CN1922007A - Embossed release paper for production of synthetic leather, support thereof, synthetic leather utilizing the release paper and process for producing the same - Google Patents

Abstract

This invention provides an embossed release paper for synthetic leather production, which has embossability, heat resistance and durability and, at the same time, has excellent separability from a two-pack curing type PU adhesive and can be used in all of synthetic leathers such as PU, PVC, and semisynthetic leathers, and a process for producing the same. The embossed release paper for synthetic leather production comprises at least paper as a support and an ionizing radiation cured film provided on the paper. The upper part of the cured film has been embossed. The ionizing radiation cured film has been formed by applying an ionizing radiation to a coating liquid having a specific composition to cure the coating liquid.

Description

Synthetic leather manufacturing synthetic leather and the manufacture method thereof that has the processing release paper and the supporter thereof of embossing and use this processing release paper

Technical field

The present invention relates to synthetic leather manufacturing synthetic leather and the manufacture method thereof that has the processing release paper and the supporter thereof of embossing and use this processing release paper.In more detail, the processing release paper that has embossing that relates to the coating material that uses ionizing radiation curing property with specific composition.

Background technology

In the past, as the technology processing release paper of synthetic leather, used the processing release paper that has embossing always.In addition, as combination of the known polyurethane of raw material (being designated hereinafter simply as PU), vinyl chloride (being designated hereinafter simply as PVC), PU and the PVC of synthetic leather etc.

Manufacture method as the PU leather, such method is for example arranged: the epidermal area PU resin of coating pasty state on processing release paper, after making it dry, solidify with 90～140 ℃ temperature, with bi-component curing type PU is after adhesive is fitted itself and base fabric, after in 40～70 ℃ curing chamber, making it to react 2～3, peel off processing release paper, make the PU leather.These PU resins, general lysotype with an organic solvent, but recently, from environmental problem, also have to make the use type.In this case, also carry out drying with 150～180 ℃ high temperature sometimes.

In addition,, coating PVC colloidal sol on processing release paper is arranged, after 200～250 ℃ of heating, making it gelation, form the PVC foaming layer, fit, after this, peel off the method for processing release paper, manufacturing PVC leather with base fabric as the manufacture method of PVC leather.

In addition,, the epidermal area PU resin of coating pasty state is arranged on processing release paper, after making it dry, solidifying,, after this peel off the method for processing release paper PVC foaming layer and base fabric applying as the manufacture method of the leather that has made up PU and PVC (being also referred to as semi-synthetic leather).

In addition, the also known amalgamation leather (splitleather) of on natural skin, fitting these synthetic leathers and forming.

In the manufacturing of PVC leather and semi-synthetic leather, use the coating silicone resin usually, process the processing release paper that extrudes ridge design by embossing again.But, because the system film temperature of PVC is than higher, so, have the embossing embossability poor, also cause the shortcoming of uneven lustre easily, use the processing release paper difficulty repeatedly.

With respect to this, in the manufacturing of PU leather, because the system film temperature of PU is a low temperature than PVC, so, use and to extrude and thermoplastic resin such as painting polypropylene and 4-methyl-1-pentene and it has been applied the processing release paper of embossing processing.The processing release paper that the PU leather is used, embossing embossability excellence, the fissility in the manufacturing of the synthetic leather that uses bi-component curing type PU is also good, and usability is also excellent repeatedly.But, because processing release paper constitutes with thermoplastic resin, so poor heat resistance has the problem that can not use in the PVC leather is made.

From such problem, extrude the also processing release paper of coating thermoplastic resin, only part is used in PVC leather, semi-synthetic leather purposes, does not have the processing release paper that can be used in PVC leather, PU leather two sides.

In recent years, embossing embossability excellence and hear resistance processing release paper also excellent, that use the such electronic beam curing resin of isodecyl acrylate all is used (special public clear 63-2780 communique) in PU, PVC.The above-mentioned processing release paper that has embossing obtains by following method: coating electron beam irradiation curing property acrylic ester coating composition on the finished aluminium sheet of embossing, on its coated face, push the gauze of the substrate lining of having implemented to comprise pigment/binder, by this gauze course coated face irradiating electron beam, make the aforementioned coating composition curing of coating, then peel off aluminium sheet.

But above-mentioned processing release paper is though have the advantage of embossing reappearance excellence, the curing agent isocyanates that is used and the electronic beam curing resin reaction on processing release paper surface, the shortcoming that has peeling off of processing release paper to become difficult in bi-component curing type PU.

In addition, because shine the intensity variation that causes paper by electron beam, the hear resistance of processing release paper and durability descend, so, when making synthetic leather, when in the drying oven at high temperature processing release paper being applied tension force, the processing release paper fracture is also arranged and the problem that can not use repeatedly.

In addition, because the coating of electronic beam solidified resin is also many, be 40～150g/m ²So,, the manufacturing cost of processing release paper is also very high.

In addition, also proposed to use by ionizing radiation shine solidify, Epocryl is such with compound with the ethene unsaturated bond scheme (special public clear 64-10626 communique) as the processing release paper of the resin of principal component.The above-mentioned processing release paper that has embossing adopts following method to obtain: the single face coating at paper is the coating material of principal component with the compound with ethene unsaturated bond, form uncured coating, this coating surface is carried out embossing processing, then, by finished coating irradiating electron beam of embossing or ultraviolet ray, coating is solidified to this.

But and similarly above-mentioned, peel off bi-component curing type PU material and be not easy, present situation is also not reach practicability.

In addition; in order to improve above-mentioned problem; promptly improve hear resistance, the fissility when using bi-component curing type PU of processing release paper, also proposed to use the method (spy opens flat 5-269931 communique, the spy opens 2001-62958 communique etc.) of silicone resin with acryloyl group.Open the disclosed processing release paper that has embossing in the flat 5-269931 communique above-mentioned spy; be that ionizing radiation curable resin layer is set on the supporter that constitutes by the paper with clay coating; coating contains the silicone resin layer of acryloyl group on this ionizing radiation curable resin layer; after its surface enforcement embossing processing; irradiation ultraviolet radiation or electron beam; ionizing radiation curable resin layer and silicone resin layer solidified, thereby obtain processing release paper.

But resin raw material is high price not only, and fissility, poor in processability, does not also have practical application.

In addition, as the disclosed processing release paper that has an embossing in public clear 64-10626 communique of spy and the flat 5-269931 communique of Te Kai, uncured ionizing radiation curable resin layer is set on supporter, after its surface enforcement embossing processing, make in the processing release paper of the type that ionizing radiation curable resin layer solidifies, because the configuration of surface of the ionizing radiation curable resin layer after solidifying is subjected to the influence of the configuration of surface of the uncured ionizing radiation curable resin layer before embossing processing, so, in order to make the processing release paper that is used to obtain having the such synthetic leather of reflecting feel style, the configuration of surface of the uncured ionizing radiation curable resin layer before the embossing processing must be suitably.

But, in the processing release paper of paper as supporter, because influence is brought on the concavo-convex surface of uncured ionizing radiation curable resin layer of also giving of paper fiber, so, also exist and be difficult to obtain having the problem of the such synthetic leather of reflecting feel style.In addition, when making synthetic leather, when in the drying oven at high temperature processing release paper being applied tension force, used the low processing release paper of hear resistance also to have fracture and the problem that can not use repeatedly.

Summary of the invention

The inventor etc. find after deliberation by using specific ionizing radiation curable resin, can obtain having embossability, hear resistance, durability, even and for the also excellent synthetic leather manufacturing processing release paper that has embossing of bi-component curing type PU adhesive fissility.

In addition, the inventor waits and find that also such processing release paper can both use in synthetic leather such as PU, PVC, semi-synthetic leather.

The inventor etc. also find by being used in processing release paper by the supporter that certain material forms, this processing release paper can be used for any of synthetic leathers such as PU, PVC, semi-synthetic leather, can obtain having embossability, hear resistance, durability, and have the synthetic leather of reflecting feel style.

In addition, also find even be used for the manufacturing of synthetic leather repeatedly, also to keep excellent fissility by adjusting the silicone compounds content of processing release paper.The present invention is based on the invention of such opinion.

Therefore, first purpose of the present invention is, be provided at have embossability, hear resistance, durability, even the time for bi-component curing type PU adhesive fissility also excellence, the synthetic leather manufacturing that in synthetic leathers such as PU, PVC, semi-synthetic leather, can both use processing release paper and the manufacture method thereof that has embossing.

In addition, second purpose of the present invention is, even the occasion of using processing release paper to make synthetic leather repeatedly is provided, release property and processability be also excellent, and obtain the processing release paper that has embossing and the manufacture method thereof of synthetic leather at an easy rate.

In addition, the 3rd purpose of the present invention is, provide a kind of being used for to use, have embossability, hear resistance, durability, and can obtain having the supporter of the processing release paper that has embossing of the synthetic leather of reflecting feel style at synthetic leathers such as PU, PVC, semi-synthetic leathers.

The processing release paper that has embossing as the synthetic leather manufacturing usefulness of the present invention's first form; be to have the paper of supporter and the ionizing radiation cured film that on this paper, is provided with at least; and the processing release paper that has embossing of the synthetic leather manufacturing usefulness that the enforcement embossing processes on this cured film; it is characterized in that; above-mentioned ionizing radiation cured film is solidified coating fluid by the irradiation ionizing radiation and is formed; it is ionizing radiation solidification compound more than 40 ℃ that described coating fluid contains softening point at least, and this solidification compound comprises by isocyanate compound and the reaction product that has (methyl) acryloyl group and can form with (methyl) acryl compound of isocyanate compound reaction; perhaps by isocyanate compound; have (methyl) acryloyl group and can form with the reaction product that does not have (methyl) acryloyl group and can form with (methyl) acryl compound of isocyanate compound reaction with the compound of isocyanates radical reaction.

In addition, the method as the processing release paper that has embossing of the above-mentioned synthetic leather manufacturing of the manufacturing usefulness of the present invention's second form is characterized in that, is included in supporting body surface coating coating fluid and makes that dry back coating weight is 1～40g/m ²Form the operation of filming, make the operation of above-mentioned solvent evaporation drying of filming; To above-mentioned dry coating or simultaneously above-mentioned supporter and dry coating are implemented the operation of embossing processing; To the above-mentioned operation of irradiation ionizing radiation of filming with formation ionizing radiation cured film; it is ionizing radiation solidification compound more than 40 ℃ that above-mentioned coating fluid contains softening point at least; this solidification compound comprises by isocyanate compound and the reaction product that has (methyl) acryloyl group and can form with (methyl) acryl compound of isocyanate compound reaction; perhaps by isocyanate compound; have (methyl) acryloyl group and can form with the reaction product that does not have (methyl) acryloyl group and can form with (methyl) acryl compound of isocyanate compound reaction with the compound of isocyanates radical reaction; above-mentioned coating fluid is with respect to 100 weight portion solid constituents in the coating fluid, forms with the solvent dilution of 10～1000 weight portions.

In addition, the manufacture method of synthetic leather that has the processing release paper of embossing as the use of the present invention's the 3rd form, it is characterized in that comprising, on the ionizing radiation cured film of having carried out above-mentioned embossing processing, be coated with the operation that polyurethane resin composition and heat drying form epidermal area; On above-mentioned epidermal area, form the operation of synthetic leather layer by adhesive applying base fabric; And the operation of peeling off above-mentioned processing release paper from above-mentioned synthetic leather layer.

In addition, synthetic leather as the 4th form of the present invention, it is characterized in that, the synthetic leather that is to use the above-mentioned processing release paper that has an embossing to make, peel off processing release paper and the stripper surface of the synthetic leather that obtains, to have ratio from the silicon of siloxanes be below 20%.

In addition, supporter as the 5th form of the present invention, be to constitute by the body paper that has the clay coating on the one side, be used for the supporter of synthetic leather manufacturing with the processing release paper that has embossing, it is characterized in that, above-mentioned body paper has the hot strength that utilization is measured based on the assay method of JIS P8113 standard after placing 3 minutes under 230 ℃ and is vertically maintaining more than the 10kN/m at least, and after placing 3 minutes under 230 ℃, utilize the tearing strength of measuring based on the assay method of JIS P8116 standard vertical, transverse direction all maintains the above such hear resistance of 500mN, and above-mentioned clay coating is formed and has utilization based on the smoothness more than 100 seconds that the assay method of JIS P8119 standard obtains, and is absorbed by the concave-convex surface due to the paper pulp fiber of above-mentioned body paper.

According to first to the 3rd form of the present invention, can realize having embossability, hear resistance, durability, even for bi-component curing type PU adhesive also fissility excellence, the while is all spendable synthetic leather manufacturing processing release paper that has embossing in synthetic leathers such as PU, PVC, semi-synthetic leather.

In addition, according to the 4th form of the present invention, even can realize using repeatedly processing release paper to make the situation of synthetic leather, release property and processability are also excellent, and can obtain the processing release paper that has embossing of synthetic leather at an easy rate.

In addition, according to the 5th form of the present invention, can be implemented in the synthetic leathers such as PU, PVC, semi-synthetic leather and all can use and have embossability, hear resistance, durability, and can obtain having the employed supporter of the processing release paper that has embossing of the synthetic leather of reflecting feel style.

Description of drawings

Fig. 1 is the figure of expression synthetic leather manufacturing of the present invention with an example of the manufacturing process of the processing release paper that has embossing.

Fig. 2 is the sectional view of synthetic leather manufacturing of the present invention with the supporter of the processing release paper that has embossing.

Fig. 3 is the sectional view of synthetic leather manufacturing of the present invention with the processing release paper that has embossing.

The specific embodiment

(1) processing release paper that has embossing and the manufacture method thereof of synthetic leather manufacturing usefulness

Based on the processing release paper that has embossing of the present invention, be to possess at least as the paper of supporter and the ionizing radiation cured film that on this paper, is provided with, and apply the processing release paper that has embossing of the synthetic leather manufacturing usefulness that embossing processes on this cured film, above-mentioned ionizing radiation cured film is solidified coating fluid by the irradiation ionizing radiation and is formed.This coating fluid at first is described.

Coating fluid

The coating fluid of Shi Yonging is to contain the composition that softening point is the ionizing radiation solidification compound more than 40 ℃ in the present invention, and described solidification compound comprises by isocyanate compound and the reaction product that has (methyl) acryloyl group and can form with (methyl) acryl compound of isocyanate compound reaction; or by isocyanate compound; have (methyl) acryloyl group and can form with the reaction product that does not have (methyl) acryloyl group and can form with (methyl) acryl compound of isocyanate compound reaction with the compound of isocyanates radical reaction.

In addition; in this manual; so-called (methyl) acryloyl group refers to acryloyl group and/or methacryl; so-called (methyl) acryl compound refers to acryl compound and/or methacryl based compound; so-called (methyl) acrylate refers to acrylate and/or methacrylate, and so-called (methyl) acrylic acid refers to acrylic acid and/or methacrylic acid.

The so-called isocyanate compound that uses in the present invention is the compound with at least 1 NCO, preferably has the compound of 2 above NCOs.For example can use the isocyanic acid phenylester, isocyanic acid xylyl ester, isocyanic acid naphthyl ester, two isocyanic acid hexa-methylene esters, the lysine methyl ester vulcabond, 2,4, the aliphatic isocyanates of 4-trimethyl hexamethylene diisocyanate etc., IPDI, 4, the alicyclic isocyanate of 4 '-di-2-ethylhexylphosphine oxide (cyclic isocyanate hexyl ester) etc., the toluylene group diisocyanate, 4,4 '-methyl diphenylene diisocyanate, naphthalene-1, the aromatic isocyanate of 5 '-vulcabond etc. also can use the trimer of toluylene group diisocyanate, with toluylene group diisocyanate and the active dydrogen compounds reaction product etc. of 3: 1 (mol ratio) of trimethylolpropane for example.

In addition, preferably use trimer and with the reaction product of active dydrogen compounds etc. with the compound of the NCO that closes with non-aromatic hydrocarbon loops, so-called ester ring type isocyanate compound.As the ester ring type isocyanate compound, the IPDI that preferred use obtains on market easily, but also can use hydrogenation toluylene group diisocyanate, hydrogenation xylyl vulcabond, hydrogenated diphenyl methane diisocyanate etc.

The reaction product of 3: 1 (mol ratio) of Trimerization of Isophorone Diisocyanate thing, IPDI and trimethylolpropane, preferably as the isocyanate compound that uses in the present invention, wherein, more preferably Trimerization of Isophorone Diisocyanate thing.Isocyanate compound also can a plurality of ground and usefulness.

As have (methyl) acryloyl group and can with (methyl) acryl compound of isocyanate compound reaction, can enumerate (methyl) acryl compound with hydroxyl and/or carboxyl.Below, will " have (methyl) acryloyl group and can abbreviate " specific (methyl) acryl compound  as sometimes with (methyl) acryl compound  of isocyanate compound reaction.

Isocyanate compound is commonly called " urethane acrylate  with the reaction product with specific (methyl) acryl compound of hydroxyl.In addition, isocyanate compound and the reaction product of specific (methyl) acryl compound with carboxyl are for combining the compound of structure of (methyl) acryloyl group of polymerism by amide groups.Below these compounds are described.

As specific (methyl) acryl compound, be representative compounds as the hydroxy ester of the reaction product of (methyl) acrylic acid and polyol with hydroxyl.Can be set forth in addition on the hydroxyl of this hydroxy ester in addition compounds that form such as oxirane, expoxy propane, caprolactone etc.Can also enumerate the compound that the part of hydroxyl by this hydroxy ester of monocarboxylic acid esterification forms.

Several these compounds of illustration, list (methyl) hydroxyethyl acrylate, (methyl) acrylic acid hydroxypropyl ester, (methyl) hydroxybutyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritoltetraacrylate, (methyl) crylic acid hydroxy ester of five acrylic acid dipentaerythritol ester etc., the isocyanuric acid diacrylate, diacrylate pentaerythritol ester monostearate, 2-hydroxyl-3-benzene oxygen propyl group acrylate, their caprolactone addition product in addition, ethylene oxide adduct, propylene oxide adduct, oxirane propylene oxide adduct etc.

In addition, also can utilize the hydroxyl of epoxy acrylate.As concrete compound, can enumerate the neopentylglycol diglycidyl ether of sening as an envoy to, 1, the reaction of the compound that in 1 molecule, has 2 epoxy radicals of 6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, ethylene glycol diglycidylether, propylene glycol diglycidylether etc. and acrylic acid and the epoxy acrylate that obtains.These compositions are because have 2 (methyl) acryloyl groups, so the effect that crosslink density is improved is also arranged in 1 molecule.

As specific (methyl) acryl compound with carboxyl; can list (methyl) acrylic acid itself, make carboxylic acid anhydrides, for example the reaction of maleic anhydride, succinyl oxide, phthalic anhydride, tetrahydrophthalic anhydride etc. and above-mentioned (methyl) crylic acid hydroxy ester and the compound that generates etc.

Its several examples of illustration can list pentaerythritol triacrylate butanedioic acid one ester, five acrylic acid dipentaerythritol ester butanedioic acids, one ester, pentaerythritol triacrylate maleic acid one ester, five acrylic acid dipentaerythritol ester maleic acids, one ester, pentaerythritol triacrylate phthalic acid one ester, three acrylic acid dipentaerythritol ester phthalic acids, one ester, pentaerythritol triacrylate tetrahydrophthalic acid one ester, five acrylic acid dipentaerythritol ester tetrahydrophthalic acids, one ester etc.

When the reaction of isocyanate compound and specific (methyl) acryl compound, also can and with can with other active dydrogen compounds of isocyanate compound reaction.That is, also can and with do not have (methyl) acryloyl group and also can with the compound of isocyanates radical reaction.

When selecting according to purpose and during with such active dydrogen compounds, the softening point of resulting solidification compound can uprise sometimes, or the flexible increase of the cured coating film that finally obtains etc.As such compound bearing active hydrogen that contains, usually use and contain the compound of hydroxyl, contain amino compound, contain the compound of carboxyl etc. but also can use.

As the compound that contains hydroxyl, use glycerine, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 2-ethoxy-1,6-hexylene glycol, 1,2, the polyalcohols with 3 above hydroxyls of 4-butantriol, erythrite, D-sorbite, pentaerythrite, dipentaerythritol etc.; Ethylene glycol, diethylene glycol, propane diols, DPG, tripropylene glycol, 1, the 2-butanediol, 1, the 3-butanediol, 1, the 4-butanediol, 2, the 3-butanediol, the 2-methyl isophthalic acid, ammediol, 2,2-diethyl-1, ammediol, 2-methyl-2-propyl group-1, ammediol, 2-butyl-2-ethyl-1, ammediol, 1, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 2-methyl-2, the 4-pentanediol, 1, the 6-hexylene glycol, 2-ethyl-1, the 3-hexylene glycol, neopentyl glycol, 1,3,5-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1, the 3-pentanediol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, the 2-methyl isophthalic acid, the aliphatic diol of 8-ethohexadiol etc., 1, the 4-cyclohexanediol, 1, the alicyclic diol of 4-cyclohexanedimethanol etc., benzene dimethanol, the aromatic diol of dihydroxy ethoxybenzene etc. etc.

In addition, also can use the high molecular weight polyols of PPG, PEPA, polyester ether polylol, polycarbonate polyol, polyacrylamide polyalcohol etc.As PPG, list the glycols of bisphenol-A and ethylene glycol, propane diols, diethylene glycol etc., the polyalcohols with 3 above hydroxyls of glycerine, trimethylolethane, trimethylolpropane, pentaerythrite etc. perhaps makes the polyamines class addition polymerization of the alkylene oxide of oxirane, expoxy propane etc. and ethylenediamine, toluenediamine etc. and the material that generates and ring-opening polymerisation oxolane and polytetramethylene ether diol of obtaining etc.

As PEPA, list and pass through butanedioic acid, adipic acid, decanedioic acid, azelaic acid, the dicarboxylic acids of phthalic acid etc., or trihemellitic acid, the carboxylic acids and the ethylene glycol of the tricarboxylic acids of pyromellitic acid etc. or tetrabasic carboxylic acid etc., propane diols, 1, the 4-butanediol, 1, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 2, the 2-DEP, 2-ethyl-2-butyl propane diols, 1, the 6-hexylene glycol, neopentyl glycol, diethylene glycol, 1, the 4-cyclohexanediol, 1, the dihydroxylic alcohols of 4-cyclohexanedimethanol etc., trimethylolpropane, the trihydroxylic alcohol of glycerine etc. or bisphenol-A, the polycondensation reaction of the fragrant family polyol of Bisphenol F etc. and the material that obtains.

As polyester ether polylol, enumerate the product of sening as an envoy to the reaction of alkylene oxide and polyester-diol and generating, maybe this contains the mixture reaction of the dihydroxylic alcohols of ether and other glycol and the product that generates to make above-mentioned dicarboxylic acids or their acid anhydrides and the dihydroxylic alcohols that contains ether, poly-(polytetramethylene ether) adipate ester etc. for example.As polycarbonate polyol, list dealcoholization condensation reaction, polyalcohol and dipheryl carbonate base ester by the dialkyl carbonate of polyalcohol and dimethyl, diethyl etc. dephenolize condensation reaction, polyalcohol and ethylene carbonate take off the polycarbonate polyol that ethylene glycol condensation reaction etc. obtains.As the polyalcohol that in this condensation reaction, uses, for example can enumerate 1,6-hexylene glycol, diethylene glycol, propane diols, 1,4-butanediol, 1,5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2, the aliphatic diol or 1 of 2-DEP, 2-ethyl-2-butyl propane diols, neopentyl glycol etc., 4-cyclohexanediol, 1, the alicyclic diol of 4-cyclohexanedimethanol etc.

In addition, as containing amino compound (amines), list hexamethylene diamine, xyxylene diamines, IPD, N, N-dimethyl-ethylenediamine etc.In addition, the amino alcohol of monoethanolamine, diethanol amine etc. also can be used as and contains the compound bearing active hydrogen use.

In addition, as the compound that contains carboxyl (organic carboxyl acid), list laurate, stearic acid, oleic acid, palmitic acid, adipic acid, decanedioic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA) etc.

These active dydrogen compounds beyond specific (methyl) acryl compound; for the characteristic of the reaction product that do not damage isocyanate compound and specific (methyl) acryl compound, the mol ratio of the reactive base of reactive base specific relatively (methyl) acryl compound of preferred active dydrogen compounds is below 50%, is preferably below 40% especially.

The reaction of isocyanate compound and specific (methyl) acryl compound preferably uses solvent to carry out.By using solvent, control reaction easily, and the viscosity that can regulate reaction product.As solvent, the atent solvent that use is used always in this kind reaction, the aromatic hydrocarbon series solvent of toluene, dimethylbenzene etc. for example, the ketone series solvent of MEK, methylisobutylketone, cyclohexanone etc., the ester series solvent of ethyl acetate, butyl acetate, isobutyl acetate etc., the glycol ether-ether series solvent of diethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, 3-methyl-3-methoxyl group butylacetic acid ester, ethyl-3-ethoxy-c acid esters etc., the ether series solvent of oxolane, two  alkane etc., the non-proton property polar solvent of N-methyl pyrrolidone etc. etc.

Reaction, can in solvent, add reaction raw materials, make the reaction product concentration in the reaction solution become 30～80 weight %, if necessary, in the presence of the organotin series catalysts of 0.01～0.1 weight %, make it reaction at 50～80 ℃ with respect to reaction raw materials.Isocyanate compound and specific (methyl) acryl compound and according to circumstances by and the input ratio of other active dydrogen compounds of usefulness; with respect to 1 mole of the NCO of isocyanate compound; can preferably reach more than 0.5 mole with specific (methyl) acryl compound of its reaction and the functional group of other active dydrogen compounds, especially preferably reach more than 1 mole.Reaction time is normally about 3～8 hours, but by analyzing, the NCO content in the following response Generation Liquid, preferably it stops reaction in the moment that arrives desired value.

As ionizing radiation solidification compound of the present invention, be the isocyanate compound of preparation like this and the reaction product of specific (methyl) acryl compound, the use softening point is the reaction product more than 40 ℃.The softening point of ionizing radiation solidification compound, preferably more than 50 ℃, be more preferably more than 60 ℃.When the softening point of ionizing radiation solidification compound is lower than 40 ℃, the middle caking (blocking) that produces of filming before curing, the embossing embossability becomes bad.

In addition, the so-called softening point of regulation in the present invention refers to the softening point that adopts following condition to measure to the part of having removed solvent from reaction product.

Use machine: レ オ メ ト リ Star Network ス company produces, ARES-2KFRTNI

Rating model: moving viscoelastic temperature dependency test, 25mm parallel-plate

Measure temperature range :-50～150 ℃

Vibration frequency: 1rad/ second

The temperature that melt viscosity when measuring under these conditions reaches 5000Pa second is defined as softening point

In addition, (methyl) acrylic in the ionizing radiation solidification compound of the present invention, (molecular weight C=C-) is calculated as 24, is preferably more than the 5 weight %, is more preferably more than the 10 weight % with the two keys of alkene.When (methyl) acrylic after a little while, the crosslink density after ionizing radiation solidifies descends, deficiencies such as solvent resistance, hear resistance, the excipient sagging when peeling off bad, vinyl chloride system film etc.

In addition, the content of the two keys of alkene is measured by IR, NMR etc., but manufacturing process also can be obtained by calculating by input amount when known.

The coating fluid of Shi Yonging in the present invention except that mentioned component, in order to give fissility to ionizing radiation cured film surface, preferably also contains silicone compounds and constitutes.In the present invention, following state bright like that, when the ionizing radiation cured film is formation more than two layers, also the layer that does not contain silicone compounds can be set.

In the present invention, the preferred ionizing radiation cured film surface release surface of synthetic leather (promptly with), to have ratio from the silicon of siloxanes be 5～30%, and it is more than 5% that there is ratio in the silicon from siloxanes when the operation of using processing release paper to make synthetic leather is repeated 5 times, above-mentioned ionizing radiation cured film surface.In addition, in this manual, so-called " there is ratio  in the silicon from siloxanes, refers to the atom % (wherein, ignoring hydrogen atom) by X linear light electronics spectrum analysis (hereinafter referred to as XPS) silicon atom from the atom that the processing release paper surface detects.The ratio that exists of the silicon by making ionizing radiation cured film surface is 5～30%, also can keep excellent fissility even use in the manufacturing of synthetic leather.Distinguish in addition, if the ratio that exists of the silicon that derives from siloxanes when the operation that will use processing release paper of the present invention to make synthetic leather repeats 5 times, above-mentioned ionizing radiation cured film surface is more than 5%, even then use processing release paper to make the fissility that synthetic leather also can fully be kept processing release paper repeatedly.

Silicone compounds content in the coating fluid that contains the ionizing radiation solidification compound is below the 20 weight %, and preferably 0.5～20 weight % is more preferably 1～15 weight %.When silicone compounds during more than 20 weight %, film and be clamminess, cost uprises, when being less than 0.5 weight %, fissility to improve effect insufficient.

The silicone compounds of Shi Yonging in the present invention can be reactive also can right and wrong reactive.As the reactive siloxane compound, can list the silicone compounds of the modification of (methyl) acryloyl group, vinyl modification, amino modified, sulfhydryl modified, epoxy radicals modification, carboxy-modified, phenol-modified, pure modification.

As concrete compound; as (methyl) acryloyl group modified siloxane; can enumerate X-22-164B; X-22-164C (production of chemical industrial company of SHIN-ETSU HANTOTAI); FM-0711; FM-0721; FM-0725 (production of チ Star ソ company); as the vinyl modified siloxane; can enumerate XF40-A1987 (the Star リ コ of Toshiba-ソ company produces); as amino modified siloxanes; can enumerate TSF4700; TSF4702; TSF4705 (the Star リ コ of Toshiba-ソ company produces); X-22-161AS; KF393; KF864 (production of chemical industrial company of SHIN-ETSU HANTOTAI); BY16-208; SF8417 (East レ ダ ウ コ-ニ ソ グ Star リ コ ソ company produces); as sulfhydryl modified siloxanes; can enumerate X-22-167B; KF-2001 (production of chemical industrial company of SHIN-ETSU HANTOTAI); as the epoxy radicals modified siloxane; can enumerate YF-3965; TSF-4730 (the Star リ コ of Toshiba-ソ company produces); KF105; X-22-169AS (production of chemical industrial company of SHIN-ETSU HANTOTAI); SF8421; SF8413 (East レ ダ ウ コ-ニ ソ グ Star リ コ ソ company produces); as carboxy-modified siloxanes; can enumerate TSF4770; XF-A9248 (the Star リ コ of Toshiba-ソ company produces); X-22-162A; X-22-3701E (production of chemical industrial company of SHIN-ETSU HANTOTAI); SF8418; BY16-750 (East レ ダ ウ コ-ニ ソ グ Star リ コ ソ company produces); as phenol-modified siloxanes; can enumerate X-22-165B (production of chemical industrial company of SHIN-ETSU HANTOTAI); BY16-752; BY16-150C (East レ ダ ウ コ-ニ ソ ダ Star リ コ ソ company produces); as pure modified siloxane, can enumerate TSF4750; TSF4751 (the Star リ コ of Toshiba-ソ company produces); BY16-848; BY16-201 (East レ ダ ウ コ-ニ ソ ダ Star リ コ ソ company produces); FM-4411; FM-4425; FM-0411; FM-0425; FM-DA21 (production of チ Star ソ company) etc.

In addition, also can use the silicone compounds that adopts these reactive siloxane synthetic.In synthetic silicone compounds, can further have reactive base, also can not have reactive base.As using the synthetic silicone compounds of reactive siloxane; can enumerate silicone-modified (methyl) propenyl polymer and silicone-modified (methyl) acrylate of having used (methyl) acryloyl group modified siloxane; use the silicone-modified epoxy acrylate of epoxy radicals modified siloxane, used the silicone-modified urethane ester polymer of pure modified siloxane and silicone-modified urethanes acrylate etc.Wherein, preferred especially silicone-modified urethanes acrylate.

As non-reacted silicone compounds, can enumerate silicone compounds with above-mentioned reactive base.As concrete compound, as dimethyl polysiloxane, can enumerate TSF451, YF3800 (the Star リ コ of Toshiba-ソ company produces), KF96A (production of chemical industrial company of SHIN-ETSU HANTOTAI), SH200 (East レ ダ ウ コ-ニ ソ グ Star リ コ ソ company produces), as methyl phenyl silicone, can enumerate TSF433, TSF434 (the Star リ コ of Toshiba-ソ company produces), SH510, SH702 (East レ ダ ウ コ-ニ ソ グ Star リ コ ソ company produces), as polyether modified siloxane, can enumerate TSF4440, TSF4445 (production of シ リ コ one Application company of Toshiba), KF-351, KF-353 (production of chemical industrial company of SHIN-ETSU HANTOTAI), SH3746, SH-3748 (East レ ダ ウ コ-ニ ソ グ Star リ コ ソ company produces), SS-2803, SS-2801 (Japanese ユ ニ カ-company produces) etc.

These silicone compounds can use, also can use two or more separately, also can use reactivity, non-reacted both mixture.In addition, from the viewpoint of intermiscibility of other composition etc., silicone compounds is preferably aromatic series, alicyclic, compound with ring structures such as isocyanuric acid skeletons.As silicone compounds with ring structure, also can be set forth in side chain import phenyl methyl phenyl siloxane etc. silicone compounds and use reactive siloxane to import the method for ring structure.As using reactive siloxane to import the method for ring structure; can enumerate (methyl) acryloyl group modified siloxane and styrene copolymerized to import the silicone compounds of phenyl, the monomer of use methyl diphenylene diisocyanate, naphthalene diisocyanate, IPDI, its trimer etc. import the silicone compounds of ring structure etc. in silicone-modified urethane ester polymer, silicone-modified urethanes acrylate.These have the silicone compounds of ring structure, can further have reactive base, also can not have reactive base.

In the present invention, be that pin hole further tails off more than two layers by making the ionizing radiation solidifying film layer, so being preferably formed is more than two layers.Preferably each layer more than two layers at least more than one deck in contain silicone compounds 0.5～20 weight %.In addition, more preferably in the superiors' (being the release surface of synthetic leather) of the side configuration opposite, contain silicone compounds 0.5～20 weight % with supporter one side.Like this,, fissility is improved, in addition,, also can fully keep the fissility of processing release paper even use processing release paper to make synthetic leather repeatedly by containing silicone compounds in uppermost surface.In addition, when constituting the ionizing radiation cured film with multilayer, the layer beyond the superiors also can not contain silicone compounds.

The coating fluid of Shi Yonging in the present invention except silicone compounds, for the curing characteristics to reaction product carries out upgrading, as any composition, also can make it to contain and has the resin of making film and inorganic pigment etc.

At this moment, further preferably in orlop, contain 0.5～50 weight %, especially preferably contain the inorganic pigment of 1～10 weight %.As the inorganic pigment that uses therein, can enumerate talcum, kaolin, silica, calcium carbonate, barium sulfate, titanium oxide, zinc oxide etc.

As preferred form, be the inorganic pigment that in the orlop that is configured in supporter one side, contains 0.5～50 weight %, the silicone compounds that contains 0.5～20 weight % in the superiors of the side configuration opposite with supporter one side forms.Like this, contain inorganic pigment, make the layer opposite (layer of synthetic leather release surface one side) contain silicone compounds, can give excellent fissility with supporter one side by the layer that makes supporter one side.Its reason is uncertain, but for example make when containing inorganic pigment and silicone compounds in the same ionizing radiation solidifying film layer, reason is the coating condition difference according to coating fluid, and silicone compounds is subjected to inorganic pigment influence (for example, silicone compounds adsorb etc.) sometimes on inorganic pigment.In addition, when for example paying attention to giving the design effect of dullish etc. to the processing release paper surface, also can be in the superiors of the side configuration opposite, adding inorganic pigment with supporter one side.

As having the resin of making film, can use methacrylic resin, chlorinated polypropylene, epoxy resin, polyurethane resin, mylar, polyvinyl alcohol, polyvinyl acetal etc.In addition, these have the resin of making film, can responding property base, also can not have reactive base.As reactive base, can enumerate (methyl) acryloyl group, vinyl, amino, sulfydryl, epoxy radicals, carboxyl, phenylol, hydroxyl etc.From to the adhesive force of base material, system film etc., be preferably methacrylic resin, but viewpoint from the embossing processability, be preferably glass transition temperature (Tg) and be the methacrylic resin more than 40 ℃, be more preferably Tg and be the methacrylic resin more than 50 ℃, except common methacrylic acid based compound, also maleic anhydride, methacrylic acid, styrene, methacrylic acid hydroxyethyl ester, the methacrylate that contains dimaleoyl imino, the methacrylate that contains isobornyl etc. can be used as copolymer composition.

Consumption with resin of making film, as the content in the coating fluid, normally below the 70 weight %, preferably 1～70 weight % is more preferably 20～60 weight %.Have the resin of making film when surpassing 70 weight %, when promptly the ionizing radiation solidification compound was less than 30 weight %, the hear resistance after ionizing radiation solidifies became insufficient.Have the resin of making film by an amount of cooperation, have pair base material adhesive force, make improved effects such as film.

In addition, in coating fluid, have the resin of making film, the silicone compounds except that above-mentioned, perhaps replace these materials, also can make it to contain reactive monomer, reactive oligomers, pigment, Photoepolymerizationinitiater initiater, polymerization inhibitor, colouring agent, surfactant etc.

As reactive monomer, preferred (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid ethylhexyl, (methyl) stearyl acrylate acyl ester, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, trimethylolpropane triacrylate, three (acryloxy ethyl) chlorinated isocyanurates, pentaerythritol tetracrylate, the six acrylic acid dipentaerythritol ester etc. used.

As reactive oligomers, preferably use epoxy acrylate, urethanes acrylate, polyester acrylate, polyether acrylate etc.

As Photoepolymerizationinitiater initiater, preferred use benzoin ethyl ether, acetophenone, diethoxy acetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methyl propiophenone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1,1-hydroxycyclohexylphenylketone, benzophenone, to chlorobenzophenone, Michler's keton, N, N-dimethylaminobenzoic acid isopentyl ester, 2-chlorothiaxanthenone, 2,4-diethyl thioxanthone etc.

In addition, add suitably that solvent is coated with and make the viscosity that reaches easy coating.As solvent, for example use aromatic hydrocarbon series solvents such as toluene, dimethylbenzene, ketone series solvents such as MEK, methylisobutylketone, cyclohexanone, ester series solvents such as ethyl acetate, butyl acetate, isobutyl acetate, the glycol ether-ether series solvent of diethylene glycol ether acetic acid esters, propylene glycol methyl ether acetate, propane diols monomethyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, ethyl-3-ethoxy-c acid esters etc., ether series solvents such as oxolane, two  alkane, the non-proton property polar solvent of N-methyl pyrrolidone etc. etc.

The ionizing radiation cured film

Constitute the ionizing radiation cured film of processing release paper of the present invention, by being coated with above-mentioned coating fluid and making it to be solidified to form.Coating fluid can use with respect to 100 weight portion solid constituents, the common coating fluid that obtains with the solvent dilution of 10～1000 weight portions.By the dilution of solvent, giving the viscosity that is suitable for being coated with, for example be in 10～3000mPa viscosity of second under 25 ℃, silicone compounds is suitably shifted to the surface.

Coating method as coating fluid, the coating of use direct-type heliogravure, the coating of reverse heliogravure, heliogravure offset printing coating, the coating of little heliogravure, direct-type roller coat cloth, contrary roller coat cloth, heavy curtain coating, scraper coating, airblade coating, rod are coated with, known method such as mould is coated with, the coating of spraying, after coating on the paper base material,, the solvent evaporation films thereby being formed.

If the dry weight after coating fluid evaporates by solvent reaches 1～40g/m ², preferably reach 5～20g/m ²Mode be coated with, just can obtain good embossing embossability.

In addition, the ionizing radiation solidifying film layer preferably is made for more than two layers, and by being made for more than two layers, pin hole further tails off.When being made for the ionizing radiation solidifying film layer more than two layers, preferably in undermost ionizing radiation solidifying film layer, containing 0.5～50 weight % inorganic pigment, especially preferably contain 1～10 weight % inorganic pigment.As inorganic pigment, can compatibly use talcum, kaolin, silica, calcium carbonate, barium sulfate, titanium oxide, zinc oxide etc.

In addition, in the ionizing radiation solidifying film layer, also can contain silicone compounds.At this moment, can only in the superiors of ionizing radiation solidifying film layer, contain silicone compounds, in addition, also can in each layer, contain.

Above-mentioned coating fluid of coating and dry filming of forming on supporter because be noncohesive, so, can not batching together with paper base material after the drying with having adhesion, the embossing of following process can be implemented with offline mode.By suitably setting the softening temperature of dandy roll temperature and coating fluid, coating fluid can not be attached to dandy roll, can obtain good embossability in addition.

Embossing processing generally is that transfer printing has the method that the metal dandy roll of ridge design comes excipient, but also can use the pressue device of belt, lithographic plate formula.When using dandy roll, the burr with respect to dandy roll is arranged, with backing roll as the two sides embossing of dimpled grain with on backing roll, there is not concavo-convex single face embossing.

On the supporter that has been coated with coating fluid, when using these Embossers to carry out excipient, the temperature of coating fluid is heated as 50～150 ℃.This temperature is preferably than the softening point height of the ionizing radiation solidification compound that contains in the coating fluid and the scope lower than the temperature of resin fusion.Mode of heating usually to dandy roll circulation steam etc., make roller heating itself, but the preheating method that also before being about to embossing, coating fluid is heated.

In order to obtain above-mentioned good no adhesive, embossability, the softening point of ionizing radiation solidification compound, as discussed previously is more than 40 ℃, preferably more than 50 ℃.When softening point during less than 40 ℃, no adhesive, embossability become insufficient.

Behind the embossing excipient,, make to be coated with the curing curing of coating that coating fluid forms from a curing property side irradiation ultraviolet radiation or electron beam of filming.As ultraviolet light source, use low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, metal halide lamp, xenon lamp, tungsten lamp etc.As the electron beam radiation modality, use scan mode, curtain bundle mode, wide beam mode etc., the accelerating potential of electron beam is advisable with 50～300kV.

Fig. 1 is the figure of an example of expression processing release paper of the present invention manufacturing process.Among the figure, 1 expression pull roll, 2 expression dandy rolls, 3 expression backing rolls, 4 expression takers-ins, 5 expressions have the paper that curing property films, the paper that 6 expressions are filmed with the curing that has embossing, the processing release paper that 7 expressions have embossing.In addition, A represents that embossing manufacturing procedure, B represent the irradiation process of ionizing radiation.

(2) supporter that on the processing release paper that has embossing of synthetic leather manufacturing usefulness, uses

Fig. 2 represents the supporter of synthetic leather manufacturing of the present invention with processing release paper.

Synthetic leather manufacturing of the present invention comprises body paper 12 and the clay coating 13 that forms thereon with the supporter 11 of the processing release paper that has embossing.Even body paper 12 was placed 3 minutes down by having at 230 ℃, the hot strength that utilization records based on the assay method of JIS P8113 standard, vertically maintaining more than the 10kN/m at least, and, the tearing strength that utilization records based on the assay method of JIS P8116 standard all maintains stable on heating neutralized paper such more than the 500mN in longitudinal and transverse direction and constitutes.In addition, the clay coating 13 that forms on this body paper has the smoothness more than 100 seconds that utilization records based on the test method of JIS P8119 standard, and it forms and makes and is absorbed by the concave-convex surface due to the paper pulp fiber of body paper.

Therefore, utilize the processing release paper that uses supporter of the present invention, can obtain having the high-fire resistance that can tolerate necessary 230 ℃ of temperature in the manufacturing of vinyl chloride resin synthetic leather, in the synthetic leather manufacturing, can tolerate the processing release paper that uses repeatedly more than 5 times.

As the paper pulp that is used for body paper,, can compatibly use the paper pulp that has mixed coniferous tree paper pulp (N material) and broad leaf tree paper pulp (L material) in order to obtain necessary strength and flatness.At this moment, in order to improve flatness, the composite rate of broad leaf tree paper pulp (L material) preferably 50～90%.The composite rate of broad leaf tree paper pulp (L material) is lower than 50% o'clock flatness and descends, so not preferred.On the other hand, the intensity of body paper descends when being higher than 90%, so not preferred.In addition, in paper pulp raw material, also can add filler, paper strength improving agent, stabilizing agent etc.

For processing release paper being given sufficient hear resistance, body paper must be a neutralized paper.Copy the packing agent of paper as neutrality, can enumerate alkyl ketene dimer (AKD), alkenyl succinic anhydrides and cation property copolymer.Wherein, because alkyl ketene dimer is more stable, so preferred.In addition, as fixative, when using aluminum sulfate, because the intensity of paper significantly descends under the high temperature more than 200 ℃, so, should not use aluminum sulfate.

The weight per unit area of body paper is processed viewpoints such as adaptability, preferably 100～200g/m from durability and embossing that intensity, synthetic leather processing operation, processing release paper as the processing release paper goods use repeatedly ²Weight per unit area is lower than 100g/m ²The time, wave when making, synthetic leather just takes place to curl, rise easily.On the other hand, weight per unit area is greater than 200g/m ²The time, the embossing processability worsens, and in addition, because the processing release paper thickening makes its drum diameter become big, operating efficiency descends.

The manufacturing paper with pulp of body paper can adopt many paper machines of fourdrinier wire, many paper machines of short net, many paper machines of cylinder, many paper machines of the short net associating of fourdrinier wire, the associating of fourdrinier wire cylinder many paper machines, fourdrinier wires to raise basic paper machine etc. to carry out.

The clay coating is by being adhesive with styrene butadiene latex, vinyl acetate emulsion, acrylic based emulsion, starch, casein etc., and contain kaolin therein, the coating of inorganic pigments such as calcium carbonate, talcum, silica, titanium oxide, aluminium hydroxide constitutes.Can adopt Kohler coater, scraper plate coating machine, rod to be coated with machine, conveying roller coating machine, contrary roll-coater, heliogravure coating machine, mould is coated with the coating machine of machine, notch rod coating machine, flow coat machine etc. or is used in combination these coating machines and be coated with these coating and form.In order to obtain necessary flatness, promptly smoothness is that coating weight is 5～40g/m preferably more than 100 seconds in utilizing based on the test method of JIS P8119 standard ²Coating weight is less than 5g/m ²The time can not get necessary flatness, on the other hand, greater than 40g/m ²The time, the embossing embossability descends.

To the carclazyte coating of body paper, can in machine hand's preface, carry out continuously, or in other operation, carry out.In addition, after coating coating, again from calender roll by improving surface smoothing.

Preferred example as supporter of the present invention, body paper is that the composite rate by broad leaf tree paper pulp (L material) is that 50～90% the broad leaf tree paper pulp and the mixed pulp of coniferous tree paper pulp constitute, even and carry out papermaking and make to have and placed 3 minutes at 230 ℃, the hot strength that utilization records based on the assay method of JIS P8113 standard, vertically maintaining more than the 10kN/m at least, and, utilization all maintains stable on heating neutralized paper such more than the 500mN based on the tearing strength that the assay method of JIS P8116 standard records in vertical, horizontal.In order to obtain such supporter, preferably on body paper with 5～40g/m ²Coating weight smoothness that form to utilize the assay method based on JIS P8119 standard to record be clay coating more than 100 seconds.With in the supporter of processing release paper, can on the clay coating, form level and smooth ionizing radiation curable resin layer in such synthetic leather manufacturing.That is, on the ionizing radiation curable resin layer that is arranged on the supporter, apply embossing processing, after this, irradiation ionizing radiation and the configuration of surface of the ionizing radiation cured film that makes it to solidify is not subjected to by the concavo-convex influence due to the body paper fiber.

Fig. 3 represents to use the synthetic leather manufacturing processing release paper of synthetic leather manufacturing of the present invention with supporter 11 formation of processing release paper.

Synthetic leather manufacturing of the present invention obtains via following operation with processing release paper: the operation that uncured ionizing radiation curable resin film is set on the clay coating of supporter; On uncured ionizing radiation curable resin film, apply the operation of embossing; With after the embossing operation, above-mentioned ionizing radiation curable resin film is shone the operation that ionizing radiation makes it to solidify.

Synthetic leather manufacturing of the present invention has the high-fire resistance that can tolerate necessary 230 ℃ of temperature in the manufacturing of vinyl chloride resin synthetic leather with the processing release paper that has embossing, can use repeatedly more than 5 times in the manufacturing process of synthetic leather.In addition, in transfer process, processing release paper can not extend, so, can be with high transfer printing precision to the type of epidermal area with transfer printing processing release papers such as polyurethane resin, polyvinyl chloride.And, because body paper is not subjected to by the concavo-convex influence due to the paper pulp fiber, so, the surface that has reflecting feel had.Therefore, can obtain to make processing release paper with the synthetic leather that has the reflecting feel style.

Supporter as other form of the present invention, except loan (paper of wood-free), brown paper, machine-processed glazed paper, pure white roll-in paper, glassine paper, cup with the uncoated papers such as body paper, also can use the art paper that is provided with the inorganic pigment coating layer, coated paper, curtain coating coated paper etc. coated paper, do not use the synthetic paper of natural pulp etc.When particularly in the manufacturing of PVC leather, using, because hear resistance for high temperature process more than 200 ℃ must be arranged, so, compared with acidic paper, more preferably use neutralized paper.In acidic paper, as packing agent, use is the rosin series packing agent of aluminum sulfate as fixative, but in neutralized paper, uses the inert filler agent of the neutral rosin series packing agent that aluminum sulfate is not used as fixative, alkyl ketene dimer (AKD), alkenyl succinic anhydrides (ASA) etc.

In addition, in embossing processing, for embossability good, full intensity is arranged, and have the flatness of appropriateness, preferred paper pulp is the mixed stocker paper pulp of coniferous tree paper pulp and broad leaf tree paper pulp, coniferous tree paper pulp contains more than 20% at least, and weight per unit area is 80～250g/m ²

In addition,, can suppress to infiltrate the pin hole that causes and take place, also can give flatness, so preferred by coating fluid when having the resin of making film or in these resins, add mixture that inorganic pigment forms when constituting shim applying on these supporters by above-mentioned.

Make the resin of film as being used to form having of shim, polyvinyl alcohol, acrylic resin, styrene acrylic resin, cellulose derivative, mylar, polyurethane resin, melmac, alkyd resins, amino-alkyd resin, Corvic, polyvinylidene chloride resin etc. are arranged, also can mix these resins and use.

Inorganic pigment as adding has talcum, kaolin, silica, calcium carbonate, barium sulfate, titanium oxide, zinc oxide etc., with respect to having the film of making resin, cooperates usually to reach 0.5～70 weight %.This shim can be 0.5～20g/m ²If very fewly just can not bring into play the filler effect, if too much just hinder the embossing embossability.The coating of filler material can be carried out with the same method of the coating fluid that contains above-mentioned ionizing radiation hardening resin composition.

(3) use has the synthetic leather and the manufacture method thereof of the processing release paper manufacturing of embossing

Synthetic leather

The synthetic leather that uses the above-mentioned processing release paper that has embossing to make, it is below 20% that there is ratio in the silicon from siloxanes on surface of having peeled off a side of processing release paper.When peeling off processing release paper making synthetic leather, just exist from the next silicone compounds to a certain degree of processing release paper transfer on this synthetic leather that obtains surface.The inventor etc. have been confirmed by the XPS analysis on processing release paper surface and synthetic leather surface should the fact.That is, shift the silicone compounds amount (there is ratio in the silicon from siloxanes) of coming from processing release paper, even refer to maximum, also the silicon from siloxanes than processing release paper surface exists ratio little.Even the inventor etc. obtain when using processing release paper to make synthetic leather repeatedly, it also is this opinion below 20% that there is ratio in the silicon from siloxanes on surface of having peeled off a side of processing release paper.

In addition, even as described above, use processing release paper of the present invention, when making synthetic leather repeatedly, it also is below 20% that there is ratio in the silicon from siloxanes of the stripper surface of this synthetic leather.Therefore, even when using processing release paper repeatedly, also keeping the fissility of processing release paper excellence.

The manufacture method of the synthetic leather of first form

The manufacture method of the synthetic leather of first form of the present invention, be to use to possess at least, and on this cured film, apply the manufacture method of the processing release paper that has embossing that embossing processes as the paper of supporter and the ionizing radiation cured film that on this paper, is provided with.About this processing release paper, record and narrate in the back.

At first, applying of above-mentioned processing release paper on the ionizing radiation cured film of embossing processing, the coating polyurethane resin composition, heat drying forms epidermal area.As polyurethane resin composition, can compatibly use polyester is that aromatic isocyanate urethane, polyethers are that aromatic isocyanate urethane, polycarbonate-based aromatic series urethane, polyester are that aliphatic isocyanates urethane, polyethers are the one-pack type of aliphatic urethane and polycarbonate-based aliphatic ethyl isocyanate urethane.The coating polyurethane resin, though also depend on its composition, usually with 90～140 ℃ of heating, make it the drying.By using the processing release paper that uses in the present invention, even when carrying out drying with 150～250 ℃ high temperature, processing release paper can not be out of shape etc. yet, can carry out the embossing excipient of synthetic leather well.On the processing release paper that has applied embossing processing in this wise, become the urethane resin layer of the epidermal area of synthetic leather.

Secondly, on this epidermal area, form the synthetic leather layer by adhesive applying base fabric.As adhesive, can use mono-component polyurethane resin, bi-component curable polyurethane resin, melmac etc., but in the time must intensity being arranged, can compatibly use bi-component curable polyurethane resin.Bi-component curable polyurethane resin in as the polyester of host system, polyethers system, polycarbonate-based prepolymer glycol, mixes in use as the bi-component of the vulcabond of the fragrant family of curing agent or fatty family and uses.Make this compound reaction, use as adhesive.Behind coating adhesive on the epidermal area, the base fabric of fitting, make the adhesive dry solidification, fit thus epidermal area and base fabric thereon.The applying of this epidermal area and base fabric is usually by making adhesive reaction carry out in 2nd～3 in 40～70 ℃ curing chamber.In the present invention, the applying of epidermal area and base fabric also can be undertaken by any one of heat lamination and wet lamination, but more preferably heat lamination.Fitted by adhesive in this wise and become synthetic leather behind epidermal area and the base fabric.

Then, just obtain synthetic leather by peeling off above-mentioned processing release paper from this synthetic leather.By using the processing release paper that uses in the present invention, even with the PU resin during as epidermal area, release property is also excellent, so, can use processing release paper to make synthetic leather repeatedly.

The manufacture method of the synthetic leather of second form

The manufacture method of the synthetic leather of second form of the present invention, be to use manufacture method with above-mentioned same processing release paper, applying of above-mentioned processing release paper be coated with polyurethane resin composition on the ionizing radiation cured film of embossing processing, heat drying forms epidermal area.About this operation and first homomorphosis, omit explanation.

Then, lamination wet type intermediate layer on its epidermal area, from above-mentioned processing release paper one side by above-mentioned epidermal area of hot-rolling pressing and wet type intermediate layer.Operation becomes synthetic leather behind epidermal area and the wet type intermediate layer after the pressing in this wise.Pressing uses hot-rolling to carry out, and this hot-rolling is preferably 110～190 ℃.Here, the wet type intermediate layer is that coating makes polyurethane resin be dissolved in the solution that forms in the dimethyl formamide (DMF) on base fabric, it is flooded in water again, and DMF is replaced into water, urethanes is solidified obtain.In the wet type intermediate layer that obtains by such operation, form little porous layer.Therefore, by in synthetic leather, containing this wet type intermediate layer, the synthetic leather that can obtain softness, have rich true feeling style.

Then, this is become part (pressing epidermal area and middle synthetic leather layer and the pressing thing) cooling of synthetic leather after, peel off processing release paper, can make synthetic leather thus.

The manufacture method of the synthetic leather of the 3rd form

The manufacture method of the synthetic leather of the 3rd form of the present invention, be to use manufacture method with above-mentioned same processing release paper, applying of above-mentioned processing release paper be coated with vinyl chloride resin composition on the ionizing radiation cured film of embossing processing, heat drying forms epidermal area.As vinyl chloride resin composition, can enumerate making VCM, and the monomer copolymerization of VCM and vinyl acetate, ethene, propylene, maleate etc. and the polymer that obtains etc.Vinyl chloride resin composition uses that to add phthalic acid in above-mentioned resin be that plasticizer, fatty acid ester are the plasticizer and the gelatinization of plasticizer etc., adds the composition that obtains behind antioxidant, stabilizing agent, filler, the pigment etc. again in this paste.

The vinyl chloride resin of coating though also depend on its composition, solidifies with 200～250 ℃ of heat dryings by making it usually.By using the processing release paper that uses in the present invention, even when carrying out drying with 200～250 ℃ of high temperature, processing release paper can not be out of shape etc. yet, can carry out the embossing excipient of synthetic leather well.

Then, comprise on the epidermal area of vinyl chloride resin at this, the vinyl chloride resin composition of coating foaminess is by adding the thermosetting intermediate layer.As the vinyl chloride resin composition of foaminess, can use at the composition same with the composition that is used for epidermal area, added blowing agent such as Celogen Az, dinitrosopentamethylene tetramine and the composition that obtains.Usually, this foamable vinyl chloride-base resin compositions of coating on epidermal area, with 180～250 ℃ of heat dryings, foamable vinyl chloride is resin expanded thus, forms the intermediate layer.

On formed intermediate layer, by adhesive applying base fabric, formation synthetic leather layer.As adhesive, can compatibly use polyurethane binder of bi-component curing type etc.Behind coating adhesive on the epidermal area, the base fabric and make the adhesive dry solidification, fit thus epidermal area and base fabric of fitting thereon again.The bonding process of this epidermal area and base fabric is usually by making adhesive reaction carry out in 2nd～3 in 40～70 ℃ curing chamber.Like this, stretch the structure of interbed/adhesive/base fabric as epidermal area and the object that forms becomes synthetic leather.

Then, by peeling off above-mentioned processing release paper, can obtain synthetic leather from this synthetic leather.By using the processing release paper that uses in the present invention, even with polyvinyl chloride resin during as epidermal area, fissility is also excellent, so, can use processing release paper to make synthetic leather repeatedly.

The manufacture method of the synthetic leather of the 4th form

The manufacture method of the synthetic leather of the 4th form of the present invention, be to use manufacture method with above-mentioned same processing release paper, applying of above-mentioned processing release paper be coated with polyurethane resin composition on the ionizing radiation cured film of embossing processing, heat drying forms epidermal area.About this operation and first homomorphosis, omit explanation.

Then, on comprising the epidermal area of polyurethane resin, this is coated with foamable vinyl chloride-base resin compositions, by adding the thermosetting intermediate layer.For this intermediate layer and above-mentioned same, omit explanation.

On formed intermediate layer, by adhesive applying base fabric, formation synthetic leather layer.That is, as the structure of epidermal area/intermediate layer/adhesive/base fabric and the object that forms becomes synthetic leather.

Then, by peeling off above-mentioned processing release paper, can obtain synthetic leather from this synthetic leather.By using the processing release paper that uses in the present invention, even make when having made up the synthetic leather (semi-synthetic leather) of PU and PVC, fissility is also excellent, therefore can use processing release paper to make synthetic leather repeatedly.

Embodiment

Then, describe the present invention in detail by embodiment, the present invention only otherwise exceeding its main idea is not just limited by following examples.

1. the processing release paper that has embossing of the present invention's first form

(1) preparation of ionizing radiation solidification compound

Following five kinds of ionizing radiation solidification compounds have been prepared.

Ionizing radiation solidification compound A

In the reactor that mixer, reflux condenser, dropping funel and thermometer are housed, the Trimerization of Isophorone Diisocyanate thing (production of degussa company, VESTANAT, T1890) that adds 206.1g ethyl acetate and 133.5g is warmed up to 80 ℃ and makes it dissolving.After in solution, being blown into air, add the pentaerythritol triacrylate of 0.38g hydroquinone monomethyl ether, 249.3g and the mixture of pentaerythritol tetracrylate (production of Osaka organic chemistry industrial group, PVC ス コ-ト 300) and 0.38g dibutyltin dilaurate.80 ℃ make it to react 5 hours after, add the cooling of 688.9g ethyl acetate.The reaction solution that obtains has confirmed that through the result of infrared absorption spectrum analysis the absorption of NCO disappears.The softening temperature of removing the material behind the ethyl acetate from reaction solution distillation is 43 ℃.

Ionizing radiation solidification compound B

In the reactor that mixer, reflux condenser, dropping funel and thermometer are housed, add the Trimerization of Isophorone Diisocyanate thing of 256.67g MEK and 110g, be warmed up to 80 ℃ and make it dissolving.After in solution, being blown into air, add 0.30g hydroquinone monomethyl ether, 381.2g six acrylic acid dipentaerythritol ester and five acrylic acid dipentaerythritol ester mixture (production of Japanese chemical drug company, KAYARAD DPHA), 21.2g 1,4-butanediol and 0.30g dibutyltin dilaurate.80 ℃ make it to react 5 hours after, add the cooling of 939.02g MEK.The reaction solution that obtains has confirmed that through the result of infrared absorption spectrum analysis the absorption of NCO disappears.The softening temperature of removing the material behind the MEK from reaction solution distillation is 42 ℃.

Ionizing radiation solidification compound C

In the reactor that mixer, reflux condenser, dropping funel and thermometer are housed, add the Trimerization of Isophorone Diisocyanate thing of 256.67g MEK and 110g, be warmed up to 80 ℃ and make it dissolving.After in solution, being blown into air, add mixture, 30.08g epoxy acrylate (production of chemical company of common prosperity company, epoxy-ester 70PA) and the 0.20g dibutyltin dilaurate of 0.20g hydroquinone monomethyl ether, 146.65g pentaerythritol tetracrylate and pentaerythritol triacrylate.80 ℃ make it to react 5 hours after, add the cooling of 412.37g MEK.The reaction that obtains generates the result through the liquid infrared absorption spectrum analysis, has confirmed that NCO absorbs disappearance.The softening temperature of removing the material behind the MEK from reaction solution distillation is 68 ℃.

Ionizing radiation solidification compound D

In the reactor that mixer, reflux condenser, dropping funel and thermometer are housed, add 256.67g MEK and 110g IPDI (production of degussa company, VESTANAT, IPDI), be warmed up to 80 ℃ and make it dissolving.After in solution, being blown into air, add the mixture and the 0.40g dibutyltin dilaurate of 0.40g hydroquinone monomethyl ether, 448.53g pentaerythritol tetracrylate and pentaerythritol triacrylate.80 ℃ make it to react 5 hours after, add the cooling of 1046.57g MEK.The reaction solution that obtains has confirmed that through the result of infrared absorption spectrum analysis the absorption of NCO disappears.Remove the liquid that MEK is exactly a thickness from the reaction solution distillation, softening temperature can not be measured.

Ionizing radiation solidification compound E

Used to former state the mixture (Japanese chemical drug company produces, KAYARAD DPHA) of six acrylic acid dipentaerythritol ester and five acrylic acid dipentaerythritol ester.

(2) has the preparation of the resin of making film

Prepare following three kinds and have the resin of making film.

Resin a

In the reactor that mixer, reflux condenser, dropping funel and thermometer are housed, heating is dissolved with the solution of 30g isobornyl methacrylate, 65g methyl methacrylate, 5g GMA in 200g toluene, when being warmed up to 65 ℃ and reach 65 ℃ after later 2 hours, add 2 of 0.5g respectively, 2 '-azo two (2, the 4-methyl pentane nitrile), 65 ℃ of reactions 5 hours, obtain copolymer again.After this, the limit is blown into air, limit and is warmed up to 108 ℃ discontinuously, behind interpolation 0.2g hydroquinone monomethyl ether, the 0.2g triphenylphosphine, adds 2.5g acrylic acid, reaction 5 hours, obtains having the resin a that having of acryloyl group made film.

Resin b

In the reactor that mixer, reflux condenser, dropping funel and thermometer are housed, add 2 of 5g methacrylic acid 4-hydroxyethyl ester, 20g isobornyl methacrylate, 75g methyl methacrylate, 200g MEK, 0.5g, 2 '-azo two (2, the 4-methyl pentane nitrile), 65 ℃ of polymerizations 6 hours.After this; be blown into air; after adding 0.2g hydroquinone monomethyl ether, 0.2g dibutyltin dilaurate; add the acrylate that 10.7g contains NCO (fragrant river chemical company produces, VI-1) back, be warmed up to 80 ℃ of afterreactions 5 hours, obtain having the resin b that having of acryloyl group made film.

Resin c

Used to former state the commercially available product (production of Network ラ レ company, パ ラ ペ Star ト GF) of methacrylate resin.

(3) preparation of silicone compounds

Following three kinds of silicone compounds have been prepared.

Silicone compounds α

Mixer is being housed; reflux condenser; in the reactor of dropping funel and thermometer; add the 23.3g MEK; the 10g IPDI; 20.4g the mixture of pentaerythritol tetracrylate and pentaerythritol triacrylate and 0.10g dibutyltin dilaurate; 0.10g hydroquinone monomethyl ether; after in solution, being blown into air; 25 ℃ the reaction 3 hours after; the limit is warmed up to 80 ℃ discontinuously; limit reaction 5 hours; in the reactant that obtains; (チ Star ソ company produces to add 240.8g alcohol modified siloxane; FMDA21); after making it again to react 5 hours; add the cooling of 609.3g MEK, obtain containing the silicone-modified urethanes acrylate (silicone compounds α) of acryloyl group and siloxanes.

Silicone compounds β

In the reactor that mixer, reflux condenser, dropping funel and thermometer are housed, the solution of methacrylic acid 2-hydroxyethyl ester, the 40g styrene of 10g, the siloxanes of 40g methacrylic acid modification (チ Star ソ company produces, FM0711), 2g lauryl mercaptan has been dissolved in heating in the 200g MEK, when being warmed up to 65 ℃ and reach 65 ℃ after later 2 hours, add 2 of 0.6g respectively, 2 '-azo two (2, the 4-methyl pentane nitrile), again 65 ℃ of reactions 5 hours, obtain copolymer.Then; the mixture that makes 22.2g IPDI, 57.1g pentaerythritol triacrylate and pentaerythritol tetracrylate is 25 ℃ of reactions after 3 hours; the limit is warmed up to 80 ℃ discontinuously; the limit makes it to react 5 hours and the addition product 79.3g that obtains; this addition product 79.3g is joined above-mentioned obtaining in the copolymer; reacted 5 hours down at 80 ℃, obtain having the copolymer (silicone compounds β) of acryloyl group and siloxanes.

Silicone compounds γ

Used to former state the commercially available product (Japanese ユ ニ カ-company's production, SS-2803) of polyether modified siloxane.

(4) preliminary treatment of supporter

As supporter applying unit area weight is 125g/m ²Neutralized paper, the lining material as shim is used is coated with the acrylic based resin that machine is coated with the adding silica of following composition with rod, and makes dried coating thick in 5g/m ²Coating back was 110 ℃ of dryings 1 minute.

[acrylic resin]

The styrene acrylic emulsion

(production of starlight Polymer Company, X-436) 25 weight portions

The water soluble acrylic resin

(production of ヅ ヨ ソ ソ ソ Polymer Company, PDX-6102) 25 weight portions

Silica

(production of the Star リ of Fuji Star ア chemical company, サ イ Star リ ア 350) 10 weight portions

Isopropyl alcohol 25 weight portions

Water 25 weight portions

(5) modulation of coating fluid

Mix 30 weight portions above-mentioned ionizing radiation solidification compound A, 60 weight portions and have resin b and the 10 weight portion silicone compounds α (above-mentioned weight portion all is the solid constituent weight portion) that make film, prepared composition 1.The sampling said composition a part, measured softening temperature, be 76 ℃.

By similarly mixing, prepared composition 2～9 with the cooperation ratio shown in the following table 1 (solid constituent weight portion) with above-mentioned.In addition, as the inorganic pigment that uses, use silica (サ イ Star リ ア 350, the Star リ of Fuji Star ア chemical company produce).The part of sampling said composition, mensuration softening temperature.Put down in writing the result in the table 1 in the lump.

Table 1

Composition

Coating fluid (solid constituent weight portion)

Coating fluid soft

	The ionizing radiation solidification compound					Resin			Silicone compounds			Inorganic content	The change temperature (℃)
														A	B	C	D	E	a	b	c	α	β	γ
	1	30	-	-	-	-	-	60	-	-	10														-	-	76
2												-	-	40	-	-	-	-	50	10	-	-	-	87
	3	-	35	-	-	-	60	-	-	-	-														5	-	80
4												-	-	80	-	-	-	10	-	10	-	-	-	75
	5	60	-	-	-	-	30	-	-	-	-														10	-	64
6												50	-	-	-	-	-	-	30	-	10	-	10	58
	7	-	-	-	-	70	-	20	-	10	-														-	-	35
8												-	-	-	40	-	-	-	50	10	-	-	-	40
	9	-	-	-	-	20	-	-	70	-	-														10	-	68

(6) making of processing release paper

For composition 1,100 weight portion solid constituents with respect to said composition, add 3 weight portion Photoepolymerizationinitiater initiaters (チ パ ス ペ Star ヤ リ テ イ-chemical company produces, イ Le ガ キ ユ ア 907) and, make solid component concentration become 30 weight % as the MEK of retarder thinner.On the neutralized paper that does not apply shim, be coated with the mixture that machine coating obtains, be coated with and make coating thickness after drying, reach about 5～10g/m with rod ², dry 1 minute of 110 ℃ of heating evaporations.

After this, applied embossing processing in this film coated surface.Embossing, with respect to the metal dandy roll with ridge design, the paper bowl that will have dimpled grain pressurizes as backing roll.

Measuring machine (Tokyo Micronics Inc. produces, サ-Off コ system 590A) with three-dimensional surface roughness measures the specific part of this dandy roll (3mm's * 3mm) is concavo-convex, and median plane mean roughness (Ra) is that 12.99 μ m, 10 mean values (Rz) are 65.78 μ m.

This moment, the dandy roll temperature was defined as 120 ℃, supporter and dry coating are carried out embossing processing simultaneously, confirmed not only also to have carried out good excipient in dry coating face, chord support body rear side, not only the dorsal part at coated face, paper has also fully carried out concavo-convex excipient.Then, use the high-pressure sodium lamp that is output as 120W/cm, carry out 600mj/cm ²Ultraviolet ray irradiation, make curing of coating, obtain processing release paper 1.

In addition, on the supporter shown in the following table 2 (shim is arranged or do not have the neutralized paper of shim) and above-mentionedly similarly be coated with each composition shown in dry table 2 first column.After the drying, similarly be coated with each composition shown in dry table 2 second column again.After this and above-mentionedly similarly implemented embossing processing.

(7) estimate

To the processing release paper 16 of the embodiment that obtains and the processing release paper 79 of comparative example, measure embossing embossability, hear resistance, fissility.

＜embossing embossability 〉

The carrying out of using three-dimensional surface roughness mensuration machine to measure to be equivalent to the dandy roll specific part processing release paper concavo-convex of embossing excipient, adopt following benchmark evaluation.

Any one value with respect to dandy roll of ◎: Ra, Rz all is more than 85%

Zero: any one value with respect to dandy roll of Ra, Rz all is more than 70%, and some be more than 85%

Any one value with respect to dandy roll of △: Ra, Rz all is more than 70%, less than 85%

*: Ra, Rz any one with respect to the value of dandy roll all less than 70%

The manufacturing of＜PVC leather 〉

Be coated with machine coating 100g/m on technology processing release paper surface with rod ²The vinyl chloride colloidal sol of following composition, with 220 ℃ be heating and curing 3 minutes, make it to form leather sheet and peel off.

Polyvinyl chloride (paste resin) 100 weight portions

Dioctyl phthalate 60 weight portions

Blowing agent (Celogen Az) 3 weight portions

Antioxidant (common drug company production, KF-80A-8) 3 weight portions

Calcium carbonate 10 weight portions

＜hear resistance 〉

Repeat the operation that forms above-mentioned leather sheet and peel off for 5 times, the decorative pattern of observing processing release paper loses shape and the deterioration of supporter, with following benchmark evaluation.

Zero: also do not have losing shape of excipient fully up to the 5th

△: cause that excipient loses shape, the surface changes, before the 5th, can not use

*: because excipient loses shape or can only use 1 time because of the fracture due to the supporter deterioration

＜fissility repeatedly 〉

Be coated with the one pack system curable polyurethane that cooperates below the machine coating with rod on technology processing release paper surface, and make it to become 20g/m after the drying ², with 120 ℃ of heat dryings 2 minutes.

[one pack system curable polyurethane]

Host (production of big Japanese ink company, CRISVON, 7367SL) 100 weight portions

Colorant (production of big Japanese ink company, DAILAC, TV-COLOR) 15 weight portions

Solvent (MEK) 30 weight portions

Solvent (dimethyl formamide) 10 weight portions

Then, become 20g/m after being coated with the following bi-component curing type urethane adhesive that cooperates of machine coating and making it drying with rod ², behind the false deerskin of fitting from it,, made it slaking 24 hours with 50 ℃ again with 120 ℃ of adhesives 2 minutes of being heating and curing, make it to form the PU leather sheet.

[bi-component curing type urethane adhesive]

Host (production of big Japanese ink company, CRISVON, 4070) 100 weight portions

Curing agent (production of big Japanese ink company, CRISVON, NX) 50 weight portions

Promoter (production of big Japanese ink company, CRISVON, ACCEL, HM) 3 weight portions

Solvent (toluene) 80 weight portions

Solvent (ethyl acetate) 40 weight portions

For the PU leather sheet that obtains, use cupping machine (production of オ リ エ ソ テ Star Network company, テ ソ Star ロ ソ RTC-1310A) that the leather sheet of width 15mm is peeled off from processing release paper 180 degree with 300mm/ minute speed, measure peel strength.It is carried out 5 times repeatedly, with following benchmark evaluation fissility.

◎: all less than 1N, fissility is almost constant up to the 5th peel strength.

Zero: also can peel off up to the 5th, but fissility has deterioration slightly, peel strength is increased to more than the 1N

△: fissility quite worsens, and becomes to peel off before the 5th

*: just can not peel off from the 1st time

The result is shown in following table 2.

Table 2

The formation of processing release paper

Estimate

	Supporter	Shim	Be coated with application layer		The embossing embossability	Hear resistance	(repeatedly) fissility
								The 1st layer	The 2nd layer
			Embodiment 1	Neutralized paper						Do not have	Composition 1	-	△	△	△
Embodiment 2	Neutralized paper	Do not have			Composition 5	Composition 2	○	△	○
			Embodiment 3	Neutralized paper						Do not have	Composition 2	Composition 4	△	○	○
Embodiment 4	Neutralized paper	Do not have			Composition 6	Composition 3	◎	○	△
			Embodiment 5	Neutralized paper						Have	Composition 5	Composition 4	○	○	◎
Embodiment 6	Neutralized paper	Have			Composition 1	Composition 5	○	△	◎
			Comparative example 1	Neutralized paper						Have	Composition 7	Composition 8	×	○	○
Comparative example 2	Neutralized paper	Have			Composition 5	Composition 7	×	×	○
			Comparative example 3	Neutralized paper						Have	Composition 9	Composition 6	△	×	△

As above shown in the table, in processing release paper 1～6 (embodiment 1～6), embossing embossability, hear resistance, fissility is all good repeatedly.On the other hand, in processing release paper 7 (comparative example 1), the softening temperature of coating material is low, and the embossing embossability is bad.In addition, in processing release paper 8 (comparative example 2), the embossing embossability is bad.In addition, in processing release paper 9 (comparative example 3), though the softening temperature height of coating material, hear resistance is bad.

2. the synthetic leather that adopts the manufacture method of other form of the present invention to obtain

Mix 30 weight portions above-mentioned ionizing radiation solidification compound A, 60 weight portions and have resin b and the 10 weight portion silicone compounds β (above-mentioned weight portion all is the solid constituent weight portion) that make film, prepared composition 10.A part of getting said composition is measured softening temperature as sample, is 76 ℃.

With similarly above-mentioned, mix 80 weight portion ionizing radiation solidification compound C, 10 weight portions have resin b and the 10 weight portion silicone compounds α (above-mentioned weight portion all is the solid constituent weight portion) that make film, have prepared composition 11.A part of getting said composition is measured softening temperature as sample, is 75 ℃.

The making of＜processing release paper 〉

For composition 10, the solid constituent of per 100 weight portion said compositions, add 3 weight portion Photoepolymerizationinitiater initiaters (チ バ ス ペ Star ヤ リ テ イ-chemical company's production, イ Le ガ キ ユ ア 907), and add MEK, and make solid component concentration become 30 weight % as retarder thinner.Be coated with the mixture that the machine coating obtains with rod on the neutralized paper that does not apply shim, coating thickness reaches about 5～10g/m after drying ²Ground coating was with dry 1 minute of 110 ℃ of heating evaporations.

Then, solid constituent 100 weight portions with respect to composition 11, add 3 weight portion Photoepolymerizationinitiater initiaters (チ パ ス ペ Star ヤ リ テ イ-chemical company's production, イ Le ガ キ ユ ア 907), and add MEK, and make solid component concentration become 30 weight % as retarder thinner.Constitute by above-mentioned composition 10 film on and the above-mentioned mixture that obtains of coating similarly, the heating evaporation drying.

After this, apply embossing processing in this film coated surface.Embossing, with respect to the metal dandy roll with ridge design, the paper bowl that will have dimpled grain pressurizes as backing roll.

The dandy roll temperature of this moment is defined as 120 ℃, supporter and dry coating are carried out embossing processing simultaneously, confirmed not only dry coating face, chord support body rear side has also been carried out good excipient, and not only the inboard of coated face paper has also been carried out concavo-convex excipient fully.Then, use the high-pressure sodium lamp that is output as 120W/cm, carry out 600mj/cm ²The ultraviolet ray irradiation so that curing of coating obtains processing release paper.

Embodiment 7 (manufacture method of the synthetic leather of first form)

As forming the coating fluid that epidermal area is used, mix following each composition, fully stir with the screw mixer, having prepared ester is the mixture of polyurethane resin composition.

＜ester is the composition of polyurethane solutions 〉

Ester is polyurethane resin 100 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ NB-637N)

Colorant 15 weight portions

(production of big Japanese ink chemical industry (strain) company, ダ イ ラ Star Network TV-COLOR)

MEK 20 weight portions

Dimethyl formamide 10 weight portions

On the above-mentioned processing release paper that obtains, be polyurethane resin with the ester of knife type coater coating preparation, and make dry thickness become 20 μ m, with 100 ℃ of heated-air dryings 2 minutes, formed polyurethane surface layer.Then, on polyurethane surface layer, the bi-component curing type polyester that is coated with following composition with knife type coater is polyurethane binder 1, and makes dry thickness become 4 μ m, with as adhesive phase, and the looped fabric of fitting again.

The composition of＜adhesive 1 〉

Host bi-component curing type ester is polyurethane resin 100 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ 4070)

Curing agent bi-component curable polyurethane resin curing agent 13 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ NX)

Promoter bi-component curable polyurethane resin curing accelerator 3 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ ア Network セ Le HM)

Solvent MEK 30 weight portions

By should the applying thing 100 ℃ of heated-air dryings 5 minutes, slaking be 48 hours again, and adhesive reaction is solidified, and peels off processing release paper, has made dry type PU synthetic leather.

Embodiment 8 (manufacture method of the synthetic leather of second form)

As forming the coating fluid that epidermal area is used, mix following each composition, fully stir with the screw mixer, having prepared ester is the mixture of polyurethane resin composition.

＜ester is the composition of polyurethane solutions 〉

Ester is polyurethane resin 100 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ NB-637N)

Colorant 15 weight portions

(production of big Japanese ink chemical industry (strain) company, ダ イ ラ Star Network TV-COLOR)

MEK 20 weight portions

Dimethyl formamide 10 weight portions

On the above-mentioned processing release paper that obtains, the ester of preparing with the knife type coater coating is a polyurethane solutions, and makes dry thickness become 20 μ m, forms polyurethane surface layer in 2 minutes with 100 ℃ of heated-air dryings.

Then, prepare to form the wet type synthetic leather intermediate layer that the intermediate layer is used.As the resin that is used to form wet type synthetic leather intermediate layer, mix following each composition, fully stir with the screw mixer, having prepared ester is the mixture of polyurethane resin composition.

The coating fluid that＜formation wet type synthetic leather intermediate layer is used 〉

Polyurethane resin 100 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ NB-637N)

Colorant 1 weight portion

(production of big Japanese ink chemical industry (strain) company, ダ イ ラ Star Network TV-COLOR)

System film auxiliary agent 160 weight portions

(big Japanese ink chemical industry (strain) company produces, Network リ ス ボ ソ ア セ ス -SD-7)

Dimethyl formamide 10 weight portions

On the base fabric that the band ringlet multi cord ( system line) by 2.4 numbers, 100% cotton forms, be coated with above-mentioned coating fluid and the feasible 700g/m that becomes with knife type coater ², after this, made film in 5 minutes by dipping in being modulated into 30 ℃ solidification liquid (the 10% dimethyl formamide aqueous solution), then, in 60 ℃ of warm water, carry out washing in 15 minutes till dimethyl formamide is extracted fully.After this, use mangrove (mangrove) to remove moisture, obtain wet type synthetic leather intermediate layer by baking oven inner drying at 120 ℃.

Use Heat sealer, at 180 ℃, 4kg/m ²Under the cramping condition, utilize hot-rolling that wet type synthetic leather intermediate layer and the above-mentioned epidermal area that obtains carried out hot pressing.Then, peel off processing release paper and made the Wet-type polyurethane synthetic leather by behind chill roll and the air-supply zone by making it.

Embodiment 9 (manufacture method of the synthetic leather of the 3rd form)

As forming the coating fluid that epidermal area is used, mix following each composition, fully stir with the screw mixer, prepared the mixture (the aqueous mixture of colloidal sol) of poly (vinyl chloride) resin composition.

＜polyvinyl chloride resin composition 〉

Emulsion polymerisation Corvic (average degree of polymerization 1000)

(the new first salt PVC company of ZEST PX-QHP produces) 20 weight portions

Plasticizer phthalic acid dioctyl ester (DOT) 80 weight portions

Stabilizing agent barium-zinc is compound stabilizer

(ア デ ガ ス Block LF-54, rising sun electrification company produce) 3 weight portions

Filler calcium carbonate 5 weight portions

Pigment oxidation 3 weight portions

On the above-mentioned processing release paper that obtains,,, form the PVC epidermal area with 150 ℃, 90 seconds and 195 ℃, 3 minutes and 30 seconds heated-air dryings with scraping the above-mentioned colloidal sol shape mixture of skill in using a kitchen knife in cookery coating and making dry thickness become 300 μ m.

Then, by the looped fabric of on the PVC epidermal area that obtains, fitting, peel off processing release paper, made the PVC synthetic leather.

Embodiment 10 (manufacture method of the synthetic leather of the 4th form)

As forming the coating fluid that epidermal area is used, mix following each composition, fully stir with the screw mixer, having prepared ester is the mixture of polyurethane resin composition.

＜ester is the composition of polyurethane solutions 〉

Ester is polyurethane resin 100 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ NB-637)

Colorant 15 weight portions

(production of big Japanese ink chemical industry (strain) company, ダ イ ラ Star Network TV-COLOR)

MEK 20 weight portions

Dimethyl formamide 10 weight portions

On the above-mentioned processing release paper that obtains, be polyurethane solutions and make dry thickness become 20 μ m with the ester of knife type coater coating modulation, with 100 ℃ of heated-air dryings 2 minutes, form polyurethane surface layer.

Then,, fully stir, prepared foaminess PVC coating fluid with the screw mixer as forming foam PVC layer with coating fluid, following each composition of mixing.

The composition of＜foaminess PVC coating fluid 〉

Emulsion polymerisation Corvic (being the resin that to contain the monomer copolymerization of epoxy radicals and to obtain, average degree of polymerization 1500)

(the new first salt PVC company of ZEST PF-821 produces) 20 weight portions

Plasticizer phthalic acid dioctyl ester (DOT) 80 weight portions

Blowing agent Celogen Az (ADCA) 3 weight portions

Stabilizing agent barium-zinc is compound stabilizer 3 weight portions

(ア デ ガ ス Block LF-54, rising sun electrification company produce)

Filler calcium carbonate 5 weight portions

Pigment titanium oxide 3 weight portions

On the above-mentioned polyurethane surface layer that obtains,,, formed foam PVC layer with 150 ℃, 90 seconds and 195 ℃, 3 minutes and 30 seconds heated-air dryings with scraping the above-mentioned foaminess PVC coating fluid of skill in using a kitchen knife in cookery coating and making dry thickness become 300 μ m.

Then, by the looped fabric of on the foam PVC layer that obtains, fitting, peel off processing release paper, made semi-synthetic leather.

＜estimate

With above-mentionedly similarly use same processing release paper, carry out the making of each synthetic leather of 5 times repeatedly, for the decorative pattern of processing release paper lose shape, the deterioration of supporter and the operability of processing release paper estimate.

The decorative pattern of processing release paper loses shape and estimates according to following benchmark.

Zero: also do not have losing shape of embossing excipient fully after making 5 times

△: generation embossing excipient loses shape or the processing release paper surface changes, and can not use repeatedly 5 times

*: losing shape or by the fracture due to the supporter deterioration, can only using 1 time of embossing excipient taken place

In addition,, use cupping machine (production of オ リ エ ソ テ Star Network company, テ ソ Star ロ ソ RTC-1310A), from 180 ° of synthetic leathers of peeling off width 15mm of processing release paper, measure peel strength with 300mm/ minute speed about the fissility of processing release paper.Use same processing release paper, 5 times and the foregoing description are similarly made synthetic leather repeatedly, and also the fissility when peeling off synthetic leather and processing release paper is measured.

◎: after carrying out 5 times repeatedly, peel strength is also almost constant less than 1N, fissility.

Zero: though can use processing release paper 5 times repeatedly, fissility has deterioration slightly, and peel strength also becomes more than the 1N

△: when using processing release paper 5 times repeatedly, fissility quite worsens, and becomes to peel off before the 5th.

*: just can not peel off processing release paper since the 1st time.

The result is shown in following table 3.

Table 3

	The state of processing release paper		Fissility
				Losing shape of embossing excipient	The variation of supporter
	Embodiment
7		○	No change	◎

Embodiment 8	○	No change	◎
				Embodiment 9	○	No change	◎
Embodiment 10	○	No change	◎

3. the processing release paper that has embossing of other form of the present invention

Embodiment 11

About becoming the resin of synthetic leather epidermal area, the ester of having prepared metering and having mixed the material shown in following is a polyurethane solutions.

＜ester is the composition of polyurethane solutions 〉

Ester is polyurethane resin 100 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ NB-637N)

Colorant 15 weight portions

(production of big Japanese ink chemical industry (strain) company, ダ イ ラ Star Network TV-COLOR)

MEK 20 weight portions

Dimethyl formamide 10 weight portions

On the processing release paper that in embodiment 7, uses, be polyurethane solutions and make dry thickness become 20 μ m,, form polyurethane surface layer with 100 ℃ of heated-air dryings 2 minutes with the ester of knife type coater coating preparation.Then, on polyurethane surface layer, the bi-component curing type polyester that is coated with following composition with knife type coater is polyurethane binder 1, and makes dry thickness become 40 μ m, with as adhesive phase, and the looped fabric of fitting again.

The composition of＜adhesive 1 〉

Host bi-component curing type ester is polyurethane resin 100 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ 4070)

Curing agent bi-component curable polyurethane resin curing agent 13 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ NX)

Promoter bi-component curable polyurethane resin curing accelerator 3 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ ア Network セ Le HM)

Solvent MEK 30 weight portions

Should the applying thing 5 minutes 100 ℃ of heated-air dryings, slaking is 48 hours again, and adhesive reaction is solidified.After this, in order to estimate by using the use adaptability of the processing release paper that obtains repeatedly, when making it to peel off, make dry type PU synthetic leather with processing release paper, there are ratio in the processing release paper surface after peel off (1) peel strength, (2) of measuring processing release paper and synthetic leather and the siloxanes of synthetic leather one side surface.In addition, carry out 5 these operations, confirm by using the variation that brings repeatedly.

Embodiment 12

With the preparation of the adhesive among the embodiment 11 1 change into following like that, in addition and embodiment 11 similarly carry out the manufacturing and the evaluation of synthetic leather.

The composition of＜adhesive 2 〉

Host bi-component curing type ester is polyurethane resin 100 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ TA-265)

Curing agent bi-component curable polyurethane resin curing agent 13 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ NX)

Promoter bi-component curable polyurethane resin curing accelerator 3 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ ア Network セ Le HM)

Solvent toluene/ethyl acetate (1/1) 25 weight portion

Embodiment 13

With the preparation of the adhesive among the embodiment 11 1 change into following like that, in addition and embodiment 11 similarly carry out the manufacturing and the evaluation of synthetic leather.

The composition of＜adhesive 3 〉

Host bi-component curing type ester is polyurethane resin 100 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ TA-205)

Curing agent bi-component curable polyurethane resin curing agent 13 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ NX)

Promoter bi-component curable polyurethane resin curing accelerator 3 weight portions

(production of big Japanese ink chemical industry (strain) company, Network リ ス ボ ソ ア Network セ Le HM)

Solvent toluene/ethyl acetate (1/1) 30 weight portion

＜fissility repeatedly 〉

Fissility during about the synthetic leather of peeling off manufacturing and processing release paper, use cupping machine (production of オ リ エ ソ テ Star Network company, テ ソ Star ロ ソ RTC-1310A), from 180 ° of synthetic leathers of peeling off width 15mm of processing release paper, measure peel strength with 300mm/ minute speed.Use same processing release paper, similarly make synthetic leather with the foregoing description repeatedly, also the fissility when peeling off synthetic leather and processing release paper is measured.The result is shown in following table 4.

Table 4

	Peel strength [gf/15mm is wide] repeatedly
						The 1st time	The 2nd time	The 3rd time	The 4th	The 5th
	Embodiment
11		10	7	17	28	45
	Embodiment 12						18	7	13	30	25
Embodiment 13		15	5	15	24	35

＜have ratio from the silicon of siloxanes 〉

Measure the silicon of making preceding processing release paper of synthetic leather and the synthetic leather that uses this processing release paper to make as described above and have ratio from siloxanes.Measure and carry out as described below.

At first, as the surface analysis device, use x-ray photoelectron spectroscopy apparatus (XPS, device name: ESCALAB220i-XL (production of Thermo VG Scientific company)), and it is square at an arbitrary position processing release paper and synthetic leather to be cut into 1cm, be placed on the objective table and vacuumize, carry out pre-treatment.

As the X line that uses, use nonmonochromatic light Al-K α line (output 300W), be shining into angle with photoelectron: 90 degree are settled sample, carry out the silicon face analysis separately of processing release paper and synthetic leather, are determined at the silicon amount from siloxanes that the surface exists.In addition, the treatment conditions of the background of measurement result (background) utilize the Shirley method to carry out.In addition and similarly above-mentioned, use same processing release paper, similarly make synthetic leather with the foregoing description repeatedly, peel off synthetic leather and processing release paper, measure silicon amount separately.The result is shown in following table 5.

Table 5

	Measure the position	There is ratio (%) in silicon from siloxanes
							Before the evaluation	The 1st time	The 2nd time	The 3rd time	The 4th

Embodiment

11	Processing release paper	19.7	11.8	10.8	8.4	6.3
							Synthetic leather	-	11.0	9.9	8.0	5.9
	Embodiment 12	Processing release paper	19.7	14.3	12.5	8.9							6.2
Synthetic leather							-	14.0	11.6	7.9	6.0
		Embodiment 13	Processing release paper	19.7	12.3	10.9						9.8	7.3
Synthetic leather	-						11.9	10.1	9.1	7.0

4. supporter of the present invention

Embodiment 14

In the pulp slurry that comprises the bleached kraft pulp that has mixed L material and N material with L material 80%:N material 20%, with respect to the alkyl ketene dimer as the inert filler agent of paper pulp amount interpolation 0.1%.Use many paper machines of the short net associating of fourdrinier wire, these slurries are copied paper form weight per unit area 140g/m ²Body paper.After this, continue, on above-mentioned body paper, utilize Kohler coater to form 9g/m with machine hand's preface ²The clay coating, give flatness by calender roll again, made body paper with clay coating.

To the body paper of making as described above, utilize the mensuration (the デ ヅ Le ベ Star Network smoothness of using Japan smart machine company to produce is measured machine) of carrying out surface smoothness based on the assay method of JIS P8119 standard with clay coating.In addition, under the following conditions, utilize the determination of test method hot strength (the テ ソ Star ロ ソ RTC-1310A that uses オ リ エ ソ テ Star Network company to produce) according to JIS P8113 standard and utilize determination of test method tearing strength (using the エ レ メ ソ De Le Off tear tester of テ ス -industry company production) based on JIS P8116 standard.

Condition (1): the condition determination under normal temperature (23 ℃, 50%RH)

Condition (2): measure (bake oven device: MUFFLE FURANCEFP-31, ヤ マ ト scientific company are produced) 230 ℃ of placements after 3 minutes

The result is shown in following table 6.

As can be known from the results of Table 6, smoothness is 153.8 seconds, in addition, about hot strength and tearing strength, even under condition (2), hot strength (kN/m) is 13.4kN/m longitudinally, more than 10kN/m, tearing strength (mN) all is more than the 500mN vertically, laterally vertically being 627mN, laterally being 627mN.

On the body paper of making as described above with clay coating, the coating coating fluid has been made coated substrate.Coating fluid uses such coating fluid: in uv curing resin (using the composition 1 that uses in the foregoing description 1), add the reaction initiator (チ パ ス ペ Star ヤ リ テ イ-chemical company produces, イ Le ガ キ ユ ア 907) of weight ratio 3% with respect to the resin solid composition, again it is dissolved in the MEK and the coating fluid that obtains.Use the commutation coating machine being coated with this coating fluid on the clay coating and making the weight after the solvent evaporation drying become 10g/m ², make the solvent evaporation drying, made coated substrate with uv curing resin layer.

Above-mentioned coated substrate is passed to the calender roll that mirror finish is crossed, and the minute surface transfer printing that makes calender roll is investigated transfer printing on the surface of uv curing resin layer.Specifically, make the uv curing resin face of surface contact coated substrate of 110 ℃ calender roll, and between pressure cylinder and calender roll, apply the 100kN/m line pressure, carry out transfer printing, after this, use high-pressure sodium lamp (output 120W/cm), carry out 600mJ/cm at transfer surface ²Ultraviolet ray irradiation, uv curing resin is solidified.

About the evaluation base material that obtains like this, use digital varied-angle glossmeter (production of ス ガ testing machine company) to measure 60 ° of mirror surface lusters (Gs (60 °)) of transfer surface, estimate transfer printing.

The result is shown in following table 7.As can be known from the results of Table 7, Gs (60 °) is 74%, and transfer printing is good.In addition, the evaluation of transfer printing adopts following standard to carry out.

Gs (60 °) 〉=80%: good (◎) especially

80%＞Gs (60 °) 〉=70%: good (zero)

70%＞Gs (60 °) 〉=60%: poor (△)

60%＞Gs (60 °): poor especially, can not use (*)

In addition, use above-mentioned evaluation base material, carry out the manufacturing test of polyvinyl chloride synthetic leather repeatedly, the access times of investigation under same base material carry out stable on heating evaluation.Metewand is as follows.

Estimating base material does not rupture, can use the base material more than 5 times: hear resistance good (zero)

Discontented 5 the i.e. fractures of evaluation base material: poor heat resistance (*)

The result is as shown in the table 7.As can be known from the results, above-mentioned evaluation base material is to have the base material that can tolerate the good heat resistance that uses more than 5 times.

Embodiment 15

In the pulp slurry that comprises the bleached kraft pulp that has mixed L material and N material with L material 80%:N material 20%, with respect to the alkyl ketene dimer as the inert filler agent of paper pulp amount interpolation 0.1%.Use many paper machines of the short net associating of fourdrinier wire, these slurries are copied paper form weight per unit area 140g/m ²Body paper.After this, continue, on above-mentioned body paper, utilize scraper plate coating machine and Kohler coater to form 18g/m with machine hand's preface ²The clay coating, give flatness by calender roll again, made body paper with clay coating.

Body paper with clay coating and the embodiment 14 that makes as described above similarly estimated.

The result is as shown in table 6.As can be known from the results of Table 6, smoothness is 462.3 seconds, in addition, about hot strength and tearing strength, even under condition (2), hot strength (kN/m) is 12.8kN/m longitudinally, more than 10kN/m, tearing strength (mN) all is more than the 500mN vertically, laterally vertically being 638mN, laterally being 578mN.

Use the body paper with clay coating and the embodiment 14 that make as described above to operate equally, form and estimate base material.

Mensuration and the transfer printing and the stable on heating evaluation of 60 ° of mirror surface lusters (Gs (60 °)) that the evaluation base material that obtains and embodiment 14 are similarly carried out transfer surface.

The result is as shown in table 7.As can be known from the results of Table 7, Gs (60 °) is 83%, and transfer printing is good.In addition, estimating base material is to have the base material that can tolerate the good heat resistance that uses more than 5 times.

Comparative example 4

In the pulp slurry that comprises the bleached kraft pulp that has mixed L material and N material with L material 80%:N material 20%, with respect to the alkyl ketene dimer as the inert filler agent of paper pulp amount interpolation 0.1%.Use many paper machines of the short net associating of fourdrinier wire, these slurries are copied paper form weight per unit area 140g/m ²Body paper, made the body paper that does not have the clay coating.

Every mensuration that the body paper that does not have the clay coating made as described above and embodiment 14 are similarly carried out surface smoothness, hot strength, tearing strength.

The result is as shown in table 6.As can be known from the results of Table 6, smoothness is lower, it is 77.2 seconds, in addition, about hot strength and tearing strength, even under condition (2), hot strength (kN/m) is 14.0kN/m longitudinally, also more than 10kN/m, tearing strength (mN) all is more than the 500mN vertically, laterally vertically being 655mN, laterally being 605mN.

Use the body paper that does not have the clay coating and the embodiment 14 that make as described above to operate equally, form and estimate base material.

To the evaluation base material that obtains and embodiment 14 similarly, carry out mensuration and the transfer printing and the stable on heating evaluation of 60 ° of mirror surface lusters (Gs (60 °)) of transfer surface.

The result is as shown in table 7.As can be known from the results of Table 7, Gs (60 °) is lower, is 52%, and transfer printing is poor especially, can not use.

Comparative example 5

In the pulp slurry that comprises the bleached kraft pulp that has mixed L material and N material with L material 80%:N material 20%, add aluminum sulfate as rosin series packing agent and fixative.Use many paper machines of the short net associating of fourdrinier wire, these slurries are copied paper form weight per unit area 140g/m ²Body paper.After this, continue, on above-mentioned body paper, utilize Kohler coater to form 9g/m with machine hand's preface ²The clay coating, give flatness by calender roll again, made body paper with clay coating.

Body paper with clay coating and the embodiment 14 same operations made are as described above estimated.

The result is as shown in table 6.As can be known from the results of Table 6, smoothness is lower, it is 77.2 seconds, in addition, about hot strength and tearing strength, under condition (2), hot strength (kN/m) is 4.2kN/m longitudinally, less than 10kN/m, tearing strength (mN) vertically is being 158mN, laterally is being 125mN, vertically, laterally all less than 500mN.

Use the body paper with clay coating and the embodiment 14 that make as described above to operate equally, form and estimate base material.

To the evaluation base material that obtains and embodiment 14 similarly, carry out mensuration and the transfer printing and the stable on heating evaluation of 60 ° of mirror surface lusters (Gs (60 °)) of transfer surface.

The result is as shown in table 7.As can be known from the results of Table 7, Gs (60 °) is higher, is 63%, and transfer printing is good, but causes fracture in the 2nd time transfer printing, does not have hear resistance, and practical value is low.

Table 6

	Smoothness (second)	Condition	Hot strength (kN/m)		Tearing strength (mN)
							Vertically	Laterally	Vertically	Laterally

Embodiment 14	153.8	(1)	13.4	7.9	1400	1315
							(2)	13.2	7.7	627	627
		Embodiment 15	462.8	(1)	13.0	7.3						1250	1177
(2)	12.8						7.0	638	578
				Comparative example 4	77.2	(1)				14.1	8.0	1470	1424
(2)	14.0	7.7	655				605
						Comparative example 5		150.1	(1)	13.7	7.7	1382	1305
(2)	4.2	2.6	158	125

Table 7

	Transfer printing		Hear resistance
					Gs(60°)	Estimate	Access times	Estimate
	Embodiment 14	74％	○	More than 5 times					○
Embodiment 15					83％	◎	More than 5 times	○
	Comparative example 4	52％	×	More than 5 times					○
Comparative example 5					73％	○	1 time	×

Claims (32)

1. the processing release paper that has embossing of a synthetic leather manufacturing usefulness; be to possess at least as the paper of supporter and the ionizing radiation cured film that on this paper, is provided with; and on this cured film, apply embossing processing and the processing release paper that has embossing of the synthetic leather manufacturing usefulness that forms; it is characterized in that; above-mentioned ionizing radiation cured film is to make coating fluid solidify the film that obtains by the irradiation ionizing radiation; it is that ionizing radiation solidification compound more than 40 ℃ forms that described coating fluid contains softening point at least, and described solidification compound is to contain by isocyanate compound and the reaction product that has (methyl) acryloyl group and can form with (methyl) acryl compound of isocyanate compound reaction; perhaps by isocyanate compound; have (methyl) acryloyl group and can form with (methyl) acryl compound of isocyanate compound reaction and the reaction product that does not have (methyl) acryloyl group and can form with the compound of isocyanates radical reaction.

2. the processing release paper that has embossing as claimed in claim 1, above-mentioned ionizing radiation cured film further contain having of 1～70 weight % to be made the resin of film and forms.

3. the processing release paper that has embossing as claimed in claim 1 or 2, the silicone compounds that above-mentioned ionizing radiation cured film further contains 0.5～20 weight % forms.

4. as wantonly 1 described processing release paper that has embossing of claim 1～3, applied the shim that comprises inorganic pigment and have the resin of making film on the surface of above-mentioned supporter.

5. as wantonly 1 described processing release paper that has embossing of claim 1～4, above-mentioned ionizing radiation cured film comprises the structure more than at least two layers.

6. the processing release paper that has embossing as claimed in claim 5 in the above-mentioned ionizing radiation cured film that comprises the structure more than two layers, contains the inorganic pigment of 0.5～50 weight % at least more than one deck.

7. as claim 5 or the 6 described processing release papers that have embossing, in the above-mentioned ionizing radiation cured film that comprises the structure more than two layers, in being disposed at the orlop that supports the side, contain the inorganic pigment of 0.5～50 weight %.

8. as wantonly 1 described processing release paper that has embossing of claim 5～7, in the above-mentioned ionizing radiation cured film that comprises the structure more than two layers, at least more than one deck, contain the silicone compounds of 0.5～20 weight %.

9. as wantonly 1 described processing release paper that has embossing of claim 5～8, in the above-mentioned ionizing radiation cured film that comprises the structure more than two layers, in the superiors that are disposed at a side opposite, contain the silicone compounds of 0.5～20 weight % with supporting the side.

10. as wantonly 1 described processing release paper that has embossing of claim 5～9, in the above-mentioned ionizing radiation cured film that comprises the structure more than two layers, the inorganic pigment that contains 0.5～50 weight % in being disposed at the orlop that supports the side contains the silicone compounds of 0.5～20 weight % in the superiors that are disposed at a side opposite with supporting the side.

11. wantonly 1 described processing release paper that has embossing as claim 5～9, in the above-mentioned ionizing radiation cured film that comprises the structure more than two layers, the inorganic pigment that contains 0.5～50 weight % in being disposed at the orlop that supports the side contains the silicone compounds of 0.5～20 weight % in each layer.

12., be neutralized paper as the paper of above-mentioned supporter as wantonly 1 described processing release paper that has embossing of claim 1～11.

13., on paper, apply embossing and process and form as supporter as wantonly 1 described processing release paper that has embossing of claim 1～12.

14. the processing release paper that has embossing as claimed in claim 3, above-mentioned ionizing radiation cured film surface, to have ratio from the silicon of siloxanes be 5～30%, it is more than 5% that there is ratio in the silicon from siloxanes when the operation of using processing release paper to make synthetic leather is carried out 5 times repeatedly, above-mentioned ionizing radiation cured film surface.

15. a manufacture method that has the processing release paper of embossing is wantonly 1 described method that has the processing release paper of embossing of making claim 1～14, it is characterized in that comprising: make dried coating weight become 1～40g/m at supporting body surface coating coating fluid ²Form the operation of filming; Make the operation of above-mentioned solvent evaporation drying of filming; Above-mentioned dry coating is implemented embossing processing or above-mentioned supporter and dry coating are implemented the operation that embossing is processed simultaneously; Above-mentioned filming shone the operation that ionizing radiation forms the ionizing radiation cured film,

It is that ionizing radiation solidification compound more than 40 ℃ forms that above-mentioned coating fluid contains softening point at least; described solidification compound is to contain by isocyanate compound and the reaction product that has (methyl) acryloyl group and can form with (methyl) acryl compound of isocyanate compound reaction; perhaps by isocyanate compound; have (methyl) acryloyl group and can form with the reaction product that does not have (methyl) acryloyl group and can form with (methyl) acryl compound of isocyanate compound reaction with the compound of isocyanates radical reaction; above-mentioned coating fluid is with respect to 100 weight portion solid constituents in the coating fluid, obtains with the solvent dilution of 10～1000 weight portions.

16. the manufacture method of a synthetic leather, be to use the described processing release paper that has embossing of claim 1～14 to make the method for synthetic leather, it is characterized in that comprising: on the above-mentioned ionizing radiation cured film of implementing embossing processing, be coated with polyurethane resin composition, heat drying, the operation of formation epidermal area; On above-mentioned epidermal area, by the operation of adhesive applying base fabric, formation synthetic leather layer; And the operation of peeling off above-mentioned processing release paper from above-mentioned synthetic leather layer.

17. method as claimed in claim 16, above-mentioned adhesive are bi-component curable polyurethane resins.

18. method as claimed in claim 16, the bonding process of above-mentioned base fabric are at coating adhesive on the above-mentioned epidermal area and after making it drying, by the operation of heat lamination applying base fabric on this adhesive.

19. the manufacture method of a synthetic leather, be to use the described processing release paper that has embossing of claim 1～14 to make the method for synthetic leather, it is characterized in that comprising: on the above-mentioned ionizing radiation cured film of implementing embossing processing, be coated with polyurethane resin composition, heat drying, the operation of formation epidermal area; Lamination wet type intermediate layer on above-mentioned epidermal area utilizes above-mentioned epidermal area of hot-rolling pressing and wet type intermediate layer from above-mentioned processing release paper one side, forms the operation of synthetic leather layer; And above-mentioned synthetic leather layer cooling is back, as to peel off above-mentioned processing release paper operation.

20. the manufacture method of a synthetic leather, be to use the described processing release paper that has embossing of claim 1～14 to make the method for synthetic leather, it is characterized in that comprising: on the above-mentioned ionizing radiation cured film of implementing embossing processing, be coated with vinyl chloride resin composition, heat drying, the operation of formation epidermal area; The vinyl chloride resin composition of coating foaminess heats on above-mentioned epidermal area, forms the operation in intermediate layer; On above-mentioned intermediate layer by adhesive applying base fabric, form the operation of synthetic leather layer; And the operation of peeling off above-mentioned processing release paper from above-mentioned synthetic leather layer.

21. the manufacture method of a synthetic leather, be to use the described processing release paper that has embossing of claim 1～14 to make the method for synthetic leather, it is characterized in that comprising: on the above-mentioned ionizing radiation cured film of implementing embossing processing, be coated with polyurethane resin composition, heat drying, the operation of formation epidermal area; The vinyl chloride resin composition of coating foaminess heats on above-mentioned epidermal area, forms the operation in intermediate layer; On above-mentioned intermediate layer by adhesive applying base fabric, form the operation of synthetic leather layer; And the operation of peeling off above-mentioned processing release paper from above-mentioned synthetic leather layer.

22. the manufacture method of a synthetic leather, be to use the described processing release paper that has embossing of claim 1～14 to make the method for synthetic leather, it is characterized in that comprising: on the above-mentioned ionizing radiation cured film of implementing embossing processing, be coated with polyurethane resin composition, heat drying, the operation of formation epidermal area; The vinyl chloride resin composition of coating foaminess heats on above-mentioned epidermal area, forms the operation in intermediate layer; On above-mentioned intermediate layer by adhesive applying base fabric, form the operation of synthetic leather layer; And, peel off the operation of above-mentioned processing release paper from above-mentioned synthetic leather layer.

23. a synthetic leather, the synthetic leather that is to use the described processing release paper that has an embossing of claim 14 to make is characterized in that, peel off processing release paper and the stripper surface of the synthetic leather that obtains, to have ratio from the silicon of siloxanes be below 20%.

24. synthetic leather as claimed in claim 23, above-mentioned processing release paper are the processing release papers that is used multiple times.

25. wantonly 1 synthetic leather that described method obtains that utilizes claim 17～22.

26. supporter, be to comprise the body paper that single face has the clay coating, have the supporter that uses in the processing release paper of embossing in synthetic leather manufacturing usefulness, it is characterized in that, above-mentioned body paper has the hot strength of utilizing after down placing 3 minutes the assay method based on JIS P8113 standard to record at 230 ℃, at least vertically maintaining more than the 10kN/m, and, 230 ℃ of tearing strengths of utilizing after down placing 3 minutes the assay method based on JIS P8116 standard to record, vertical, laterally all maintain the above hear resistance of 500mN, and, above-mentioned clay coating has utilization based on the smoothness more than 100 seconds that the assay method of JIS P8119 standard records, and is absorbed by the concave-convex surface due to the paper pulp fiber of above-mentioned body paper.

27. supporter as claimed in claim 26, above-mentioned body paper are to use the mixed pulp of broad leaf tree paper pulp and coniferous tree paper pulp to copy paper and the body paper that obtains, contain 50～90% broad leaf tree paper pulp and form in above-mentioned mixed pulp.

28. as claim 25 or 27 described supporters, above-mentioned body paper is the neutralized paper that adopts alkyl ketene dimer to carry out starching.

29. as wantonly 1 the described supporter of claim 26～28, above-mentioned body paper has 100～200g/m ²Weight per unit area.

30. as wantonly 1 the described supporter of claim 26～29, above-mentioned clay coating has 5～40g/m ²Coating weight.

31. the synthetic leather manufacturing manufacture method of the processing release paper that has embossing, be to use wantonly 1 described synthetic leather manufacturing of claim 26～30 to use the supporter of the processing release paper that has embossing to make the method for processing release paper, it is characterized in that comprising: the operation that uncured ionizing radiation curable resin film is set on the clay coating of supporter; On uncured ionizing radiation curable resin film, apply the operation of embossing; And after the embossing operation, to above-mentioned ionizing radiation curable resin film irradiation ionizing radiation, the operation that makes it to solidify.

32. synthetic leather manufacturing processing release paper that has embossing that utilizes the described method manufacturing of claim 31.

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