CN110067157A - The manufacturing method of synthetic leather release paper and synthetic leather - Google Patents

The manufacturing method of synthetic leather release paper and synthetic leather Download PDF

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Publication number
CN110067157A
CN110067157A CN201910062420.5A CN201910062420A CN110067157A CN 110067157 A CN110067157 A CN 110067157A CN 201910062420 A CN201910062420 A CN 201910062420A CN 110067157 A CN110067157 A CN 110067157A
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CN
China
Prior art keywords
synthetic leather
release paper
agent layer
peeling agent
manufacture
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Granted
Application number
CN201910062420.5A
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Chinese (zh)
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CN110067157B (en
Inventor
露崎贵宏
森刚志
原卓哉
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Lintec Corp
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Lintec Corp
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Publication of CN110067157A publication Critical patent/CN110067157A/en
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Classifications

    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/001—Release paper

Abstract

The present invention provides synthetic leather with release paper (1), its peeling agent layer (3) for having substrate (2) and being formed on substrate (2), wherein, the mirror surface luster of the peeling agent layer (3) measured based on 8741 standard of JIS Z is calculated as 30% or less with 20 ° of gloss values, 70% is calculated as hereinafter, being calculated as 100% or less with 85 ° of gloss values with 60 ° of gloss values.

Description

The manufacturing method of synthetic leather release paper and synthetic leather
Technical field
The present invention relates to synthetic leather release paper and the manufacturing methods of synthetic leather.
Background technique
Synthetic leather manufactures by the following method: being formed using having on the substrates such as paper by remover resin combination Peeling agent layer release paper (engineering paper), on peeling agent layer be coated with carbamate resins, vinyl chloride resin etc. synthesis Resin is the coating liquid of principal component, and is dried, and is then further bonded base fabric by bonding agent on it as needed, most Synthetic leather is removed from release paper at last.
In the manufacturing method of such synthetic leather, since the surface state of the peeling agent layer of release paper is needed on conjunction At the surface of leather, therefore, according to the surface state of release paper, the differences such as gloss, delustring or the decorative pattern of synthetic leather.
For adding the release paper of synthetic leather of glaze type, it is desirable that high surface smoothness, to coarse shape synthetic leather For release paper, it is desirable that the high extinction equipped with concave-convex surface.
For example, disclosing one kind in document 1 (Japanese Unexamined Patent Publication 10-306253 bulletin) contains organic-silicon-modified alkyd tree The release paper removing resin combination of rouge, it is very high, referred to as so-called plus glaze type to be commonly used for manufacture glossiness Synthetic leather.
In addition, in document 2 (Japanese Unexamined Patent Publication 2004-115972 bulletin), as without embossing processing, fluffing processing etc. And the rough layer for being suitable for the manufacture of coarse shape synthetic leather forms and uses composition, discloses one kind and contains porous microparticles as delustring Composition is used in the rough layer formation of agent.
However, gloss is too strong in the case where adding the synthetic leather of glaze type, glittering impression is felt, there is cheap sense instead, In the case where coarse shape synthetic leather, feel is dull, all has the tendency for lacking feeling of high class.Consumers'attitudes in recent years In, it is desirable that the synthetic leather of pitch-dark property is had both while building reflecting feel.
Synthetic leather with such " moist sense " can not have been recorded in having used document 1 plus glaze type synthetic leather institute It is obtained in the synthetic leather manufacture of release paper used in the coarse shape synthetic leather recorded in the release paper that uses, document 2.
Its reason is: the release paper of the release paper or coarse shape that add glaze type does not have " moist sense " for rendering Surface state.
In addition, release paper needs are finally removed from synthetic leather, it is desirable that appropriate removing in the manufacture of synthetic leather Power.
For the release paper of coarse shape, since concave-convex surface is significant, release paper and synthetic resin Contact area increases and increases bonding force (peeling force), according to circumstances, can not remove sometimes, therefore in the production of synthetic leather Property aspect generate obstruction.
The content of invention
The purpose of the present invention is to provide by fine concave-convex surface have appropriateness bonding force (peeling force) and The synthetic leather release paper of the synthetic leather of desired texture and the manufacturing method of synthetic leather can be manufactured.
Synthetic leather release paper of the invention has the peeling agent layer of substrate and formation on the substrate, wherein base 30% is calculated as hereinafter, with 60 ° in the mirror surface luster for the peeling agent layer that 8741 standard of JIS Z measures with 20 ° of gloss values Gloss value is calculated as 70% hereinafter, being calculated as 100% or less with 85 ° of gloss values.
According to the invention, the release of gloss value as described above is limited to by using the mirror surface luster of peeling agent layer Paper has carried out manufacture synthetic leather, and the outer surface of synthetic leather can be made to have desired texture as " moist sense ".
In the present invention, the peeling agent layer is preferably formed by remover combination, and the remover combination includes super It crosses 0 mass % and is lower than the filler of 15 mass %, the filler is formed by amorphous particle.
It is more than 0 mass % and the filling for being lower than 15 mass % by the inclusion of being formed by amorphous particle according to the invention Agent manufactures the release paper for having desired mirror surface luster and becomes easy.
In the present invention, the film thickness of the peeling agent layer is preferably 3.0 μm or more and 12 μm or less.
When film thickness is lower than 3.0 μm, the filler exposed from peeling agent layer is excessive and enhances harsh feeling, can not manufacture tool The synthetic leather of promising texture.In addition, filler becomes difficult to be fixed on peeling agent layer, filler can be from peeling agent layer It falls off, the synthetic leather with desired texture can not be manufactured.
On the other hand, when film thickness is more than 12 μm, filler is buried in peeling agent layer, the filling exposed from peeling agent layer Agent reduces and can enhance reflecting feel, can not manufacture the synthetic leather with desired texture.
In the present invention, the average grain diameter D50 of the amorphous particle is preferably 0.5 μm or more and 5.0 μm or less.
For the particle diameter distribution of the amorphous particle, the partial size D10 for being preferably based on cumulative distribution is average grain diameter 0.8 times of D50 is hereinafter, and partial size D90 is 1.2 times or more of average grain diameter D50.
According to the invention, by making the such range of average grain diameter D50 of amorphous particle, and the grain of amorphous particle Diameter is distributed as such range, and it is prominent from peeling agent layer surface can to make amorphous particle, so that appropriate concave-convex surface is formed, Therefore, suitable for manufacturing the synthetic leather with desired texture.
In the present invention, the amorphous particle is preferably amorphous silica particles.
According to the invention, amorphous particle is made of inorganic material, therefore even if by synthetic leather manufacture in heating, Also it does not deform, melt, therefore the synthetic leather with desired texture can be manufactured.
In the present invention, the peeling agent layer preferably comprises silicone alkyd.
According to the invention, can be made by using silicone alkyd with heat resistance and and synthetic leather The good release paper of fissility.
The manufacturing method of synthetic leather of the invention includes following process: the stripping in the synthetic leather release paper From the process for being coated with the coating liquid containing synthetic resin in oxidant layer；The coating liquid after coating is dried and forms synthesis The process of leather；And the process for after the drying removing the synthetic leather from the synthetic leather with release paper.
According to such present invention, it is also possible to obtain functions and effects same as described above.
Detailed description of the invention
Fig. 1 is the sectional view for showing the structure of release paper of embodiments of the present invention.
Specific embodiment
In the following, being illustrated based on attached drawing to an embodiment of the invention.Embodiment party of the invention is shown in Fig. 1 The synthetic leather of formula release paper 1.Synthetic leather release paper 1 has substrate 2 and peeling agent layer 3.
[1] substrate 2
It, can be appropriate as long as aftermentioned peeling agent layer 3 can be supported as the substrate 2 of synthetic leather release paper 1 Selection, can enumerate paper base material, resin film etc..
As paper base material, it can be mentioned, for example: full slurrying paper, intermediate paper, glassine paper, art paper, coated paper and cast-coated paper Paper base materials such as (cast coated paper), in addition, the thermoplastic resins such as laminated polyethylene on these paper base materials can also be enumerated Obtained from laminated paper.
As resin film, it can be mentioned, for example: by polyethylene terephthalate, polyethylene naphthalate, poly- pair The film etc. that the polyolefin such as the polyester such as benzene dicarboxylic acid butanediol ester, polyethylene, polypropylene, polymethylpentene are formed.
In addition, these substances can be single layer, or 2 layers or more of multilayer of the same race or not of the same race.
The thickness of substrate is not particularly limited, preferably 5~300 μm, more preferably 10~200 μm.
In these substrates, from intensity and from the viewpoint of being easy to get, preferred paper base material, more preferable cast-coated paper.Pass through Use cast-coated paper, it can be ensured that flatness, heat resistance, barrier property.
As cast-coated paper (burmished paper), it can be mentioned, for example: with direct method, the cast-coated paper that wet process, freezing method manufacture again, make It for commercially available product, can enumerate: the Mirror that the ESPRIT series of Jujo Paper Co., Ltd's manufacture, Oji Paper manufacture Coat series etc..
[2] peeling agent layer 3
As shown in Figure 1, peeling agent layer 3 is formed by remover combination 31.
[2-1] remover combination 31
The remover combination 31 for forming peeling agent layer 3 has fissility host agent and filler 32, is to cooperate as needed Made of additive, solvent.
As the fissility host agent for forming remover combination 31, can enumerate:
(1) low polarity and its own show fissility polymer compound,
(2) had been assigned and being modified by sulphation fissility polymer material,
(3) add in the polymeric material fissility low molecule or oligomer ingredient and impart the composition of fissility Deng.
As low polarity and its own show the polymer compound of fissility, can enumerate: polysiloxane；Fluorine is poly- Close object；The polyolefin such as polyethylene, polypropylene, polymethylpentene；Diolefinic polymers such as polybutadiene, polyisoprene etc..
In the polymer material for having been assigned fissility and being modified by sulphation, as the polymer being modified by sulphation Ingredient can be enumerated: polyvinyl alcohol, partly-hydrolysed polyvinyl acetate, the acrylate copolymer of hydroxyl, carbamate tree Rouge, alkyd resin, amino resins, epoxy resin, phenolic resin etc..If these component of polymer are not modified by sulphation, greatly Fissility is not shown mostly.
In addition, in the polymer material for having been assigned fissility and being modified by sulphation, as being chemically modified Ingredient, can enumerate: with functional group polysiloxane or organosiloxane oligomers；Carbon with functional group, which is fluorinated, to be closed Object；Long chain alkyl compound with functional group.It as long chain alkyl compound therein, can enumerate: there is lauryl, palm The compound of the alkyl of 12 or more the carbon atom numbers such as base, stearyl.
The functional group of compound as pending chemical modification can enumerate: hydroxyl, amino, carboxyl, epoxy group, isocyanide Perester radical, (methyl) acryloyl group, mercapto, alkoxysilyl etc..
The polymer material that fissility is imparted and being modified by sulphation is commonly known as organic-silicon-modified resin, fluorine changes Property resin, long chain alkyl modified resin.
In the polymeric material add fissility low molecule or oligomer ingredient and impart in the composition of fissility, It as used polymer material, can enumerate: polyvinyl alcohol, partly-hydrolysed polyvinyl acetate, acrylate copolymer, ammonia Carbamate resin, polyester resin, polyamide, alkyd resin, amino resins, epoxy resin, phenolic resin etc..
As the low molecule or oligomer ingredient of the fissility for making an addition to these polymer materials, can enumerate: wax (close by hydrocarbonylation Object)；Polysiloxane or organosiloxane oligomers；Fluorocarbon；Long chain alkyl compound can further enumerate them Polyethers addition product, polyester addition product etc..
Wherein, from being easy to improve fissility, heat resistance and can become good with the compatibility of filler, other additives From the viewpoint of good, preferably to impart the polymer material of fissility and being modified by sulphation as fissility host agent, more Alkyd resin, the so-called silicone alkyd of chemical modification have preferably been carried out with polysiloxane.On in addition, The fissility host agent stated can be used alone, and can also be applied in combination two or more.
[2-2] filler 32
It as the filler 32 for making an addition to remover combination 31, can enumerate: unbodied silica, aluminium oxide, oxygen Change titanium, zinc oxide, calcium carbonate, magnesium hydroxide, aluminium hydroxide, kaolin, talcum, clay etc., it is excellent from the viewpoint of heat resistance Amorphous silica particles, amorphous aluminum particulate are selected as, from the viewpoint of economy, more preferably use amorphous two Silica.
In addition, for these fillers, for ease of improving dispersibility, capable of assigning and removing reacting for host agent Property, particle surface can use organic group, functional group etc. and be modified.
In remover combination 31, preferably addition is formed by amorphous particle is more than 0 mass % and is lower than 15 matter Measure the filler 32 of %.The compounding ratio of more preferable filler 32 is more than 1 mass % and to be lower than 12.5 mass %, particularly preferably For more than 2 mass % and lower than 10 mass.By setting it as the range, it can have desired mirror surface luster, and obtain appropriateness Peeling force.
The average grain diameter D50 of amorphous particle is preferably 0.5 μm or more and 5.0 μm or less.Average grain diameter D50 is less than should When lower limit value, exist because filler is difficult to the hidden danger for enhancing reflecting feel due to exposing from peeling agent layer.In addition, average grain diameter D50 When greater than the upper limit value, there is the hidden danger for enhancing harsh feeling because filler excessively exposes from peeling agent layer.It needs to illustrate It is that for average grain diameter, can be spread out using the remover combination for being combined with filler 32 as measurement object using laser The formula particle size distribution meter of penetrating is measured.
Amorphous particle used in remover combination 31 preferably has wide particle diameter distribution.Namely based on iterated integral The difference of the partial size D10 and partial size D90 of cloth are preferably very big, specifically, it is preferable that D10 be 0.8 times of average grain diameter D50 hereinafter, and D90 is 1.2 times or more of average grain diameter D50.
By making particle diameter distribution have the width, the concave-convex surface of peeling agent layer 3 randomly forms relatively rough part Therefore the gloss value relative to the incidence angle of light can be controlled as desired range, knot with the smooth part compared Fruit is the available synthetic leather release paper 1 with desired reflecting feel.In addition, by keeping filler 32 amorphous Particle is easy to that particle diameter distribution is made to have width, therefore it is preferable to use amorphous particles.
Amorphous particle used in filler 32 it is preferable to use by the blocks of the raw material such as silica, aluminium oxide into The particle of state that is broken, crushing is gone, specific surface area is preferably 10m2/ g or more, preferably 20m2/ g or more and 1000m2/g Hereinafter, more preferably 50m2/ g or more and 500m2/ g or less.
Remover combination 31 can further cooperate curing agent, crosslinking agent, reaction in fissility host agent and filler The additives such as initiator, catalyst, in addition, remover combination 31 can also be diluted with organic solvent.
Workable curing agent in remover combination 31, crosslinking agent and reaction initiator may be selected to have can be with removing The compound for the functional group that functional group possessed by property host agent is chemically bonded.Curing agent, crosslinking agent, reaction initiator pass through It is reacted with removing host agent and forms three-dimensional mesh structure, thus make being improved by film strength, heat resistance for peeling agent layer 3.
As long as workable curing agent, crosslinking agent or reaction initiator can be with removing host agent institutes in remover combination 31 The functional group having is reacted, and is not particularly limited, it can be mentioned, for example: the organosilicon of polynary containing hydrogenated silicyl It is siloxane compound, melamine compound, polyhydric isocyanate compound, polynary epoxide, polynary aldehyde compound, polynary Amine compounds, multivalenceIsoxazoline compound, metal complex etc..
Workable catalyst is to can promote the curing reaction of remover combination (crosslinking is anti-in remover combination 31 Answer) at low temperature or the short time in carry out compound, may be selected compound corresponding with the chemical reaction.For example, polynary Containing hydrogenated silicyl organosilicone compounds addition reaction used in the case of, can be used such as platinum catalysis Agent.In addition, the acid catalysis such as p-methyl benzenesulfonic acid can be used in the reaction with dehydration, the dealcoholysis of melamine compound Agent.
In remover combination 31, the match ratio of curing agent, crosslinking agent or reaction initiator relative to fissility host agent Rate can be selected suitably, so as to be suitable for need release paper various physical property, for example, relative to removing host agent it is non-volatile at Point 100 mass parts, more than preferably 0.1 mass parts and 400 below the mass, more than more preferably 10 mass parts and 200 matter Measure part or less.In addition, the compounding ratio of catalyst similarly can be selected suitably, to be suitable for the remover needed combination The various physical property of the release paper of the reaction speed and needs of object, for example, 100 mass of nonvolatile component relative to fissility host agent Part, more than preferably 0.01 mass parts and 10 below the mass, more than more preferably 0.5 mass parts and 5 below the mass.
Above-mentioned peeling agent layer 3 uses preferably in the form of the solution containing organic solvent.As the organic solvent, Ke Yicong Dissolubility and volatility for peeling agent layer 3 are good and are chemically nonactive for each ingredient of remover combination 31 Well known solvent in suitably select and use.
As such solvent, it can be mentioned, for example: toluene, dimethylbenzene, hexane, heptane, methanol, ethyl alcohol, isopropanol, isobutyl Alcohol, n-butanol, acetone, methyl ethyl ketone, tetrahydrofuran etc..These solvents can be used alone, and can also be applied in combination two kinds More than.
From the viewpoint of coating applicability and drying property, the nonvolatile component concentration of the solution of remover combination 31 is excellent 5 mass % or more are selected as and 60 mass % hereinafter, more preferably 10 mass % or more and 50 mass % are hereinafter, further preferably For 20 mass % or more and 40 mass % or less.
[3] manufacturing method of synthetic leather release paper 1
The peeling agent layer 3 that synthetic leather release paper 1 has substrate 2 and is formed on the substrate 2.Synthetic leather is with release The manufacturing method of paper 1 is not particularly limited, for example, can add filler 32 in right amount in fissility host agent, curing agent etc., makes At remover combination 31, remover combination 31 is coated on substrate 2, and makes the curing of coating, thus the shape on substrate 2 At peeling agent layer 3.
As coating method, it can be mentioned, for example: spin-coating method, spray coating method, stick coating method, cutter painting method, rolling method, roller cutter painting method, Scraper coating method, die coating method, gravure coating process etc..
In the case where stating remover combination solution in use, preferably by the solution coating on substrate, film is formed, The film is heated and made it dry.
The film being formed on substrate 2 can make its solidification by heating while dry, have in ingredient in activity When the functional group to react under energy line, its solidification can be made by the irradiation of active energy ray, can also be applied in combination Heating and active energy ray irradiation and make its solidification.As active energy ray, ultraviolet light, electron beam etc. can be enumerated.
Heating temperature is preferably 80~250 DEG C, and more preferably 100~230 DEG C, heating time is preferably 15 seconds~5 points Clock, more preferably 20 seconds~3 minutes.
The heating when film being formed on substrate 2 can use dry and make its solidification, can also by except heating with The irradiation of outer other way, such as active energy ray and make its solidification.
In synthetic leather in release paper 1, the film thickness of the peeling agent layer 3 after solidification is not particularly limited, and preferably 3.0 μm Above and 12 μm hereinafter, more preferably 3 μm or more and 8 μm or less.
Synthetic leather can be manufactured to replace above-mentioned method with release paper 1 by following manufacturing method.Firstly, making It uses thermoplastic resin as polymer material used in fissility host agent, remover combination 31 is coated with or melting extrusion exists On substrate 2, peeling agent layer 3 is formed.In addition, prepare to be implemented with the knurling rolls of given shape, with knurling rolls to above-mentioned on substrate 2 The surface for being formed with the peeling agent layer 3 of the laminated body of peeling agent layer 3 is suppressed, and given concaveconvex shape is transferred to remover Layer 3, it is possible thereby to manufacture desired synthetic leather release paper 1.
For synthetic leather of the invention release paper 1, during such manufacturing method, removing can adjust The composition and processing conditions of agent composition 31 make the bright luster of the above-mentioned peeling agent layer 3 measured based on 8741 standard of JIS Z Degree is calculated as 30% hereinafter, being calculated as 70% hereinafter, being calculated as 100% with 85 ° of gloss values with 60 ° of gloss values with 20 ° of gloss values Below.
In addition, the arithmetic average roughness Ra on the surface of peeling agent layer 3 be 0.05 μm or more and 0.30 μm of range below, And maximum height Rz is 3.0 μm or less.However, even if the arithmetic average roughness Ra on the surface of peeling agent layer 3, maximum height Rz For the range, the mirror surface luster of peeling agent layer 3, which may not also can use, to be able to 20 ° of gloss values and is calculated as 30% or less, with 60 ° of gloss Angle value is calculated as 70% or less, is calculated as 100% balance below with 85 ° of gloss values, therefore, as generating " moist sense " Index is inappropriate.
[4] application method of synthetic leather release paper 1
Synthetic leather is used in the manufacturing process of synthetic leather with release paper 1.
As the manufacturing method for the synthetic leather for having used synthetic leather release paper 1, can make by the following method Make: coating is on the peeling agent layer 3 of the synthetic leather release paper 1 with carbamate resins, vinyl chloride resin, polyamide resin The synthetic resin such as rouge are the coating liquid of principal component and are dried and form resin layer, are then further led on it as needed Bonding agent fitting base fabric is crossed after the drying to remove synthetic leather in release paper 1 from synthetic leather.
Synthetic resin used in manufacturing method as above-mentioned synthetic leather, from the feel, durable as synthetic leather From the viewpoint of property, preferably carbamate resins.
Specifically, carbamate tree can be coated on the peeling agent layer 3 of synthetic leather of the invention with release paper 1 Rouge is simultaneously suitably dried and forms carbamate resins layer, is then bonded base fabric by bonding agent again, is then cured, Carbamate resins layer is finally manufactured into synthetic leather from synthetic leather with removing in release paper 1 together with base fabric.
Synthetic leather is preferably 30~3000mN/30mm relative to the peeling force of the resin layer of synthetic leather with release paper 1, More preferably 50~2000mN/30mm, further preferably 60~1000mN/30mm are still more preferably 70~500mN/ 30mm is still more preferably 90~200mN/30mm.When above-mentioned peeling force is these upper limit values or less, even if reusing After synthetic leather release paper 1, the stable stripping performance from synthetic leather can be also obtained, furthermore it is possible to manufacture tool There is the synthetic leather of high gloss.When it is these lower limit values or more, resin layer can be prevented from the unexpected stripping of peeling agent layer 3 From.
Embodiment
Hereinafter, being illustrated to the embodiment of the present invention.It should be noted that the present invention is not limited to embodiments.
[1] embodiment
[embodiment 1]
Using will mix as the silicone alkyd of fissility host agent and the melamine resin as curing agent (the trade name: Tesfine 309, the manufacture of chemical conversion polymer Co., Ltd., Hitachi, fissility host agent: curing agent of solution made of conjunction =65: 35, solid component concentration 50%) 100 mass parts, it is diluted with 109.2 mass parts of toluene, 46.9 mass parts of ethyl acetate Made of amorphous silica particles (trade name: Sylysia 420, Fuji Silysia is added in mixed solution The manufacture of Chemical company) 3.5 mass parts, using disperser with 3,000rpm dispersion 30 minutes.Conduct is added in the liquid P-methyl benzenesulfonic acid methanol solution (50 mass % of solid component concentration) 2.5 mass parts of curing catalysts, using disperser with 1, 500rpm is stirred 5 minutes, has prepared the solution of remover combination.
By the solution coating in the cast-coated paper (trade name: ESPRIT COATED E (UT) 165SW, Japan as paper base material The manufacture of Zhi Zhi Co., Ltd., weight per unit area 150g/m2) the cated face of formation on, make it dry at 210 DEG C and solid Change 60 seconds, the synthetic leather manufacture release paper with a thickness of about 8.0 μm of peeling agent layer after having obtained with solidification.
[embodiment 2]
In addition to being changed to amorphous silica particles (trade name: Sylysia 310P, Fuji Silysia The manufacture of Chemical company) other than, prepare remover combination solution same as Example 1, by same as Example 1 Method has obtained synthetic leather manufacture release paper.
[embodiment 3]
In addition to being changed to amorphous silica particles (trade name: Sylysia 430, Fuji Silysia Chemical Company's manufacture) other than, prepare remover combination solution same as Example 1, is obtained by method same as Example 1 Release paper is used in synthetic leather manufacture.
[embodiment 4]
The additive amount of amorphous silica particles is changed to 1.3 mass parts, in addition to this, is prepared and 1 phase of embodiment Same remover combination solution, has obtained synthetic leather manufacture release paper by method same as Example 1.
[embodiment 5]
The additive amount of amorphous silica particles is changed to 5.4 mass parts, in addition to this, is prepared and 1 phase of embodiment Same remover combination solution, has obtained synthetic leather manufacture release paper by method same as Example 1.
[embodiment 6]
Remover combination solution same as Example 1 has been used, and the thickness of the peeling agent layer after solidification has been changed It is about 4.0 μm, in addition to this, synthetic leather manufacture release paper has been obtained by method same as Example 1.
[embodiment 7]
In addition to be changed to will as the chain alkyl of fissility host agent stearyl modified alkyd resin with as curing agent Melamine resin mix solution (trade name: Tesfine 303, Hitachi chemical conversion polymer Co., Ltd. manufacture, stripping From property host agent: curing agent=80: 20, solid component concentration 48%) other than, prepare remover combination same as Example 1 Solution has obtained synthetic leather manufacture release paper by method same as Example 1.
[2] comparative example
[comparative example 1]
Other than being not added with amorphous silica particles, prepare remover combination solution same as Example 1, Synthetic leather manufacture release paper has been obtained by method same as Example 1.
[comparative example 2]
In addition to having used spherical silicon dioxide granule (trade name: Seahostar KE-P250 Nippon Shokubai Co., Ltd Manufacture) other than, prepare remover combination solution same as Example 1, is closed by method same as Example 1 At leather manufacture release paper.
[comparative example 3]
The additive amount of amorphous silica particles is changed to 9.0 mass parts, in addition to this, is prepared and 1 phase of embodiment Same remover combination solution, has obtained synthetic leather manufacture release paper by method same as Example 1.
[comparative example 4]
It has used 2 kinds of spherical silicon dioxide granules (trade name: Seahostar KE-P250 Japan catalyst strain formula meeting Society's manufacture and the manufacture of Seahostar KE-P100 Nippon Shokubai Co., Ltd) partial size that mixes of each half amount is different fills out Agent is filled, in addition to this, prepares remover combination solution same as Example 1, is obtained by method same as Example 1 Release paper is used in synthetic leather manufacture.
The cooperation of Examples and Comparative Examples is shown in table 1.
[3] test, evaluation method
[3-1] surface roughness
The light interference type surface-profile measuring instrument manufactured using Veeco company determines the rough surface of peeling agent layer 3 Degree.
[3-2] mirror surface luster
20 °, 60 °, 85 ° of glossiness are determined using vancometer " VG7000 " (Nippon Denshoku Industries Co., Ltd.).
[3-3] reflecting feel
In the evaluation of reflecting feel, will have a case that gloss and it is not glittering be evaluated as A, gloss and will not have slightly The case where glittering situation is evaluated as B, will in addition to this is evaluated as C.
[3-4] peeling force
Use one-pack type polyurethane resin solution (trade name: CRISVON 5516S, the manufacture of DIC company) as synthesis The coating liquid of the resin layer of leather, by the solution coating in the peeling agent layer surface of synthetic leather manufacture release paper, at 140 DEG C Lower drying 2 minutes forms 25 μm of thickness of urethane resin layer.
Then, the surface mount polyester binding adhesive tape of the urethane resin layer of formation (Nitto Denko Corp manufacture, Goods number No.31B), after placing 30 minutes in 23 DEG C, the thermostatic chamber of relative humidity 50%, cut into width 30mm, length 150mm.Using cupping machine (device name: Tensilon, A&D company manufacture), the poly- of adhesive tape is laminated with by above-mentioned Urethane resin layer is stretched with 1000mm/ points of speed in 180 ° of directions, and peeling force when removing is determined.
Show the result in table 2 and table 3.It should be noted that be assumed to be the calculated value of the specific surface area of proper sphere according to 6/ (density × partial size) (m2/ g) it calculates, silica density is 2.2g/cm3, partial size is set as average grain diameter D50.
For comparative example 1, due to not containing silicon dioxide granule in peeling agent layer, the synthesis skin of manufacture The gloss value of leather is excessively high, can not generate " moist sense ".
In addition, can produce some glittering senses for having used the comparative example 2 of spherical silicon dioxide granule, but Similarly the gloss value of synthetic leather is high, is not implemented and generates " moist sense ".
In addition, for comparative example 3, since the additive amount of amorphous silica particles is excessive, release paper Gloss value is beyond the scope of this invention, and the gloss value of the synthetic leather of manufacture is too low, becomes the synthetic leather of coarse shape, nothing Method generates " moist sense ".In addition, the peeling force of synthetic leather is also 510mN/30mm, it is thus identified that be difficult to be removed.
In addition, for comparative example 4, containing 2 kinds of preparing spherical SiO 2 particles that diameter is different in peeling agent layer, but The gloss value of the synthetic leather of manufacture is excessively high, can not generate " moist sense ".
In contrast, for 1~embodiment of embodiment 7, by the peeling agent layer 3 for making synthetic leather release paper 1 Gloss value be set as the scope of the present invention, can make the gloss value of the synthetic leather of manufacture that can feel the model of " moist feel " It encloses.
In addition, the peeling force of synthetic leather also can be set to the range of 110mN/30mm~150mN/30mm, it is thus identified that energy Enough prevent the productivity in the stripping process of damage synthetic leather.

Claims (8)

1. a kind of synthetic leather release paper, the peeling agent layer for having substrate and being formed on the substrate, wherein
The mirror surface luster of the peeling agent layer measured based on 8741 standard of JIS Z with 20 ° of gloss values be calculated as 30% with Under, 70% is calculated as hereinafter, being calculated as 100% or less with 85 ° of gloss values with 60 ° of gloss values.
2. synthetic leather release paper according to claim 1, wherein
The peeling agent layer is formed by remover combination, and the remover combination comprises more than 0 mass % and lower than 15 matter The filler of % is measured, the filler is formed by amorphous particle.
3. synthetic leather release paper according to claim 2, wherein
The film thickness of the peeling agent layer is 3.0 μm or more and 12 μm or less.
4. synthetic leather release paper according to claim 2, wherein
The average grain diameter D50 of the amorphous particle is 0.5 μm or more and 5.0 μm or less.
5. synthetic leather release paper according to claim 4, wherein
In the particle diameter distribution of the amorphous particle, the partial size D10 based on cumulative distribution be 0.8 times of average grain diameter D50 hereinafter, And partial size D90 is 1.2 times or more of average grain diameter D50.
6. synthetic leather release paper according to claim 2, wherein
The amorphous particle is amorphous silica particles.
7. synthetic leather release paper described according to claim 1~any one of 6, wherein
The peeling agent layer contains silicone alkyd.
8. a kind of manufacturing method of synthetic leather, this method include following process:
Coating contains synthetic resin on the peeling agent layer of synthetic leather release paper according to any one of claims 1 to 7 Coating liquid process；
The process that the coating liquid after coating is dried and forms synthetic leather；
After drying, process that the synthetic leather is removed from the synthetic leather with release paper.
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