CN101821094B - Base material sheet for process strippable sheet, process strippable sheet, and process for producing synthetic leather - Google Patents
Base material sheet for process strippable sheet, process strippable sheet, and process for producing synthetic leather Download PDFInfo
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- CN101821094B CN101821094B CN2008801115787A CN200880111578A CN101821094B CN 101821094 B CN101821094 B CN 101821094B CN 2008801115787 A CN2008801115787 A CN 2008801115787A CN 200880111578 A CN200880111578 A CN 200880111578A CN 101821094 B CN101821094 B CN 101821094B
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- strippable
- coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/46—Non-macromolecular organic compounds
- D21H19/48—Diolefins, e.g. butadiene; Aromatic vinyl monomers, e.g. styrene; Polymerisable unsaturated acids or derivatives thereof, e.g. acrylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Laminated Bodies (AREA)
- Paper (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
This invention provides a base material sheet which, when used in a process strippable sheet, can improve the strippability of a synthetic leather from the process strippable sheet. There is also provided a process strippable sheet which can improve the strippability of a synthetic leather. The base material sheet for a process strippable sheet comprises a cast coated paper comprising a support and a cast coating layer containing a binder and a pigment for a coating layer. The binder contains a styrene-butadiene copolymer comprising more than 40% by mass of butadiene units. The process strippable sheet comprises the base material sheet for a process strippable sheet and a strippable layer arranged on the cast coating layer on its side remote from the support in the base material sheet. The strippable layer contains a stripping agent component and a silica-containing pigment for a strippable layer.
Description
Technical field
The present invention relates to a kind of for the synthesis of the process strippable sheet in the manufacturing of leather, be used for the base material sheet for process strippable sheet of process strippable sheet and use the manufacture method of the synthetic leather of process strippable sheet.
The application advocates on October 17th, 2007 in Patent 2007-270432 number priority of Japanese publication, and its content is incorporated herein.
Background technology
The synthetic leather of polyurethane leather, polychloroethylene leather etc. is owing to compare the goods that can make in a large number certain quality with natural leather, and the restriction of shape is few, so be used in the wide spectrums such as clothes, footwear, bag, sofa.
Manufacture method as synthetic leather, for example can enumerate, the synthetic leather manufacturing coating that contains polyurethane resin, vinyl chloride resin, amide resin, amino resins etc. in the process strippable sheet coating, and make its dry solidification, then, the synthetic leather manufacturing that is coated with coating on across bonding agent fit weave cotton cloth etc. after, it is passed through between the chill roll, then the method for stripping technology stripping film.
In the manufacture method of the synthetic leather of such use process strippable sheet, because the surface state of process strippable sheet is transferred on the synthetic leather, so by changing the surface state of process strippable sheet, can obtain the different various synthetic leathers of liquor style.
As the process strippable sheet that uses in the manufacture method of above-mentioned synthetic leather, normally used is to be formed with the process strippable sheet that the peel ply of coating is used in the manufacturing of coating synthetic leather in substrate sheets.Sometimes for example use cast-coated paper as substrate sheets, be provided with in the described cast-coated paper and contain adhesive and pigment as the casting coating (with reference to patent documentation 1) of main component.
Patent documentation 1: TOHKEMY 2001-98495 communique
Summary of the invention
The problem that invention will solve
Yet, when the process strippable sheet that uses patent documentation 1 to put down in writing is made synthetic leather, sometimes be difficult to peel off from process strippable sheet the situation of synthetic leather.
The present invention In view of the foregoing carries out, and it is a kind of when being used for process strippable sheet that its purpose is to provide, and can improve synthetic leather from the substrate sheets of the fissility of process strippable sheet.Further purpose is to provide a kind of process strippable sheet that can improve the fissility of synthetic leather.
For the scheme of dealing with problems
[1] base material sheet for process strippable sheet is characterized in that, described base material sheet for process strippable sheet is made of cast-coated paper, and described cast-coated paper has supporter and contains adhesive and the coating layer casting coating with pigment,
Adhesive contains the SB more than the butadiene unit of 40 quality %.
[2] according to [1] described base material sheet for process strippable sheet, wherein, the content of the SB in the adhesive is more than the 50 quality % when establishing adhesive and totally being 100 quality %.
[3] according to [1] or [2] described base material sheet for process strippable sheet, wherein, adhesive contains casein.
[4] process strippable sheet is characterized in that, described process strippable sheet has each described base material sheet for process strippable sheet of [1]～[3] and is formed on peel ply on the casting coating and the face supporter opposition side of described substrate sheets,
Peel ply contains stripper composition and silica containing peel ply pigment.
[5] according to [4] described process strippable sheet, remover is the alkyd resins that has added the formalin adsorbent.
[6] according to [4] described process strippable sheet, peel ply is that 1～3 μ m and maximum particle diameter are below the 10 μ m with the average grain diameter of silica contained in the pigment.
[7] according to [4] or [5] described process strippable sheet, the 75 degree glossiness of measuring based on JISZ8741 with the surface base material sheet for process strippable sheet opposition side peel ply are 30～90%.
[8] a kind of manufacture method of synthetic leather is characterized in that, it has:
Each described process strippable sheet coating synthetic leather forms the operation of leather layer with cold coating in [4]～[7], peels off the operation of described process strippable sheet from the leather layer of synthetic leather.
The effect of invention
When substrate sheets of the present invention is used for process strippable sheet, can improve synthetic leather from the fissility of process strippable sheet.
According to process strippable sheet of the present invention, can improve the fissility of synthetic leather.
Description of drawings
Fig. 1 represents the profile of an embodiment of substrate sheets of the present invention.
Fig. 2 represents the profile of an embodiment of process strippable sheet of the present invention.
Description of reference numerals
1 process strippable sheet
10 substrate sheets (base material sheet for process strippable sheet)
11 supporters
12 casting coatings
13 barrier layers
20 peel plies
The specific embodiment
＜base material sheet for process strippable sheet 〉
Base material sheet for process strippable sheet of the present invention (is designated hereinafter simply as substrate sheets.) an embodiment describe.
Fig. 1 represents the substrate sheets of present embodiment.The substrate sheets 10 of present embodiment is made of cast-coated paper, and described cast-coated paper is formed across barrier layer 13 laminations by supporter 11 and casting coating 12.
(supporter)
For example can enumerate fine paper, intermediate paper, coarse paper, art paper base material, coated paper base material, cast-coated paper base material, brown paper, glassine paper etc. as stationery.As plastic sheeting, for example can enumerate the various macromolecule membranes such as the polyester such as polypropylene, polyethylene, PETG, polybutylene terephthalate (PBT), polyvinyl chloride.In addition, also can use evaporation paper, synthetic paper, cloth, nonwoven, metal forming etc.And then the layered product that adopts them etc. that also can suit.Wherein owing to can form easily the process strippable sheet of the synthetic leather that can obtain pitch-dark property excellence, so the preferably copper millboard with base material, coated paper with base material, cast-coated paper base material.Further because the reasons such as embossing fitness of process excellence of synthetic leather, so more preferably cast-coated paper base material.
The basic weight of supporter 11 is preferably 50～400g/m
2If the basic weight 50g/m of supporter 11
2More than, then can easily make the process strippable sheet that can repeatedly recycle, if 400g/m
2Below, process strippable sheet that then can the manufacturing operation excellence.
(casting coating)
Contained adhesive comprises SB in the casting coating 12, and described copolymer contains styrene units and butadiene unit as essential component.
[adhesive]
Contained SB comprises the butadiene unit more than 40 quality % in the adhesive, preferably comprises more than the 45 quality %, more preferably comprises more than the 50 quality %.When the butadiene unit of SB is below the 40 quality %, when making synthetic leather by the process strippable sheet of having used described substrate sheets 10, then be difficult to peel off synthetic leather from process strippable sheet.In addition, the outward appearance on the surface of synthetic leather produces bad easily.
In addition, because the reason of coating adaptive excellence etc., below the preferred 60 quality % of the butadiene unit of SB, more preferably below the 58 quality %, particularly preferably below the 55 quality %.
In addition, SB can also contain other monomeric unit of (methyl) acrylic ester unit, vinyl cyanide base unit etc.
Preferred 90～100 quality % of the gel fraction of SB.If the gel fraction of SB is when 90 quality % are above, when then making synthetic leather by the process strippable sheet of having used described substrate sheets 10, the fissility of synthetic leather becomes higher.In addition, more be difficult to produce the bad order on the surface of synthetic leather.
Here, gel fraction is the value of utilizing following method to obtain.
That is, at the latex of the sheet material of polytetrafluoroethylene (PTFE) coating SB, 50 ℃ of dryings 24 hours, formations thickness was the epithelium of 0.3～0.5mm (afterwards dry).Then, it is square that described epithelium is cut into 3cm, measure its quality after, be immersed in the toluene 24 hours.Then, more than 3 hours, toluene is volatilized 105 ℃ of dryings fully, measure the quality of the solid matter that obtains.And utilize formula (1) to obtain gel fraction.
Formula (1) gel fraction=(quality before the quality behind the toluene dipping/toluene dipping) * 100 (%)
The gel fraction of SB can be adjusted by the butadiene unit of Change Example such as SB, the polymerizing condition of SB (addition of polymerization temperature, polymerization pressure, crosslinking agent etc.).
Particularly, the butadiene unit of SB is more, and gel fraction is higher.
Polymerization temperature is higher, and gel fraction is higher.
Add crosslinking agent, its addition is more, and gel fraction is higher.
In addition, cast other adhesive that can also contain in the coating 12 except SB.As other adhesive, for example can enumerate the starch based such as casein, polyvinyl alcohol, enzymically modified starch, oxidation modification starch, cationic starch; The cellulose derivative such as carboxymethyl cellulose, hydroxyethylcellulose etc.Wherein, owing to can improve the Reusability adaptive of process strippable sheet, so preferred casein.
More than the 50 quality % the when content of the SB in the adhesive is preferably and establishes adhesive and totally be 100 quality %, more preferably more than the 60 quality %, particularly preferably more than the 70 quality %.If more than the content of the SB 50 quality %, when then making synthetic leather by the process strippable sheet of having used described substrate sheets 10, the appearance of synthetic leather is good.
In addition, because casting is coated with the good reason of adaptive, below the preferred 95 quality % of the content of SB, more preferably below the 90 quality %, particularly preferably below the 80 quality %.
Binder content in the casting coating 12 is with respect to coating layer preferred 5～50 mass parts of pigment 100 mass parts, more preferably 10～30 mass parts.When if binder content 5 mass parts are above, the intensity of then casting coating 12 improves, if below 50 mass parts, then can easily form the peel ply that is suitable for process strippable sheet on casting coating 12.
[coating layer pigment]
As coating layer pigment, for example can enumerate clay, kaolin, precipitated calcium carbonate, powdered whiting, titanium dioxide, satin white, barium sulfate, aluminium hydroxide, zinc oxide, plastic pigment etc.
Wherein, from the coated face sliding aspect that flattens, preferred kaolin, precipitated calcium carbonate.Further more preferably also with kaolin and precipitated calcium carbonate.
Coating layer can be in 1 particle, 2 particles any with pigment, if 2 particles then can easily form the peel ply that is suitable for process strippable sheet on casting coating 12.
Coating layer is preferably 0.01～10 μ m with the average grain diameter of pigment.If coating layer is with more than the average grain diameter 0.01 μ m of pigment, the drying property of then filming is excellent, if below the 10 μ m, the surface smoothness of then filming is excellent.
Coating layer is to be the average grain diameter of 1 particle in the situation of 1 particle at pigment with the average grain diameter of pigment, is the average grain diameter of 2 particles in the situation of 2 particles.In addition, coating layer is to use the particle diameter of 50% volume accumulated value of laser diffraction formula particles distribution instrument mensuration with the average grain diameter of pigment.
[thickness]
Preferred 5～50 μ m of thickness of casting coating 12.If more than the thickness 5 μ m of casting coating 12, then the peel ply that is suitable for process strippable sheet can be formed easily on casting coating 12, if below the 50 μ m.Then can form easily casting coating 12.
Cast 75 degree glossiness preferred 80～99% coating 12 and surperficial 12a supporter 11 opposition sides.Herein, 75 degree glossiness are based on the value that JISZ8741 measures.If the glossiness more than 80% of casting coating 12 then can easily form the peel ply that be suitable for process strippable sheet on casting coating 12, be not easy but surpass 99% glossiness making.
(barrier layer)
As the material that forms barrier layer 13, can enumerate such as carboxymethyl cellulose, casein, dextrin, starch, modified starch, polyvinyl alcohol, modified polyvinylalcohol, polyethylene glycol oxide, PVP, polyvinyl methyl ether, polyacrylic acid, polyacrylamide, acrylic resin, polyester, polyurethane etc.
Wherein, from excellent to the barrier of solvent, and set out preferred starch, modified starch, polyvinyl alcohol with the good aspect of congruence of casting coating 12.
By forming barrier layer 13, when making substrate sheets 10, can prevent that the adhesive and the coating layer that are used to form casting coating 12 from penetrating in the supporter 11 with pigment.
The thickness on barrier layer 13 is preferably 1～10 μ m.If more than the thickness on the barrier layer 13 1 μ m, then can further prevent from infiltrating, if below the 10 μ m, then can suppress cost.
(basic weight)
Preferred 50～the 500g/m of basic weight that substrate sheets 10 is overall
2Since when making synthetic leather sometimes in the high temperature drying more than 150 ℃, so require substrate sheets 10 to have heat resistance, in addition owing to reuse process strippable sheet, substrate sheets 10 demands intensity to a certain degree.If basic weight 50～500g/m that substrate sheets 10 is overall
2, then can guarantee heat resistance and intensity.
(manufacture method of substrate sheets)
As the manufacture method of the cast-coated paper that becomes substrate sheets 10, representational method can be enumerated following 3 methods.
(1) wet type casting is coated with method, and the casting coating that will be in moisture state is close on the surface of the minute surface ornamenting drum (casting is coated with drum) that has been heated, dry after the demoulding, thereby carry out the gloss ornamenting.
(2) rewetting formula casting is coated with method, after the temporary transient drying of the coating layer of moisture state, utilizes wetting solution to make its again moistening and plasticized again, then is close to the casting that has been heated and is coated with on the bulging surface, dry after the demoulding, thereby carry out the gloss ornamenting.
(3) gelation casting is coated with method, after the coating layer gelation with moisture state, is close to the casting that has been heated and is coated with on the bulging surface, dry after the demoulding, thereby carry out the gloss ornamenting.
The common ground that these castings are coated with finishing process is, all will be in coating layer moistening, the plasticized state and be close to the casting that has been heated and be coated with on the bulging surface, dry after the demoulding, thereby the transfer printing casting is coated with bulging minute surface.
In (1)～(3), from obtaining the viewpoint as the base material sheet for process strippable sheet superior quality, the manufacture method of preferred (2).Below an example of the manufacture method of (2) is described.
At first, on a face of supporter 11, the coating fluid that coating contains the composition that is used to form barrier layer 13 forms barrier layer 13.Then, on the barrier layer 13 surface coating contain adhesive and coating layer with the casting coating formation of pigment with coating fluid and dry, thereby form coating layer.Then, be coated with again wetting solution at coating layer, and be close to the casting that has been heated and be coated with on the bulging mirror-like metal covering and carry out drying, and form casting coating 12, obtain substrate sheets 10.
When coating contains the coating fluid of the composition that is used to form the barrier layer, can use roll coater, knife type coater, rod to be coated with the known coating machines such as machine, Kohler coater, intaglio plate coating machine, curtain coating machine, die lip formula coating machine, mouthful mould coating machine.
The coating weight on barrier layer 13 is in the preferred 1～20g/m of drying coated amount
2If the drying coated amount 1g/m on barrier layer 13
2More than, then can further prevent from containing adhesive and coating layer and use the coating fluid of pigment in supporter 11, to infiltrate, if 20g/m
2Below, then can make substrate sheets 10 attenuation.
The coating weight of casting coating 12 is in the preferred 5～50g/m of drying coated amount
2If the drying coated amount 5g/m of casting coating 12
2More than, then can access the cast-coated paper that more is suitable for process strippable sheet.If 50g/m
2Below, then can make substrate sheets 10 attenuation.
Behind the surface that utilizes again wetting solution rewetting profit casting coating 12, being close to casting with following temperature, to be coated with drum upper, dry, is coated with drum from casting and peels off, and is coated with ornamenting thereby cast.
As wetting solution again, be not particularly limited, for example can enumerate, contain polyethylene emulsion, fatty acid soaps, calcium stearate, ammonium stearate, microcrystalline wax, the surfactant of 0.01～3.0 quality %, the aqueous solution of Turkey red wet goods releasing agent; Contain the inorganic salts such as zinc sulfate, calcium phosphate, sodium polyphosphate, calgon, sodium formate, ammonium formate, potassium tartrate, natrium citricum, potassium citrate, dioctyl sodium sulfosuccinate of 0.01～3.0 quality % or aqueous solution of organic salt etc.
Moistening again coating layer is close to casting was coated with preferred 50～150 ℃ of the temperature of drum when upper.If the temperature when being close to more than 50 ℃, then can make the abundant and rapid draing of the coating layer of rewetting profit, if below 150 ℃, can make the surface state of casting coating 12 better.
And then, also can use supercalender to carry out press polish and process.
Substrate sheets described above 10 is owing to be comprised of cast-coated paper, so have thickness, paper power is strong.Therefore, be suitable for the process strippable sheet of synthetic leather manufacturing usefulness.
In addition, because the adhesive of casting coating 12 contains the SB more than the butadiene unit of 40 quality %, so the solvent resistance of casting coating 12 is excellent.Therefore, when casting coating 12 coating remover coating fluid, can prevent from casting the dissolving of coating 12 in order to obtain process strippable sheet.As a result, the composition of casting coating 12 is difficult to be blended into peel ply, and casting coating 12 in apparent good order and condition is so when substrate sheets 10 is used for process strippable sheet, can peel off easily synthetic leather from process strippable sheet.And then, infer owing to contain the SB of the above butadiene unit of 50 quality %, thereby have the good tendency of liquor style after peeling off.
In addition, substrate sheets of the present invention is not limited by above-mentioned embodiment.For example, substrate sheets of the present invention can not form barrier layer 13 yet between supporter 11 and casting coating 12.
＜process strippable sheet 〉
Embodiment to process strippable sheet of the present invention describes.
Fig. 2 illustrates the process strippable sheet of present embodiment.The process strippable sheet 1 of present embodiment has above-mentioned substrate sheets 10 and peel ply 20, described peel ply 20 be formed on substrate sheets 10 casting coating 12, with the face of supporter 11 opposition sides on.
(peel ply)
Peel ply 20 contains stripper composition and silica containing peel ply pigment.
Can use such as, silicone, alkyd resins, alkyd/silicone copolymer, silicone modified amido alkyd resins, silicone modified amido acrylic resin, and their mixture etc. as stripper composition.
Wherein, consider the preferred alcohols acid resin from the aspect as the homogeneity excellence of the heat resistance of the process strippable sheet of synthetic leather manufacturing usefulness, coated face.And then when carrying out the polymerization of resin, the material of preferred interpolation and formalin generation chemical reaction is as the formalin adsorbent.For for example, contain the compound of amino, amide groups, imide, imino group, diazanyl, hydrazide group, hydrazone group as adsorbent.Can remove the formalin that produces as accessory substance thus, can reduce the glossiness of the surperficial 20a of peel ply 20 simultaneously, therefore can reduce peel ply with the content of pigment, improve the coating adaptive, so be preferred mode.
Peel ply is that 1～3 μ m and maximum particle diameter are below the 10 μ m with the preferred average grain diameter of the contained silica of pigment.If more than the average grain diameter of the silica 1 μ m, then become and adjust easily desirable gloss number, if below the average grain diameter of the silica 3 μ m, then can obtain stable uniform coated face.In addition, if below the maximum particle diameter 10 μ m, then the appearance of synthetic leather becomes good.
The average grain diameter of silica is 1.5～2.5 μ m more preferably, particularly preferably 1.7～2.2 μ m.In addition, the maximum particle diameter of silica is more preferably below the 8 μ m.
About the average grain diameter of silica, be the average grain diameter of 1 particle when silica is 1 particle, be the average grain diameter of 2 particles when silica is 2 particles.In addition, the average grain diameter of silica is to use the particle diameter of the 50% volume accumulated value that the laser diffraction granularity distribution instrument measures.
Silica can be any in 1 particle, 2 particles, if 2 particles, then embossing adds the lustrous surface of adjusting easily peel ply 20 man-hour.
Peel ply in the peel ply 20 is preferably 1～20 mass parts with the content of pigment with respect to stripper composition 100 mass parts, more preferably 3～15 mass parts.If peel ply then makes gloss reach below 90% with more than pigment content 1 mass parts easily, if below 20 mass parts, then obtain easily uniform coated face.
Can contain as required pigment except silica in pigment at peel ply.Pigment except silica for example can be enumerated, kaolin, talcum, gypsum, blanc fixe, alumina white, titanium dioxide, calcium carbonate etc.
5～50 quality % the when content of the pigment except silica is preferably and establishes peel ply and totally be 100 quality % with pigment.If more than the content of the pigment except the silica 5 quality %, then can easily adjust by the pigment except silica the characteristic of peel ply 20, if below the 50 quality %, can prevent that then the pigment except silica from hindering effect of the present invention.
In peel ply 20, in the scope that does not hinder effect of the present invention, can contain the various auxiliary agents such as dyestuff, ultra-violet absorber, defoamer, levelling agent, antistatic additive.
In peel ply 20, be preferably 30～90% with the 75 degree glossiness of the surperficial 20a of substrate sheets 10 opposition sides.Herein, 75 degree glossiness are based on the value that JISZ8741 measures.
If the glossiness 30～90% of the surperficial 20a of peel ply 20 then can access the synthetic leather with feeling of high class of moderate inhibition gloss.
(using method)
The manufacture method of synthetic leather of the present invention is following method, and it has: form the operation of leather layer at above-mentioned process strippable sheet coating synthetic leather with cold coating, peel off the operation of described process strippable sheet from the leather layer of synthetic leather.
With the contained resin of cold coating, for example can enumerate polyurethane resin, vinyl chloride resin, amide resin, amino-acid resin etc. as synthetic leather herein.When the coating synthetic leather is used cold coating, can use the device identical with the device that in the coating of above-mentioned remover coating, uses.
For example can use, roll coater, knife type coater, rod are coated with the known coating machines such as machine, Kohler coater, intaglio plate coating machine, curtain coating machine, die lip formula coating machine, mouthful mould coating machine.In addition, can use printing machine, unqualified to them.
(manufacture method of synthetic leather)
In the manufacture method of synthetic leather of the present invention, form leather layer after, also can fit at leather layer weave cotton cloth, the base cloth of nonwoven etc.At this moment, also can be between leather layer and base cloth the known various bonding agents of sandwiched.
The synthetic leather that obtains by such manufacture method is because the surface of the above-mentioned process strippable sheet of its moderate reflecting feel that is transfer printing, so have the liquor style of uniform moderate reflecting feel.In addition, because the fissility of above-mentioned process strippable sheet is high, can easily peel off synthetic leather from process strippable sheet, so can easy manufacturing synthetic leather.
(manufacture method of process strippable sheet)
An example to the manufacture method of process strippable sheet 1 describes.
The manufacture method of this routine process strippable sheet 1 is as follows: at the surperficial 12a coating remover coating fluid of the casting coating 12 of above-mentioned substrate sheets 10, the dry peel ply 20 that forms as required, carries out embossing processing to peel ply 20.
The remover coating fluid is that above-mentioned stripper composition dissolving or be dispersed in the solvent forms.As solvent, for example can enumerate benzene,toluene,xylene, methyl alcohol, ethanol, isobutanol, n-butanol, MEK, acetone, oxolane etc.Solvent can use separately a kind, also can mix more than 2 kinds and use.
From taking into account the viewpoint of productivity ratio and coating, the solid component concentration of remover coating fluid is preferably 10～60 quality %.
As the device of coating remover coating fluid, can use and employed device is identical in the coating of cold coating of synthetic leather usefulness when synthetic leather is made device.
As the coating weight of remover coating fluid, preferably count 1～10g/m with drying coated amount
2If the coating weight of remover coating fluid is 1g/m
2More than, then the fissility of resulting process strippable sheet 1 is abundant, on the other hand, if 10g/m
2So excellent with the unsaturated economy of next because fissility.
For example can use heated-air drying, infrared drying etc. as the drying means after the coating.Baking temperature can be selected preferred 80～250 ℃ according to employed solvent is suitable.If baking temperature is more than 80 ℃, then can rapid draing, if below 250 ℃, then can suppress the hot deteriorated of peel ply 20.
According to process strippable sheet 1 described above, can easily peel off synthetic leather.Can think that its reason is: because the solvent resistance of the casting coating 12 of substrate sheets 10 is excellent, therefore, even if coating remover coating fluid, casting coating 12 is not dissolved yet, and the composition of casting coating 12 is difficult to sneak in the peel ply 20, and surface state becomes good.
Embodiment
With comparative example the present invention is carried out specific description by the following examples, but the present invention is not limited to these.In addition, " section " in the example, " % " are respectively " mass parts ", " quality % " except the unit " % " of glossiness.
(embodiment 1)
[making of body paper]
Preparation contains the pulp of following composition, and described composition is with hardwood pulp (CSF430mL) the 85 quality % of the order multistep bleaching of oxygen-ozone-NaOH-hydrogen peroxide-chlorine dioxide and softwood pulp (CSF450mL) the 15 quality % that bleach with the order multistep of oxygen-ozone-NaOH-hydrogen peroxide-chlorine dioxide.In this pulp, reach 10 quality % as filler with the body paper ash content and add precipitated calcium carbonate (Ao Duomo industrial group system, trade name TAMAPEARL TP-121), then with respect to the paper pulp solid constituent, add successively: aluminum sulfate 0.5 quality %, cationic starch (OjiCornstarch Co., Ltd. make, trade name エ one ス K-100) 0.5 quality %, alkyl ketene dimer sizing agent (waste river chemical industrial company system, trade name サ イ ズ パ イ Application K-287) 0.1 quality %, polyacrylamide (waste river chemical industrial company system, trade name Port リ ス ト ロ Application 851) 0.02 quality %, the modulation paper stock.The test portion of gained is copied paper with folder net paper machine (on top type twin wire paper machine), so with a roller sizing applicator with 1.5g/m
2(solid constituent conversion) is coated on oxidized starch (Oj i CornstarchCo., Ltd. system, trade name エ one ス A) on two faces, carries out drying.Then, carry out smoothing techniques with machine calender, obtain quantitative 119g/m
2, tightness 0.75g/cm
3, paper pH7.6 body paper.
[formation on barrier layer]
Contain the coating fluid of polyvinyl alcohol (KURARAYCO., LTD. system, trade name PVA110) so that drying coated amount is 10g/m with knife type coater in above-mentioned body paper coating
2, carry out heated-air drying at 200 ℃, form the barrier layer.
[modulation of coating fluid of casting coating formation]
Use Kao Laisi (コ one レ ス) dispersion machine that kaolin (Engelhard company system, trade name UW-90) 85 mass parts, precipitated calcium carbonate (Shiraishi Kogyo Kaisha Ltd.'s system, trade name PX) 15 mass parts, Sodium Polyacrylate 0.5 mass parts are dispersed in water, the pigment slurry of modulation solid component concentration 65 quality %.In this pigment slurry, with respect to 100 mass parts pigment add ammonium stearate 1.0 mass parts as releasing agent, as SB latex 18.75 mass parts (solid constituent conversion) that 15 quality % caseic aqueous solutions, 6.25 mass parts (solid constituent conversion) and the butadiene content with ammonia solvent of adhesive is 41 quality %, modulating solid component concentration is the casting coating formation coating fluid of 54 quality %.At this moment, SB and caseic mass ratio (SB/casein) are 75/25.
With roll coater on above-mentioned barrier layer take drying coated amount as 10g/m
2Be coated with above-mentioned casting coating formation with coating fluid and dry, then be coated with again wetting solution, be coated with drum from the casting of 80 ℃ of surface temperatures and peel off, cast and be coated with ornamenting.
Form thus casting coating (75 degree glossiness 93%), obtain basic weight 157g/m
2Cast-coated paper.
In addition, to amodimethicone modified alkyd resin (chemical industrial company of SHIN-ETSU HANTOTAI system, trade name KS883) mix in 100 parts 5 parts of the pelletized silicas (marshy land chemical industrial company system, trade name P527) of average grain diameter 2.0 μ m, maximum particle diameter 10 μ m, as 3 parts of the p-methyl benzenesulfonic acid of acid catalyst, interpolation as the toluene of solvent so that solid component concentration becomes 30%, modulation remover coating fluid.
Then, with the intaglio plate coating machine on the casting coating of cast-coated paper with drying coated amount 6g/m
2Be coated with described remover coating fluid, and form peel ply 150 ℃ of lower dryings.
And, with knurling rolls peel ply is carried out embossing processing and obtains process strippable sheet.
Contain the synthetic leather manufacturing of polyurethane resin at the remover surface-coated of resulting process strippable sheet with knife type coater with coating and dry, leather layer is set.Then, be coated with polyurethane adhesive with knife type coater at leather layer, the dry bond layer that forms, then, in this bond layer base cloth of fitting, drying.Thus, form by leather layer and base cloth across the bonding synthetic leather that forms of bond layer at process strippable sheet, obtain the synthetic leather with process strippable sheet.Then, peel off synthetic leather from process strippable sheet.
(embodiment 2)
Be 45% the SB except the SB that the casting coating of cast-coated paper is contained changes to butadiene content, obtain similarly to Example 1 process strippable sheet and synthetic leather.
(embodiment 3)
Be 50% the SB except the SB that the casting coating of cast-coated paper is contained changes to fourth-diene content, obtain similarly to Example 1 process strippable sheet and synthetic leather.
(embodiment 4)
Be 55% the SB except the SB that the casting coating of cast-coated paper is contained changes to butadiene content, obtain similarly to Example 1 process strippable sheet and synthetic leather.
(embodiment 5)
Except the silica that pelletized silica is changed to average grain diameter 1.0 μ m, maximum particle diameter 8 μ m, obtain similarly to Example 3 process strippable sheet and synthetic leather.
(embodiment 6)
Except the silica that pelletized silica is changed to average grain diameter 1.8 μ m, maximum particle diameter 8 μ m, obtain similarly to Example 3 process strippable sheet and synthetic leather.
(embodiment 7)
Be 61% the SB except the SB that the casting coating of cast-coated paper is contained changes to butadiene content, obtain similarly to Example 1 process strippable sheet and synthetic leather.
(embodiment 8)
Except the SB that the casting coating of cast-coated paper is contained and caseic mass ratio change to 40/60, obtain similarly to Example 4 process strippable sheet and synthetic leather.
(embodiment 9)
Except the silica that pelletized silica is changed to average grain diameter 3.6 μ m, maximum particle diameter 15 μ m, obtain similarly to Example 3 process strippable sheet and synthetic leather.
(embodiment 10)
Except the SB that the casting coating of cast-coated paper is contained and caseic mass ratio change to 40/60, obtain similarly to Example 1 process strippable sheet and synthetic leather.
(embodiment 11)
Except the silica that pelletized silica is changed to average grain diameter 0.6 μ m, maximum particle diameter 6 μ m, obtain similarly to Example 3 process strippable sheet and synthetic leather.
(embodiment 12)
Except the silica that pelletized silica is changed to average grain diameter 1.8 μ m, maximum particle diameter 15 μ m, obtain similarly to Example 3 process strippable sheet and synthetic leather.
(embodiment 13)
Except when carrying out the polymerization of amodimethicone modified alkyd resin, having added 0.1 part of dicyandiamide (Northeast chemical company special grade chemical processed) as the formalin adsorbent, obtain similarly to Example 3 process strippable sheet and synthetic leather.
(embodiment 14)
Except the interpolation umber with pelletized silica changes to 4 parts, obtain similarly to Example 13 process strippable sheet and synthetic leather.
(comparative example 1)
Be 38% the SB except the SB that the casting coating of cast-coated paper is contained changes to butadiene content, obtain similarly to Example 1 process strippable sheet and synthetic leather.
(comparative example 2)
Except using following press polish finished coated paper as the substrate sheets, obtain similarly to Example 1 process strippable sheet and synthetic leather.The basic weight of wherein said press polish finished coated paper is 157g/m
2, have contain butadiene content be 38% SB as the adhesive in the pigment application layer with contain kaolin as the coating layer of coating layer with pigment, and coating layer has carried out the minute surface ornamenting by supercalender.
In the process strippable sheet of embodiment 1～14 and comparative example 1～2, the 75 degree glossiness based on JI SZ8741 mensuration on the mass ratio of the kind of the butadiene unit content of SB (SBR), the gel fraction of SBR, substrate sheets, kind, SB and other adhesives of other adhesives, the average grain diameter of silica and maximum particle diameter, peel ply surface come together in table 1 and illustrate.
In addition, gel fraction is measured by following method.
That is, at the latex of polytetrafluoroethylsheet sheet coating SB, drying is 24 hours under 50 ℃, and having formed thickness is the epithelium of 0.3～0.5mm (after dry).Then, it is square that described epithelium is cut into 3cm, measure its quality after, be impregnated in the toluene 24 hours.Then, 105 ℃ of lower dryings toluene is volatilized fully, measure the quality of resulting solid matter.And, utilize formula (1) to obtain gel fraction.
Formula (1) gel fraction=(quality before the quality behind the toluene dipping/toluene dipping) * 100 (%)
[table 1]
Use the process strippable sheet of embodiment 1～14 and comparative example 1～2, made synthetic leather by following method.
Use knife type coater, on the surface of the peel ply of process strippable sheet with drying coated amount 25g/m
2The polyurethane solutions that coating synthetic leather epidermis is used (NE310 processed of industrial group refines large day) 100 ℃ of heated-air dryings, is made epidermis.Then, be coated with polyurethane adhesive (UD603 processed of industrial group refines large day) with knife type coater at resulting epidermis, and across this bonding agent applying base cloth (NT ベ one ス processed of ACHILLES company), 150 ℃ of dryings.Then, peel off from process strippable sheet, obtain synthetic leather.
Carry out following evaluation for the synthetic leather that in above embodiment, comparative example and reference example, obtains process strippable sheet and use these process strippable sheets to make, the results are shown in table 2.
[the coating adaptive of remover coating fluid]
The surface state of the peel ply that forms by visualization coating remover coating fluid is estimated the coating adaptive of remover coating fluid.
Zero: the uniform coated face that is not coated with striped.
△: a part can be seen the coating striped, but is usage level.
*: the coating striped is arranged, be inhomogeneous coated face.
[fissility of synthetic leather]
Visual valuation the fissility when peeling off synthetic leather from process strippable sheet.
Zero: have practical no problem fissility.
△: peeling off and have some setbacks, is to deposit the in practical fissility of problematic possibility.
[appearance of synthetic leather]
The appearance of the resulting synthetic leather of visualization, and estimate.
◎: even and pitch-dark property is excellent.
Zero: almost do not have speckle and pitch-dark property good.
△: can see some speckles or striped.
*: can see inhomogeneous speckle or striped.
In addition, if more than the △, then has practicality.
[Reusability adaptive]
In the darkroom, to peeling off for the first time afterwards and the light of the surface irradiation NI-G lamp of the synthetic leather that obtains after peeling off for the second time, by the visual valuation outward appearance, and judge.
Zero: do not see albefaction, blur, peel off speckle.
*: see albefaction, blured, peeled off speckle.
[table 2]
| The coating adaptive of remover coating fluid | The fissility of synthetic leather | The appearance of synthetic leather face | The Reusability adaptive | |
| Embodiment 1 | ○ | ○ | △ | ○ |
| Embodiment 2 | ○ | ○ | ○ | ○ |
| Embodiment 3 | ○ | ○ | ◎ | ○ |
| Embodiment 4 | ○ | ○ | ◎ | ○ |
| Embodiment 5 | ○ | ○ | ◎ | ○ |
| Embodiment 6 | ○ | ○ | ◎ | ○ |
| Embodiment 7 | ○ | ○ | ◎ | ○ |
| Embodiment 8 | ○ | ○ | △ (speckle) | ○ |
| Embodiment 9 | △ | ○ | △ (striped) | ○ |
| Embodiment 10 | ○ | ○ | * (inhomogeneous speckle) | ○ |
| |
○ | ○ | Zero (gloss is high) | ○ |
| |
* (striped) | ○ | * (striped) | ○ |
| Embodiment 13 | ○ | ○ | ◎ | ○ |
| Embodiment 14 | ◎ | ○ | ◎ | ○ |
| Comparative example 1 | ○ | △ | * (inhomogeneous speckle) | ○ |
| Comparative example 2 | ○ | △ | ○ | × |
Contain the process strippable sheet more than the embodiment 1～14 of the SB of 40% butadiene unit of containing more than the 50 quality % according to the adhesive of the casting coating of substrate sheets, can peel off easily synthetic leather.In addition, the Reusability adaptive is also excellent.
Especially be that the appearance of synthetic leather is more excellent in the situation of embodiment 2～7,13,14 process strippable sheet more than 45% at the butadiene unit that uses SB.
In addition, the maximum particle diameter of the silica in peel ply is among the embodiment 1～8,10,11,13,14 process strippable sheet below the 10 μ m, can be coated with easily when substrate sheets coating remover coating fluid.Namely be coated with the adaptive excellence.
Relative therewith, in the butadiene unit of the contained SB of adhesive of casting coating was comparative example 1,2 process strippable sheet below 40%, the fissility of synthetic leather was low.Especially use in the comparative example 2 of supercalender finished coated paper as substrate sheets, do not have the Reusability adaptive.
Utilizability on the industry
Substrate sheets of the present invention can be used in process strippable sheet, when peeling off synthetic leather from process strippable sheet, can realize the raising of fissility.
The process strippable sheet of the application of the invention can realize that the fissility of synthetic leather improves.
Claims (7)
1. base material sheet for process strippable sheet, it is characterized in that, described base material sheet for process strippable sheet is made of cast-coated paper, described cast-coated paper has supporter and contains adhesive and the coating layer casting coating with pigment, wherein, adhesive contains the SB more than the butadiene unit of 40 quality %, and the content of the SB in the adhesive is below the above 95 quality % of 50 quality % when establishing adhesive and totally being 100 quality %.
2. base material sheet for process strippable sheet according to claim 1, wherein, adhesive contains casein.
3. process strippable sheet, it is characterized in that, described process strippable sheet has base material sheet for process strippable sheet claimed in claim 1 and is formed on peel ply on the casting coating and the face supporter opposition side of described substrate sheets, and peel ply contains stripper composition and silica containing peel ply pigment.
4. process strippable sheet according to claim 3, remover is the alkyd resins that has added the formalin adsorbent.
5. process strippable sheet according to claim 3, peel ply is that 1～3 μ m and maximum particle diameter are below the 10 μ m with the average grain diameter of the contained silica of pigment.
6. process strippable sheet according to claim 3, the 75 degree glossiness of measuring based on JISZ8741 with the surface base material sheet for process strippable sheet opposition side peel ply are 30～90%.
7. the manufacture method of a synthetic leather is characterized in that, it has:
Be coated with synthetic leather forms leather layer with cold coating operation at process strippable sheet claimed in claim 3,
Peel off the operation of described process strippable sheet from the leather layer of synthetic leather.
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| JP2007-270432 | 2007-10-17 | ||
| JP2007270432 | 2007-10-17 | ||
| PCT/JP2008/065767 WO2009050951A1 (en) | 2007-10-17 | 2008-09-02 | Base material sheet for process strippable sheet, process strippable sheet, and process for producing synthetic leather |
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| JP5809566B2 (en) * | 2012-01-18 | 2015-11-11 | 恵和株式会社 | Process paper |
| WO2014183631A1 (en) * | 2013-05-14 | 2014-11-20 | 金东纸业（江苏）股份有限公司 | Film-transfer mirror copper coating and coated paper using same |
| CN103266533B (en) * | 2013-05-14 | 2015-12-02 | 金东纸业（江苏）股份有限公司 | Film shifts mirror copper coating and applies its art paper |
| CN103306160A (en) * | 2013-05-14 | 2013-09-18 | 金东纸业（江苏）股份有限公司 | Transfer membrane mirror copper coating and coated paper using same |
| JP6707795B2 (en) * | 2016-03-29 | 2020-06-10 | リンテック株式会社 | Synthetic leather manufacturing process paper |
| JP6991831B2 (en) * | 2016-11-08 | 2022-01-13 | 恵和株式会社 | Process paper for forming polyurethane coat layer |
| JP7133929B2 (en) * | 2018-01-24 | 2022-09-09 | リンテック株式会社 | Casting paper for synthetic leather and method for producing synthetic leather |
| JP7040214B2 (en) * | 2018-03-29 | 2022-03-23 | 大日本印刷株式会社 | Release paper, method of manufacturing release paper, shaped body and synthetic leather |
| WO2019188003A1 (en) * | 2018-03-30 | 2019-10-03 | 日本製紙株式会社 | Cast-coated paper for process-paper base material |
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| CN1858337A (en) * | 2006-05-28 | 2006-11-08 | 宋健 | Butyl acetate-polyvinyl alcohol copolymer emulsion color coating canvas and its producing process |
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| JPH07300797A (en) * | 1994-04-27 | 1995-11-14 | New Oji Paper Co Ltd | Production of cast-coated paper |
| JP3475571B2 (en) * | 1995-03-29 | 2003-12-08 | Ｊｓｒ株式会社 | Method of producing copolymer latex for coated paper for offset printing |
| JPH10168789A (en) * | 1996-12-10 | 1998-06-23 | Nippon Paper Ind Co Ltd | Cast-coated paper and its production |
| JP2000027096A (en) * | 1998-07-09 | 2000-01-25 | Oji Kako Kk | Release paper in process for synthetic leather production |
| JP3751777B2 (en) * | 1999-09-27 | 2006-03-01 | 特種製紙株式会社 | Substrate sheet for process release paper and process release paper using the same |
| JP4663144B2 (en) * | 2001-02-06 | 2011-03-30 | 日本製紙株式会社 | Cast coated paper and method for producing the same |
| JP4686057B2 (en) * | 2001-06-08 | 2011-05-18 | 大日本印刷株式会社 | Release paper and synthetic leather produced using it |
| JP2004299322A (en) * | 2003-03-31 | 2004-10-28 | Matsushita Electric Works Ltd | Kenaf board |
| JP2005097781A (en) * | 2003-09-24 | 2005-04-14 | Nippon Paper Industries Co Ltd | Cast coated paper and process paper for producing synthetic leather using the same |
| JP4927544B2 (en) * | 2004-07-13 | 2012-05-09 | リンテック株式会社 | Release sheet and molded product obtained using the release sheet |
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| CN1858337A (en) * | 2006-05-28 | 2006-11-08 | 宋健 | Butyl acetate-polyvinyl alcohol copolymer emulsion color coating canvas and its producing process |
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| JP特开2004-299322A 2004.10.28 |
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| TW200927494A (en) | 2009-07-01 |
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