CN206591367U - Waterproof paper - Google Patents

Abstract

Disclose a kind of waterproof paper, waterproof paper includes the paper substrate (1) containing cellulose, the transfer film layer (3) for being located at the graphene layer (2) on the paper substrate (1) at least one surface and being located on the graphene layer (2), wherein, the transfer film layer (3) is the coating supported by thermoplastic resin film, coating includes olefin copolymer, polyamide, wax and the barium sulfate of unsaturated carboxylic acid anhydrides, and the paper substrate (1) includes the nethike embrane for the filamentary structure being made up of cellulose.

Description

Waterproof paper

Technical field

The utility model belongs to cellulosic substrates, and water proofing property is assigned by graphene layer, and for duplicating, printing and writing Paper, more particularly to a kind of waterproof paper.

Background technology

Paper has fluid drainage or liquid repellency, or it is a focus in field of papermaking to improve its wet strength.Signified liquid It is water or the aqueous solution.Paper can with waterproof, i.e., resistance to moistening, most commonly prevent the ink diffusion that is applied on paper or " emergence ".This is commonly known as " starching ".Bonded between the fiber of general enhancing paper fiber so that paper can more resist the attack of water, Rather than prevent water from penetrating into paper fiber.Generally, compare easily way be coated or impregnated with suitable material surface come for Water-fast protection is provided in the paper of printing or writing.Profit allows using the various originals that can have been obtained from paper manufacturer in this way Paper, for handling of paper, so that its many own perception method for having more water repellency is related to paper sizing.Top sizing is by non-pigment Sizing agent be used as paper surface coating, and internal sizing need paper pulp formation paper forward direction paper pulp in add applying glue Agent.Except using making paper surface smooth, and postpone or prevent from being applied to liquid thereon, such as printing and writing ink are inhaled Receive.

Patent document US5139614 discloses a kind of polymer prepared by styrene and methacrylic acid, for being glued Paper, to make it have resistance to ink and liquid, aqueous permeability.

Patent document US4820582 describes this method, is used as one kind side for protecting printing paper to be permeated from water and the aqueous solution Method.Above-mentioned patent, which is also mentioned that, needs the edge of protection sheet, makes it from this infiltration.

Patent document EP018767320 is described arrests composition dipping paper with based on the PVOH related to aldehyde such as glyoxal.

Patent document US 5330622 is introduced by using comprising glyoxal, the composition of dimerization alkylketene and fluoride salt Impregnate and provide hydrophobicity, oleophobic property and thin solvent barrier for paper.

Patent document US 4110155 is also described by extrusion coated thereon or it is adhesively laminated to synthesis film For example make paper waterproof on polyolefin, polyester, polyamide and cellulose esters.

The above method is related to so that print has enough water proofing properties with writing paper so that the ink applied produces minimum Emergence phenomenon, so as to more clearly print or write.But, it is impossible to for machine printing, writing or duplicating, and lead to Holding writing complete and clear enough drainage or water proofing property can not be had under dampness by crossing the paper of above method preparation. That is, water proofing property of the prior art has its limitation, although can waterproof to a certain degree, for example, in writing in use, can With waterproof, but can also waterproof when can not be used in duplicator and laser copier.

As above-mentioned method one kind no in the prior art provide for coat it is various can be used for write or print Body paper with assigning general-purpose comprehensive waterproof.

Therefore, still needing in the art for example may be in boisterous region, and it is protected in humidity Sufficiently complete is held and interference-free surface, to continue the image for significantly carrying machine printing or writing.In the art Such paper is also needed to, it has the surface that pen or pencil writing can be used under wet or drying condition.In addition, in this area In there is still a need for also be used as copy paper or laser printer paper this property paper.Paper should also be Repulpable With it is reproducible.The utility model meets these needs and provides further associated advantages.

Disclosed above- mentioned information is used only for strengthening the understanding to the utility model background in the background section, therefore The information of prior art known to a person of ordinary skill in the art in not constituting home may be included.

Utility model content

In brief, the utility model refers to the waterproof paper for writing and printing, in addition to applies similar approach The waterproof paper products produced.

The purpose of this utility model is to be achieved by the following technical programs.

A kind of waterproof paper includes the paper substrate containing cellulose, is located at the graphene layer at least one surface of paper substrate With the transfer film layer being located on the graphene layer, wherein, the transfer film layer is the coating supported by thermoplastic resin film, is applied Layer includes olefin copolymer, polyamide, wax and the barium sulfate of unsaturated carboxylic acid anhydrides, and the paper substrate includes what is be made up of cellulose The nethike embrane of filamentary structure.

Preferably, the cellulose is native cellulose and/or synthetic cellulose, and the coating passes through in the thermoplasticity Aqueous resin dispersion is coated with and dried on resin film to be formed, in the aqueous resin dispersion, based on solid weight part, insatiable hunger With 3-5 parts of 5-10 parts of 60-70 parts of olefin copolymer, polyamide, the wax and 20-25 parts of barium sulfate of carboxylic acid anhydrides.

Preferably, the graphene layer is single or multiple lift, and graphene layer and transfer film the layer weight sum is often to put down About 3.9 grams to about 4.6 grams of rice.

Preferably, the cellulose is is 1~90nm containing single fiber number average diameter, and single fiber ratio is 70% with Pa The fiber dispersion of thermoplastic polymer above, the thermoplastic polymer is selected from polyester, polyamide, polyolefin, polyphenylene sulfide At least one in ether, phenol resin, polyacrylonitrile, polyvinyl alcohol, polysulfones, polyurethane, poly- fluorine system polymer and their derivative Kind.

Preferably, the wax is selected from paraffin, polypropylene wax mixture, polyethylene wax mixture, palm wax, microwax, illiteracy One or more in denier wax, fibre wax, beeswax.

Preferably, the olefin copolymer of unsaturated carboxylic acid anhydrides is selected from ethene-(methyl) acrylic copolymer, ethene-(first Base) acrylic copolymer alkali (alkaline earth) metal salt, ethene-(methyl) Acrylic Ester-Maleic Anhydride, (methyl) propylene Sour grafted polyethylene, maleic anhydride grafted polyethylene, maleated ethylene vinyl acetate copolyme, maleic anhydride connect Branch (methyl) ester-vinyl copolymer, maleic anhydride inoculated polypropylene, maleic anhydride grafted ethene-propylene copolymer, horse Maleic anhydride grafted ene-propylene-butene copolymer, maleic anhydride grafted ethene-butylene copolymer, maleic anhydride grafted propylene- One or more in butylene copolymer.

Preferably, the paper substrate includes the nethike embrane of the filamentary structure of synthetic fibers formation.

Preferably, the paper substrate contain in nitrogen polymer antistatic additive, the transfer film layer coating comprising styrene and The waterproof lustre adding layer of 2-ethyl hexyl acrylate.

The utility model is different from prior art, and the utility model causes the anti-of waterproof paper by graphene coated layer Water function is significantly improved, and waterproof paper of the present utility model not only can reach waterproof requirement when writing, and it is simultaneously The demand of waterproof when can also meet printing and print, that is to say, that waterproof paper of the present utility model is a kind of waterproof of general-purpose Paper.

Described above is only the general introduction of technical solutions of the utility model, in order to cause technological means of the present utility model It is more clearly understood, reaches the degree that those skilled in the art can be practiced according to the content of specification, and in order to Above and other objects, features and advantages of the present utility model can be become apparent, below with of the present utility model specific Embodiment is illustrated.

Brief description of the drawings

By reading the detailed description hereafter in preferred embodiment, the various other advantage of the utility model and Benefit will be clear understanding for those of ordinary skill in the art.Figure of description is only used for showing the mesh of preferred embodiment , and be not considered as to limitation of the present utility model.It should be evident that drawings discussed below is only of the present utility model Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this A little accompanying drawings obtain other accompanying drawings.And in whole accompanying drawing, identical part is presented with like reference characters.

In the accompanying drawings：

Fig. 1 is the structural representation of the waterproof paper according to the utility model one embodiment.

Below in conjunction with drawings and examples, the utility model is further explained.

Embodiment

Specific embodiment of the utility model is more fully described below with reference to accompanying drawings.Although showing this reality in accompanying drawing With new specific embodiment, it being understood, however, that may be realized in various forms the utility model without that should be illustrated here Embodiment limited.It is opposite to be able to be best understood from the utility model there is provided these embodiments, and can be by Scope of the present utility model completely convey to those skilled in the art.

It should be noted that having used some vocabulary to censure specific components among specification and claim.Ability Field technique personnel it would be appreciated that, technical staff may call same component with different nouns.This specification and right It is required that not in the way of the difference of noun is used as differentiation component, but differentiation is used as with the difference of component functionally Criterion."comprising" or " comprising " as mentioned in working as in specification in the whole text and claim are an open language, therefore should be solved It is interpreted into " include but be not limited to ".Specification subsequent descriptions are implementation better embodiment of the present utility model, the right description It is for the purpose of the rule of specification, to be not limited to scope of the present utility model.Protection domain of the present utility model It is defined when depending on the appended claims person of defining.

For ease of the understanding to the utility model embodiment, below in conjunction with accompanying drawing done by taking several specific embodiments as an example into The explanation of one step, and each accompanying drawing does not constitute the restriction to the utility model embodiment.

The utility model refers to the waterproof paper and its manufacture method for writing and printing, in addition to applies similar side The waterproof paper products that method is produced.In the various embodiments that the utility model is related to, so-called waterproof paper is to use in fact Cellulose paper such as printing paper, writing paper, copy paper and laser stamping paper are bottom, and then at least one side dipping durability waterproof is applied Layer is fabricated by.Vocabulary " waterproof " used herein above is although refer to that above-mentioned waterproof paper is such as big exposed to wet environment for a long time Measure caused by rainfall, still possess completely waterproof performance, its practicality does not go to pot.Either in printing or drafting, waterproof paper Upper pattern is clear and legible；No matter paper dry and wet whether, with pencil and pen writing and can be used on waterproof paper Printing, duplicating and printing.In addition, waterproof paper more specifically performance also includes：Do not ruptured after immersion, its surface is kept without breakage As former state.Waterproof paper water resistance is mainly reflected in its water resistance and wet strength two indices.Water resistance refers to that paper resists water logging The performance of profit, i.e., do not allow hydrone to be penetrated into by capillarity inside paper.Wet strength refers to that paper is submerged in water, internal fine Adhesion occurs between dimension, produces anti-pull intensity, prevents hydrone from penetrating further into inside.

Fig. 1 is the structural representation of the waterproof paper of one embodiment of the present utility model, and the utility model embodiment will knot Fig. 1 is closed to be specifically described.

As shown in figure 1, a kind of waterproof paper includes the paper substrate 1 containing cellulose, described at least one table of paper substrate 1 is located at The graphene layer 2 in face and the transfer film layer 3 being located on the graphene layer 2, wherein, the transfer film layer 3 is by thermoplastic resin The coating that adipose membrane is supported, coating includes olefin copolymer, polyamide, wax and the barium sulfate of unsaturated carboxylic acid anhydrides.

Graphene layer is both most thin material, is also most tough material, and its fracture strength is more taller than best steel 200 times, it has good elasticity again, and stretch range can reach the 20% of own dimensions, and with fabulous electric conductivity, it is special It is not the water resistance for significantly improving cellulose paper basic unit 1.The graphene coated layer 2 of cellulose paper basic unit 1 and transfer film layer 3 are given birth to The paper that output is come both has significant water-proof function, can also allow and not fallen off with after the upper content of traditional printing method printing, such as Lithography, silk-screen printing, letterpress, aniline printing and photograph rotate intaglio, and waterproof paper is adapted to duplicating Used on machine and laser printer, can equally reach significant water proofing property.

In one embodiment, the Main Ingredients and Appearance of the paper substrate 1 of cellulose is cellulose fibre, such as cellulose paper is with regard to one Plant typical cellulose paper base.The manufacture composition of cellulose paper can be derived from multiple fiber, such as wood-fibred, cotton fiber and other Cellulose fibre, in addition to recycled fibers cellulose fiber.

In preferred embodiment of the present utility model, the cellulose is single to be 1~90nm containing single fiber number average diameter Ratio of fibers and Pa for more than 70% thermoplastic polymer fiber dispersion, the thermoplastic polymer be selected from polyester, Polyamide, polyolefin, polyphenylene sulfide, phenol resin, polyacrylonitrile, polyvinyl alcohol, polysulfones, polyurethane, poly- fluorine system polymer and it At least one of derivative.It is used as the thermoplastic polymer for constituting the utility model fiber dispersion., can as polyester To include PET (PET), polytrimethylene-terephthalate (PTT), polybutylene terephthalate Ester (PBT), PLA (PLA) etc..In addition, as polyamide, nylon 6 (N6), nylon66 fiber (N66), nylon 11 can be included (N11) etc..In addition, as polyolefin, polyethylene (PE), polypropylene (PP), polystyrene (PS) etc. can be included.Except upper Beyond the thermoplastic polymer stated, naturally it is also possible to using phenol resin or polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polysulfones, Fluorine system polymer or their derivative.

In these polymer, from the viewpoint of heat resistance, preferably fusing point is more than 165 DEG C of polymer.More preferably There is dystectic polymer in birdsing of the same feather flock together compound as the polycondensation of representative using polyester or polyamide, for example, PP is 165 DEG C, PLA is 170 DEG C, N6 be 220 DEG C, PET be 255 DEG C.In addition, in these polymer, particulate, fire retardant, antistatic additive can also be contained Deng compounding ingredient.In addition, in the scope for the property for not damaging polymer, can also the other compositions of combined polymerization.And then, from easy Carry out from the viewpoint of melt spinning, preferably fusing point is less than 300 DEG C of polymer.

Especially, because the polyamide using N6, N66 as representative has excellent water imbibition, water-retaining property, so by abundant Coordinate the nanofiber of polyamide using these characteristics, in conjugate solutions of the present utility model, emulsion and gelling material, Cosmetic use etc. can be suitable for.

In addition, PPS shows excellent heat resistance, chemical resistance and then with agent of low hygroscopicity, so during as synthetic paper Dimensional stability be also excellent, therefore the use of insulating paper, the electronics basal disc that can be preferred in electronic information field etc. On the way.

The fiber dispersion used in the utility model is the equal single fiber diameter of index (single fiber number average diameter) 1 Nanofiber in the range of~90nm, its form is that single fiber is in dispersity.In addition, as long as fibrous form is Can, it is not limited to its length, cross sectional shape.In addition, in the utility model, the average value and deviation of the single fiber diameter of fiber It is important.In conjugate solutions, emulsion, gelling material and synthesis paper substrate, in order to be uniformly dispersed nanofiber, be particularly In conjugate solutions, emulsion, gelling material, in order to improve nanofiber not with long-term as time passage and aggregation, sedimentation Stability, and then preferably 1~70nm.Especially, when in the filter using synthesis paper substrate of the present utility model, as requiring Characteristic, it is desirable to which high-performance high efficiency is trapped, when in for barrier film etc., as requiring characteristic, it is desirable to which the shielding of liquid is high, because This wishes that the single fiber diameter of fiber is smaller, in this case, and single fiber number average diameter is preferably 1-60nm.The fibre of utility model Conjugate solutions, emulsion, gelling material are tieed up, is made up of fiber dispersion with solvent or gel.Conjugate solutions of the present utility model, Emulsion, gelling material refer to the liquid for coordinating nanofiber or nanofiber and other medicaments in solvent or gel State thing or solid content.Described conjugate solutions, refers to fiber dispersion with than relatively low concentration in a solvent in the utility model The scattered, solution that ratio of viscosities is relatively low, mobility is high.In addition, by fiber dispersion with relatively higher concentration in solvent or gel Present in, ratio of viscosities is higher, mobility is low Material Definitions be gelling material.In addition, by conjugate solutions form emulsion, Fiber dispersion is dispersed in Material Definitions in emulsion as emulsion using the concentration compared.Here, solvent or gel be not only The gradation composition beyond the nanofiber in conjugate solutions or emulsion, gelling material is dissolved, is also sent out as the decentralized medium of fiber The effect of waving.In addition, as solvent, can be with appropriately combined use water and/or oil and/or organic solvent (including emulsion).As oil, Have linseed oil, corn oil, olive oil, sunflower oil, rapeseed oil, sesame oil, soybean oil, cupu oil, coconut oil, palm oil, Natural oil or paraffin, vaseline, ceresin, atoleine, saualane, wax, higher fatty acids, silicone oil, the crosslinking silicon of haze tallow etc. Oil etc., these oil can be used alone, can also two or more combination use.In addition, as organic solvent, there is alcohols, ester The lower aliphatic acids of class, glycols, glycerols, ketone, ethers, amine, lactic acid butyric acid etc., pyridine, tetrahydrofuran, chaff Alcohol, acetonitrile class, methyl lactate, ethyl lactate etc., these solvents can be used alone, and can also combine two or more and use.

In preferred embodiment of the present utility model, the cellulose is native cellulose and/or synthetic cellulose.

In preferred embodiment of the present utility model, the coating on the thermoplastic resin film by being coated with and drying Aqueous resin dispersion is formed, in the aqueous resin dispersion, based on solid weight part, the olefin-copolymerization of unsaturated carboxylic acid anhydrides 20-25 parts of 60-70 parts of thing, 5-10 parts of polyamide, 3-5 parts of wax and barium sulfate.In transfer film layer 3 of the present utility model, 60-70 parts The olefin copolymer of unsaturated carboxylic acid anhydrides significantly increases the adhewsive action with hot melt printing ink.5-10 parts of polyamide are added in coating Afterwards, wet strength is substantially increased, so as to improve the fire resistance characteristic of paper.The content of wax is just right in coating, it is necessary to reach Steam is allowed to form the globule, the standard that paper surface still can duplicate or write in coating surface.If wax content is excessive, paper surface is just very Hardly possible is duplicated and write, but if wax is inadequate, steam would not form the globule on paper surface, and there will be no expected waterproof for product Characteristic.3-5 parts of waxes are in addition to it can provide water resistance and allow steam to form the globule on paper coating surface, moreover it is possible to provide bonding resistance Power and surface scratch resistance performance.20-25 parts of barium sulfate provides significant block resistance function, can both avoid waterproof paper from existing Paper surface is inter-adhesive during stacking or when volume is wrapped.Increase paper surface roughness and make with good impressionability with can book The property write.

In preferred embodiment of the present utility model, the graphene layer 2 is single or multiple lift, the He of graphene layer 2 It is per about 3.9 grams to about 4.6 grams of square meter to transfer the weight sum of film layer 3.It is described in the utility model used on duplicator it is anti- Water paper be related to the operation of machine with water content.Such as, if water content is too high, machine will paperboard, just irregular working.If Water content is too low, and paper is excessively crisp, and machine coil paper can be caused after upper machine.So, in another embodiment, as long as duplicating The waterproof paper used on machine and laser printer, its water content is by weight from 4% to 7%.In other related implementation In example, for producing the thickness of cellulose base ply of paper 1 of waterproof duplicator from 0.003 inch to 0,013 inch, this is to duplicate Machine and laser printer can be with the paper sheet thickness scopes of normal work.But in another related embodiment, cellulose base paper 1 thickness of layer is from 0.004 inch to 0.006 inch, and this thickness range is very suitable for manufacture construction and significantly drawn Paper.Finally, in another related embodiment, the utility model further mentions waterproof paper and can applied in large size copier or laser On printer, printing can reach the requirement for significantly printing and replicating with replicating heavy construction construction drawing paper, antiquarian.On Face refers in embodiment that waterproof paper used also has not yellowing, biodegradable, Repulpable, recyclable the spy such as utilizes Property.

In preferred embodiment of the present utility model, the wax is selected from paraffin, polypropylene wax mixture, Tissuemat E mixing One or more in thing, palm wax, microwax, montanin wax, fibre wax, beeswax.

In preferred embodiment of the present utility model, the olefin copolymer of unsaturated carboxylic acid anhydrides is selected from ethene-(methyl) third Alkali (alkaline earth) metal salt, ethene-(methyl) acrylate-maleic of olefin(e) acid copolymer, ethene-(methyl) acrylic copolymer Anhydride copolymer, (methyl) acrylic acid-grafted polyethylene, maleic anhydride grafted polyethylene, maleic anhydride grafted ethene-vinyl acetate Ester copolymer, maleic anhydride grafting (methyl) ester-vinyl copolymer, maleic anhydride inoculated polypropylene, maleic anhydride connect Branch ethylene-propylene copolymer, maleic anhydride grafted ethene-propene-1-butene copolymer, maleic anhydride grafted ethene-butene One or more in thing, maleic anhydride grafted propylene-butylene copolymer.

In preferred embodiment of the present utility model, the paper substrate 1 includes the filamentary structure of synthetic fibers formation Nethike embrane.Waterproof paper of the present utility model is penetrated into inside paper by hydrone by capillarity, it is to avoid fibrous binding force disappears； Waterproof paper remains able to ensure preferable transfer performance in wet condition, i.e., normally can write and print.

In preferred embodiment of the present utility model, the paper substrate 1 contains nitrogen polymer antistatic additive, the transfer film Waterproof lustre adding layer of the coating comprising styrene and 2-ethyl hexyl acrylate on layer 3.

Waterproof paper of the present utility model cannot be only used for writing, inkjet printing, laser printing, printing and manifolding, this reality With new synthetic paper can be used for battery diaphragm or abrasive material, air cleaner or liquid filter etc. filter for industry use, Circuit basal disc of medical product, the insulating paper of blood filter etc. etc. etc..

Although embodiment of the present utility model is described above in association with accompanying drawing, the utility model does not limit to In above-mentioned specific embodiments and applications field, above-mentioned specific embodiment be only it is schematical, guiding, without It is restricted.One of ordinary skill in the art is under the enlightenment of this specification and is not departing from the utility model claim In the case of the scope protected, the form of many kinds can also be made, these belong to the row of the utility model protection.

Claims (10)

1. a kind of waterproof paper, it is characterised in that：The waterproof paper includes the paper substrate (1) containing cellulose, is located at the paper substrate The graphene layer (2) on layer (1) at least one surface and the transfer film layer (3) being located on the graphene layer (2), wherein, it is described Transfer film layer (3) is the coating supported by thermoplastic resin film, and coating includes olefin copolymer, the polyamides of unsaturated carboxylic acid anhydrides Amine, wax and barium sulfate, the paper substrate (1) include the nethike embrane for the filamentary structure being made up of cellulose.

2. waterproof paper according to claim 1, it is characterised in that：The cellulose is that native cellulose and/or synthesis are fine Dimension element.

3. waterproof paper according to claim 1, it is characterised in that：The graphene layer (2) is single or multiple lift.

4. waterproof paper according to claim 1, it is characterised in that：It containing single fiber number average diameter is 1 that the cellulose, which is, ~90nm, the fiber dispersion of thermoplastic polymer single fiber ratio and that Pa is more than 70%, the thermoplastic polymer Gather selected from polyester, polyamide, polyolefin, polyphenylene sulfide, phenol resin, polyacrylonitrile, polyvinyl alcohol, polysulfones, polyurethane, poly- fluorine system At least one of compound and their derivative.

5. waterproof paper according to claim 1, it is characterised in that：The wax is selected from paraffin, polypropylene wax mixture, poly- second One or more in alkene wax mixture, palm wax, microwax, montanin wax, fibre wax, beeswax.

6. waterproof paper according to claim 1, it is characterised in that：The olefin copolymer of unsaturated carboxylic acid anhydrides be selected from ethene- Acrylic copolymer, the alkali metal salt of ethylene-acrylic acid copolymer, ethylene-acrylate-copolymer-maleic anhydride, acrylic acid Grafted polyethylene, maleic anhydride grafted polyethylene, maleated ethylene vinyl acetate copolyme, maleic anhydride grafting Ester-vinyl copolymer, maleic anhydride inoculated polypropylene, maleic anhydride grafted ethene-propylene copolymer, maleic anhydride connect Branch ene-propylene-butene copolymer, maleic anhydride grafted ethene-butylene copolymer, maleic anhydride grafted propylene-butene One or more in thing.

7. waterproof paper according to claim 1, it is characterised in that：The paper substrate (1) includes the fibre of synthetic fibers formation Tie up the nethike embrane of shape structure.

8. waterproof paper according to claim 1, it is characterised in that：The paper substrate (1) contains nitrogen polymer antistatic additive.

9. waterproof paper according to claim 1, it is characterised in that：The graphene layer (2) and transfer film layer (3) weight it With for about 3.9 grams to about 4.6 grams of every square meter.

10. waterproof paper according to claim 1, it is characterised in that：Coating includes styrene on the transfer film layer (3) With the waterproof lustre adding layer of 2-ethyl hexyl acrylate.