CN100484981C - Sheetlike products and interior finishing materials - Google Patents
Sheetlike products and interior finishing materials Download PDFInfo
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- CN100484981C CN100484981C CNB2005800106166A CN200580010616A CN100484981C CN 100484981 C CN100484981 C CN 100484981C CN B2005800106166 A CNB2005800106166 A CN B2005800106166A CN 200580010616 A CN200580010616 A CN 200580010616A CN 100484981 C CN100484981 C CN 100484981C
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Abstract
A sheetlike product comprising a nonwoven fabric obtained by entangling ultrafine-denier fibers having single-fiber finenesses of 0.5dtex or below and an elastic resin binder containing a polyurethane as the main component, wherein the polyurethane is a polycarbonate-base polyurethane which has polycarbonate skeletons represented by the general formulae (1) and (2) and a gel point of 2.5 ml or above but below 6 ml: (1) wherein R1 and R2 are each independently an aliphatic hydrocarbon group having 7 to 11 carbon atoms; n and m are each a positive integer; and when R1 and R2 are different, the two kinds of units may be copolymerized in block or at random] and (2) wherein R3 and R4 are each independently an aliphatic hydrocarbon group having 3 to 6 carbon atoms; x and y are each a positive integer; and when R3 and R4 are different, the two kinds of units may be copolymerized in block or at random.
Description
Technical field
The present invention relates to flap, relate in particular to plucking and transfer simulated leather sheet thing.
Background technology
Impregnation urethane resin in the base material that constitutes by fiber and the surface of the flap that forms, by adopting sand paper etc. with its fiber plucking, the plucking that can obtain imitative chamois leather, the young ox-hide of imitative sand milling is transferred simulated leather sheet thing, and this is that people know.As the characteristic of the simulated leather sheet thing of target, can come broadly to design arbitrarily by base material and the urethane resin that combination is made of fiber.For example, in patent documentation 1, disclose, used the urethane resin of polytetramethylene glycol, organic diisocyanate, glycol chains growing agent by employing, though can obtain with the high-grade woollen grey cloth that is used for Western-style clothes etc. than also not inferior, have an extremely imitation leather shape thing of soft hand feeling.
On the other hand, plucking is transferred leather-like, have the outward appearance and the surface that exactly like in natural leather, and can see advantage with the unexistent homogeneity of natural leather and dyeing fastness etc., not only in the dress material purposes, in recent years, in the purposes that the epidermis of furniture such as sofa, the sheet epidermis that automobile is used etc. can use in 5 years～10 years long-term, the use scale is constantly expansion also.
Yet, resemble in patent documentation 1 record use the polyethers of polytetramethylene glycol be urethane resin aging easily owing to be subjected to the effect of ultraviolet ray, heat, therefore in the process of using, the surface fiber balling-up, come off or bobbles takes place, existence can not stand the problem of life-time service.In addition, the urethane resin of polyester system also is the urethane that can be used for simulated leather sheet thing well, and it is good to be subjected to ultraviolet ray etc. to make the photostabilization of time spent, but since ester bond through hydrolysis meeting deterioration, therefore in secular use, there is the surface fiber balling-up, this same problem of bobbles takes place.
In patent documentation 2, disclose:, be to have useful urethane resin in the purposes of weather resistance of height with sheet material etc. with, vehicle at furniture by the polycarbonate-based urethane that polycarbonate polyol and ester ring type polymeric polyisocyanate and aromatic poly-isocyanate reaction obtain.But, Ji Zai use here the polycarbonate-based urethane resin of polyhexamethylene carbonic ether, under the situation that is used as the resin that infiltrates in the non-woven fabrics that is formed by the ultra-fine fibre complexing, the feel of flap is thick and stiff as plastics.Particularly the surface is made by sand paper under the situation of fiber plucking,, become the short surface of poor quality of plucking on surface, thereby it is extremely difficult to obtain having the good grade of graceful plucking because urethane is really up to the mark.
In patent documentation 3, with the weather resistance that has both plucking grade and photostabilization, hydrolytic resistance etc. is purpose, disclose a kind of plucking and transferred simulated leather sheet thing, this flap has used: polycarbonate diol, mainly be polyhexamethylene carbonic ether glycol be 30～90 weight % and and used polyether glycol or polyester glycol, polycarbonate/polyethers is that urethane resin, polycarbonate/polyester are urethane resin.Yet, under the situation of ratio less than 70 weight % of polycarbonate diol, because polyether components or polyester composition is aging, it is insufficient that weather resistance becomes, on the other hand, and under the ratio of polycarbonate diol is situation more than the 70 weight %, it is really up to the mark that urethane becomes, by grinding skins such as sand paper the time, the plucking on surface becomes short and of poor quality, and very difficult acquisition is satisfied the plucking of plucking grade and weather resistance simultaneously and transferred simulated leather sheet thing.
In addition, be coated with or pasted the leather-like of resin layer on fibrous substrate, in the promptly so-called synthetic leather, for the purpose that improves weather resistance, use polycarbonate-based urethane resin in resin layer, this is known.Mainly be for the purpose of the feel of improvement synthetic leather, proposed all schemes for polycarbonate-based urethane resin used in this resin layer.
For example, disclose in patent documentation 4: used by 1,6-hexylene glycol and 1, has used by 1 6-hexylene glycol and 1, the urethane resin of 4-butyleneglycol deutero-copolymerization polycarbonate glycol at the urethane resin of 5-pentanediol deutero-copolymerization polycarbonate glycol; In patent documentation 5, disclose: used methyl isophthalic acid, the urethane resin of 8-ethohexadiol deutero-polycarbonate diol by 2-; In patent documentation 6, disclose: will be 5～6 alkanediol and di-carboxylic acid deutero-polyester glycol and be that 8～10 the alkanediol deutero-polycarbonate diol and the polyester/polycarbonate of usefulness are urethane resin by carbonatoms by carbonatoms; In patent documentation 7, disclose: will be that 8～10 the alkanediol deutero-polycarbonate diol and the polycarbonate/polyethers of polyether glycol and usefulness are urethane resin by carbonatoms.
These urethane resins, be applicable to as resin to the non-woven fabrics infiltration that forms by the ultra-fine fibre complexing, make it to be present in the internal space of non-woven fabrics and the flap that obtains, particularly the plucking that the surface fiber plucking is obtained by grinding skins such as sand paper is transferred under the situation of simulated leather sheet thing, for example, the carbonatoms of record is that 4～6 copolymerization polycarbonate is a urethane resin in patent documentation 4, can not obtain to adopt the softness effect of the degree of sand paper grinding, become the short surface of poor quality of plucking on surface, thereby the good grade that will obtain to have graceful plucking is extremely difficult.In addition, in patent documentation 5 record by the 2-methyl isophthalic acid, the polycarbonate-based urethane resin of 8-ethohexadiol deutero-, because used the long-chain alkylene glycol, therefore in immersing non-woven fabrics the back, make it under the situation that wet type solidifies, setting rate is fast significantly, the foaming of the urethane of non-woven fabrics inside is big and thick assorted, in addition, produce the bad result of partial foaming, have following problems: undertaken by sand paper under the situation of grinding, the length that can only obtain the plucking on surface produces inhomogenous plucking grade flap very of poor quality.In addition, when the flap that adopts the gained that nuzzles up such as brush surperficial, fibre shedding is many, goes wrong on wear resistance.The urethane resin of record in patent documentation 6,7, and used on polyester glycol, the polyether glycol this point, from hydrolytic resistance or sunproof viewpoint, can't improve the problem that plucking is transferred the balling-up of weather resistance, the particularly surface fiber of simulated leather sheet thing in life-time service, bobbles is taken place.
In addition, the technology of record in these patent documentations 4～7, mainly be feel, the surface smoothing that will be arranged on the smooth feeling and so on of the urethane resin layer on the base material, be clamminess and the improvement of broken surface physical property as purpose, be present in the raising of grindability under the situation in the non-woven fabrics internal space, sand paper etc. but show no sign of consideration at urethane resin, the plucking length of the gratifying ultra-fine fibre that embodies thus, the aesthetic look of bringing by plucking and submissive surface touch, soft hand feeling.
On the other hand, in patent documentation 8, disclose: a kind of polyurethane series multi-constituent fibre that has used the flexible fibre matter sheet of the thermoplastic polyurethane that in main chain and/or side chain, has the polysiloxane segment and be suitable for its manufacturing.。Undertaken under the situation of grinding by sand paper etc. on the surface that will be somebody's turn to do the flap that constitutes by fiber, urethane is contained in ultra-fine fibre bundle inside, each ultimate fibre of urethane and ultra-fine fibre is bonding and exist, thereby the cut-out of fiber is obvious during grinding, it is inadequate obtaining by the aesthetic look that plucking brings, meanwhile, can not meet the demands aspect the flexibility of sheet, the feel.
In addition, a kind of flap and manufacture method thereof are disclosed in patent documentation 9, this flap is under the non-existent in fact state in fibrous bundle inside of the ultra-fine fibre that constitutes non-woven fabrics, the urethane resin that existence is obtained by the polysiloxane polyhydric alcohol modification, it is the dimethyl siloxane structural unit of 5～30 weight % that described polysiloxane polyhydric alcohol has with respect to the polymer diol composition.Yet, for polysiloxane polyhydric alcohol, only put down in writing the dimethyl polysiloxane structure that has hydroxyl at two ends, used this to have the urethane resin that the polysiloxane polyhydric alcohol of hydroxyl obtains, become the block polymer of in polyurethane backbone, having introduced the dimethyl polysiloxane chain at two ends.By common grinding, to immersed with adopt this polysiloxane polyhydric alcohol modification that has hydroxyl at two ends polycarbonate be that the flap of the urethane resin of principal constituent carries out the occasion that plucking is handled, in order to obtain ideal plucking length, graceful outward appearance, the content of polysiloxane polyhydric alcohol, with respect to being the polymer diol of principal constituent with the polycarbonate diol, at least need is more than the 10 weight %, but when in making urethane resin, containing the polysiloxane polyhydric alcohol that reaches unexpectedly more than the 10 weight %, the photostabilization of urethane resin obviously worsens, the balling-up and the bobbles of fiber easily take place, and can not get can gratifying flap on weather resistance.
As mentioned above, in existing technology, it is extremely difficult stably obtaining all excellent plucking accent simulated leather sheet thing of feel, plucking grade, weather resistance.
Patent documentation 1: the spy opens clear 59-192779 communique
Patent documentation 2: the spy opens flat 3-244619 communique
Patent documentation 3: the spy opens the 2002-30579 communique
Patent documentation 4: the spy opens flat 5-5280 communique
Patent documentation 5: the spy opens flat 2-33384 communique
Patent documentation 6: the spy opens flat 4-300368 communique
Patent documentation 7: the spy opens flat 5-9875 communique
Patent documentation 8: the spy opens flat 4-202861 communique
Patent documentation 9: the spy opens flat 7-150478 communique
Summary of the invention
The objective of the invention is to, in view of the prior art background, provide a kind of plucking to transfer simulated leather sheet thing, described plucking is transferred simulated leather sheet thing, has the aesthetic look brought by plucking, the feel resemble the natural leather concurrently and all few high-durability of generation of the coming off of fiber, balling-up, bobbles in life-time service.
The present invention has following formation in order to solve above-mentioned problem.
Promptly, flap of the present invention, be to be the non-woven fabrics that forms of the ultra-fine fibre complexing below the 0.5dtex and to be the flap that the elastic resin tackiness agent of principal constituent constitutes with urethane by the ultimate fibre fiber number, in this flap, above-mentioned urethane is the polycarbonate-based urethane with polycarbonate skeleton of following general formula (1) and (2) expression, and gelation point is that 2.5ml is above but less than 6ml.
(in the formula, R
1And R
2Be that carbonatoms is 7～11 aliphatic alkyl, can be the same or different.In addition, n and m are positive integer, at R
1And R
2Under the different situations, be block copolymerization or random copolymerization.)
(in the formula, R
3And R
4Be that carbonatoms is
3～
6Aliphatic alkyl, can be the same or different.In addition, x and y are positive integer, at R
3And R
4Under the different situations, be block copolymerization or random copolymerization.) further preferably, described urethane is the urethane with the side chain that contains the organopolysiloxane skeleton shown in the following general formula (3).
(in the formula, R
5And R
6Be aliphatic alkyl or aryl, can be the same or different.In addition, p is a positive integer.)
In addition, inner decoration material of the present invention is to use above-mentioned flap to constitute.
The invention effect
According to the present invention, can provide to have the aesthetic look of bringing by plucking, and the also excellent plucking of weather resistance such as hydrolytic resistance, photostabilization is transferred simulated leather sheet thing.
Embodiment
Flap of the present invention is to be the non-woven fabrics that forms of the ultra-fine fibre complexing below the 0.5dtex and to be that the elastic resin tackiness agent of principal constituent constitutes with urethane by the ultimate fibre fiber number.
As the starting material of the ultra-fine fibre that constitutes non-woven fabrics, can use thermoplastic resin polymeric amide such as polyester, nylon 6, nylon 66 such as polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid trimethylene ester etc., can melt-spinning.Wherein, from intensity, dimensional stability, sunproof viewpoint, preferably use polyester.In addition, in non-woven fabrics, can be mixed with different raw-material ultra-fine fibres.
Constitute the ultimate fibre fiber number of the ultra-fine fibre of non-woven fabrics, from the flexibility of sheet, the viewpoint of plucking grade, for being important below the 0.5dtex.Be more preferably below the 0.3dtex, further preferably below the 0.2dtex.On the other hand, the dispersiveness of the color developing after dyeing, the bundle fiber the when plucking that is undertaken by rubbing down is handled, open the viewpoint of fine easness, be preferably more than the 0.005dtex, more preferably more than the 0.01dtex.Here said ultimate fibre fiber number, be that the flap that will obtain cuts off in the direction of thickness, utilize scanning electron microscope (SEM) to observe the cross section, measure the fiber footpath of the ultra-fine fibre at 100 positions arbitrarily, calculate its mean value, convert by the proportion of the thermoplastic resin that in ultra-fine fibre, uses and obtain.
As the method that obtains ultra-fine fibre, preferably use ultra-fine fibre generation fiber type.Ultra-fine fibre generation fiber type can adopt islands-in-sea bicomponent fibre, exfoliated conjugated fibre, multi-layered type conjugated fibre etc., described islands-in-sea bicomponent fibre, be will be to the solvability of solvent the thermoplastic resin of different two compositions as the sea component island component, only the sea component dissolving is removed by using solvent etc., with the conjugated fibre of island component as ultra-fine fibre, described exfoliated conjugated fibre, the multi-layered type conjugated fibre, be that thermoplastic resin with two compositions is radial or lamellated mode alternately configured by the fibre section, cut apart each composition by peeling off, cut the conjugated fibre that is made into ultra-fine fibre.
Non-woven fabrics, the non-woven fabrics that can use the fibrous bundle complexing of non-woven fabrics that each ultimate fibre complexing of ultra-fine fibre forms, ultra-fine fibre to form, but from the intensity of flap, the viewpoint of feel, the non-woven fabrics that the fibrous bundle complexing of preferred ultra-fine fibre forms.From the viewpoint of flexibility, feel, particularly preferably be the non-woven fabrics in the space that between the ultra-fine fibre of fibrous bundle inside, has appropriateness.The fibrous bundle complexing of ultra-fine fibre and the non-woven fabrics that constitutes can make it to produce ultra-fine fibre and obtain by with after the complexing in advance of ultra-fine fibre generation fiber type again in this wise.In addition, the non-woven fabrics that between the ultra-fine fibre of fibrous bundle inside, has the space of appropriateness, can obtain by using following islands-in-sea bicomponent fibre, described islands-in-sea bicomponent fibre, be by removing sea component, can promptly give the islands-in-sea bicomponent fibre in the space of appropriateness between the ultra-fine fibre of fibrous bundle inside between the island component.
For islands-in-sea bicomponent fibre, can use: use the compound spinning nozzle of using of fabric of island-in-sea type, the resin of arranging these 2 kinds of compositions of island mutually carries out the mutual arrange body mode of polymer of spinning; With, the blend spinning mode that the two composition resins in island are carried out melting mixing and carry out spinning, or the like, but from the viewpoint of the ultra-fine fibre that obtains the homogeneous fiber number, the preferably islands-in-sea bicomponent fibre that obtains by the mutual arrange body mode of polymer.
Particularly about the homogeneity of fiber number, the fiber number CV in the optimum fiber bundle is below 10%.Here said fiber number CV is a value of representing the value that the fiber number standard deviation of the fiber of formation fibrous bundle obtains divided by average size in the bundle with percentage (%), is worth more little expression homogeneous more.By making fiber number CV below 10%, can make the plucking outward appearance grace on sheet surface, and the also even and good flap of dyeing.
As the sea component of islands-in-sea bicomponent fibre, can use polyethylene, polypropylene, polystyrene, sodiosulfoisophthalic acid, polyoxyethylene glycol etc. as the copolyester of copolymer composition, poly(lactic acid) etc.Solvent as the dissolving sea component, at copolymer composition is under the situation of polyethylene, polypropylene, polystyrene, can use organic solvents such as toluene, trieline, be divided at marine origin under the situation of copolyester, poly(lactic acid), can use alkaline aqueous solutions such as sodium hydroxide, by in solvent, flooding islands-in-sea bicomponent fibre, and carry out mangle, can remove sea component.
The cross-sectional shape of ultra-fine fibre can be common circular section, also can adopt polygons such as ellipse, flat, triangle, special crosssection such as fan-shaped, cross.
Constituting the non-woven fabrics of flap of the present invention, can be any non-woven fabrics in staple fiber nonwoven fabric, the nonwoven fabric of long fibers, but under the situation of paying attention to feel, grade, preferred staple fiber nonwoven fabric.In addition, in the inside of non-woven fabrics,, can insert fabric, knitted fabrics for the purpose that improves intensity etc.
Obtain the method for non-woven fabrics as making the ultra-fine fibre complexing, can adopt the method for stinging complexing by acupuncture, water.
As the principal constituent of the used elastic resin tackiness agent of the present invention and the urethane that uses, be that the carbonic ether with the polycarbonate skeleton shown in following general formula (1) and (2) is a urethane, this is important.
(in the formula, R
1And R
2Be that carbonatoms is 7～11 aliphatic alkyl, can be the same or different.In addition, n and m are positive integer, at R
1And R
2Under the different situations, be block copolymerization or random copolymerization.)
(in the formula, R
3And R
4Be that carbonatoms is 3～6 aliphatic alkyl, can be the same or different.In addition, x and y are positive integer, at R
3And R
4Under the different situations, be block copolymerization or random copolymerization.)
That is to say, have by having simultaneously that to resemble the carbonatoms shown in the general formula (1) be that the polycarbonate skeleton of 7～11 long-chain fat family alkyl resembles the different structure that the carbonatoms shown in the general formula (2) is the polycarbonate skeleton of 3～6 short-chain fat family alkyl with having, urethane becomes non-crystal structure easily, and reach hardness suitable when grindings such as employing sand paper, can obtain very surface of good fiber plucking.
R shown in the above-mentioned general formula (1)
1And R
2, the R shown in the above-mentioned general formula (2)
3And R
4Can be that identical respectively aliphatic alkyl also can be respectively different aliphatic alkyl, but when being when distinguishing different aliphatic alkyls, the easier non-crystal structure that becomes of urethane, so flexibility and the good tendency of plucking grade with the flap that obtains are preferred.
In addition, the polycarbonate skeleton shown in above-mentioned general formula (1), (2) can be any copolymerization of block copolymerization or random copolymerization, but from the easier aspect that becomes non-crystal structure of urethane, preferred random copolymerization.
Similarly from the flexibility of flap and the viewpoint of plucking grade, more preferably R
1, R
2, R
3, R
4Be whole 4 kinds of different aliphatic alkyls.Preferred especially R
1And R
2In at least one side, and, R
3And R
4In at least one side be by methyl or ethyl branching aliphatic alkyl.
Used urethane among the present invention, carbonatoms is arranged is polycarbonate skeleton at least a of 7～11 long-chain fat family alkyl and carbonatoms is arranged is at least a urethane of the polycarbonate skeleton of 3～6 short-chain fat family alkyl if having, and then can be the urethane with the carbonic ether skeleton more than 5 kinds.
More preferably, this urethane is the urethane with the side chain that contains the organopolysiloxane skeleton shown in the following general formula (3).
(in the formula, R
5And R
6Be aliphatic alkyl or allyl group, can be identical or different.And p represents positive integer.)
Flap of the present invention, finally can be used as very suitably its make the ultra-fine fibre plucking on one side at least plucking transfer simulated leather sheet thing.Its plucking is handled, and can adopt the method for using sand paper, roll-type sand mill etc. to carry out grinding to wait and implement, but usually in order to obtain the fiber plucking of surface of good, preferably gives the lubricant of polysiloxane latex etc. before plucking is handled.
Yet, under situation about making with lubricator, on sand paper, cause accumulation significantly from the grinding powder that flap produces by grinding, there is the tendency that production efficiency is worsened that produces obstruction etc. in early days.
To this, by making this urethane for having the urethane of the side chain that contains the organopolysiloxane skeleton shown in the above-mentioned general formula (3), before handling, plucking do not need to give the lubricant of polysiloxane latex etc., also can obtain the very fiber plucking of surface of good, and the deterioration of production efficiency can prevent that plucking from handling the time.
R shown in the above-mentioned general formula (3)
5And R
6Be aliphatic alkyl or aryl, can be the same or different, but consider, preferred R from the manufacturing cost aspect
5And R
6Be methyl.In addition, p is a positive integer.For the number-average molecular weight (Mn) with polysiloxane polyhydric alcohol described later (C) is adjusted in the preferred range, p is preferably 100～300.This organopolysiloxane skeleton, be essential in order to obtain graceful plucking form, when containing too in a large number sometimes, the photostabilization of urethane significantly worsens, because deterioration takes place, thereby balling-up, the bobbles of fiber easily take place, can not reach plucking and transfer the endurance quality as target of simulated leather sheet thing, but by making side chain contain this skeleton, even also can obtain graceful outward appearance, grade on a small quantity, therefore, can obtain to have concurrently the graceful grade and the simulated leather sheet thing of weather resistance.
This urethane, more particularly, the polycarbonate diol (A) that preferably has hydroxyl by two ends at molecular chain with the polycarbonate skeleton shown in the above-mentioned general formula (1), the polycarbonate diol (B) that has hydroxyl at two ends of molecular chain with the polycarbonate skeleton shown in the above-mentioned general formula (2), with the reaction of organic diisocyanate and chain propagation agent and the urethane that obtains, be more preferably by only further comprising the urethane that reaction that a end at the molecular chain with the organopolysiloxane skeleton shown in the above-mentioned general formula (3) has the polysiloxane polyhydric alcohol (C) of 2 hydroxyls obtains.
Said polycarbonate skeleton among the present invention is to form the skeleton that comes the banded macromolecular chain by carbonic acid ester bond, and so-called polycarbonate diol is the polycarbonate diol that has 1 hydroxyl on two ends of this macromolecular chain respectively.Polycarbonate diol, the transesterification reaction that can be by alkylene glycol and carbonic ether or the reaction of phosgene or chloro-formic ester and alkylene glycol wait makes.
As obtaining to have the alkylene glycol of polycarbonate diol (A) that carbonatoms is the polycarbonate skeleton of 7～11 long-chain fat family alkyl that has shown in the above-mentioned general formula (1), can use 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, 1, straight chain alkylene glycol and 2-methyl isophthalic acids such as 10-decanediol, 8-ethohexadiol, 2,7-dimethyl-1,8-ethohexadiol, 2,8-dimethyl-1, side chain alkylene glycols such as 9-nonanediol.Particularly preferably, employing is by 1,9-nonanediol and 2-methyl isophthalic acid, the copolymerization polycarbonate glycol that straight chain alkylene glycol that 8-ethohexadiol etc. obtains and side chain alkylene glycol obtain, from flexibility when making plucking and transfer simulated leather sheet thing and the easness by grindings such as sand paper, the tendency that obtains good plucking grade is arranged, thus preferred.
As obtaining to have the alkylene glycol of polycarbonate diol (B) that carbonatoms is the polycarbonate skeleton of 3～6 aliphatic alkyl that has shown in the above-mentioned general formula (2), can use 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1, straight chain alkylene glycols such as 6-hexylene glycol and propylene glycol, neopentyl glycol, 3-methyl isophthalic acid, side chain alkylene glycols such as 5-pentanediol.Particularly preferably, employing is by 1,6-hexylene glycol and 3-methyl isophthalic acid, the copolymerization polycarbonate glycol that straight chain alkylene glycol that 5-pentanediol etc. obtains and side chain alkylene glycol obtain, from flexibility when making plucking and transfer simulated leather sheet thing and the easness by grindings such as sand paper, the tendency that obtains good plucking grade is arranged, thus preferred.As the carbonic ether that in transesterification reaction, uses, can exemplify diethyl carbonate, diphenyl carbonate etc.
As polycarbonate diol (A) and number-average molecular weight (B) (Mn), be preferably 500～3,000, more preferably 1,500～2,500.By making number-average molecular weight is more than 500, can prevent the feel hardening, is below 3,000 by making number-average molecular weight, can keep the intensity as urethane.
Polysiloxane polyhydric alcohol (C) is not the polysiloxane polyhydric alcohol that respectively has a hydroxyl at two ends of macromolecular chain, but only has the polysiloxane polyhydric alcohol of 2 hydroxyls at an end of its macromolecular chain.By regulation in this wise, can obtain not to be on the straight chain but on side chain, contain the urethane of organopolysiloxane skeleton.
Number-average molecular weight (Mn) as polysiloxane polyhydric alcohol (C) is preferably 500～30,000.When number-average molecular weight less than 500 the time, carrying out plucking by sand paper etc. when handling, the plucking of flap has the tendency that shortens, on the contrary when surpassing 30,000 o'clock, the intermiscibility variation of polysiloxane polyhydric alcohol (C) and other polyvalent alcohol had the tendency that is difficult to obtain stable urethane.For number-average molecular weight, more preferably in the scope more than 5,000, below 25,000, particularly preferably in surpassing 10,000 but be scope below 20,000.Especially using number-average molecular weight to surpass 10,000 but be under the situation of polysiloxane polyhydric alcohol of the scope 20,000 below,, also can obtain all simulated leather sheet things of excellence of plucking grade, outward appearance even use on a small quantity.
As the ratio of polysiloxane polyhydric alcohol (C) with respect to polycarbonate diol (A) and summation (B), it is above but less than 5 weight % to be preferably 0.1 weight %.Be more preferably 0.5～4 weight %, further 1～3 weight % preferably.By the ratio that makes polysiloxane polyhydric alcohol (C) is more than the 0.1 weight %, and the grinding by sand paper etc. can obtain the plucking length as target.In addition, by making it, can prevent that photostabilization from worsening less than 5 weight %.
In addition,, be used for the polymer diol of synthesis of polyurethane, preferably do not use polycarbonate diol and polysiloxane polyhydric alcohol polyether glycol, polyester glycol in addition from improving the viewpoint of hydrolytic resistance, this weather resistance of photostabilization.
As the organic diisocyanate that is used for synthesis of polyurethane, for example can enumerate 4,4 '-diphenylmethanediisocyanate, to phenylene vulcabond, 1, aromatic diisocyanates, 4 such as 5-naphthalene diisocyanate, p-Xylol vulcabond, m xylene diisocyanate, ester ring type such as 4 '-dicyclohexyl methane diisocyanate, isophorone diisocyanate vulcabond, 1, aliphatic diisocyanates such as 6-hexamethylene diisocyanate.Wherein,, preferably use aromatic diisocyanate, especially preferably use 4,4 '-diphenylmethanediisocyanate from the viewpoint of weather resistance such as the intensity of the urethane that obtains, thermotolerance.
The ratio of polycarbonate diol (A) and summation (B) and organic diisocyanate, preferably both molar ratios reach 1:2～1:5.In addition, in this scope, under the situation of the flexibility of the urethane of paying attention to obtaining, can adjust by the ratio that reduces organic diisocyanate, under the situation of paying attention to intensity, thermotolerance, weather resistance etc., can adjust by the ratio that increases organic diisocyanate.
In addition, under the situation that further contains polysiloxane polyhydric alcohol (C), polycarbonate diol (A) and (B) and the summation of polysiloxane polyhydric alcohol (C) and the ratio of organic diisocyanate, preferably both molar ratios reach 1:2～1:5.In addition, in this scope, under the situation of the flexibility of the urethane of paying attention to obtaining, can adjust by the ratio that reduces organic diisocyanate, under the situation of paying attention to intensity, thermotolerance, weather resistance etc., can adjust by the ratio that increases organic diisocyanate.
Synthetic chain propagation agent as being used for urethane can use organic diol, organic diamine, hydrazine derivative etc.
Example as organic diol, can exemplify ethylene glycol, propylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,5-pentanediol, methyl pentanediol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1, aliphatic diols, 1 such as 9-nonanediol, decamethylene-glycol, aromatic diols such as ester ring type glycol, Xylene glycol such as 4-cyclohexanediol, hydrogenation Xylene glycol.
As the example of organic diamine, but exemplified by ethyl enediamine, isophorone diamine, benzene dimethylamine, phenyl diamines, 4,4-diaminodiphenyl-methane etc.
As the example of hydrazine derivative, can exemplify hydrazine, adipic dihydrazide, m-phthalic acid hydrazides etc.
Under the situation of the hydrolytic resistance of paying attention to urethane, preferably use organic diol, wherein, according to intensity, thermotolerance, the resistance Huang of urethane, the carbonatoms of preferred alkyl chain is 2～6 aliphatic diol, preferred especially ethylene glycol.In addition, under the stable on heating situation of paying attention to urethane, the preferred organic diamine that uses, wherein, preferred use 4, the aromatic diamine of 4 '-diaminodiphenyl-methane and so on or preferably 4 adds water to convert 4 in 4 '-diphenylmethanediisocyanate, 4 '-diaminodiphenyl-methane uses.
In urethane synthetic,, for example can use metallic compounds such as amines such as triethylamine, tetramethyl butane diamine, potassium acetate, Zinic stearas, stannous octoate as catalyzer.
The weight-average molecular weight of urethane (Mw) is preferably 100,000～300,000, and more preferably 150,000～250,000.By making weight-average molecular weight (Mw) is more than 100,000, can keep the intensity of the flap that obtains, can also prevent the balling-up of plucking and the generation of bobbles.Be below 300,000 by making it in addition, the viscosity that can suppress polyurethane solution increases, and easily carries out the infiltration to non-woven fabrics.
In addition, the urethane that uses as the principal constituent of elastic resin tackiness agent in the present invention, gelation point be 2.5ml above, be important less than 6ml.Be more preferably the scope that 3ml is above, 5ml is following.Said gelation point among the present invention, be to stir the N that contains 1 weight % urethane on one side, N '-dimethyl formamide (below, be called for short DMF) solution 100g, in this solution, drip distilled water on one side, under 25 ± 1 ℃ temperature condition, urethane solidify beginning, and the value of the water droplet dosage when little gonorrhoea takes place.Therefore, in the mensuration used DMF need to use moisture be DMF below 0.03%.Above-mentioned measuring method, transparent with the DMF solution of urethane is that prerequisite is put down in writing, but at the DMF of urethane solution in advance under the situation of little gonorrhoea, can with urethane solidify beginning, water droplet dosage when the gonorrhoea degree changes is for the first time regarded gelation point as.In addition, the gelation point of the urethane that exists in flap can extract urethane by using DMF from flap, and adjusts polyurethane concentration and make it become 1 weight % to measure.
This gelation point is the expression DMF solution that uses urethane, the moisture permission when the urethane wet type is solidified, and exists the low urethane setting rate of gelation point fast, the slow tendency of urethane setting rate that gelation point is high.Therefore, under the situation of gelation point less than 2.5ml, when the urethane wet type is solidified, the result that setting rate is too fast, the polyurethane foam that exists in the non-woven fabrics internal space is big and slightly assorted, produces the bad result of part foaming in addition, under the situation on the surface of passing through sand paper grinding flap, the length of surface galling takes place irregular, and the plucking grade is very bad.In addition, because the polyurethane film attenuation,, under the situation that adopts the surface gallings that nuzzle up such as brush, there are the many problems of fibre shedding as the effect of fixed tackiness agent is little each other with fiber.On the other hand, under gelation point is situation more than the 6ml, when the urethane wet type is solidified, the result that setting rate is slow excessively, the urethane that exists in the non-woven fabrics internal space almost be can't see foaming, and the urethane very thick and hard as thickness exists, therefore under the situation on the surface of passing through sand paper grinding flap, difficulty is carried out the grinding of urethane, and surface galling is very short, and grade is of poor quality.
Making the gelation point of the urethane that uses in the present invention is more than 2.5, less than 6ml, though also depend on the polysiloxane polyhydric alcohol (C), organic diisocyanate, the kind of chain propagation agent, the amount that are used for synthesis of polyurethane, can be by at the polycarbonate diol (A) that has hydroxyl on two ends of the molecular chain that the polycarbonate skeleton shown in the above-mentioned general formula (1) is arranged with there is being the weight ratio that has the polycarbonate diol (B) of hydroxyl on two ends of molecular chain of the polycarbonate skeleton shown in the above-mentioned general formula (2) to adjust.
In scope as the gelationization of target, in order to suppress gelation point low, can adjust by the ratio that improves polycarbonate diol (A), on the contrary,, can adjust by the ratio of reduction polycarbonate diol (A) in order to improve gelation point.
In addition, the elastic resin tackiness agent, though use the urethane that uses as principal constituent, but in the performance of not damaging as tackiness agent, in the scope of feel, also can contain polyester system, polyamide-based, the elastomer resin of polyolefin etc., acrylic resin, ethylene-vinyl acetate resin etc., also can contain various additives, for example pigment such as carbon black, phosphorus system, halogen system, the fire retardant of inorganic system etc., phenol system, sulphur system, the antioxidant of phosphorus system etc., benzotriazole system, benzophenone series, salicylate system, vinylformic acid cyano group ester system, the UV light absorber of oxaluric acid anilide system etc., hindered amine system, the photostabilizer of benzoic ether system etc., the stabilizer against hydrolysis of polycarbodiimide etc., softening agent, static inhibitor, tensio-active agent, coagulation regulator, dyestuff etc.
The front has been narrated non-woven fabrics used in the flap of the present invention and has preferably been formed by the fibrous bundle complexing of ultra-fine fibre, but preferably be that the elastic resin tackiness agent of principal constituent does not exist in fact in the inside of the fibrous bundle of ultra-fine fibre in this case, with urethane.All there is the elastic resin tackiness agent in inside as fibrous bundle, the tendency that then has the excellent handle be difficult to obtain the sheet that the space by fibrous bundle inside obtains, because it is bonding and exist with the ultimate fibre of the ultra-fine fibre that constitutes fibrous bundle, therefore adopt sand paper etc. to carry out plucking when handling, easily cause the cut-out of fiber, the tendency that exists grade to worsen.
As obtaining with urethane is that the elastic resin tackiness agent of principal constituent is present in the internal space of non-woven fabrics but in the method for the non-existent in fact form in the fibrous bundle inside of ultra-fine fibre, can preferably use following method: after utilizing dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), diox equal solvent to make solution urethane
(1) in the islands-in-sea bicomponent fibre complexing of ultra-fine fibre generation type and in the non-woven fabrics that obtains, the solution of infiltration urethane, after in water or aqueous solutions of organic solvent, making it to solidify, the method that the sea component of islands-in-sea bicomponent fibre is removed with the dissolution with solvents of dissolve polyurethane not,
(2) to the islands-in-sea bicomponent fibre complexing of ultra-fine fibre generation type and the non-woven fabrics that obtains give saponification degree and be preferably polyvinyl alcohol more than 80%; protect after the fiber major part on every side; the sea component of islands-in-sea bicomponent fibre is removed with the dissolution with solvents of dissolve polyvinyl alcohol not; the solution of urethane then infiltrates; after in water or aqueous solutions of organic solvent, making it to solidify, remove polyvinyl alcohol method, or the like.
In addition, as the form that exists at non-woven fabrics inner elastomeric resin glue, for make fiber come off and balling-up few, and obtain good hand feeling, preferred at least a portion is bonding with the ultimate fibre of the outermost of the fibrous bundle that is positioned at ultra-fine fibre.This form can obtain by the method for above-mentioned (2).Therefore that is, because polyvinyl alcohol is being protected more than half periphery of ultra-fine fibre bundle, prevent that urethane from invading to fibrous bundle is inner, urethane is partly bonding with the peripheral part of the fibrous bundle of the protection that does not have polyvinyl alcohol.
Flap of the present invention, elastic resin tackiness agent shared ratio in flap is preferably 10～50 weight %, more preferably 15～35 weight %.By this ratio is more than the 10 weight %, can obtain sheet intensity, and prevent fibre shedding, and be below the 50 weight % by making this ratio, can prevent the feel hardening, thereby obtain good plucking grade as target.
Flap of the present invention can be to carry out before plucking handles, in double cutting of sheet thickness direction or be divided into several and obtain.
In addition, before handling, give static inhibitor,, thereby can preferably use because the grinding powder that produces from flap by grinding has the tendency that is difficult to be deposited on the sand paper at plucking.
As mentioned above, flap of the present invention finally can be used as very suitably at its plucking that ultra-fine fibre has been carried out plucking on one side at least and transfer simulated leather sheet thing.
This flap, particularly on the one side at least of sheet, ultra-fine fibre has been carried out plucking and the plucking that obtains is transferred simulated leather sheet thing, as the skin material of the seat in the compartment of furniture, chair, wall fitting and automobile, electric car, aircraft etc., ceiling, interior trim etc., can use very suitably as inner decoration material with very graceful outward appearance.
Embodiment
Below, further specifically describe the present invention with embodiment, but the present invention not only is defined in following embodiment.
[evaluation method]
(1) gelation point of urethane
Stir on one side the DMF solution 100g of 1 weight % urethane, to this solution in drip distilled water on one side, under 25 ± 1 ℃ temperature condition, the value of the water droplet dosage when measuring the solidifying beginning and little gonorrhoea has taken place of urethane.In addition, in the mensuration used DMF to use moisture be DMF below 0.03%.At the DMF of urethane solution in advance under the situation of little gonorrhoea, with the beginning of solidifying of urethane, and the water droplet dosage of gonorrhoea degree when changing for the first time is as gelation point.
(2) outward appearance grade
The plucking that obtains transfers the surperficial grade of simulated leather sheet thing to estimate like that according to following by visual sensory evaluation.
◎: the dispersion state of plucking length and fiber is all very good.
Zero: the dispersion state of plucking length and fiber is all good.
*: plucking length is good, but the dispersion of fiber is bad.
* *: plucking length is short and bad.
* * *: plucking does not almost have, for bad significantly.
(3) fiber number CV
Utilize scanning electron microscope (SEM) to observe the cross section of the thickness direction of flap inside, from its photo, measure the Fibre diameter of the ultra-fine fibre of the 1 bundle inside that constitutes bundle fiber, be converted into each filamentary fiber number from Fibre diameter, the fiber number standard deviation that constitutes the fiber of fibrous bundle is represented with percentage (%) divided by the resulting value of average size in the bundle.To 5 bundle fibers, carry out same mensuration, with mean value as fiber number CV.
(4) brush wearing and tearing decrement
Nylon wire arrangement bunchy with 100 long 11mm, diameter 0.4mm, in the circle of diameter 110mm, be 97 these bundles of 6 layers of concentric circles ground configuration, use the round-type brush (9700 in nylon wire) that obtains thus, under the condition that 8 pounds of load (about 3629g), rotating speed 65rpm, rotation revolution 45 change, transfer the surface of the circular sample (diameter 45mm) of simulated leather sheet thing to wear and tear to plucking, with the changes in weight of the sample before and after the wearing and tearing as the brush decrement of wearing and tearing.
(5) weather resistance-hydrolytic resistance
The plucking that obtains is transferred simulated leather sheet thing, use the constant temperature and humidity cabinet of ダ バ イ エ ス ペ Star Network corporate system, in the atmosphere of 70 ℃ of temperature, relative humidity 95%, place and implemented in 10 week to use James H.Heal﹠amp after the forced aging processing; Co. Zhi Model406 is used as Martindel abrasion trier, use the ABRASTIVE CLOTH SM25 of the said firm's system to be used as standard friction cloth, apply the load that is equivalent to 12kPa, at the friction revolution is 20, under 000 condition of changeing, the outward appearance of the sample after the visual observation friction, and estimate.Metewand is, the outward appearance of sample is chosen as 5 grades than unconverted fully before with friction, and what most bobbles took place is chosen as 1 grade, divides by per 0.5 grade between 5 grades and 1 grade.In addition, the qualified rank among the present invention is defined as 4 grades.
(6) weather resistance-photostabilization
The plucking that obtains is transferred simulated leather sheet thing, use and adopted 150W/m
2The test a machine xenon lamp weathering resistance instrument of corporate system of the ス ガ of xenon lamp, the light of illumination wavelength 300～400nm were implemented to use James H.Heal﹠amp after forced aging handles in 144 hours; Co. Zhi Model406 is used as Martindel abrasion trier, use the ABRASTIVE CLOTH SM25 of the said firm's system to be used as standard friction cloth, apply the load that is equivalent to 12kPa, at the friction revolution is 20, under 000 condition of changeing, the outward appearance of the sample after the visual observation friction, and estimate.Metewand is, the outward appearance of sample is chosen as 5 grades than unconverted fully before with friction, and what most bobbles took place is chosen as 1 grade, divides by per 0.5 grade between 5 grades and 1 grade.In addition, the qualified rank among the present invention is defined as 4 grades.
(7) processibility evaluation
That puts down in writing among the embodiment 1 (manufacturing of flap) as described later is such, when using ring-type sand paper that flap is carried out the plucking processing, even process continuous 3, more than the 000m, the evaluation that the obstruction of sand paper is also few also is designated as " well ", 3, the obstruction of sand paper significantly, is also interrupted the evaluation of processing and is designated as " bad " before the 000m.
[souvenir of chemical substance]
The meaning of the dummy suffix notation of the chemical substance of using in embodiment, comparative example as shown below.
PU: urethane
MDI:4,4 '-diphenylmethanediisocyanate
EG: ethylene glycol
DMF:N, dinethylformamide
PNMOC: the number-average molecular weight shown in the following general formula (4) be 2,000 by 1,9-nonanediol and 2-methyl isophthalic acid, 8-ethohexadiol deutero-copolymerization polycarbonate glycol
(in the formula, n, m are positive integers, are random copolymers.In addition, R represents (CH
2)
9Or CH
2-CH (CH
3)-(CH
2)
6In any aliphatic alkyl.)
PHC: number-average molecular weight is 2,000 polyhexamethylene carbonic ether glycol
PHMPC: the number-average molecular weight shown in the following general formula (5) be 2,000 by 1,6-hexylene glycol and 3-methyl isophthalic acid, 5-pentanediol deutero-copolymerization polycarbonate glycol
(in the formula, x, y are positive integers, are random copolymers.In addition, R represents (CH
2)
6Or CH
2-CH (CH
3)-(CH
2)
2In any aliphatic alkyl.)
PTMG: number-average molecular weight is 2,000 polytetramethylene glycol
PCL: number-average molecular weight is 2,000 polycaprolactone glycol
KSi-1000: the number-average molecular weight shown in the following general formula (6) is 1,000 the polysiloxane polyhydric alcohol that has 2 hydroxyls on an end of polydimethylsiloxane
KSi-1500: the number-average molecular weight shown in the following general formula (6) is 15,000 the polysiloxane polyhydric alcohol that has 2 hydroxyls on an end of polydimethylsiloxane
(in the formula, p is a positive integer)
BSi-1800: the number-average molecular weight shown in the following general formula (7) is 18,00 the polysiloxane polyhydric alcohol that respectively has 1 hydroxyl on two ends of polydimethylsiloxane
(in the formula, p is a positive integer)
Embodiment 1
(manufacturing of non-woven fabrics)
Use polystyrene as sea component, use polyethylene terephthalate as island component, using the island number is the compound spinning nozzle of using of fabric of island-in-sea type on 16 islands, after the compound ratio spinning formation islands-in-sea bicomponent fibre with 55 weight % sea components, 45 weight % island components, stretch, curl and process, cut, obtain the raw cotton of non-woven fabrics.
With the raw cotton that obtains, use cross lapping machine to make net, handle forming non-woven fabrics through acupuncture.
After this non-woven fabrics that is made of islands-in-sea bicomponent fibre being immersed in 10% polyvinyl alcohol water solution of saponification deg 87%, drying.Then, extract the polystyrene remove as sea component in trieline, carry out drying, obtaining by the ultimate fibre fiber number is the non-woven fabrics that the ultra-fine fibre of 0.1dtex constitutes.
(manufacturing of urethane)
To put into as 60 weight part PNMOC of polyvalent alcohol and 40 weight part PHMPC, as the MDI of organic diisocyanate and have in the removable flask of four-hole of cooling tube, with DMF as solvent, and make that the molar ratio of polyvalent alcohol total amount: MDI is 1:3, under nitrogen atmosphere, under 40～60 ℃, carry out stirring reaction, further under the state that has diluted with DMF, after 50～60 ℃ of EG that drip down as chain propagation agent carry out dropwise reaction, slowly dilute with DMF, after about 10 hours, obtained solids component and be 25% PU solution.The gelation point of the urethane that obtains is 3.5ml.
(manufacturing of flap)
The above-mentioned non-woven fabrics that is made of ultra-fine fibre is immersed in concentration with the DMF solution of above-mentioned urethane is adjusted in 12% the solution, regulate the adhesion amount of PU solution with mangle roller after, in 30 ℃ DMF concentration are 30% the aqueous solution, PU is solidified.Then, remove polyvinyl alcohol and DMF with 90 ℃ hot water, after the drying, then being immersed in silicone emulsions solution and nonionic is static inhibitor (エ レ Na イ ト 139, high terebinth (strain) system) in the mixed aqueous solution, drying has obtained PU content and is 32 weight %, polysiloxane level and be 0.2%, static inhibitor content is the flap of 0.1 weight %.The one side of this flap is used 150 orders earlier, then used 240 purpose ring-type sand paper to carry out the plucking processing, implement dyeing, obtained plucking and transferred simulated leather sheet thing with dispersed dye.
Observe the cross section of the thickness direction of resulting simulated leather sheet thing inside with scanning electron microscope (SEM), confirmed that urethane is not present in the inside of ultra-fine fibre bundle in fact, but partly be bonding with the ultimate fibre of the most peripheral that is positioned at the ultra-fine fibre bundle.In addition, fiber number CV is 7.5%.
The plucking that obtains is transferred simulated leather sheet thing, and the plucking length of fiber, favorable dispersity have graceful outward appearance.In addition, have have the appropriateness rebound resilience and the excellent handle of sense of fulfillment.Brush wearing and tearing decrement is few, is 15mg, all is 4.5 grades as the hydrolytic resistance of durability evaluation, sunproof evaluation result, has excellent endurance quality.
Embodiment 2～4, comparative example 1～5
In the manufacturing of urethane, except the composition of polyvalent alcohol and weight ratio are altered to respectively shown in the table 1, other carry out similarly to Example 1, have made plucking and have transferred simulated leather sheet thing.
Observe the cross section of the thickness direction of the simulated leather sheet thing inside in embodiment and the comparative example with scanning electron microscope (SEM), the result, urethane is not present in the inside of ultra-fine fibre bundle in fact, but partly is bonding with the ultimate fibre of the most peripheral that is positioned at the ultra-fine fibre bundle.The composition and the gelation point of the urethane of each embodiment and comparative example have been shown in the table 1, and the outward appearance grade of the flap of gained, brush wearing and tearing decrement, endurance quality.
Table 1
Any plucking of embodiment 1～4 transfers simulated leather sheet thing all to have graceful outward appearance grade, and also excellent on brush wearing and tearing decrement and endurance quality.The outward appearance product potential difference of the flap of comparative example 1,2,3, the brush wearing and tearing decrement and the poor durability of the flap of comparative example 4,5.
In addition, aspect processibility, any one of embodiment 1～4 and comparative example 1～5, in processing length 3, the sand paper before the 000m during rubbing down stops up significantly, and processibility is " bad ".
Embodiment 5
(manufacturing of non-woven fabrics)
Use polystyrene as sea component, use polyethylene terephthalate as island component, using the island number is the compound spinning nozzle of using of fabric of island-in-sea type on 16 islands, after the compound ratio spinning formation islands-in-sea bicomponent fibre with sea component 55 weight %, island component 45 weight %, stretch, curl and process, cut, obtain the raw cotton of non-woven fabrics.
With the raw cotton that obtains, use cross lapping machine to make net, handle forming non-woven fabrics through acupuncture.
After this non-woven fabrics that is made of islands-in-sea bicomponent fibre being immersed in 10% polyvinyl alcohol water solution of saponification deg 87%, drying.Then, extract the polystyrene remove as sea component in trieline, carry out drying, obtaining by the ultimate fibre fiber number is the non-woven fabrics that fibrous bundle complexing that the ultra-fine fibre of 0.1dtex constitutes forms.
(manufacturing of urethane)
Will be as 60 weight part PNMOC of polycarbonate diol (A), 40 weight part PHMPC as polycarbonate diol (B), 2 weight part KSi-15000 as polysiloxane polyhydric alcohol (C), MDI threading as organic diisocyanate has in the removable flask of four-hole of cooling tube, with DMF as solvent, and make polyvalent alcohol total amount { (A)+(B)+(C) }: the molar ratio of MDI is 1:3, under nitrogen atmosphere, under 40～60 ℃, carry out stirring reaction, further under the state that has diluted with DMF, after 50～60 ℃ of EG that drip down as chain propagation agent carry out dropwise reaction, slowly dilute with DMF, after about 10 hours, obtained solids component and be 25% PU solution.The gelation point of the urethane that obtains is 3.5ml.
(manufacturing of flap)
The above-mentioned non-woven fabrics that is made of ultra-fine fibre is immersed in concentration with the DMF solution of above-mentioned urethane is adjusted in 12% the solution, regulate the adhesion amount of PU solution with mangle roller after, in 30 ℃ DMF concentration are 30% the aqueous solution, PU is solidified.Then, remove polyvinyl alcohol and DMF with 90 ℃ hot water, after the drying, then being immersed in nonionic is static inhibitor (エ レ Na イ ト 139, high terebinth (strain) system) in the aqueous solution, after the drying, having obtained PU content is that 32 weight %, static inhibitor content are the flap of 0.1 weight %.One side to this flap is used 150 orders earlier, is then used 240 purpose ring-type sand paper to carry out grinding, and plucking is handled thus, implements dyeing with dispersed dye, has obtained plucking and has transferred simulated leather sheet thing.
Observe the cross section of the thickness direction of resulting simulated leather sheet thing inside with scanning electron microscope (SEM), confirmed that urethane is not present in the inside of ultra-fine fibre bundle in fact, but partly be bonding with the ultimate fibre of the most peripheral that is positioned at the ultra-fine fibre bundle.In addition, fiber number CV is 7.3%.
The plucking that obtains is transferred simulated leather sheet thing, and the plucking length of fiber, favorable dispersity have graceful outward appearance.In addition, have have the appropriateness rebound resilience and the excellent handle of sense of fulfillment.Brush wearing and tearing decrement is few, is 12mg, all is 4.5 grades as the hydrolytic resistance of durability evaluation, sunproof evaluation result, has excellent endurance quality.And then in plucking was handled, with flap processing 3 continuously, behind the 000m, the obstruction of sand paper was also few, and processibility is " well ".
Embodiment 6～11
In the manufacturing of urethane, except the composition of polyvalent alcohol and weight ratio, gelation point are changed to respectively shown in the table 2, other carry out similarly to Example 5, have made plucking and have transferred simulated leather sheet thing.
Processibility among each embodiment, with flap processing 3 continuously, behind the 000m, the obstruction of sand paper is also few, and processibility is " well ".
Table 2 shows outward appearance grade, brush wearing and tearing decrement, the endurance quality of flap of composition, the gained of the urethane of each embodiment.
Table 2
In the manufacturing of urethane, use has the polysiloxane polyhydric alcohol of 2 hydroxyls on an end of polydimethylsiloxane, and any one the plucking that has been suitable for the embodiment 5～9 of the urethane that has the organopolysiloxane skeleton in side chain is transferred simulated leather sheet thing, even using sand paper to carry out not being immersed in the silicone emulsions before the plucking processing, also have graceful outward appearance grade, brush wearing and tearing decrement, endurance quality be excellence all.Particularly, using number-average molecular weight is the flap that 15,000 polysiloxane polyhydric alcohol (KSi-15000) obtains, though use a small amount of, also excellent on the outward appearance grade.On the other hand, used the embodiment 10 that on two ends of polydimethylsiloxane, respectively has the polysiloxane polyhydric alcohol (BSi-1800) of 1 hydroxyl, compare with embodiment 5 that has used the polysiloxane polyhydric alcohol that on an end of polydimethylsiloxane, has 2 hydroxyls and embodiment 9, outward appearance product potential difference, in order to use the polysiloxane polyhydric alcohol (BSi-1800) that on two ends of polydimethylsiloxane, respectively has 1 hydroxyl to obtain the good surface appearance grade, the composition of polyvalent alcohol need be 10 weight parts, if but content is more than 10 weight parts, then photostabilization is poor.
Utilizability on the industry
According to the present invention, the outward appearance with grace of being brought by plucking can be provided, and hydrolytic resistance, The durability of light resistance etc. the also plucking of excellence is transferred leather like sheet material. Its result is even can obtain warp The rheological parameters' change with time that year uses the plucking grade resemble the TOWEL is few advantage also, as furniture, chair, The table of the seat in the compartment of wall fitting and automobile, electric car, aircraft etc., ceiling, interior trim etc. Leather material can use very suitably as the inner decoration material with very graceful outward appearance.
Claims (17)
1. flap, be to be the non-woven fabrics that forms of the ultra-fine fibre complexing below the 0.5dtex and to be that the elastic resin tackiness agent of principal constituent forms with urethane by the ultimate fibre fiber number, in this flap, described urethane is the polycarbonate-based urethane with the polycarbonate skeleton shown in following general formula (1) and (2), the weight-average molecular weight of urethane is 100,000～300,000, gelation point is more than the 2.5ml, less than 6ml
In the formula, R
1And R
2Be that carbonatoms is 7～11 aliphatic alkyl, identical or different, in addition, n and m are positive integer, at R
1And R
2Under the different situations, be block copolymerization or random copolymerization;
In the formula, R
3And R
4Be that carbonatoms is 3～6 aliphatic alkyl, identical or different, in addition, x and y are positive integer, at R
3And R
4Under the different situations, be block copolymerization or random copolymerization.
2. flap as claimed in claim 1, described urethane are the urethane that further has the side chain that contains the organopolysiloxane skeleton shown in the following general formula (3),
In the formula, R
5And R
6Be aliphatic alkyl or aryl, identical or different, in addition, p is 100～300.
3. flap as claimed in claim 1, described gelation point are 3～5ml.
4. flap as claimed in claim 1, described urethane is that the reaction by following substances obtains, and described material is: at the polycarbonate diol (A) that hydroxyl is arranged on two ends of the molecular chain with the polycarbonate skeleton shown in the above-mentioned general formula (1), have polycarbonate diol (B), organic diisocyanate and chain propagation agent that hydroxyl is arranged on two ends of molecular chain of the polycarbonate skeleton shown in the above-mentioned general formula (2).
5. flap as claimed in claim 2, described urethane is that the reaction by following substances obtains, and described material is: the polycarbonate diol (A) that hydroxyl is arranged on two ends of the molecular chain with the polycarbonate skeleton shown in the above-mentioned general formula (1), the polycarbonate diol (B) that hydroxyl is arranged on two ends of the molecular chain with the polycarbonate skeleton shown in the above-mentioned general formula (2), the polysiloxane polyhydric alcohol (C) that two hydroxyls are only arranged on an end of the molecular chain with the organopolysiloxane skeleton shown in the above-mentioned general formula (3), organic diisocyanate and chain propagation agent.
6. flap as claimed in claim 5, the number-average molecular weight of described polysiloxane polyhydric alcohol (C) surpass 10,000 but be below 20,000.
7. flap as claimed in claim 5, above-mentioned polysiloxane polyhydric alcohol (C) is more than the 0.1 weight %, less than 5 weight % with respect to the ratio of the summation of above-mentioned polycarbonate diol (A) and above-mentioned polycarbonate diol (B).
8. flap as claimed in claim 1, the R that in the formula shown in above-mentioned general formula (1) and (2), puts down in writing
1, R
2, R
3, R
4Be whole different aliphatic alkyls to each other.
9. flap as claimed in claim 1, the R that in the formula shown in the above-mentioned general formula (1), puts down in writing
1And R
2At least one side, be by methyl or ethyl branching aliphatic alkyl.
10. flap as claimed in claim 1, the R that in the formula shown in the above-mentioned general formula (2), puts down in writing
3And R
4At least one side, be by methyl or ethyl branching aliphatic alkyl.
Form 11. flap as claimed in claim 1, described non-woven fabrics are the fibrous bundle complexings by ultra-fine fibre, described elastic resin tackiness agent does not exist in fact in the inside of the fibrous bundle of this ultra-fine fibre.
12. flap as claimed in claim 11, described elastic resin tackiness agent is bonding with filamentary at least a portion of the most peripheral of the fibrous bundle that is positioned at this ultra-fine fibre.
13. the filamentary fiber number CV in the flap as claimed in claim 1, the fibrous bundle of this ultra-fine fibre is below 10%.
14. flap as claimed in claim 1, described ultra-fine fibre comprises polyester.
15. flap as claimed in claim 1, above-mentioned elastic resin tackiness agent shared ratio in flap is more than the 10 weight %, below 50% weight.
16. flap as claimed in claim 1, this ultra-fine fibre is in the plucking attitude on the one side at least of flap.
17. an inner decoration material uses each described flap of claim 1～16 and constitutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004098099 | 2004-03-30 | ||
| JP098099/2004 | 2004-03-30 | ||
| JP119938/2004 | 2004-04-15 |
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|---|---|---|---|
| CN2009101266374A Division CN101525847B (en) | 2004-03-30 | 2005-03-29 | Sheet and interior material |
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| CN1938476A CN1938476A (en) | 2007-03-28 |
| CN100484981C true CN100484981C (en) | 2009-05-06 |
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| CNB2005800106166A Active CN100484981C (en) | 2004-03-30 | 2005-03-29 | Sheetlike products and interior finishing materials |
| CN2009101266374A Active CN101525847B (en) | 2004-03-30 | 2005-03-29 | Sheet and interior material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107531861A (en) * | 2016-04-14 | 2018-01-02 | Dic株式会社 | Aqueous urethane resin composition and synthetic leather |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10480121B2 (en) * | 2014-10-24 | 2019-11-19 | Toray Industries, Inc | Sheet-like article |
| JP7043841B2 (en) * | 2017-01-23 | 2022-03-30 | 東レ株式会社 | Sheet-like material |
| RU2751008C2 (en) | 2017-02-28 | 2021-07-07 | Торэй Индастриз, Инк. | Sheet material |
| BR112019019187B1 (en) * | 2017-03-29 | 2023-04-04 | Toray Industries, Inc | ARTIFICIAL LEATHER |
| EP3399086B1 (en) * | 2017-05-02 | 2019-11-20 | Autoneum Management AG | Lofty fibrous trim part |
| KR20200142502A (en) * | 2018-04-12 | 2020-12-22 | 도레이 카부시키가이샤 | Sheet-like material and its manufacturing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU651378B2 (en) * | 1990-09-28 | 1994-07-21 | Kuraray Co., Ltd. | Suede-like napped sheet excellent in sweat resistance |
| TW284771B (en) * | 1994-03-22 | 1996-09-01 | Kuraray Co | |
| US6503997B1 (en) * | 1999-03-17 | 2003-01-07 | Asahi Glass Company, Limited | Polyurethane/polyurethane-urea resin and process for producing the same |
-
2005
- 2005-03-29 CN CNB2005800106166A patent/CN100484981C/en active Active
- 2005-03-29 CN CN2009101266374A patent/CN101525847B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107531861A (en) * | 2016-04-14 | 2018-01-02 | Dic株式会社 | Aqueous urethane resin composition and synthetic leather |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101525847B (en) | 2011-01-19 |
| CN101525847A (en) | 2009-09-09 |
| CN1938476A (en) | 2007-03-28 |
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