the composition heating,
To contain (A) reactive silicone resin, (B) and be selected from poly-metal carbon silane resin, zinc powder, tin powder and the aluminium powder form at least a kind, (C) adhesive coating of solvent is coated the operation of the adhesion side of supporter with composition, and the adhesive coating of coating is made semi-harden operation of filming with composition dries.
15. the manufacture method of heat-resisting label as claimed in claim 14 is characterized by, and is 50～240 ℃ with the adhesive coating of coating with the temperature of composition dries.
16. temperature is the heat-resisting label of 670～1100 ℃ stickup usefulness when pasting, it is by the heat-resisting label of the sequential cascade of label substrate layer, supporter, adhesion metal paper tinsel layer, it is characterized by,
(1) the label substrate layer is the stable on heating label substrate layer that contains hardened coating film, described hardened coating film is to coat the label substrate layer on the demonstration side of supporter with composition, and the heating said composition obtains, described label substrate layer contains following substances with composition: (A) the poly-metal carbon silane resin of reactive silicone resin, (B-1) and (C) solvent, and (A) reactive silicone resin and (B-1) mixing ratio by weight of poly-metal carbon silane resin be 1: 9～9: 1;
(2) supporter is for to have stable on heating tinsel more than 670 ℃;
(3) the tackiness metal foil layer is at least a kind that is selected from aluminium foil, alloy foil, tinfoil paper and the tin alloy foil.
17. heat-resisting label as claimed in claim 16 is characterized by, adhesion metal paper tinsel layer be by bonding coat with the supporter adherent.
18. as claim 16 or 17 described heat-resisting labels, it is characterized by, the thickness of adhesion metal paper tinsel layer is 5～100 μ m.
19. as claim 16 or 17 described heat-resisting labels, it is characterized by, supporter is stainless steel foil, Copper Foil or iron foil.
20. as claim 16 or 17 described heat-resisting labels, it is characterized by, the label substrate layer further contains (D) inorganic filling material with composition.
21. as claim 16 or 17 described heat-resisting labels, it is characterized by, with in the composition, (B-1) poly-metal carbon silane resin is at least a kind that is selected from poly-titanium carbon silane resin and the poly-zirconium carbon silane resin at the label substrate layer.
22. as claim 16 or 17 described heat-resisting labels, it is characterized by, have identification division on the label substrate layer.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49886703P | 2003-08-28 | 2003-08-28 | |
| US60/498,867 | 2003-08-28 | ||
| US60/531,496 | 2003-12-19 | ||
| JPPCT/JP04/006297 | 2004-04-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1845976A CN1845976A (en) | 2006-10-11 |
| CN100393840C true CN100393840C (en) | 2008-06-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800249625A Active CN100393840C (en) | 2003-08-28 | 2004-08-24 | Heat-resistant label applicable at high temperature |
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| CN (1) | CN100393840C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8617128B2 (en) * | 2012-02-15 | 2013-12-31 | Medtronic, Inc. | Labeling of medical devices |
| CN111105697B (en) * | 2019-11-27 | 2022-03-11 | 苏州三帆包装材料有限公司 | High-temperature-resistant photosensitive label and processing method thereof |
| CN112920605A (en) * | 2020-11-10 | 2021-06-08 | 金冠电气股份有限公司 | Silicone rubber composite material for bonding polybutylene terephthalate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62138574A (en) * | 1985-12-13 | 1987-06-22 | Ube Ind Ltd | Binding agent composition |
| CN1109993A (en) * | 1993-10-15 | 1995-10-11 | 日本油脂株式会社 | Label |
| JP2000098899A (en) * | 1998-09-25 | 2000-04-07 | Nof Corp | Tacky adhesive label |
-
2004
- 2004-08-24 CN CNB2004800249625A patent/CN100393840C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62138574A (en) * | 1985-12-13 | 1987-06-22 | Ube Ind Ltd | Binding agent composition |
| CN1109993A (en) * | 1993-10-15 | 1995-10-11 | 日本油脂株式会社 | Label |
| JP2000098899A (en) * | 1998-09-25 | 2000-04-07 | Nof Corp | Tacky adhesive label |
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|---|---|
| CN1845976A (en) | 2006-10-11 |
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