• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a method for labeling a tree trunk with an aqueous solution of a biodegradable marker ink which also contains an anticorrosive agent. The method comprises spraying an aqueous solution of a marking dye containing 35-55 wt% water and 40-60 wt% glycerol with a maximum of 30 days biodegradability according to the OECD 301 test method, 0.05-1 wt% dye, 0.1 -2% by weight of the corrosion inhibitor, however, the total amount of glycerol and water in said aqueous solution is more than 95%, preferably more than 97% by weight.
    公开号:FI20175711A1
    申请号:FI20175711
    申请日:2017-08-04
    公开日:2019-02-05
    发明作者:Pekka Majamäki
    申请人:Reclog Oy；
    IPC主号:
    专利说明:

    The invention relates to a method according to the preamble of claim 1 for labeling a tree trunk with an aqueous solution of a biodegradable marker paint which also contains an anticorrosive agent.
    The invention also relates to an aqueous solution of a biodegradable marker ink according to the preamble of claim 11 for marking a tree trunk which also contains an anti-corrosion agent.
    The tree trunks are marked by means of a spraying device 10 attached to the harvester head of the forest machine when watering, with water-soluble marking colors for sorting the tree trunks. The marking inks used in aqueous solutions of marker paints are very low temperature resistant, but in order to prevent the freezing of water in spraying equipment, the aqueous solution should contain a suitable antifreeze to raise the freezing point of the aqueous solution.
    Since the tree trunks are labeled with a mechanical spraying device attached to the harvester head in connection with felling, said aqueous solutions should contain a suitable anti-corrosion agent to protect the marking paint spraying equipment from rusting.
    The corrosion inhibitors and antifreeze agents used in the aqueous solutions of these marker dyes should also be compatible with the marker dye, i.e., no constituent of the composition should settle, precipitate or otherwise separate during storage.
    Due to the mechanical implementation of the marking process, the marker ink often also enters the environment of the stump, which may cause unnecessary environmental loading if the aqueous ink solution contains non-biodegradable or environmentally toxic ingredients.
    Another major problem with marker inks is the amount of use and how they are used: aqueous solutions of marker inks have to be applied to the spraying device and used in relatively large amounts, so there is always a risk that they will come into contact with the user's skin.
    The object of the invention was to eliminate and / or alleviate the problems encountered in the prior art.
    20175711 prh 04-08- 2017
    Accordingly, it was an object of the invention to provide a fully biodegradable aqueous dye solution in which the components of the aqueous dye solution would be biodegradable.
    Further, at least the major components of the aqueous solution of the marking ink should be as non-irritating as possible and should be as non-toxic as possible both by inhalation and dermal exposure. The latter means that their LD50 values should be high in mammals, especially humans.
    In addition, the other components used in the aqueous ink solution should be compatible with the ink itself, but at the same time the aqueous ink solution 10 should be applied to the wood as quickly as possible, since the marking is done mechanically when the wood is felled.
    The above objects are achieved by the method of marking the tree trunks according to claim 1 and by the aqueous solution of the biodegradable marking ink according to claim 1 for the marking of the tree trunk which also contains an anti-corrosion agent.
    More particularly, the invention relates to a method for labeling a tree trunk with an aqueous solution of a biodegradable marker ink which also contains an anticorrosive agent. In the method, an aqueous solution of a marking dye containing 35-55 wt.% Water and 40-60 wt.% Glycerol is injected on the body with a test biodegradability of not more than 30 days according to OECD 301, 0.1-2 wt. 2 wt% corrosion inhibitor, however, the total amount of glycerol and water in said aqueous solution is more than 95%, preferably more than 97 wt%.
    The invention also relates to an aqueous solution of a biodegradable marker paint for marking a tree trunk, which also contains an anti-corrosion agent. The aqueous solution of the marking ink consists of 40-60 wt% glycerol, 35-55 wt% water, 0.1-2 wt% dye,
    0.1 to 2% by weight of an anticorrosive agent and 0 to 3% by weight of an additive such as an antifoam agent, however, the total amount of glycerol and water in said aqueous solution is more than 95%, preferably more than 97% by weight.
    The process according to the invention employs an aqueous solution of a marking dye, the major components of which are completely biodegradable, non-toxic and do not cause skin irritation. More particularly, the invention is based on the fact that the major components of an aqueous solution of marking ink, water and glycerol, are non-irritating, non-toxic and completely biodegradable.
    20175711 prh 04-08- 2017
    The skin irritation of glycerol is only 0-0.4 as measured by the Draize scale at a maximum of 30. Preferably, the aqueous solution contains water and glycerol in a ratio of 1: 1 (w / w) and additionally, the total amount of water and glycerol is at least 95 wt. This achieves the notable advantage that most of the aqueous solution contains non-flammable, non-toxic components of water and glycerol, which are rapidly degraded upon release into the environment.
    From the Finnish patent FI-116679 there is known an aqueous solution of a marking material for a tree trunk which contains glycol that causes skin irritation. The lethal toxicity of ethylene glycol to humans is estimated to be only about 10 1.4 ml / kg, whereby approximately 50 ml of oral ethylene glycol may be fatal. Glycerol is not toxic to humans even at 100 times the dose of glycol and is approved as a food additive. In addition to that. the components of the aqueous solution are incompatible with many biodegradable anti-rust agents, which significantly limits its use.
    Instead, in the preferred embodiment of the invention, the corrosion inhibitor is also essentially biodegradable. Preferably, 95 wt% of the anticorrosive agent, preferably greater than 99 wt%, is biodegradable in less than 10 days, preferably less than 4 days, as tested by OECD 301.
    In a preferred embodiment of the invention, the marker ink itself is biodegradable.
    In a preferred embodiment of the invention, the biodegradable corrosion inhibitor comprises water, sodium salts of organic acids, sodium benzoate, and sodium nitrite.
    In another preferred embodiment of the invention, the biodegradable corrosion inhibitor is an anionic corrosion inhibitor containing disodium (tetrapropenyl) succinate.
    In yet another preferred embodiment of the invention, the biodegradable corrosion inhibitor contains polyhydroxyamides as the anticorrosive agent.
    For purposes of this application, the biodegradability of an aqueous solution or its components refers to the biodegradability according to European Standard No. 13432.
    As a test method for the determination of biodegradability, the aqueous solution and its components of the present application were tested by the OECD 301 test method, which contains e.g. test methods OECD 301A and OECDD.
    In the following, the invention is further illustrated by the following examples. The aqueous solutions prepared in Examples 1-3 were all clear and free of turbidity. All aqueous solutions were tested by spraying or applying them manually to the trunk of the truncated tree or by means of an automatic spraying device coupled to the saw flange, connected to the harvester grapple. In this case, the saw flange in the grapple was capable of first felling the wood and then, or at the same time, spraying the marker paint onto the tree trunk. The spraying device coupled to the harvester grapple had a spraying device operatively coupled to the hydraulics of the harvester grapple. The injection device comprised the injection nozzles, a reservoir containing the aqueous solution, and pumping means for pumping the aqueous solution onto the nozzles of the injection device.
    Example 1
    The staining mark of the strain was made by making an aqueous solution containing the components listed in Table 1 in a clean container. The marking paint was then applied to the trunk of the truncated wood.
    table 1
    20175711 prh 04-08- 2017
    Cover mark, aqueous solution 1
    Ingredient number / kg wt% The volume / l vol% Water 50 43.98 50.6 49.7 glycerol 62.07 54.60 49.2 48.9 Ecozol Red LY 0,800 0.7 0.7 0.69 25 Rima Flash B5 0,500 0.4 0.4 0.39 In total 113.67 100 100.50 100
    20175711 prh 04-08- 2017
    In the same way as aqueous solution 1, other aqueous solutions of marker ink were made, varying the proportions of the above components as follows:
    Water 35-50% by weight and 35-50% by volume
    Glycerol 40-55% by weight and 35-50% by volume
    Rima flash B5 (corrosion inhibitor) 0.1-2% by weight preferably 0.1-1% by weight.
    The Ecozol Red LY 0.1-2% by weight is preferably 0.1-1% by weight.
    However, the total amount of water and glycerol in the aqueous solution was always greater than 95%, preferably greater than 98% by weight, of the total aqueous solution.
    Preferably, the aqueous marker dye solution contained glycerol and water in a ratio of 1: 1 (v / v).
    Dyes used in Test 1:
    Puricolor Rot ARE18
    Puricolor Red Pre 5-1 New
    Ecozol Red LY
    Ecozol Blue N (LiOH, monohydrate)
    Iragon Blau ABL 9 HFC
    Rima flash B5® is an anticorrosion agent containing sodium nitrite as active ingredient.
    All aqueous solutions tested in Example 1 were clear without turbidity.
    In aqueous solutions of Example 1, adjuvants such as antifoams of 0.2 to 1% by weight may also be used. The total amount of water and glycerol is then more than 95% by weight of the total aqueous solution, preferably more than 97% by weight.
    20175711 prh 04-08- 2017
    Example 2
    Aqueous solutions of the marking dye were made containing:
    Water 35-50% by weight
    Glycerol 40-55 wt%
    Rewocoros B3010® (corrosion inhibitor) 0.1-2 wt%
    0.1-2% by weight of dye
    The dyes were used at 1.5% by weight based on 2% of the total aqueous solution. Preferably, aqueous solution 2 contained glycerol and water in a ratio of 1: 1 (v / v).
    Dyes used in Test 2:
    Puricolor Rot ARE18
    Puricolor Ter Pre 5-1 New
    Ecozol Red LY
    Ecozol Blue N (LiOH, monohydrate)
    Iragon Blau ABL 9 HFC
    Rewocoros B3010 is an anionic surfactant containing disodium (tetrapropenyl) succinate as an active ingredient and has anticorrosive properties.
    All aqueous solutions tested in Example 2 were clear without turbidity.
    In aqueous solutions of Example 2, adjuvants such as antifoams of 0.2 to 1% by weight may also be used.
    Example 3
    The following aqueous marker solution was made
    Water 35-50% by weight
    Glycerol 40-55 wt%
    20175711 prh 04-08- 2017
    Anticor A 40 ® (corrosion inhibitor) 0.1-2% by weight
    Dye 0.1-2% by weight
    The dyes were preferably used at 0.7% by weight of the total aqueous solution. Preferably, the aqueous solution contained glycerol and water in a ratio of 1: 1.
    In the aqueous solution of Example 3, adjuvants such as antifoams of 0.2 to 1% by weight may also be used. A typical defoamer is Defoamer 700, which is based on a stabilized copolymer.
    In all Examples 1-3, the effoamer 700 is an antifoam based on a stabilized copolymer. It can be used in the aqueous solutions of the invention at 0.2 to 1% by weight.
    Other dyes used in Example 3:
    Metric Blue B
    Metric Blue containing 10-30% acetic acid and 1-5% diethylene glycol
    Metric Red
    Metric Red containing 10-30% acetic acid and 1-5% diethylene glycol
    Puricolor Rot ARE18
    Puricolor Ter Pre 5-1 New
    Ecozol Red LY
    Ecozol Blue N (LiOH, monohydrate)
    Iragon Blau ABL 9 HFC
    Anticor A 40 is a corrosion inhibitor containing polyhydroxyamides.
    All aqueous solutions tested in Example 3 were clear without turbidity.
    20175711 prh 04-08- 2017
    Example 4
    Toxicity and biodegradability of some of the active substances in the aqueous dye solutions used in Examples 1-3
    Example 4A: Glycerol and glycol
    Physical Properties of Glycerol (Source: SIDS Initial Assessment Report for SIAM 14, Paris 2002):
    Gas pressure at 25 ° C 0.000106 kPa.
    Solubility in water 100,000 mg / l (completely soluble in water).
    Toxicological properties of glycerol
    Log K ow = - 1.76.
    The LD50 (oral and dermal) is greater than 4000 mg / kg, generally between 23,000 and 38,000 mg / kg. The LD50 for mammals ranges from 4000 to 60,000 mg / kg, depending on the test method and the mammal. There are few tests in humans, one unconfirmed estimate of the lethal dose level is 1428 mg / kg.
    LC50 for fish above 5000 mg / l and marine mammals 10 000 mg / l.
    In a so-called closed bottle test according to OECD 301, aerobic biodegradation was less than 30 days. More than 60% biodegradability after 10 days as determined by ThOD.
    BOD5 was 82% of ThOD and 86% of COD. BOD5 / COD = 0.86.
    Skin irritation on a Draize scale of 0-0.4 (maximum is 30).
    Glycerol is also approved as a food additive, so it is quite safe when swallowed.
    Comparative Example: Comparison of Glycerol Toxicity with Ethylene Glycol C 2 H 6 O 2 :
    Ethylene Glycol: LD50 (oral 584 mg / kg rat), but human fatal toxicity is estimated to be only about 1.4 ml / kg, whereby approximately 50 ml oral glycol may be fatal. This is significantly lower than glycerol
    20175711 prh 04-08- 2017
    LD50 (dermal, rabbit) ca. 9500 mg / kg
    LC50, Fish 18500 mg / L
    Ethylene glycol is classified as harmful to health.
    Example 4B) Dyes
    1) Iragon Blue ABL9 HFC (Basf)
    CAS # 3844-45-9; EC # 223-339-8, a magenta dye based on the disodium salt of triphenylmethane
    LC50 (Fish, 90h) 220 -460 mg / L
    EC50 (Marine Invertebrates, 48h)
    Effect on activated sludge performance: EC10> 10,000 mg / l (standard 38412 part 27)
    Based on this, the Iragon blue dye is not acutely toxic to aquatic organisms.
    Biodegradability COD 1640 mg / g (non-biodegradable).
    2) Ezocol colors
    Ecozol Yellow MR, Ecozol Red LY, Ecozol Blue NC, Ecozol MYCR meet the European Standard 13432 for biodegradability as well as ecotoxicity when added to less than 1 wt.
    4C) Anti-corrosion agents
    1) Rima flash B5®
    Rima Flash is a liquid corrosion inhibitor containing mainly water, sodium salts of organic acids, sodium benzoate and sodium nitrite.
    pH 8.1 -8.7
    Point / boiling point
    100 ° C
    Density 1.12-1.16 g / cm 3 at 20 ° C
    Dynamic viscosity: 70 mPa at 20 ° C
    Of these, the sodium salts of organic acids and sodium benzoate are degraded in less than 4 days when tested according to OECD 301D. OECD 301D 5 cannot be used for sodium nitrite, which is only 1-5 wt% of the mixture. Conclusion 95-99% Rima flash anticorrosive is extremely fast biodegradable.
    Other properties: LD50 (rat)> 2000 mg / kg.
    2) Anticor 40, an anticorrosive solution based on polyhydroxyamines
    Density (at 20 ° C)
    1.30-1.35 g / cm 3
    Flash point above 65 ° C pH
    2-4
    Completely soluble in water
    Non-foaming
    Biodegradability: In a so-called "closed bottle" test according to OECD 301, the aerobic biodegradability of anticor 40 is less than 30 days.
    权利要求:
    Claims (17)
    [1]
    A method for marking a tree trunk with an aqueous biodegradable marker ink solution, also containing an anticorrosive agent, characterized in that an aqueous marker solution containing 35-55 wt% water is sprayed or applied to the tree body
    5 and 40-60% by weight of glycerol having a biodegradability according to test method OECD 301 of not more than 30 days, 0.1-2% by weight of dye, 0.1-2% by weight of corrosion inhibitor, but the total amount of glycerol and water in said aqueous solution is more than 95% preferably more than 97% by weight.
    [2]
    Method according to Claim 1, characterized in that the wood frame
    10 marking with an aqueous solution of marking ink is accomplished by spraying the aqueous solution onto a tree trunk with a mechanical spraying device coupled to the harvester grapple of a forestry machine.
    [3]
    The process according to claim 1, characterized in that the aqueous solution of the marking ink contains glycerol and water in a ratio of 1: 1 (v / v / v).
    15
    [4]
    A process according to claim 1, characterized in that the aqueous solution of the marking ink contains a colorant selected such that when present in an amount of less than 1% by weight of the total aqueous solution, it is biodegradable as defined by European Standard 13432.
    [5]
    Method according to Claim 1, characterized in that
    The 20 µl aqueous solution contains 0.12.0% by weight of anionic, cationic or nonionic corrosion inhibitor, preferably 0.1 to 1% by weight.
    [6]
    Method according to Claim 5, characterized in that the major part of the corrosion inhibitor is also biodegradable as defined in European Standard 13432.
    25
    [7]
    Method according to Claim 5 or 6, characterized in that 95% by weight of the corrosion inhibitor preferably greater than 99% by weight is biodegradable in less than 10 days, preferably less than 4 days when tested by the OECD 301 method.
    [8]
    Process according to Claim 5, characterized in that the corrosion inhibitor contains water, sodium salts of organic acids, sodium benzoate 30 and sodium nitrite
    20175711 prh 04-08- 2017
    [9]
    Method according to Claim 5, characterized in that the corrosion inhibitor is an anionic corrosion inhibitor containing disodium (tetrapropenyl) succinate.
    [10]
    Process according to Claim 5, characterized in that the corrosion inhibitor contains polyhydroxyamides as an anticorrosive agent.
    [11]
    11. Biodegradable aqueous inking solution for marking a tree trunk which also contains an anticorrosive agent, characterized in that the aqueous inking solution consists of 40-60 wt% glycerol, 35-55 wt% water, 0.1-2 wt% dye, 0.1 -2% by weight of corrosion inhibitor and 0-3% by weight of additive such as antifoam
    However, the total amount of glycerol and water in said aqueous solution is more than 95%, preferably more than 97% by weight.
    [12]
    Labeling ink according to Claim 11, characterized in that the aqueous marking solution contains from 0.1 to 1% by weight, preferably from 0.5 to 0.9% by weight, of the total weight of the aqueous solution, wherein the coloring agent is biodegradable according to the European standard.
    15 as defined by 13432.
    [13]
    The marking ink according to claim 11, characterized in that the aqueous marking solution contains from 0.1 to 1% by weight of the total weight of the aqueous solution of corrosion inhibitor, wherein the dye is biodegradable as defined in European Standard 13432.
    20
    [14]
    An aqueous marking dye solution according to claim 13, characterized in that the anti-corrosion agent contains sodium nitrite.
    [15]
    An aqueous marking dye solution according to claim 13, characterized in that the corrosion inhibitor contains polyhydroxyamides.
    [16]
    An aqueous marking dye solution according to claim 12, characterized in that the anti-corrosion agent contains an alkenyl succinate such as sodium (tetrapropenyl) succinate.
    [17]
    An aqueous marking ink solution according to claim 11, characterized in that the marking ink contains acetic acid.
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    同族专利:
    公开号 | 公开日
    DE202018006403U1|2020-04-20|
    FI128607B|2020-08-31|
    EP3473083A1|2019-04-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5735940A|1994-09-23|1998-04-07|Coller; Miriam|Marking composition|
    FI116679B|2001-10-25|2006-01-31|Jarmat Oy|Method and color for marking wood|
    US9790808B2|2005-04-04|2017-10-17|Ecoservices, Llc|Mobile on-wing engine washing and water reclamation system|
    DE102006011677A1|2006-03-14|2007-09-20|Werner Wieland|Tree-cutting surface marking device for evacuation of e.g. firewood, has marking section adapted for marking desired tree-cutting surface at chopped down trunk, and arranged for applying color marks, while holding color spray can|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FI20175711A|FI128607B|2017-08-04|2017-08-04|Method for marking a tree trunk with a biodegradable aqueous solution of marking colour, and a biodegradable aqueous solution of marking colour|FI20175711A| FI128607B|2017-08-04|2017-08-04|Method for marking a tree trunk with a biodegradable aqueous solution of marking colour, and a biodegradable aqueous solution of marking colour|
    DE202018006403.3U| DE202018006403U1|2017-08-04|2018-08-06|A biodegradable aqueous marker paint solution|
    EP18187559.2A| EP3473083A1|2017-08-04|2018-08-06|Method for marking a tree trunck with biodegradable aqueous marking paint solution and biodegradable aqueous marking paint solution|
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