CN1165197A - Method of improving pull-up characteristic of leather substrate and modified finishing oil used therein - Google Patents
Method of improving pull-up characteristic of leather substrate and modified finishing oil used therein Download PDFInfo
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- CN1165197A CN1165197A CN96112937A CN96112937A CN1165197A CN 1165197 A CN1165197 A CN 1165197A CN 96112937 A CN96112937 A CN 96112937A CN 96112937 A CN96112937 A CN 96112937A CN 1165197 A CN1165197 A CN 1165197A
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- finishing oil
- ester
- oil
- methylacrylic acid
- leather
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to a method of improving the pull-up characteristic of a leather substrate darkened with a finishing oil modified by dissolving a modifier in a conventional finishing oil. The modifier may be polymerized from a monomer mix of alkyl acrylates and alkyl methacrylates. Improved pull-up characteristic of a leather substrate is esthetically very appealing and is highly desired by a consumer. The modifier of the present invention increases the viscosity of the finishing oil, thereby extending the open time, which is a time duration during which the oil applied over the leather substrate surface stays on the surface. Increased open time permits a manufacturer to spread the oil over more area of the leather substrate than conventional unmodified finishing oils, without substantially affecting the pull-up characteristic of a leather substrate darkened with the finishing oil.
Description
The present invention relates generally to a kind of method of finishing leather substrate, particularly relate to the tensile properties of the leather substrate that improves finishing and a kind of as used herein improved finishing oil.
A kind of leather is being carried out before the typical finishing step, the rawhide that peels from carcase, give birth to sheepskin or animal skin be transformed into one attractive in appearance attracting, before the leatherware after the solid and softish finishing of quality, need carry out several steps earlier, the rawhide base material typically will carry out the processing step that two covers are had any different.The first step exemplary steps is a wet process, in this step, at first removes hair and all residual tissues of rawhide flesh noodles of rawhide grain.Rawhide, give birth to sheepskin or animal skin by tanning drying operation and be transformed into the crust leather base material then.
In the second step exemplary steps, by drawing and stretching, this crust leather base material is mechanically softened, is carried out the finishing process then usually, and this process has typically related to various method.For example, use painted or bright film, or use dye coating, oil reservoir or wax layer at grain side of leather.On leather substrate, use a kind of finishing oil to become one of important finishing process gradually, it causes the grain deepening of the leather of finishing, this leather finishing process also is commonly referred to as " scrounging " process, one of key property of the leather substrate of this deepening is its stretch characteristic, when flesh side of a belt is stretched to a hard root face, cause producing light tone, often can observe this characteristic at the grain surface of leather substrate.When the flesh noodles that pulls at the leather of deepening with finger, can produce light tone at the grain of leather, also can be observed this tensile properties.When the finger pressure under the friction grain side of leather brighten regional the time, the light tone of this leather substrate grain can typically be taken off.The brightness of the light tone that produces at grain side of leather is high more, and the tensile properties on the leather substrate surface of deepening will be good more, and the human consumer thinks that it is perfect more.
The main difficult problem that used traditional finishing oil runs into when the tensile properties of the leather surface that improves deepening is exactly that they always tend to move to flesh side of a belt from the grain of leather, the result, and the finishing oil of staying leather surface does not reach the quantity of hope.In order to improve the tensile properties of leather substrate, must use more at the leather substrate grain surface, but not finishing oil still less.The present invention has reduced its translational speed from the grain side of leather to the flesh noodles, thereby has solved this difficult problem by improving traditional finishing oil.As a result, more finishing oil is stayed grain side of leather, thereby helps to improve the tensile properties of leather.
And, since the improved finishing oil among the present invention can directly be kept here for a long time at leather surface, important longer " opening the time " is provided valuably, the meaning is for some time that provides to the producer " to open the time ", during this period, finishing oil launched at the leather substrate grain before being absorbed by leather.Like this, longer " opening the time " of being provided by improved finishing oil of the present invention allows the producer to cover the surface area of the leather substrate more than 30% with traditional finishing oil phase ratio more.And, obtain this leather surface and cover the not tensile properties of direct adverse influence leather of increase.
Yet another favourable aspect of method of the present invention and composition is owing to there is less finishing oil to move to flesh noodles from the grain of leather substrate (as footwear, it typically contacts clothing), makes its clothes of less making dirty, as the socks of dress.
The method of the tensile properties of raising leather involved in the present invention comprises:
In order to improve described finishing oil viscosity 10%-50%, molten a kind of improving agent forms a kind of improved finishing oil in finishing oil.
On described leather substrate, use the improved finishing oil of one deck, improve its described stretch characteristic by this finishing oil.
The invention further relates to a kind of finishing oil that is suitable for improving the tensile properties of leather substrate, comprising:
A kind of finishing oil and:
Be dissolved in a kind of improving agent in the finishing oil of being mentioned, to form a kind of improved finishing oil.At this, the improving agent of being mentioned is polymerized by a kind of monomer mixture.This monomer mixture comprises:
A kind of monomer (i) comprise 0～40wt%, alkyl group contains the methylacrylic acid alkyl ester or the alkyl acrylate of 1～6 carbon atom and different mixtures thereof.
A kind of monomer (ii) comprise 30～90wt%, alkyl group contains the methylacrylic acid alkyl ester or the alkyl acrylate of 7～15 carbon atoms and different mixtures.
A kind of monomer (iii) comprise 0～40wt%, alkyl group contains the methylacrylic acid alkyl ester or the alkyl acrylate of 16～24 carbon atoms and different mixtures thereof.All weight percents are according to the improving agent solid gross weight of being mentioned.
" GPC weight-average molecular weight " meaning is the weight-average molecular weight of being measured by gel permeation chromatography (GPC).This chromatogram is at the chapter 1 of " The Characterization of Polymers ", and page 4 is described, and uses polyisobutene acid methyl esters to be standard.This book is Pennsylvania in 1976, and Philadelphia Rohm and Haas Company publishes.
The first step of method of the present invention comprises: a kind of improving agent of dissolving forms the improved finishing oil that a kind of viscosity increases in a kind of traditional finishing oil.For the improvement oil viscosity that makes generation increases by 10%～50% than the finishing oil before improving with present method, preferred 50%～200%, the amount that is dissolved in the improving agent in the finishing oil is 10～50wt%, preferred 15～40wt%, most preferably 25～35wt%.All weight percents are according to the gross weight of improved finishing oil.
Be suitable for the polymkeric substance that improving agents more of the present invention comprise oily following monomer polymerization.For example, being used for monomer of the present invention may be a kind of single monomer or the monomer mixture that the different quantities carbon atom is arranged at moieties.The moieties of methacrylic acid ester and acrylate is an important factor for the performance characteristic of polymkeric substance of the present invention.By means of this mean number (n) of carbonatoms (Cn) that means the side chain alkyl group that should select acrylate or methacrylic acid ester trunk polymer farthest to increase the viscosity of gained improving agent.Improving agent of the present invention is a kind of from by methylacrylic acid (C
1～C
24) alkyl ester, vinylformic acid (C
1-C
24) the monomer institute polymeric multipolymer selected in the group formed of alkyl ester and composition thereof.Normally, when mean number Cn was less than 7, the polymkeric substance of generation may have relatively poor solvability in finishing oil, and this expects for the tensile properties that improves leather.Be used to prepare the acrylate of aggretion type additive or the average carbon atom number on the monomeric alkyl group of methacrylic acid ester between 7～18, preferred 8～12.Monomer be full acrylate or be entirely basically acrylate in this case, the average carbon atom number of the side chain alkyl group of trunk polymer will have certain variation, and average carbon atom number will adapt to the solubility parameter of corresponding methacrylic acid ester trunk polymer.Such solubility parameter is understood and is understood by those skilled in the art.
For obtaining desirablely being related to that viscosity improves and the balance of unfolded service performance on leather preferably.Use contains the monomer of the mixture of methylacrylic acid alkyl ester and alkyl acrylate.The result, on embodiment of the present invention, improving agent is polymerized by a kind of monomer mixture, this mixture comprises a kind of monomer (i) and comprises 0～40wt%'s, alkyl group contains methylacrylic acid alkyl ester or the alkyl acrylate and the different mixtures thereof of 1～6 carbon atom, a kind of monomer (ii) contains 30～90wt%'s, alkyl group contains the methylacrylic acid alkyl ester of 7～15 carbon atoms or alkyl acrylate and different mixture and a kind of monomers thereof and (iii) contains 0～40wt%'s, alkyl group contains methylacrylic acid alkyl ester or the alkyl acrylate and the different mixtures thereof of 16～24 carbon atoms.All per-cent is according to improving agent solid, gross weight.Monomer (i) (ii) (iii) total amount equals 100% of improving agent weight.Preferred 0～the 25wt% of amount of monomer in the improving agent (i); Preferred 45～the 85wt% of monomer amount (ii), more preferably 50～60wt%; Preferred 5～the 35wt% of monomer amount (iii), more preferably 25～35wt%.
Contain the example that contains the monomer mixture of the methylacrylic acid alkyl ester of 1～6 carbon atom or alkyl acrylate at alkyl group and also be known as " low cut (low-cut) " methylacrylic acid alkyl ester or alkyl acrylate, some suitable monomers are methyl methacrylate (MMA), methyl acrylate and ethyl ester, the methylacrylic acid propyl ester, butyl isocrotonate (BMA) butyl acrylate (BA), methylacrylic acid isobutyl ester (IBMA), methylacrylic acid caproic acid and cyclohexylenedinitrilotetraacetic acid, cyclohexyl acrylate and composition thereof.It is preferred low that to cut the methylacrylic acid alkyl ester be methyl methacrylate and butyl isocrotonate.
Contain at the example that alkyl group contains the monomeric mixture of the methylacrylic acid alkyl ester of 7～15 carbon atoms or alkyl acrylate and be also referred to as " in cut (mid-cut) " methylacrylic acid alkyl ester or alkyl acrylate.Some suitable monomers are 2-EHA (EHA), methylacrylic acid 2-ethylhexyl, and the methylacrylic acid monooctyl ester, methylacrylic acid ester in the last of the ten Heavenly stems, (IDMA is with (the C of branching for methylacrylic acid isodecyl ester
10) isomer mixture of alkyl is the basis), methylacrylic acid undecane ester, methylacrylic acid dodecane ester (also claiming the methylacrylic acid lauryl), methylacrylic acid tridecane ester, methylacrylic acid tetradecane ester (also claiming the methylacrylic acid myristin), methylacrylic acid pentadecane ester and composition thereof.Useful also has: methylacrylic acid dodecane ester-pentadecane ester (DPMA), and a kind of methylacrylic acid dodecane ester, the tridecane ester, tetradecane ester, the isomer linearity of pentadecane ester and branching mixes; With methylacrylic acid dodecane ester-tetradecane ester (LMA), the mixture of a kind of methylacrylic acid dodecane ester and tetradecane ester.Cutting the methylacrylic acid alkyl ester in preferred is methylacrylic acid dodecane ester-tetradecane ester and methylacrylic acid isodecyl ester.
Contain the example that contains the monomeric mixture of the methylacrylic acid alkyl ester of 16～24 carbon atoms or alkyl acrylate at alkyl group and be also referred to as " height is cut (high-cut) " methylacrylic acid alkyl ester or alkyl acrylate.Some suitable monomers are methylacrylic acid n-Hexadecane ester, methylacrylic acid heptadecane ester, methylacrylic acid octadecane ester, methylacrylic acid nonadecane ester, 20 grades of alkane esters of methylacrylic acid, methylacrylic acid eicosane ester and composition thereof.Useful also has: methylacrylic acid n-Hexadecane ester-eicosane ester (CEMA), a kind of methylacrylic acid n-Hexadecane ester, the octadecane ester, the mixture and the methylacrylic acid n-Hexadecane ester-octadecane ester (SMA) of 20 grades of alkane esters and eicosane ester, the mixture of a kind of methylacrylic acid n-Hexadecane ester and methylacrylic acid octadecane ester.It is methylacrylic acid n-Hexadecane ester-eicosane ester and methylacrylic acid n-Hexadecane ester-octadecane ester that preferred height is cut the methylacrylic acid alkyl ester.
Cut in above-mentioned with height cut methylacrylic acid alkyl ester and alkyl acrylate monomer usually with the technical grade long chain aliphatic alcohol by the preparation of standard esterification procedure, these commercially available alcohols are the mixtures of alcohol that contain the different chain length of 7～15 or 16～20 carbon atoms on alkyl group.As a result, be purpose of the present invention, the methylacrylic acid alkyl ester not only will comprise the one methylacrylic acid alkyl ester product of mentioning, and comprises the mixture of the methylacrylic acid alkyl ester that the specific methylacrylic acid alkyl ester of mentioning occupies the majority.The use of the commercial alcohol of preparation alkyl acrylate and methylacrylic acid alkyl ester has produced above-mentioned LMA, DPMA, SMA, the monomeric mixture of CEMA.
Preferred polymkeric substance is from a kind of monomer mixture polymerization, and wherein, monomer (i) is from by methyl methacrylate, and butyl isocrotonate is selected in the group of methylacrylic acid isobutyl ester and different mixture composition thereof.Monomer (ii) is from by methylacrylic acid-2-ethylhexyl, methylacrylic acid isodecyl ester, and methylacrylic acid dodecyl ester-pentadecyl ester is selected in the group that methylacrylic acid dodecyl ester-tetradecane ester and different mixtures thereof are formed.Monomer (iii) is from by methylacrylic acid cetyl ester-stearyl, selects in the group that methylacrylic acid cetyl ester-eicosyl ester and different mixtures thereof are formed.
A kind of preferred polymkeric substance is to come from a kind of monomer mixture polymerization a kind of mineral oil.As paraffin oil, wherein monomer mixture comprises the 28.5wt% butyl isocrotonate, the monomer mixture of the methylacrylic acid stearyl of 38.3wt% methylacrylic acid isobutyl ester and 33.2wt%.All wt percentage ratio is to propose according to the total weight percent of polymer solids.
A kind of preferred polymkeric substance is to be polymerized by a kind of monomer mixture in the solvent oil, wherein monomer mixture contains the 10wt% methyl methacrylate, 62wt% methylacrylic acid isodecyl ester, 28wt% methylacrylic acid n-Hexadecane ester-octadecane ester or methylacrylic acid n-Hexadecane ester-eicosane ester and different mixtures thereof, all weight percents all propose according to total weight of solids per-cent.
Another kind of suitable polymer blend is to be polymerized by a kind of monomer mixture in the mineral oil, wherein this monomer mixture contains 5～10wt% methyl methacrylate, 85～90wt% methylacrylic acid dodecane ester-tetradecane ester, methylacrylic acid isodecyl ester or methylacrylic acid dodecane ester-pentadecane ester, 0-5wt% methylacrylic acid n-Hexadecane ester-eicosane ester and different mixtures thereof.All weight percents propose according to the polymer solids total weight percent.
Another kind of suitable polymer blend is to be polymerized by a kind of monomer mixture in the mineral oil.Wherein contain 0～5wt% methyl methacrylate in the monomer mixture, 80～90wt% methylacrylic acid dodecane ester-tetradecane ester, 0～10wt% methylacrylic acid n-Hexadecane ester-eicosane ester and different mixtures thereof, all weight percents propose according to the polymer solids total weight percent.
Another kind of suitable polymer blend is to be polymerized by a kind of monomer mixture in the mineral oil.Contain 0～20wt% butyl isocrotonate in this monomer mixture, 65～90wt% methylacrylic acid dodecane ester-tetradecane ester, 0～10wt% methylacrylic acid n-Hexadecane ester-eicosane ester and different mixtures thereof.All weight percents propose according to the polymer solids total weight percent.
The mean number (n) of the carbon atom (Cn) on the side chain groups of acrylate, methacrylic acid ester trunk polymer, the character of the moieties of methacrylic acid ester and acrylate monomer also is an important factor in the action characteristic of polymkeric substance improving agent of the present invention.For example, a kind of methylacrylic acid (C
1-C
6) alkyl ester or vinylformic acid (C
1-C
6) mixture of alkyl ester.As a result, a part contains 5～40wt%, preferred 5～35wt%, more preferably 25～35wt% methylacrylic acid (C
16-C
24) alkyl ester and vinylformic acid (C
16-C
24) monomer mixture of alkyl ester is preferred.Wherein alkyl portion sends out C preferred
16～C
20
High, medium and low optimal selection of cutting methylacrylic acid alkyl ester ratio certainly is taken at finishing oil in the prescription and the exposure level of expecting.In case optimization height cut monomer, so with in cut and hang down and cut monomer than going balance the suitableeest viscosity consistence and solvability, alkyl carbon content (Cn) is about 8～10 in the prescription after the balance.
In order to realize the solvability of improving agent in the finishing oil, viscosity consistence and it is the easily combination of unfolded ability on leather substrate, the low (C that cuts
1-C
3) amount of methylacrylic acid alkyl ester such as methyl methacrylate may be 0～25wt%, preferred 5～15wt%, used weight percent are the gross weights according to polymer solids.The solvability of polymkeric substance refers to following these character: the same polymkeric substance that is formed by more hydrophobic monomer is (as the higher (C of those carbon contents on alkyl chain
4Or greater than C
4)) compare, hydrophilic or polar monomer is many more (as those at the lower (C of moieties carbon content
1-C
3), the solvability of the polymkeric substance of formation in finishing oil is low more.
The weight-average molecular weight of improving agent of the present invention should be able to give finishing oil desirable viscometric properties fully.Along with the increase of polymkeric substance weight-average molecular weight, its more effective thickness that becomes.Yet they may must be difficult to be applied on the leather by thickness.Like this, the GPC weight-average molecular weight is finally controlled by multiviscosisty effect and type used.Normally, improving agent of the present invention has GPC weight-average molecular weight 50,000～2,000,0000, and is preferred 250,000～1,000,000, and more preferably 80,000～150,000.
Polymkeric substance of the present invention is in the presence of a kind of polymerization starter, a kind of thinner and optional a kind of chain transfer agents, relies on mix monomer to prepare.60～140 ℃ of temperature, preferred 115～125 ℃, in the inert environments, under agitation react.Typically, reaction material reaches 115～125 ℃ of polymerization temperatures with heat release.Reaction was carried out 4～10 hours or usually up to reaching the desirable polymerization degree.Just as is known to the person skilled in the art, the time of reaction and temperature are correspondingly different according to the selection of initiator.
To the useful initiator of this polyreaction is compound such as peroxidation, hydroperoxidation and the azo initiator of any generation free radical that is known, comprise acetyl peroxide, benzoyl peroxide, laurylperoxide acyl, peroxidation tert-butyl isobutyrate, the peroxidation hexanoyl, cumene hydroperoxide, 1,1-two (tert-butyl peroxide)-3,3,5-trimethyl-cyclohexane, Diisopropyl azodicarboxylate and the sad tert-butyl ester of mistake.Initiator concentration changes in 0.025～1Wt% of total monomer weight usually, preferred 0.05～0.25wt%.For the molecular weight of controlling polymers, also can add chain-transfer agent in the polyreaction.Preferred chain-transfer agent is alkyl sulfhydryl such as bay (dodecyl) mercaptan, and the concentration of used chain-transfer agent is 0～0.5% (weight).
The thinner that is suitable for this polyreaction is aromatic hydrocarbons such as benzene, and toluene, dimethylbenzene and aromatic series petroleum naphtha, chlorating hydrocarbon polymer is as 1, the 2-ethylene dichloride; Ester such as ethyl propionate, or butylacetate and petroleum oil.
After the polymerization, the polymers soln of generation contains the polymkeric substance of 50～95wt% of improving agent gross weight.Polymkeric substance can be separated or directly use or polymkeric substance and diluent solution use with conc forms in mineral oil or synthetic base oil.When concentrating use, polymer concentration can be deployed into desirable value with other thinner (paraffin-base petroleum).Preferred polymer concentration is 30～70wt%, most preferably 35～45wt% in enriched material.When directly enriched material being sneaked into thinner, more preferably thinner is a mineral oil arbitrarily, as the 100-150 neutral oil molten with the finishing oil phase (100N or 150N oil).Preferred mineral oils is by the Pennsylvania, and the Sun oil Corporation in Philadelphia provides, its commercial Sun HPO by name
TM100 mineral oil.
The finishing oil that is suitable for the present invention's use can be any traditional oil base finishing oil known in the art, comprises oil in water emulsion.This finishing oil also is known as " fat liquor " or " emulsion of scrounging " sometimes.Same example like this can be found at following several places: at the Pocket Book for theLeather Technologist, second edition, the 139-151 page or leaf, be identified as B352e/ (791) 8.82, this book is by BASF Aktiengesellchaft, D-6700, Ludwiqshafen, Fed-eral Republic of Germany publishes; At the 40th of Science and Technology, 42,43,80 and 81 pages, among the Synthetic fatliquors in theoryand practice that Dr.Th Bohme writes, 1～23 page of Technical Director etc., among the Fatliquors and Fatliquoring of Leather. that writes by Samir Das Gup-ta, technical director Atlas Re-finery, Newark, New Jersey; In Material Safety Date Sheet by Henkel Corporation, the Aversin that Oak Creek Wisconsin provides
RKCO grease mixture and at Rohm and Haas Company., Philadelphia, the United States Patent (USP) NO.5 of Pennsylvania is in 330,537.All these are all listed herein as the reference data.Preferred non-emulsification finishing oil.Especially preferably by Henkel Corporation, the finishing oil that OakCreek, Wisconsin provide, its commercial Aversin by name
RKCO grease mixture.
Second of the inventive method goes on foot the improved finishing oil that is coated with on the grain surface that is included in leather substrate among one deck the present invention.Any traditional equipment of smearing as a contact conveying roller, all is fit to, and this cylinder constantly is coated with from traditional reservoir as the improved finishing oil of the present invention of sending out the storage tank, and this storage tank and conveying roller are in contact with one another.Being coated with this cylinder with the improved finishing oil of the present invention contacts leather surface again and oil is applied to herein.The amount of the improved finishing oil of the present invention of sending out from traditional bunkerage such as storage tank can be measured effectively by metering methods such as blade coatings.Normally, coated equipment is applied to the effect that measures the tensile properties that improves leather substrate of the of the present invention improved finishing oil of grain side of leather.Typically, be coated with 2.5～50g at the grain of every square feet leather, preferred 5～20g, 20～35g most preferably, this improved finishing oil can obtain the tensile properties of desired leather substrate best.
If wish, before the grain of leather bottom is coated with improved finishing oil, the inventive method can further be included in and improve this improved finishing oil of heating under the temperature, typical temperature range is 30～120, preferred 30～70 ℃, the degree of improved finishing oil heating depends on the amount of the paraffin composition that the typical case exists in the finishing oil and their fusing point usually.Like this, if in improved finishing oil, exist the paraffin composition of a large amount of higher melt, so in being applied to the step of leather surface, for the homogeneity that guarantees improved finishing oil with flow smoothly, must need more heat heating.
If wish, after grain side of leather had been coated the improved finishing oil of the present invention, method of the present invention can further comprise the flatiron of leather and smooth, with its tensile properties of further raising." flatiron " this term meaning is to press a cylinder on the leather substrate that coats.Normally, in iron process, the pressure of cylinder can be 25-300kg/cm
2, preferred 100～250kg/cm
2, for further improving the tensile properties of leather substrate, in the flatiron step, cylinder can be heated to 50～300 ℃, preferred 90～200 ℃.
Optionally or with the flatiron step carry out simultaneously, the grain of leather be coated with last layer the present invention improved finishing oil with its tensile properties of further raising after, method of the present invention can further comprise the smooth of leather." smooth " this term meaning is to press a shape and a big or small pressing step of wanting arranged on the leather substrate that coats.The pressure of the pressing plate that normally, uses in planarization step is 25～300kg/cm
2, preferred 100～250kg/cm
2, for further improving the tensile properties of leather substrate, pressing plate preferably is heated to 50～300 ℃, more preferably 90～200 ℃.
If wish, can engrave pattern on above-described cylinder and the pressing plate, protrude or add the figure of wanting with grain, as a kind of more expensive leather leather pattern or other any pattern of wanting at leather substrate.
The present invention also relates to a kind of improved finishing oil that utilizes the inventive method to be applicable to the tensile properties that improves leather, its concrete composition is foregoing with those to be consistent.
The present invention can be advantageously used in the coating leather goods, as footwear, gloves, wallet, clothing, cap and any its their need attractive in appearance and look the leatherware that attracts the human consumer.
The following example can further specify this invention.
Improving agent
A kind of monomer mixture is by 33.2 parts of methylacrylic acid octadecane ester (benchmark 100%, purity 95%), 38.3 part methylacrylic acid isodecyl ester (benchmark 100%, purity 98%), 28.5 part butyl isocrotonate, 0.06 part of lauryl mercaptan and 0.17 part of sad tert-butyl ester of mistake (white spirits moderate purity 50%) preparation.The residue charging is prepared by 20 parts of paraffinic based oils (the 100N oil that is provided by Britain BPoil) and 0.028 part of sad tert-butyl ester of mistake (white spirits moderate purity 50%).A kettle of filling nitrogen is injected in the residue charging, a thermometer and Thermowatch are housed on this kettle
TMControlled temperature, the water-cooled reflux condenser that nitrogen outlet is arranged, an agitator, a nitrogen inlet and a funnel that in kettle, adds reactant.Thing is heated and maintains 120 ℃ in the kettle, keeps in the kettle when being 115～120 ℃ polymerization temperature, evenly adds monomer mixture (100 parts) in 90 minutes in kettle.
After 20 minutes, add two batches postpone the initiator particulate first, every batch of inducer contains 0.10 part of sad tert-butyl ester of mistake (white spirits moderate purity 50%) in 5 parts of paraffin-base petroleums.After 20 minutes, add second batch of inducer, second batch of inducer added after 20 minutes, added 62 parts of paraffinic based oils in still, made and expected to reach theoretic 50% polymer solids level in the still.In the polymerization process, the still temperature keeps 115～120 ℃, and after 30 minutes, 95% of monomer mixture aggregates into improving agent.
In finishing oil, dissolve in above-mentioned improving agent, this finishing oil man Aversin already by name
RKCO is Henkel Corproation, and the mixture of a kind of grease that Oak Creek, Wisconsin provide is prepared as follows a series of improved finishing oil in the table 1.Use different per-cent to obtain the improved finishing oil of different viscosity, the example 1 in the table 1 be do not have the dissolved improving agent with reference to sample.
Table 1
Example example example example example example example example
1234567 8A
1650 600 550 500 450 400 350 300B
2350 350 350 350 350 350 350 350C
30 50 100 150 200 250 300 350D
465 65 72 80 92 100 110 110A
1Refer to Aversin
KCO, a kind of grease mixture, unit: gB
2The white spirits that finger is provided by Exxon Chemical Americas; Unit: gC
3Refer to improving agent mentioned above; Unit: gD
4The finger method is the shear viscosity of the improved finishing oil of being measured by ICI high-shear zahn viscosity instrument (cone plateviscometer) of ASTM D 4287, unit: CPS.
By table 1, can draw: along with the increase that is dissolved in the improving agent per-cent in the finishing oil, improved finishing oil viscosity also increases to some extent.
Use fixed amount such as the table 1 of 0.1ml, the described improved finishing oil of routine 1-8 at the grain of different leathers, rely on the different leather surfaces of measurement to absorb the improved used time (opening the time) of finishing oil fully, promptly absorb the improved required time of finishing oil of fixed amount fully at different leather surfaces, the effect that increasing amount improving agent of the present invention is produced is dissolved in decision in finishing oil, the result is as shown in table 2 below.
Table 2
Example example example example example example example example
The 2.31 2.47 4.02 4.07 4.45 5.40 5.15 6.22F 1.27 1.45 152 1.55 2.17 2.30 2.22 2.22* times of 1.10 1.20 1.30 2.10 2.57 3.37 3.07 3.20G of 1234567 8E, to divide and to remember that (every minute and second) E refers to a kind of leather substrate sample (thick 1.5mm) second, it is a kind of lightweight, softer, the leather substrate that grain is all slightly tanned by chrome yellow again.F refers to a kind of leather sample (thick 2.5mm), and it is a kind of grain flour milling, Heavy Weight, the leather that chrome yellow tanning, synthetic tanning agent are tanned again.G refers to a kind of leather substrate sample (thick 2.5mm), and it is a kind of Heavy Weight, the deerskin of the chrome yellow tanning of tanning again with heavy vegetable tanning agent.
By table 2, as can be seen,, on bigger zone, launch the also increase to some extent of the required time of opening of improved finishing oil along with the increase of improved finishing oil viscosity.And, when analyzing the flesh noodles of different substrate materials, can draw increase along with the improving agent per-cent that is dissolved in finishing oil, the amount of finishing that is seeped into the improving agent of flesh noodles reduces gradually, example 1 (do not have improving agent with reference to sample) has shown maximum infiltration capacity, and example 8 has shown minimum infiltration capacity.
Claims (12)
1. improve the method for leather substrate tensile properties, comprising:
In order to increase 10%～500% of a kind of finishing oil viscosity, a kind of improving agent of dissolving is to form a kind of improved finishing oil in this finishing oil.
The improved finishing oil that uses one deck to mention on described leather by means of this, can improve said tensile properties.
2. the process of claim 1 wherein the improving agent that contains the 10～50wt% that improves finishing oil gross weight in the improved finishing oil.
3. the improving agent that the process of claim 1 wherein is from by methylacrylic acid C
1-C
24Alkyl ester, vinylformic acid (C
1-C
24) the monomeric multipolymer selected in the group formed of alkyl ester and composition thereof.
4. the method for claim 1 further comprises the improved finishing oil that heating is mentioned, and the temperature range of rising is 30～120 ℃.
5. claim 1 or 4 method after described base material is coated with the improved finishing oil of last layer, further comprise flatiron, and smooth or flatiron and smooth this base material are with its tensile properties of further raising.
6. the method for claim 5, flatiron step wherein comprises the hot cylinder with 50～300 ℃ of temperature, with 25～300kg/cm
2Different pressures on the base material of being mentioned, pass through.
7. the method for claim 5, planarization step wherein comprise that being heated to temperature with one is 50～300 ℃ heating platen.Apply 25～300kg/cm
2Pressure.
8. the process of claim 1 wherein the usage quantity of using the improved finishing oil described in the step be on every square feet of leather substrate by 2.5g to 50g.
9. a kind of leather substrate of producing by claim 1 that improves tensile properties.
10. an improved finishing oil that is suitable for improving the tensile properties of leather substrate comprises:
A kind of finishing oil and
A kind ofly be dissolved in improving agent in the related finishing oil to form a kind of improved finishing oil.Improving agent wherein is polymerized by a kind of monomer mixture.This monomer mixture comprises:
A kind of monomer (i) comprises methylacrylic acid alkyl ester or alkyl acrylate and the different mixtures thereof that 0～40wt%, alkyl group contain 1-6 carbon atom.
A kind of monomer (ii) comprise 30～90wt%, alkyl group contains 7～15 former methylacrylic acid alkyl esters of carbon or alkyl acrylate, and different mixture.
A kind of monomer (iii) comprise 0～40wt%, alkyl group contains the methylacrylic acid alkyl ester or the alkyl acrylate of 16～24 carbon atoms and different mixtures thereof.All weight percents are according to the improving agent solid gross weight of being mentioned.
11. the improved finishing oil of claim 1, improved finishing oil wherein contains the described improving agent of 10～50wt%, and all weight percents are according to the gross weight of the improved finishing oil of being mentioned.
12. the improved finishing oil of claim 1, improving agent wherein have the heavy molecular-weight average 50,000～2,000,000 of GPC.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US384395P | 1995-09-15 | 1995-09-15 | |
| US003843 | 1995-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1165197A true CN1165197A (en) | 1997-11-19 |
Family
ID=21707856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96112937A Pending CN1165197A (en) | 1995-09-15 | 1996-09-13 | Method of improving pull-up characteristic of leather substrate and modified finishing oil used therein |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0768385B1 (en) |
| KR (1) | KR970015750A (en) |
| CN (1) | CN1165197A (en) |
| AR (1) | AR003510A1 (en) |
| AU (1) | AU6440696A (en) |
| BR (1) | BR9603893A (en) |
| DE (1) | DE69605006D1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6437070B1 (en) | 1998-09-22 | 2002-08-20 | Rohm And Haas Company | Acrylic polymer compositions with crystalline side chains and processes for their preparation |
| ITVR20040012A1 (en) * | 2004-02-03 | 2004-05-03 | Prialpas S P A | PROCEDURE FOR OBTAINING PULL-UP EFFECT RUBBER SHEETS. |
| CN115651993B (en) * | 2022-11-05 | 2023-08-15 | 江西兆丰皮业有限公司 | Ox head layer waterproof frosted leather production device and method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4313714A1 (en) * | 1993-04-27 | 1994-11-03 | Roehm Gmbh | Graft polymers for the treatment of flexible fabrics |
| DE4422484A1 (en) * | 1994-06-28 | 1996-01-04 | Roehm Gmbh | Graft polymers for coating fabrics |
-
1996
- 1996-09-02 AU AU64406/96A patent/AU6440696A/en not_active Abandoned
- 1996-09-05 AR ARP960104243A patent/AR003510A1/en unknown
- 1996-09-09 EP EP96306524A patent/EP0768385B1/en not_active Expired - Lifetime
- 1996-09-09 DE DE69605006T patent/DE69605006D1/en not_active Expired - Lifetime
- 1996-09-13 KR KR1019960039864A patent/KR970015750A/en not_active Application Discontinuation
- 1996-09-13 CN CN96112937A patent/CN1165197A/en active Pending
- 1996-09-16 BR BR9603893A patent/BR9603893A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| MX9604057A (en) | 1997-07-31 |
| KR970015750A (en) | 1997-04-28 |
| BR9603893A (en) | 1998-06-02 |
| AU6440696A (en) | 1997-03-20 |
| EP0768385A1 (en) | 1997-04-16 |
| DE69605006D1 (en) | 1999-12-09 |
| AR003510A1 (en) | 1998-08-05 |
| EP0768385B1 (en) | 1999-11-03 |
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