CN116024847A - Anti-delamination aluminized transfer paper and preparation method and application thereof - Google Patents
Anti-delamination aluminized transfer paper and preparation method and application thereof Download PDFInfo
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- CN116024847A CN116024847A CN202211725729.6A CN202211725729A CN116024847A CN 116024847 A CN116024847 A CN 116024847A CN 202211725729 A CN202211725729 A CN 202211725729A CN 116024847 A CN116024847 A CN 116024847A
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- 238000012546 transfer Methods 0.000 title claims abstract description 163
- 238000002360 preparation method Methods 0.000 title description 22
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- 239000012790 adhesive layer Substances 0.000 claims abstract description 101
- 239000011248 coating agent Substances 0.000 claims abstract description 77
- 238000000576 coating method Methods 0.000 claims abstract description 77
- -1 silane compound Chemical class 0.000 claims abstract description 60
- 239000004094 surface-active agent Substances 0.000 claims abstract description 59
- 230000032798 delamination Effects 0.000 claims abstract description 58
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 57
- 229910000077 silane Inorganic materials 0.000 claims abstract description 54
- 230000002265 prevention Effects 0.000 claims abstract description 42
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 22
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- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 8
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- 239000000853 adhesive Substances 0.000 claims description 50
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- 238000000034 method Methods 0.000 claims description 32
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 21
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Abstract
The application relates to an aluminum-plated transfer paper containing delamination prevention, which comprises a transfer coating, an aluminum-plated layer, delamination prevention, an adhesive layer and a raw paper layer which are sequentially laminated; delamination prevention includes adhesion promoters and surfactants; wherein the adhesion promoter is a silane compound, and the silane compound is composed of unsaturated carbonyl and bridging group X, C which are sequentially connected 3‑10 An alkylene group and a silicon group; wherein the unsaturated carbonyl group is an acryloyl or methacryloyl group, the bridging group is-O-or-NH-, and the silicon group contains at least two C 1‑6 An alkoxy group. By plating an aluminized layerDelamination prevention containing silane compounds and adhesion promoters is added between the aluminum-plated transfer paper and the adhesive layer, so that the problem of aluminum powder falling off of the aluminum-plated transfer paper is solved.
Description
Technical Field
The invention relates to the technical field of aluminized transfer paper, in particular to an aluminized transfer paper containing delamination prevention, a preparation method and application of the aluminized transfer paper as cigarette packaging paper.
Background
With the improvement of technical progress and the improvement of living standard of people, the aluminized transfer paper is widely applied as a packaging material with environmental protection and good metallic luster. In recent years, in order to meet the requirements of WTO and WHO, the technical standards of cigarette materials are correspondingly revised, and the environment-friendly property, low cost and excellent color of aluminized transfer paper become the first choice of cigarette packaging.
The method for producing the aluminum plating transfer paper for cigarettes in the market comprises a transfer method and a direct plating method, wherein the direct plating method often causes scrapping of products due to the fact that the problems of flatness of a base material, aluminum plating uniformity and the like in the technological process are difficult to control; the transfer method uses a release film as a transfer substrate, and the product obtained through processes of coating, aluminizing, compounding, stripping and the like can overcome the problems of the direct plating method to a large extent, but still has the condition of poor adhesive force of an aluminum layer of the product.
Disclosure of Invention
Based on the above, the invention aims to provide an aluminized transfer paper, the adhesion of an aluminized layer is obviously improved, and a preparation method and application of the aluminized transfer paper are also provided.
Based on the above, the invention aims to provide an aluminized transfer paper, the adhesion of an aluminized layer is obviously improved, and a preparation method and application of the aluminized transfer paper are also provided.
In a first aspect of the present application, there is provided an aluminum-plated transfer paper comprising a transfer coating layer, an aluminum-plated layer, an anti-delamination layer, an adhesive layer, and a raw paper layer laminated in this order; the delamination prevention comprises an adhesion promoter and a surfactant;
the adhesion promoter is a silane compound, and the silane compound is composed of unsaturated carbonyl, bridging group X, C3-10 alkylene and silicon base which are sequentially connected; wherein the unsaturated carbonyl is an acryloyl or methacryloyl, the bridging group is-O-or-NH-, and the silicon group contains at least two C1-6 alkoxy groups.
In some embodiments, the aluminized transfer paper satisfies at least one of the following characteristics:
the C3-10 alkylene is C3-6 alkylene;
the silicon base is trimethoxysilicon base, triethoxy silicon base, methyldiethoxy silicon base or methyldimethoxy silicon base;
the surfactant is an anionic surfactant.
In some embodiments, the aluminized transfer paper satisfies at least one of the following characteristics:
the silane compound is selected from one or more of gamma-methacryloxypropyl trimethoxy silane, gamma-methacryloxypropyl methyl diethoxy silane and gamma-methacryloxypropyl methyl dimethoxy silane;
the surfactant is sodium dodecyl benzene sulfonate;
the weight ratio of the adhesion promoter to the surfactant is (3-4:): 1.
in some embodiments, the aluminized transfer paper satisfies at least one of the following characteristics:
the weight ratio of the delamination prevention layer to the adhesive layer is (0.3-0.9): 1, a step of;
the delamination-resistant areal density was 0.4g/m 2 ～1.0g/m 2 。
In some embodiments, the aluminized transfer paper satisfies at least one of the following characteristics:
The adhesive layer contains one or two adhesives of acrylic resin and polyurethane resin;
the adhesive layer has an areal density of 1.1g/m 2 ～1.3g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the aluminized layer is 300 nm-500 nm.
In a second aspect of the present application, there is provided a method for producing the aluminized transfer paper according to the first aspect, comprising the steps of:
coating a transfer coating on a transfer substrate to form the transfer coating;
vacuum aluminizing is carried out on the transfer coating to form the aluminized layer;
coating an anti-dealumination solution on the aluminized layer to form the anti-delamination layer; wherein the anti-dealumination solution contains the adhesion promoter, the surfactant and a solvent;
coating adhesive mucus on the delamination prevention layer, and drying at the temperature of 90-100 ℃ to form the adhesive layer;
compounding a base paper onto the adhesive layer to form a multi-layer composite;
and (3) after curing the multilayer composite, peeling the transfer substrate to prepare the aluminized transfer paper.
In some embodiments, the methods of preparation meet one or more of the following characteristics:
the weight percentage of the adhesion promoter in the anti-dealumination solution is 60-80 wt%;
The weight percentage of the surfactant in the anti-dealumination solution is 15-25 wt%;
the weight percentage of the solvent in the anti-dealumination solution is 2.5-10wt%; the solvent is an alcohol-water mixed solvent; optionally, the solvent is a mixed solvent of ethanol and water, and further optionally, the volume ratio of the ethanol in the mixed solvent of ethanol and water is 50% -80%.
In some embodiments, the step of applying an anti-dealumination solution on the aluminized layer satisfies one or more of the following characteristics:
the coating density of the anti-dealumination solution on the aluminized layer is 0.5g/m 2 ～1g/m 2 Calculated by dry weight;
the coating speed is 70 m/min-120 m/min;
the viscosity of the coating layer is 15 s-25 s;
air-drying for 20-40 s after coating.
In some embodiments, the preparation method is carried out at a curing temperature of 40-70 ℃ for a curing time of 12-36 hours.
According to a third aspect of the application, the aluminum-plated transfer paper in the first aspect or the aluminum-plated transfer paper prepared by the preparation method in the second aspect is provided to be used as cigarette packaging paper and packaging aluminum-plated paper.
By introducing delamination prevention between the aluminized layer and the adhesive layer of the aluminized transfer paper, the problem of aluminum powder falling from the aluminized transfer paper can be improved. The delamination-resistant layer contains an adhesion promoter and a surfactant. Wherein, the adhesion promoter can be a silane compound with a specific structure, which contains alkoxy silicon group, carbon-carbon double bond and carbon chain spacing group between the two; on the one hand, the alkoxy silicon group can be hydrolyzed and converted into organic silanol, so that covalent bonds and/or hydrogen bonds are formed with the aluminized layer, and the bonding is firm; on the other hand, the carbon-carbon double bond can react with the carbon-carbon double bond in the adhesive layer to form covalent bond connection, in addition, the carbon chain spacer in the silane compound has a certain length and can form physical entanglement with the resin in the adhesive layer, so that a reinforced polymer network (such as interpenetrating polymer network structure) can be formed by utilizing the dual functions of physical entanglement and covalent crosslinking; therefore, the bonding strength between the aluminized layer and the adhesive layer can be greatly enhanced. Furthermore, the surfactant introduced in the delamination prevention is also helpful to solve the problem of weak bonding caused by gaps between the aluminized layer and the adhesive layer due to uneven transfer film layer or uneven tension during the lamination of the raw paper layer.
The application also provides a preparation method of the aluminized transfer paper, which is simple in preparation process and high in reliability.
The application provides an aluminized transfer paper can be used to flexible package to be applied to cigarette packing as the example, at this moment, combine firmly between aluminized layer and the former ply in the aluminized transfer paper, the aluminum layer is difficult for droing, and further, the aluminum layer is even more dense, does not have the condition of falling aluminium, and whole packing effect is also more pleasing to the eye.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application and to more fully understand the present application and its advantageous effects, the following brief description will be given with reference to the accompanying drawings, which are required to be used in the description of the embodiments. It is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained from these drawings without inventive effort to a person skilled in the art. It should be further noted that the drawings are drawn in a simplified form and serve only to facilitate a convenient and clear illustration of the invention. The various dimensions of each of the components shown in the figures are arbitrarily, may be exact or may not be drawn to scale. For example, the dimensions of the elements are exaggerated in some places in the drawings for clarity of illustration. Unless otherwise indicated, the various elements in the drawings are not drawn to scale. The present invention is not limited to each size of each component.
Wherein like reference numerals refer to like parts throughout the following description.
FIG. 1 is a schematic diagram of an aluminized transfer paper according to an embodiment of the present invention.
Reference numerals illustrate: 100-raw paper layer, 120-adhesive layer, 140-delamination preventing, 160-aluminized layer and 180-transfer coating.
Detailed Description
In order that the invention may be understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the invention are shown in the figures. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
In the present invention, the terms "plurality", "plural", and the like are referred to, and the terms "a plurality", and the like are not particularly limited, and are 2 or more in number. For example, "one or more" means one kind or two or more kinds.
In the present invention, "preferred", "better", "preferred" are merely embodiments or examples which are better described, and it should be understood that they do not limit the scope of the present invention. If there are multiple "preferences" in a solution, if there is no particular description and there is no conflict or constraint, then each "preference" is independent of the others.
In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, a numerical range (i.e., a numerical range) is referred to, and, unless otherwise indicated, a distribution of optional values within the numerical range is considered to be continuous and includes two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range, and each numerical value between the two numerical endpoints. When a numerical range merely points to integers within the numerical range, unless expressly stated otherwise, both endpoints of the numerical range are inclusive of the integer between the two endpoints, and each integer between the two endpoints is equivalent to the integer directly recited. When multiple numerical ranges are provided to describe a feature or characteristic, the numerical ranges may be combined. In other words, unless otherwise indicated, the numerical ranges disclosed herein are to be understood as including any and all subranges subsumed therein. The "numerical value" in the numerical interval may be any quantitative value, such as a number, a percentage, a proportion, or the like. "numerical intervals" allows for the broad inclusion of numerical interval types such as percentage intervals, proportion intervals, ratio intervals, and the like.
In the present invention, the temperature parameter is allowed to be constant temperature processing, and also allowed to vary within a certain temperature range, unless otherwise specified. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
In the present invention, referring to a unit of a data range, if a unit is only carried behind a right end point, the units indicating the left and right end points are the same. For example, 3 to 5h means that the units of the left end point "3" and the right end point "5" are both h (hours).
The term "alkoxy" refers to a group having the structure-O-alkyl, i.e., the alkyl group is attached to an adjacent group via an oxygen atom. Phrases containing this term, e.g., "C 1 ～C 6 Alkoxy "or" C 1-6 Alkoxy "means that the alkyl moiety contains from 1 to 6 carbon atoms and, at each occurrence, can be independently of one another C 1 Alkoxy, C 4 Alkoxy, C 5 Alkoxy or C 6 An alkoxy group. Examples of suitable alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, t-butoxy, and the like.
The term "alkyl" refers to a monovalent residue formed by the loss of one hydrogen atom from a saturated hydrocarbon. Phrases containing this term, e.g. "C1-C6 alkyl" or "C 1-6 Alkyl "refers to alkyl groups containing from 1 to 6 carbon atoms, and each occurrence may be, independently of the other, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, or C6 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH) 3 ) Ethyl (Et, -CH) 2 CH 3 ) 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH 3 ) 2-propyl (i-Pr, i-propyl, -CH (CH) 3 ) 2 ) 1-butyl (n-Bu, n-butyl, -CH) 2 CH 2 CH 2 CH 3 ) 2-methyl-1-propyl (i-Bu, i-butyl, -CH) 2 CH(CH 3 ) 2 ) 2-butyl (s-Bu, s-butyl, -CH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH) 3 ) 3 ) 1-pentyl (n-pentyl, -CH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH 3) CH2CH2CH 3), 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) 1-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-hexyl (-CH (CH) 3 )CH 2 CH 2 CH 2 CH 3 ) 3-hexyl (-CH (CH) 2 CH 3 )(CH 2 CH 2 CH 3 ))。
The term "alkylene" refers to a hydrocarbon group derived by removing one more hydrogen atom on an alkyl basis to form a center having two monovalent radicals, which may be a saturated branched alkyl group or a saturated straight chain alkyl group. For example, "C 3 ～C 10 Alkylene "or" C 3-10 Alkylene "means that the alkyl moiety contains from 3 to 10 carbon atoms and, at each occurrence, can be independently of one another C 3 Alkylene, C 4 Alkylene, C 5 Alkylene group、C 6 Alkylene, C 7 Alkylene, C 8 Alkylene, C 9 Alkylene or C 10 An alkylene group. Suitable examples include, but are not limited to: 1, 1-propyl (-CH (CH) 2 CH 3 ) (-), 1, 2-propyl (-CH) 2 CH(CH 3 ) (-), 1, 3-propyl (-CH) 2 CH 2 CH 2 (-) and 1, 4-butyl (-CH) 2 CH 2 CH 2 CH 2 -)。
The aluminized transfer paper, also called aluminized paper, mainly consists of base paper, a coating and an aluminum layer, is a novel environment-friendly packaging material and is mainly used for packaging cigarette packets.
The traditional aluminum plating transfer paper for producing cigarette packets uses a transfer method, which is a method of using films such as PET or BOPP as a transfer substrate, and transferring an aluminum molecular layer with metallic luster to the surface of paper or paperboard through processes such as coating, aluminum plating, compounding, stripping and the like. However, in the use process of the aluminized transfer paper produced by the method, the phenomenon of falling off of the aluminized layer can be caused due to factors such as mechanical friction force and the like. The inventors of the present application have studied a lot of times, presumably for the following reasons: because the molecular structure difference between the aluminized layer and the adhesive layer is large, the combination of the aluminized layer and the adhesive is not tight; meanwhile, in production, the adhesion process surface often has poor flatness of the transfer film layer or gaps due to the problem of mechanical precision, so that the physical and chemical bonding force effect of the adhesive layer and the aluminized layer is further influenced, and finally the phenomenon of serious powder falling of aluminized transfer paper is caused.
In a first aspect of the present application, there is provided an aluminum-plated transfer paper comprising an anti-delamination layer,
comprises a transfer coating, an aluminized layer, an anti-delamination layer, an adhesive layer and a raw paper layer which are sequentially laminated; the delamination prevention comprises an adhesion promoter and a surfactant;
wherein the adhesion promoter is a silane compound, and the silane compound is composed of unsaturated carbonyl and bridging group X, C which are sequentially connected 3-10 An alkylene group (which may be denoted as L) and a silicon group; wherein the unsaturated carbonyl group is an acryloyl group or a methyl groupA radical-acryl group, the bridging group being-O-or-NH-, the silicon radical comprising at least two C' s 1-6 An alkoxy group.
The delamination prevention containing the adhesion promoter and the surfactant can effectively improve the aluminum powder removal condition of the aluminized transfer paper. Specifically, the silane compound serving as the adhesion promoter is added to hydrolyze to generate organic silanol, silanol groups at one end of the silane compound can form strong covalent bonds and hydrogen bonds with the aluminum plating layer, and meanwhile, long-chain hydrocarbon groups containing double bonds at the other end of the silane compound can be physically entangled with resin in the adhesive layer, and carbon-carbon double bond end groups of the silane compound on the long-chain hydrocarbon groups can also react with double bonds in the adhesive layer, so that an interpenetrating polymer network structure with the common reinforcement of long-chain physical entanglement and double bond reaction is formed, and the interaction force between the aluminum plating layer and the adhesive layer is greatly enhanced. The addition of the surfactant is also beneficial to solving the problem of unstable combination caused by the fact that gaps exist between the aluminum plating layer and the adhesive layer due to uneven transfer film layer or tightness at the same time when paper is compounded in production, and greatly increasing the adhesive strength between the adhesive layer and the aluminum plating layer. The problem of aluminum powder falling from the aluminized transfer paper can be effectively solved by arranging an anti-delamination layer comprising an adhesion promoter and a surfactant between the aluminized layer and the adhesive layer.
The anti-delamination layer is arranged between the aluminized layer and the adhesive layer, so that the anti-delamination layer can possibly play a role in improving the wear resistance, and the packaging effect is further improved.
When the silane compound contains alkylene and heteroalkyl, the silane compound can carry out addition and crosslinking reaction with double bond and ester group in the adhesive layer. The polymer network interpenetrating structure is formed by the alkyl group of the silane compound and the adhesive to cooperate, so that the interaction between the delamination prevention layer and the adhesive layer is enhanced.
In some embodiments, the C in the structure of the silane-based compound 3-10 Alkylene is C 3-6 An alkylene group. In some embodiments, the C in the structure of the silane-based compound 3-10 The alkylene group may be propylene, butylene, pentylene, hexylene. In some embodiments, theIn the structure of the silane compound, the C 3-10 The alkylene group may be- (CH) 2 ) q -wherein q is an integer selected from 3 to 10, further may be an integer selected from 3 to 6; non-limiting examples of q may include 3, 4, 5, 6.
In some embodiments, the silane-based compound has a structure wherein the silicon group is trimethoxysilicon group, triethoxysilyl group, methyldiethoxysilyl group, or methyldimethoxysilicon group.
In some embodiments, the silicon group is trimethoxysilicon group, triethoxysilyl group, methyldiethoxysilyl group, or methyldimethoxysilicon group.
In some embodiments, the C in the structure of the silane-based compound 3-10 Alkylene is C 3-6 Alkylene, wherein the silicon group is trimethoxy silicon group, triethoxy silicon group, methyl diethoxy silicon group or methyl dimethoxy silicon group.
In some embodiments, the surfactant is an anionic surfactant.
The number of main chain carbon atoms of L in the structure of the silane compound needs to be controlled in a proper range, otherwise, the silane compound and the adhesive layer are unfavorable to form a polymer network. If the number of main chain carbon atoms of L in the structure of the silane compound is too small, the alkyl length of the silane compound is short, which may cause difficulty in forming a tightly-combined polymer network with the adhesive layer; if the number of main chain carbon atoms of L in the structure of the silane compound is too large, the alkyl chain length of the silane compound is too long, and the polarity is too large, the alkyl end of the silane compound can be combined with the aqueous substance in the aluminized layer or the adhesive layer, so that an interpenetrating network structure is formed with the adhesive layer.
In the present invention, "number of main chain carbon atoms" means the minimum number of carbon atoms required to link two monovalent radical sites, for example, methylene corresponds to 1, para-phenylene corresponds to 4, ortho-phenylene corresponds to 2, -CH (Ph) -corresponds to 1.
In some embodiments, the silane-based compound is selected from one or more of gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl methyl diethoxysilane, gamma-methacryloxypropyl methyl dimethoxysilane in the anti-delamination aluminized transfer paper.
In some embodiments, the surfactant is sodium dodecyl benzene sulfonate in the anti-delamination aluminum coated transfer paper.
The weight ratio of the adhesion promoter and the surfactant needs to be controlled in a proper range, otherwise the anti-dealumination performance may be deteriorated. If the weight ratio of the adhesion promoter to the surfactant is too small, the delamination may be prevented, and the aluminum-plated layer and the adhesive layer may be difficult to form tight bonding; if the number of main chain carbon atoms of L in the structure of the silane compound is too large, the alkyl chain length of the silane compound is too long, and the polarity is too large, so that the delamination prevention layer, the aluminum plating layer and the adhesive layer are difficult to form tight combination.
In some embodiments, the weight ratio of the adhesion promoter and the surfactant in the anti-delamination-containing aluminum-plated transfer paper is (3-4:): 1, further may be (3 to 3.75): 1, further may be (3.5 to 3.75): 1, can also be selected from the following one weight ratio or two kinds of intervals: 3:1, 3.25:1, 3.5:1, 3.75:1, 4:1, etc.
The weight ratio of the delamination prevention layer relative to the adhesive layer is controlled in a proper range, which is beneficial to obtaining better adhesion between the aluminized layer and the adhesive layer. When the weight is relatively small, delamination prevention may be unfavorable to exert a good effect, and the falling-off of aluminum powder cannot be prevented; when the weight ratio is large, excessive delamination-preventing specific gravity may affect the adhesion of the adhesive layer, and also cause easy detachment of aluminum powder in the aluminum-plated layer.
In some embodiments, the weight ratio of the delamination-preventing layer to the adhesive layer in the aluminized transfer paper containing delamination-preventing layer is (0.3 to 0.9): 1, further may be (0.33 to 0.83): 1, further may be (0.35 to 0.8): 1, can also be selected from the following one weight ratio or two kinds of intervals: 0.3:1, 0.31:1, 0.32:1, 0.33:1, 0.34:1, 0.35:1, 0.36:1, 0.37:1, 0.38:1, 0.39:1, 0.4:1, 0.41:1, 0.42:1, 0.43:1, 0.44:1, 0.45:1, 0.46:1, 0.47:1, 0.48:1, 0.49:1, 0.5:1, 0.51:1, 0.52:1, 0.53:1, 0.54:1, 0.55:1, 0.56:1, 0.57:1, 0.58:1, 0.59:1, 0.6:1, 0.46:1 0.61:1, 0.62:1, 0.63:1, 0.64:1, 0.65:1, 0.66:1, 0.67:1, 0.68:1, 0.69:1, 0.7:1, 0.71:1, 0.72:1, 0.73:1, 0.74:1, 0.75:1, 0.76:1, 0.77:1, 0.78:1, 0.79:1, 0.8:1, 0.81:1, 0.82:1, 0.83:1, 0.84:1, 0.85:1, 0.86:1, 0.87:1, 0.88:1, 0.89:1, 0.9:1, etc.
In some embodiments, in the aluminized transfer paper, the weight ratio of the adhesion promoter and the surfactant is (3-4:): 1, wherein the weight ratio of the delamination prevention layer to the adhesive layer is (0.3-0.9): 1.
the control of the delamination-preventing areal density in a proper range helps to obtain aluminized transfer papers with better anti-dealumination effects. When the surface density of the delamination prevention layer is smaller, the surface density of the silane adhesion promoter and the surfactant in the delamination prevention layer is possibly smaller, long-chain physical entanglement and double bond reaction chemical bonding between the silane containing specific groups and the adhesive layer are possibly caused, covalent bonds and hydrogen bonds formed by the organosilicon alcohol and the aluminum plating layer are weaker, the bonding between the adhesive layer and the aluminum plating layer is still weaker, and the anti-dealumination effect is poor; when the surface density of the delamination prevention layer is high, the surface density of the surfactant in the delamination prevention layer may be high, and the aluminized layer and the adhesive layer are easy to slip, so that the bonding between the aluminized layer and the adhesive layer is loose.
In some embodiments, the aluminum-plated transfer paper has an areal density of 0.4g/m 2 ～1.0g/m 2 Further, the concentration may be 0.45g/m 2 ～0.95g/m 2 Further, the concentration may be 0.5g/m 2 ～0.9g/m 2 The following interval of one or two of the following surface densities may also be selected: 0.4g/m 2 、0.5g/m 2 、0.6g/m 2 、0.7g/m 2 、0.8g/m 2 、0.9g/m 2 、1.0g/m 2 Etc.
In some embodiments, the weight ratio of the adhesion promoter and the surfactant in the anti-delamination-containing aluminum-plated transfer paper is (3-4:): 1,the weight ratio of the delamination prevention layer to the adhesive layer is (0.3-0.9): 1, the delamination-resistant areal density is 0.4g/m 2 ～1.0g/m 2 。
In some embodiments, the adhesive layer of the aluminum-plated transfer paper containing the delamination-preventing layer contains one or two adhesives of acrylic resin and polyurethane resin.
In some embodiments, in the aluminum-plated transfer paper containing the delamination-preventing layer, the adhesive layer further contains rosin resin, so that the holding viscosity of the acrylic resin-based adhesive can be further improved.
In some embodiments, the adhesive layer has an areal density of 1.1g/m in the delamination-resistant aluminized transfer paper 2 ～1.3g/m 2 Further, it may be 1.15g/m 2 ～1.25g/m 2 Further, it may be 1.15g/m 2 ～1.2g/m 2 The following interval of one or two of the following surface densities may also be selected: 1.1g/m 2 、1.15g/m 2 、1.2g/m 2 、1.25g/m 2 、1.3g/m 2 Etc.
In some embodiments, the aluminum-plated transfer paper has an areal density of 0.4g/m 2 ～1.0g/m 2 The adhesive layer has an areal density of 1.1g/m 2 ～1.3g/m 2 。
In some embodiments, in the aluminized transfer paper, the thickness of the aluminized layer is 300 to 500nm, further may be 350 to 450nm, further may be 375 to 425nm, and may be selected from the following one thickness or two ranges: 300nm, 325nm, 350nm, 375nm, 400nm, 425nm, 450nm, 475nm, 500nm, etc.
In some embodiments, the aluminized transfer paper has an areal density of the adhesive layer of 1.1g/m 2 ～1.3g/m 2 The thickness of the aluminized layer is 300-500 nm.
In a second aspect of the present application, a method for producing an aluminized transfer paper is provided, which can produce an aluminized transfer paper.
The preparation method of the second aspect of the application can be used for preparing the aluminized transfer paper of the first aspect
In some embodiments, a method of making an aluminized transfer paper is provided that includes the steps of:
s100: forming the transfer coating on a transfer substrate;
s200: forming the aluminized layer on the transfer coating;
s300: forming the delamination prevention layer on the aluminized layer; wherein the anti-dealumination solution contains the adhesion promoter, the surfactant and a solvent;
S400: forming the adhesive layer on the delamination-preventing layer;
s500: compounding a base paper onto the adhesive layer to form a multi-layer composite;
s600: and (3) after curing the multilayer composite, peeling the transfer substrate to prepare the aluminized transfer paper.
In some embodiments, a method of making an aluminized transfer paper is provided that includes the steps of:
s100: forming the transfer coating on a transfer substrate;
s200: forming the aluminized layer on the transfer coating;
s300: coating an anti-dealumination solution on the aluminized layer to form the anti-delamination layer; wherein the anti-dealumination solution contains the adhesion promoter, the surfactant and a solvent;
s400: coating adhesive on the delamination preventing layer, and drying at a proper temperature to form the adhesive layer;
s500: compounding a base paper onto the adhesive layer to form a multi-layer composite;
s600: and (3) after curing the multilayer composite, peeling the transfer substrate to prepare the aluminized transfer paper.
In some embodiments, a method of making an aluminized transfer paper is provided that includes the steps of:
s100: coating a transfer coating on a transfer substrate to form the transfer coating;
S200: vacuum aluminizing is carried out on the transfer coating to form the aluminized layer;
s300: coating an anti-dealumination solution on the aluminized layer to form the anti-delamination layer; wherein the anti-dealumination solution contains the adhesion promoter, the surfactant and a solvent;
s400: coating adhesive mucus on the delamination prevention layer, and drying at the temperature of 90-100 ℃ to form the adhesive layer;
s500: compounding a base paper onto the adhesive layer to form a multi-layer composite;
s600: and (3) after curing the multilayer composite, peeling the transfer substrate to prepare the aluminized transfer paper.
In some embodiments, a method of making an aluminized transfer paper is provided that includes the steps of:
s100: and (3) coating a polyurethane aqueous transfer coating on the PET base film to form a transfer coating.
S200: and carrying out vacuum aluminizing on the transfer coating to form an aluminized layer.
S300: coating an anti-aluminum solution on an aluminum plating layer at a proper coating density and a proper coating speed through a gravure printing machine, wherein the anti-aluminum solution has proper viscosity, and the formed anti-delamination layer has proper surface density;
s400: coating adhesive liquid on the delamination preventing layer with proper coating density to form the adhesive layer, and drying at proper drying temperature to obtain the adhesive layer, wherein the formed adhesive layer has proper surface density;
S500: compounding base paper onto the adhesive layer, and drying at a proper temperature to form a multi-layer compound;
s600: curing for a proper time at a proper painting and calligraphy temperature, and stripping the release film to obtain the aluminum-removing-preventing aluminum-plating transfer paper.
By adding the silane compound with specific end groups, one end of the silane compound is hydrolyzed to generate organic silanol to form covalent bonds and hydrogen bonds with the aluminized layer, and the hydrocarbon group at the other end and the resin in the adhesive layer form an interpenetrating polymer network structure, so that the interaction force between the aluminized layer and the adhesive layer is enhanced, and the chemical adhesive force of the aluminized layer is obviously enhanced. Increasing the adhesive strength of the two. The problem of aluminum powder falling from the aluminized transfer paper can be effectively solved by arranging an anti-delamination layer comprising an adhesion promoter and a surfactant between the aluminized layer and the adhesive layer.
Coating an anti-dealumination solution containing a silane compound and an adhesion promoter between the aluminized layer and the adhesive layer, so that anti-delamination is formed between the aluminized layer and the adhesive layer, the combination between the aluminized layer and the adhesive is improved, and the problem of aluminum powder falling off of aluminized transfer paper is solved.
An adhesion promoter content higher than the proper range may result in better anti-delamination affinity and poorer hydrophilicity, the hydration between the aluminized layer and the anti-delamination layer is reduced, and slippage between the aluminized layer and the adhesive layer is easy to occur when the transfer substrate is peeled off; the content of the adhesion promoter is lower than a proper range, so that the adhesion between the aluminum plating layer and the adhesive layer is loose, and aluminum powder in the aluminum layer is easy to fall off.
In some embodiments, in the preparation method, the weight percentage of the adhesion promoter in the anti-dealumination solution is 60wt% to 80wt%, further may be 65wt% to 80wt%, further may be 75wt% to 80wt%, and may be selected from the following ranges: 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, etc.
The pH of the surfactant needs to be controlled in a suitable range, otherwise the contact with the aluminized layer is not tight. The pH value of the surfactant is lower than a proper range, so that covalent bond and hydrogen bond between the organosilicon alcohol and the aluminum plating layer can be influenced, and the aluminum layer can be subjected to pitting corrosion, so that the aluminum plating layer is loose in structure and easy to remain in the process of transferring the substrate to subsequent glass; the pH of the surfactant is higher than a proper range, so that covalent bond and hydrogen bond between the organosilicon alcohol and the aluminized layer are possibly weakened, and an oxide film of the aluminized layer is possibly slowly dissolved for environment to generate slow self-corrosion, so that the friction of the aluminized layer receiving external force is easy to fall off and white.
In some embodiments, in the preparation method, the pH of the surfactant in the anti-dealumination solution is 6 to 8, further may be 6.5 to 7.5, and may be selected from one or two of the following pH ranges: 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, etc.
In some embodiments, in the preparation method, the weight percentage of the surfactant in the anti-dealumination solution is 15wt% to 25wt%, further may be 17.5wt% to 22.5wt%, further may be 20wt% to 22.5wt%, and may be selected from the following one weight percentage or two ranges: 15wt%, 17.5wt%, 20wt%, 22.5wt%, 25wt%, etc.
In some embodiments, in the preparation method, the pH of the surfactant in the anti-dealumination solution is 6-8, and the weight percentage of the surfactant in the anti-dealumination solution is 15-25 wt%.
In some embodiments, in the preparation method, the weight percentage of the solvent in the anti-dealumination solution is 2.5wt% to 10wt%, further may be 2.5wt% to 7.5wt%, further may be 5wt% to 7.5wt%, and may be selected from the following one weight percentage or two ranges: 2.5wt%, 5wt%, 7.5wt%, 10wt% and the like.
In some embodiments, the solvent is an alcohol-water mixed solvent in the preparation method.
In some embodiments, the solvent is a mixed solvent of ethanol and water.
In some embodiments, in the preparation method, the volume ratio of the ethanol in the alcohol-water mixed solvent is 50% -80%, further may be 60% -70%, further may be 60% -65%, and may be selected from the following one weight percentage or two ranges: 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.
In some embodiments, in the preparation method, the weight percentage of the adhesion promoter in the anti-dealumination solution is 60wt% to 80wt%, the weight percentage of the surfactant in the anti-dealumination solution is 15wt% to 25wt%, and the weight percentage of the solvent in the anti-dealumination solution is 2.5wt% to 10wt%.
The coating density of the anti-dealumination solution should be controlled in a proper range. If the coating density is higher than the proper range, the bonding effect of the adhesive layer may be affected, so that the aluminized layer is easy to fall off from the adhesive layer; if the coating density is lower than the proper range, the delamination preventing effect may be weak, the combination of the aluminized layer and the adhesive is not tight enough, and the aluminized layer is still easy to fall off.
In some embodiments, in the step of applying the anti-dealumination solution on the aluminized layer, the anti-dealumination solution is applied on a dry weight basis to the aluminized layer at a coating density of 0.5g/m 2 ～1g/m 2 Further, the concentration may be 0.8g/m 2 ～0.9g/m 2 Further, the concentration may be 0.7g/m 2 ～0.9g/m 2 The coating density may also be selected from the following interval of one coating density or two types: 0.5g/m 2 、0.6g/m 2 、0.7g/m 2 、0.8g/m 2 、0.9g/m 2 、1.0g/m 2 Etc.
In some embodiments, in the step of coating the aluminum-release preventing solution on the aluminum-plated layer, the coating speed is 700m/min to 120m/min, further may be 800m/min to 110m/min, further may be 900m/min to 100m/min, and may be selected from the following coating speeds or intervals consisting of two types: 700m/min, 800m/min, 900m/min, 1000m/min, 1100m/min, 1200m/min, etc.
In the present application, the viscosity of the anti-dealumination solution is measured by using an ink 2# coating cup (also called an ink paint viscosity cup, GB/T1723-93), specifically, the anti-dealumination solution is filled in the whole measuring cup, the measuring cup is quickly lifted, and the time for completely emptying the anti-dealumination solution is observed, so that the unit is "seconds(s)". The specific operation steps are that the inner wall of the viscosity cup body and the discharge spout are wiped clean, and the horizontal screw of the bracket is adjusted to enable the viscosity cup to be in a horizontal state. A200 mL measuring cup is placed under the leakage mouth of the viscosity cup, and the stopwatch is reset to zero. The leakage mouth hole of the viscosity cup is blocked by a stop block, the ink which is uniformly stirred and is regulated to (25+/-0.2) DEG C is poured into the cup body of the viscosimeter, and bubbles and redundant samples are scraped into the grooves by a glass rod. The stop block is loosened, the stopwatch is started at the same time, and when the ink flow wire is interrupted and the first drop appears, the timing is stopped. The time indicated by the stopwatch at this time is the ink viscosity.
In some embodiments, in the step of coating the aluminum-plated layer with the anti-dealumination solution, the viscosity of the anti-dealumination solution measured by the method is 15 to 25s, may be 16 to 24s, may be 17 to 22s, and may be selected from one or two of the following viscosity ranges: 15s, 16s, 17s, 18s, 19s, 20s, 21s, 22s, 23s, 24s, 25s, etc.
In some embodiments, in the step of applying the adhesive cement on the delamination prevention layer, the adhesive cement has an application density of 1.1g/m on a dry weight basis 2 ～1.3g/m 2 Further, it may be 1.15g/m 2 ～1.25g/m 2 Further, it may be 1.15g/m 2 ～1.2g/m 2 The coating density may also be selected from the following interval of one coating density or two types: 1.1g/m 2 、1.15/m 2 、1.2g/m 2 、1.25g/m 2 、1.3g/m 2 Etc.
In some embodiments, in the step of coating the aluminum-plated layer with the anti-dealumination solution, the aluminum-plated layer is air-dried for 20s to 40s after coating, further may be 25s to 35s, further may be 30s to 35s, and may be selected from one or two of the following air-drying time intervals: 20s, 25s, 30s, 35s, 40s, etc.
In some embodiments, in the step of coating the aluminum-release preventing solution on the aluminum-plated layer, the coating apparatus is a gravure printing machine.
The drying temperature after the adhesive is coated on the anti-delamination layer needs to be controlled in a proper range, which is favorable for obtaining aluminized transfer paper with better anti-dealumination effect. If the drying temperature of the adhesive mucus coated on the delamination prevention layer is lower, the reaction degree of the adhesive mucus and the adhesion promoter in the delamination prevention layer is lower, the chain segment movement level of long chains in the silane compound is low, a compact polymer network is difficult to form with the adhesive, the reactivity of functional groups such as double bonds and functional groups such as double bonds in the adhesive is low, and the dealumination prevention effect is weaker; if the drying temperature of the adhesive applied on the delamination preventing layer is high, it may be difficult to form a polymer network with a tight interlacing due to the shortened long chain segment in the silane compound, and the functional groups such as double bonds may excessively react and crosslink with the functional groups such as double bonds in the adhesive, so that the chemical bonding level of part of the interlayer area is low, the adhesion between the aluminized layer and the adhesive layer is not obvious, and the anti-dealumination effect is also weak.
The adhesive may be an aqueous adhesive such as acrylic.
In some embodiments, in the preparation method, after the anti-delamination layer is coated with the adhesive, the drying temperature is 90 ℃ to 100 ℃, further may be 92 ℃ to 98 ℃, further may be 93 ℃ to 97 ℃, and may be selected from one or two of the following temperatures: 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃ and the like.
In some embodiments, the curing temperature for curing the multi-layer composite is 40 to 70 ℃, more preferably 45 to 65 ℃, still more preferably 45 to 60 ℃, and further preferably one or two of the following curing temperatures: 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ and the like.
In some embodiments, in the preparation method, the curing time of curing the multi-layer composite is 12 h-36 h, further may be 14 h-34 h, further may be 16 h-32 h, and may be selected from one curing temperature or two ranges: 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, etc.
According to a third aspect of the application, the aluminum-plated transfer paper in the first aspect or the aluminum-plated transfer paper prepared by the preparation method in the second aspect is provided to be used as cigarette packaging paper and packaging aluminum-plated paper.
The silane compound containing specific groups and the surfactant are introduced into the aluminized transfer paper, so that the problem that the aluminized transfer paper drops aluminum powder is effectively solved, and when the prepared aluminized paper is used as cigarette packaging paper and packaging aluminized paper, the aluminized paper has good anti-dealumination performance, and the problems that aluminum powder drops off and white is not easy to appear on the aluminized layer on the surface.
In order that the invention may be more readily understood and put into practical effect, the following more particular examples and comparative examples are provided as reference.
Unless otherwise specified, the raw materials used in each of the following experiments are commercially available.
Polyurethane water-based transfer paint, GCS205, guangzhou Hui Valley chemical Co.
The following materials and performance test methods are used, for example, without particular limitation:
preparing an anti-dealumination solution (I):
according to the weight percentage (adhesion promoter: surfactant: solvent=15:4:1), firstly adding gamma-methacryloxypropyl trimethoxy silane (adhesion promoter) into a mixed solvent of ethanol and water (weight ratio of ethanol to water is 60:40), and finally slowly adding sodium dodecyl benzene sulfonate (surfactant) for mixing to prepare the anti-dealumination solution.
Preparing an anti-dealumination solution (II):
according to the weight percentage (adhesion promoter: surfactant: solvent=10:9:1), firstly adding gamma-methacryloxypropyl trimethoxy silane (adhesion promoter) into a mixed solvent of ethanol and water (weight ratio of ethanol to water is 60:40), and finally slowly adding sodium dodecyl benzene sulfonate (surfactant) for mixing to prepare the anti-dealumination solution.
Preparing an anti-dealumination solution (III):
according to the weight percentage (adhesion promoter: surfactant: solvent=1:18:1), firstly adding gamma-methacryloxypropyl trimethoxy silane (adhesion promoter) into a mixed solvent of ethanol and water (weight ratio of ethanol to water is 60:40), and finally slowly adding sodium dodecyl benzene sulfonate (surfactant) for mixing to prepare the anti-dealumination solution.
Preparing an anti-dealumination solution (IV):
according to the weight percentage (adhesion promoter: surfactant: solvent=12:2:1), firstly adding gamma-methacryloxypropyl trimethoxy silane (adhesion promoter) into a mixed solvent of ethanol and water (weight ratio of ethanol to water is 60:40), and finally slowly adding sodium dodecyl benzene sulfonate (surfactant) for mixing to prepare the anti-dealumination solution.
Glue mucus:
the acrylic resin with the component 6008 model is water-based resin.
Evaluation criteria test of anti-dealumination performance:
the method for evaluating the aluminum release resistance of the aluminized transfer paper comprises the following specific operations:
firstly, longitudinally cutting a paper strip with the length of 25.5mm along the aluminized transfer paper.
And secondly, wrapping the cut aluminized transfer paper on a cigarette imitation filter rod by adopting a cigarette tipping paper imitation cigarette rolling method.
And thirdly, placing the wrapped aluminized transfer paper filter rod into normal-temperature clean water to be soaked for 10 seconds.
And thirdly, starting a test after 10 seconds, lightly rubbing the aluminized transfer paper filter stick dipped with water outwards along the filter stick by a finger, recording whether the finger is provided with the aluminum powder which is detached and embedded or not once rubbing, stopping rubbing by hands until the aluminized transfer paper is exposed due to the powder detachment of the aluminum layer, recording the hand rubbing times, and counting.
Fourth, friction is carried out from one end to the other end of the filter rod by using a force of 6 N+/-1N, whether the aluminum powder falls off from the friction surface is recorded once every friction, and the number of times of friction that the aluminum powder falls off from the friction surface is recorded and observed to be M 1 The method comprises the steps of carrying out a first treatment on the surface of the The friction is needed urgently, whether the transfer paper on the filter stick exposes the white ground color or not is observed once every friction, and the number of times of observing that the transfer paper on the filter stick exposes the white ground color is recorded as M 2 。
Judgment standard: and tightly wrapping the prepared aluminized transfer paper on a cigarette imitation filter stick, soaking the aluminized transfer paper in water for 10 seconds, and after 25 times of friction, judging that the aluminized transfer paper is qualified in anti-dealumination performance if the aluminized transfer paper does not fall off and is not exposed after 25 times of friction.
The delamination preventing compositions in examples 1 to 3 and comparative examples 1 to 12 below are shown in Table 1; the corresponding delamination resistance, adhesive layer parameters, and anti-dealumination performance index of the aluminized transfer paper are shown in table 2.
TABLE 1
Example 1
S100: coating polyurethane aqueous transfer paint on PET base film with thickness of 12 μm, wherein the coating density is 1.2g/m 2 The viscosity was 16s, forming a transfer coating.
S200: vacuum aluminizing is carried out on the transfer coating to form an aluminized layer with the thickness of 380 nm.
S300: coating an aluminum release preventing solution (I) on the aluminum plating layer by a gravure printing machine, wherein the coating density is 0.5g/m 2 The coating speed (dry weight) was 90m/min, the viscosity of the anti-dealumination solution was controlled to 18s, the anti-delamination layer was formed, and the surface density of the anti-delamination layer was 0.5g/m 2 ；
S400: applying an adhesive composition 6008 to the delamination-resistant layer to form the adhesive layer, the application density being 0.5g/m 2 Drying (based on dry weight) to obtain adhesive layer with a drying temperature of 95deg.C and an areal density of 0.5g/m 2 ；
S500: compounding base paper on the adhesive layer, and drying at 80 ℃;
s600: curing for 24 hours at 50 ℃, and stripping the release film to obtain the anti-dealumination aluminized transfer paper.
The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder does not fall off after being soaked in water for 10 seconds and rubbed for 25 times, and the aluminized transfer paper is not exposed after being rubbed for 25 times.
Example 2
Example 2 use of ANDThe procedure of example 1 is essentially the same, except that: in the S300 step, the coating density of the anti-dealumination solution was 0.7g/m 2 The delamination-preventing surface density was 0.7g/m 2 。
The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder does not fall off after being soaked in water for 10 seconds and rubbed for 25 times, and the aluminized transfer paper is not exposed after being rubbed for 25 times.
Example 3
Example 3 uses substantially the same method as example 1, except that: in the S300 step, the coating density of the anti-dealumination solution was 0.9g/m 2 The delamination-preventing surface density was 0.9g/m 2 . The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder does not fall off after being soaked in water for 10 seconds and rubbed for 25 times, and the aluminized transfer paper is not exposed after being rubbed for 25 times.
Comparative example 1
Comparative example 1 the same procedure as in example 1 was used, except that: in the S300 step, the coating density of the anti-dealumination solution was 0.1g/m 2 The delamination-preventing surface density was 0.1g/m 2 . The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after being soaked in water for 10 seconds and rubbed for 5 times, and white exposure can be observed after being rubbed for 7 times.
Comparative example 2
Comparative example 2 was conducted in substantially the same manner as in example 1 except that: in the S300 step, the coating density of the anti-dealumination solution was 0.3g/m 2 The delamination-preventing surface density was 0.3g/m 2 . The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after 6 times of friction after being soaked in water for 10 seconds, and white exposure can be observed after 9 times of friction.
Comparative example 3
Comparative example 3 was conducted in substantially the same manner as in example 1 except that: in the S300 step, the coating density of the anti-dealumination solution was 1.2g/m 2 The delamination-preventing surface density was 1.2g/m 2 . Is prepared intoThe aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after being soaked in water for 10 seconds and rubbed for 9 times, and white exposure can be observed after 20 times of rubbing.
Comparative example 4
Comparative example 4 the same procedure as in example 2 was used, except that: in step S300, an anti-dealumination solution (ii) is coated on the aluminized layer, and an adhesion promoter in the formed anti-delamination layer: surfactant=10:9. The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after 18 times of friction after being soaked in water for 10 seconds, and white exposure can be observed after 21 times of friction.
Comparative example 5
Comparative example 5 the same procedure as in example 2 was used, except that: in step S300, an anti-dealumination solution (iii) is coated on the aluminized layer, and an adhesion promoter in the formed anti-delamination layer: surfactant=1:18. The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after 3 times of friction after being soaked in water for 10 seconds, and white exposure can be observed after 5 times of friction.
Comparative example 6
Comparative example 6 was conducted in substantially the same manner as in example 2 except that: in the step S300, coating an anti-dealumination solution (IV) on the aluminized layer to form an adhesion promoter in the anti-delamination layer: surfactant=12:2. The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after 19 times of friction after being soaked in water for 10 seconds, and white exposure can be observed after 22 times of friction.
Comparative example 7
Comparative example 7 was conducted in substantially the same manner as in example 2 except that: in step S400, the drying temperature after the application of the adhesive composition 6008 on the delamination prevention layer is 65 ℃. The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after 19 times of friction after being soaked in water for 10 seconds, and white exposure can be observed after 21 times of friction.
Comparative example 8
Comparative example 8 was conducted in substantially the same manner as in example 2 except that: in step S400, the baking temperature after the adhesive composition 6008 is applied on the delamination is 75 ℃. The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after 22 times of friction after being soaked in water for 10 seconds, and white exposure can be observed after 25 times of friction.
Comparative example 9
Comparative example 9 was conducted in substantially the same manner as in example 2 except that: in step S400, the baking temperature after the adhesive composition 6008 is applied on the delamination prevention layer is 85 ℃. The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after 22 times of friction after being soaked in water for 10 seconds, and white exposure can be observed after 25 times of friction.
Comparative example 10
Comparative example 10 was conducted in substantially the same manner as in example 2 except that: in step S400, the baking temperature after the adhesive composition 6008 is coated on the delamination is 110 ℃. The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after 23 times of friction after being soaked in water for 10 seconds, and white exposure can be observed after 24 times of friction.
Comparative example 11
Comparative example 11 was conducted in substantially the same manner as in example 2 except that: in step S400, the baking temperature after the adhesive composition 6008 is coated on the delamination prevention layer is 120 ℃. The prepared aluminized transfer paper is tightly wrapped on a cigarette imitation filter stick, aluminum powder begins to fall off after 22 times of friction after being soaked in water for 10 seconds, and white exposure can be observed after 21 times of friction.
Comparative example 12
Comparative example 12 was conducted in substantially the same manner as in example 1 except that: the step S300 is omitted.
In comparative example 12, no delamination was provided, and the produced aluminum-plated transfer paper was wrapped around a simulated cigarette filter rod, and after immersing in water for 10 seconds, aluminum powder began to fall off after 3 times of rubbing, and white exposure was observed after 5 times of rubbing.
Comparative example 13
Comparative example 13 is substantially the same as comparative example 1 except that: in step S400, an adhesive composition 6008 type acrylic resin was blended with γ -methacryloxypropyl trimethoxysilane in the same amount as the corresponding dry weight in example 2, and the blended composition was coated to form an adhesive layer.
In comparative example 13, no delamination was set, and the blended composition of γ -methacryloxypropyl trimethoxysilane and glue 6008 was coated to give an aluminized transfer paper wrapped around a simulated cigarette filter stick, which was immersed in water for 10 seconds, rubbed 4 times, and the aluminum powder began to drop off, and white exposure was observed after 5 rubs.
Furthermore, through experimental studies, the inventors have also found that when the adhesion promoter in the delamination-preventing layer is omitted, the bond between the aluminum-plated layer and the adhesive layer is loose, and the aluminum powder in the aluminum layer is easily detached. When the surfactant in the delamination prevention was omitted, the inventors found that the aluminum-plated transfer paper was less likely to wrinkle or blister than the combination during the rolling of the aluminum-plated transfer paper without the delamination prevention. The adhesion promoter in the delamination prevention layer is replaced by triethoxy octyl silane from gamma-methacryloxypropyl trimethoxy silane, the combination of the aluminum plating layer and the adhesive layer is also weaker, and aluminum powder is easy to fall off after the aluminum plating layer is immersed in water. The adhesion promoter in the delamination prevention layer is replaced by vinyl trimethyl silane from gamma-methacryloxypropyl trimethoxy silane, the combination of the aluminized layer and the adhesive layer is loose, and aluminum powder is easy to fall off after the aluminized layer is immersed in water.
The composition of the delamination inhibitors in examples 1 to 3 and comparative examples 1 to 13 is summarized in Table 1.
The test results of the aluminum release resistance of the prepared aluminum-plated transfer paper are shown in table 2.
TABLE 2 anti-delamination, adhesive layer parameters, and anti-dealumination performance index for aluminized transfer papers
Wherein, the liquid crystal display device comprises a liquid crystal display device,m as described above in connection with the method for evaluating the anti-aluminum properties of aluminum-plated transfer paper 1 The number of times of friction, M, of the aluminum powder falling off on the friction surface is observed 2 The number of rubs in which the transfer paper on the filter rod was observed to reveal the white ground color is shown.
The comparative example 1 was inferior in the anti-aluminum effect, presumably because the surface density of the anti-delamination was small, resulting in the low surface density of the gamma-methacryloxypropyl trimethoxysilane and the surfactant in the anti-delamination, which had weak long-chain physical entanglement and double bond reaction chemical bonding action with the acrylic resin between the adhesive layers, so that the bonding between the adhesive layer and the aluminum plating layer was still weak, and the aluminum powder was easily peeled off under the action of a certain friction force after the aluminum plating layer was immersed in water.
The reason why the anti-dealumination effect of comparative example 2 was poor is presumably similar to comparative example 1, probably because the surface density of the anti-delamination was also small, resulting in the surface density of the gamma-methacryloxypropyl trimethoxysilane and the surfactant in the anti-delamination being small, the physical entanglement of long chains between the acrylic resin and the adhesive layer, the double bond reaction chemical bonding action were weak, and thus the bonding between the adhesive layer and the aluminum plating layer was still weak, and the aluminum powder was easily exfoliated under the action of a certain friction force after the aluminum plating layer was immersed in water.
Comparative example 3 is inferior in the anti-dealumination effect, probably due to the fact that the surface density of the anti-delamination is high, and when the surface density of the anti-delamination is high, the surface density of the surfactant in the anti-delamination is high; although the gamma-methacryloxypropyl trimethoxy silane has higher surface density, the chemical bonding with components such as acrylic ester in the adhesive layer and the physical entanglement effect of a long chain are stronger, the aluminum plating layer and the adhesive layer are easy to slide, the combination between the aluminum plating layer and the adhesive layer is loose, and aluminum powder is still easy to fall off under the action of external force.
The comparative example 4 is inferior in the anti-dealumination effect, presumably because the ratio of the adhesion promoter to the surfactant in the anti-delamination is small, and when the surface density of the anti-delamination is the same as that of example 2, the surface density of the adhesion promoter in the anti-delamination in comparative example 4 is significantly smaller than that of example 2, and the effect of the long chain physical entanglement and double bond reaction bonding formed by the gamma-methacryloxypropyl trimethoxysilane and the modified acrylic resin in the adhesive and the effect of the hydrolysis to form the organosilicon alcohol are weaker than that of example 2, so that the bonding between the adhesive layer and the aluminized layer is still weak, and the aluminum powder is peeled off after the aluminized layer is immersed for approximately 20 times of friction.
The reason why the anti-dealumination effect of comparative example 5 was poor is presumed to be similar to comparative example 4, and it is possible that the specific weight of the adhesion promoter in the anti-delamination layer was small, and the effect of improving the bonding between the aluminum plating layer and the adhesive layer by gamma-methacryloxypropyl trimethoxysilane was quite weak, and the aluminum powder easily dropped off under the action of a certain friction force after the aluminum plating layer was immersed in water.
The reason for the poor anti-dealumination effect of comparative example 6 may be that the specific gravity of the surfactant in the anti-delamination layer is small, and when the paper is compounded, the aluminum layer and the adhesive layer cannot be better attached due to uneven transfer film layer or uneven tension, so that the adhesive strength between the adhesive layer and the aluminum-plated layer is reduced, and the aluminum powder is easy to fall off under the action of a certain friction force after the aluminum-plated layer is immersed in water.
Comparative example 7 is inferior in anti-dealumination effect, presumably because the drying temperature of the adhesive is too low, the reaction degree of the adhesive and the adhesion promoter in the anti-delamination is low, the long chain segment movement level of gamma-methacryloxypropyl trimethoxy silane is low, a compact polymer network is difficult to form with the adhesive, the reactivity of silane double bond and modified acrylic ester is low, the adhesion between an aluminized layer and an adhesive layer is weak, and aluminum powder is easy to fall off under the action of a certain friction force after the aluminized layer is immersed in water.
The reason why the anti-dealumination effect of comparative example 8 was poor is presumed to be similar to comparative example 7 in that the drying temperature of the tacky adhesive was low and the degree of reaction of the tacky adhesive with the adhesion promoter in the anti-delamination was low. The gamma-methacryloxypropyl trimethoxy silane and the adhesive are difficult to form a tight polymer network, the chemical bonding effect is weak, the bonding effect between the aluminized layer and the adhesive layer is weak, and the aluminized layer is easy to fall off aluminum powder under the action of a certain friction force after being immersed in water.
Comparative example 9 is a poor anti-dealumination effect because it is presumed that similar to comparative example 7, the drying temperature of the adhesive is low, and the reaction degree of the adhesive with the adhesion promoter in the anti-delamination agent is still lower than that in example 2. If the polymer network formed by the gamma-methacryloxypropyl trimethoxy silane and the adhesive is dried at 95 ℃, the chemical bonding action is also weaker, so that the adhesion between the aluminized layer and the adhesive layer is weaker, and the phenomenon of aluminum powder falling off occurs after 22 times of friction after the aluminized layer is immersed in water.
The comparative example 10 was inferior in the anti-dealumination effect, presumably because the drying temperature of the adhesive slurry was high, and the long chain segment in the gamma-methacryloxypropyl trimethoxysilane was shortened, and it was also difficult to form a polymer network which was compact in interlacing, and the double bond of silane was excessively reacted and crosslinked with the double bond of modified acrylate, resulting in a lower degree of chemical bonding in a part of the region, and the adhesion between the aluminum plating layer and the adhesive layer was weakened as a whole, so that the anti-dealumination effect was weaker than in example 2.
The reason why the anti-dealumination effect of comparative example 11 was poor is presumed to be similar to comparative example 10 in that the drying temperature of the tacky adhesive was higher, and the degree of reaction of the tacky adhesive with the adhesion promoter in the anti-delamination layer was still lower than that of example 2. The polymer network which is tightly staggered is difficult to form, double bonds of silane and double bonds of modified acrylic ester are excessively reacted and crosslinked, the chemical bonding degree of partial areas is low, the bonding effect between the aluminum plating layer and the adhesive layer is weakened as a whole, and the anti-dealumination effect is further weakened.
Comparative example 12 was inferior in the anti-aluminum effect, presumably because the adhesion between the aluminum plating layer and the adhesive layer was not tight when the anti-delamination layer was not provided, resulting in easy removal of aluminum powder under the action of a certain friction force after the aluminum plating layer was immersed in water.
The reason why the anti-aluminum effect of comparative example 13 was poor is presumably that, after blending of the silane compound γ -methacryloxypropyl trimethoxysilane with the glue 6008, the hydrolysis of the silane compound therein formed an organosilicon alcohol which improved the bonding effect with the aluminum plating layer, and at the same time, the silane compound formed a polymer network with the acrylic resin in the glue 6008, thereby improving the bonding between the aluminum plating layer and the adhesive layer to some extent. However, since the silane compound was not completely diffused to the surfaces of the glue layer and the aluminum plating layer after mixing with the glue solution 6008, contact with the aluminum plating layer was reduced, and the degree of hydrolysis of the silane compound was related to the water content, pH, and the like of the solution, the silane compound was not applied as a dealumination preventing aqueous solution in comparative example 13, and the silane compound failed to exert its original effect; in addition, the lack of surfactant, in addition to adversely affecting the hydrolysis process of the silane compound, does not improve the paper compounding problem in production, and eventually results in poor bonding of the aluminized layer and the adhesive layer of comparative example 2. That is, the lack of delamination prevention results in significant degradation of the anti-dealumination properties after blending the silane compound with the glue 6008 compared to the coated delamination prevention aluminized transfer paper.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted in accordance with the contents of the claims.
Claims (10)
1. An aluminum-plated transfer paper containing delamination prevention, which is characterized by comprising a transfer coating, an aluminum-plated layer, delamination prevention, an adhesive layer and a raw paper layer which are sequentially laminated; the delamination prevention comprises an adhesion promoter and a surfactant;
wherein the adhesion promoter is a silane compound, and the silane compound is composed of unsaturated carbonyl and bridging group X, C which are sequentially connected 3-10 Alkylene groupA base and a silicon base; wherein the unsaturated carbonyl group is an acryloyl group or a methacryloyl group, the bridging group is-O-or-NH-, and the silicon group contains at least two C' s 1-6 An alkoxy group.
2. The aluminized transfer paper according to claim 1, characterized in that at least one of the following features is satisfied:
the C is 3-10 Alkylene is C 3-6 An alkylene group;
the silicon base is trimethoxysilicon base, triethoxy silicon base, methyldiethoxy silicon base or methyldimethoxy silicon base;
the surfactant is an anionic surfactant.
3. The aluminized transfer paper according to claim 2, characterized in that at least one of the following features is satisfied:
the silane compound is selected from one or more of gamma-methacryloxypropyl trimethoxy silane, gamma-methacryloxypropyl methyl diethoxy silane and gamma-methacryloxypropyl methyl dimethoxy silane;
the surfactant is sodium dodecyl benzene sulfonate;
the weight ratio of the adhesion promoter to the surfactant is (3-4:): 1.
4. an aluminized transfer paper according to any one of claims 1 to 3, characterized in that at least one of the following characteristics is satisfied:
The weight ratio of the delamination prevention layer to the adhesive layer is (0.3-0.9): 1, a step of;
the delamination-resistant areal density was 0.4g/m 2 ～1.0g/m 2 。
5. The aluminized transfer paper according to claim 1 or 2, characterized in that at least one of the following features is satisfied:
the adhesive layer contains one or two adhesives of acrylic resin and polyurethane resin;
the adhesive layer has an areal density of 1.1g/m 2 ～1.3g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the aluminized layer is 300 nm-500 nm.
6. The method for producing an aluminum-plated transfer paper according to any one of claims 1 to 5, comprising the steps of:
coating a transfer coating on a transfer substrate to form the transfer coating;
vacuum aluminizing is carried out on the transfer coating to form the aluminized layer;
coating an anti-dealumination solution on the aluminized layer to form the anti-delamination layer; wherein the anti-dealumination solution contains the adhesion promoter, the surfactant and a solvent;
coating adhesive mucus on the delamination prevention layer, and drying at the temperature of 90-100 ℃ to form the adhesive layer;
compounding a base paper onto the adhesive layer to form a multi-layer composite;
and (3) after curing the multilayer composite, peeling the transfer substrate to prepare the aluminized transfer paper.
7. The method of manufacturing according to claim 6, wherein one or more of the following characteristics are satisfied:
the weight percentage of the adhesion promoter in the anti-dealumination solution is 60-80 wt%;
the weight percentage of the surfactant in the anti-dealumination solution is 15-25 wt%;
the weight percentage of the solvent in the anti-dealumination solution is 2.5-10wt%; the solvent is an alcohol-water mixed solvent; optionally, the solvent is a mixed solvent of ethanol and water, and further optionally, the volume ratio of the ethanol in the mixed solvent of ethanol and water is 50% -80%.
8. The method of claim 6, wherein the step of applying an anti-dealumination solution on the aluminized layer satisfies one or more of the following characteristics:
the coating density of the anti-dealumination solution on the aluminized layer is 0.5g/m 2 ～1g/m 2 Calculated by dry weight;
the coating speed is 70 m/min-120 m/min;
the viscosity of the coating layer is 15 s-25 s;
air-drying for 20-40 s after coating.
9. The process according to claim 6, wherein the curing is carried out at a temperature of 40 to 70℃for a period of 12 to 36 hours.
10. Use of the aluminized transfer paper according to any one of claims 1 to 5 or the aluminized transfer paper produced by the production method according to any one of claims 6 to 9 as a cigarette wrapping paper or a packaging aluminized paper.
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| CN113403883A (en) * | 2021-05-19 | 2021-09-17 | 安徽集友新材料股份有限公司 | Anti-reverse light aluminizing transfer tipping paper, preparation method thereof and cigarette |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE684093A (en) * | 1965-07-15 | 1967-01-13 | ||
| JPH01180400A (en) * | 1988-01-12 | 1989-07-18 | Dainippon Printing Co Ltd | Transfer sheet |
| WO2000038844A1 (en) * | 1998-12-30 | 2000-07-06 | Senco Products, Inc. | Method of improving adhesion to galvanized surfaces |
| WO2003035781A1 (en) * | 2001-10-26 | 2003-05-01 | Rhodia Chimie | Liquid silicone formulation for producing release and water-repellent crosslinked elastomer coatings on a solid support, such as a paper support |
| JP2008081785A (en) * | 2006-09-27 | 2008-04-10 | Nippon Paint Co Ltd | Coated zinc based plated steel sheet treated with chromium-free water base rust preventive coating agent |
| CN113403883A (en) * | 2021-05-19 | 2021-09-17 | 安徽集友新材料股份有限公司 | Anti-reverse light aluminizing transfer tipping paper, preparation method thereof and cigarette |
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