JPS599675B2 - Method for manufacturing woolen fabric-like composite sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a high-quality wool-like composite sheet.

The present invention has an appearance similar to high-grade woolen fabric, is soft (flexible, soft to the touch, has moderate slippage and gloss, and has relatively good melting resistance against cigarette fire, The present invention relates to a method for manufacturing a sheet material that does not fray like textiles, is lightweight, and is less prone to wrinkles.

Woolen textiles are effectively used in everything around us, including clothing.

Although handmade and woolen fabrics have many excellent features, they also have many drawbacks.

For example, hair must be taken from animals, which means that animals are abused.

There is a limit to the amount of food that animals can eat, and there are limits to production as it requires vast amounts of land.

In addition, woolen fabrics have drawbacks such as being prone to fraying, being susceptible to stains and other insect bites, being heavy, and easily losing shape when washed.

The vicuña's hair is fine and of high quality, making it extremely useful, but its habitat is limited and hunting is no longer allowed.

There have been many attempts to create artificial hair comparable to this, but it cannot be said that they have necessarily been successful.

On the other hand, the present inventors have already invented a woolen fabric-like composite raised sheet in Japanese Patent Publication No. 56-50031.

This is a woolen fabric-like nappy sheet that is specially processed by adding a non-woven fabric made of ultra-fine fibers and a curable organic silicon compound, and although it is new, the product quality (mainly the nap quality) is sometimes unstable. For stability, strict process control is required when processing silicon.

Furthermore, the reason why the raised surface tends to whiten due to abrasion when management is poor, and the product is not always satisfactory is that the properties of the cured silicone have a subtle effect on the quality of the raised product. .

This is largely related to the composition of the curable silicone and the curing speed of the silicone.

In other words, if there are many components in the silicone composition that are likely to form a three-dimensional structure, and if the curing speed is slow, it is difficult to respond to the optimum processing timing that is unique to processing that involves chemical reactions. In addition, the cured silicone becomes brittle, and when the product sheet is rubbed, the silicone in the napped area may peel off and fall off, leading to splitting of the napped area, leading to the problem of whitening of the napped area. 《It is.

An object of the present invention is to provide a method for producing a high-grade woolen napkin sheet that does not have the above-mentioned drawbacks.

In other words, (1) it can be made artificially, (2) it has a good surface touch, (3) it has the appearance of high-quality wool, and (4) it does not fray like textiles, and can be sewn without the need for overlocking. (5) It should not be easily pierced by a cigarette. (6) It should have a smooth touch, a fluffy feel, and a sense of volume. (7) It should be lightweight. (8) Its appearance and dimensions remain stable even after washing. What is happening (9)
Easy care and wrinkle resistance (10) In addition, silicone processing process control is easy 01) Product sheets can be manufactured stably with uniform quality (1)
2) Even when rubbed during practical use, the cured silicone does not peel off or fall off easily, and the quality of the pilage does not change easily. The purpose is to provide an improved manufacturing method in that it does not fall under similar substances.

In order to achieve this object, as a result of extensive research, we have finally come to invent a means that satisfies the above object, such as the present invention.

The structure and means of the present invention are mainly as shown below.

(1) At least a portion of the napped hair is bound with a hardened polymeric organosilicon compound, and the majority of the tips of the bundled napped hair are in the form of ultrafine fibers of 0.7 denier or less, and /or a single yarn 0,7 that is thinner than the binding part
When producing a wool-like composite sheet material consisting of an aggregate of ultrafine fibers of denier or less, ■ Formation of a nonwoven fabric entangled sheet consisting mainly of bundles of ultrafine fibers or ultrafine fiber-generated fibers; It includes the following steps: applying a curable organic silicon compound which is a dialkoxyamino silane and whose curing catalyst is zinc octylate and/or zirconium octylate; ■ applying a polymeric elastomer other than the silicon compound; and ■ buffing. A method for producing a woolen fabric-like composite sheet characterized by:

To put it simply, the present invention provides 0.7 denier or less,
More preferably, it can be said that the intended purpose has been achieved by subjecting a three-dimensional entangled sheet mainly composed of bundles of ultrafine fibers of 0.5 denier or less to a specific processing.

Furthermore, regarding silicon processing, microfibers and hardened polymeric organosilicon compounds (including compositions),
In order to ensure that the unique napping and sheet quality formed by these organic silicon compounds (sometimes simply referred to as silicon) are stable and high quality, and do not change easily even in practical use, three-dimensional reaction The tangled sheet of ultrafine fibers is specially processed using a silicone composition containing a combination of an organic silane compound that does not easily cause curing and a curing catalyst that has relatively low activity but is good in terms of quality.

There are various methods for obtaining ultrafine fiber bundles.

For example, there is a type of fiber called a polymeric interlayer fiber, commonly called a seabird type fiber.

(This will be explained in more detail later in FIG. 4) This is a multi-component fiber, and if at least one component is removed, a bundle of ultra-fine fibers consisting of the remaining components can be obtained.

Looking at the cross section, the island components are distributed in a large number and dispersedly in relation to the sea component, and the island components are continuous in the fiber axis direction.

This type of fiber is most preferably used in the present invention.

This is because it has many advantages.

The above shape does not matter whether it is hollow or a fiber with a deformed cross section.

The microfiber bundles are most preferably made from polymeric interlayer fibers such as those shown in Figures 4 and 5a and b.

FIG. 4 is a perspective view of the fiber, and FIG. 5a is a cross-sectional view of the fiber of FIG.

FIG. 5b shows the fiber cross section when the number of islands is increased to 36.

This is based on many reasons such as ease of production, yield, dispersibility, stability of quality, reproducibility, structure that is easy to control, and ease of formation into entangled bodies.

In Figure 4, 6 is an island component and 7 is a sea component, which together form a composite fiber.

Several of the island components 6 are bound together by the sea component 7 with some spacing between them.

8 shows one of the island components viewed in the fiber axis direction, showing that the islands are long and continuous in the fiber axis direction.

Except for the sea component 7, an island component consisting of n fibers is obtained as a bundle of ultrafine fibers.

In FIG. 4, the number is (n=16), and n can be arbitrarily set.

For example, in FIG. 5b, n=36.

n is usually selected as 10000>n.

The shape and arrangement of the island components of the polymeric mutually arranged fibers are not particularly limited. However, as shown in Figures 4 and 5 a and b, the island shapes vary in size and shape and denier. Fibers that are substantially uniform and substantially regularly arranged are particularly preferred, as they are favorable for making homogeneous and superior products, and also improve the uniformity, productivity, and productivity of the fibers.
This is because it is excellent in terms of island component yield, cost, stretchability, uniformity of branching during napping, etc.

Figures 4 and 5 show the fiber cross section when the island shape is circular, but even if it is not only circular but polygonal or other shapes, the shape and denier are almost uniform and the fibers are regular. It is preferable in the present invention that such a structure is arranged.

Examples of island components include polyethylene terephthalate copolymers (isophthalic acid, sodium isophthalate sulfonate, etc.), polyesters such as polybutylene terephthalate, polyamides 6, 66, 6-10, etc., polypropylene, polyethylene, polyacrylonitrile, etc. Polymers are often used.

Many studies on similar fibers have been conducted since then, including the following.

■Polymer whose properties, blending conditions, and spinning conditions have been selected so that the components are long and thin in the other components.
Blend spinning, a method in which two types of polymers are distributed and integrated through a maze-like mixer (pipe mixer, static mixer, etc.), and then passed through a filter to change the film shape into dots and spin the yarn, Super Draw. These include fibers bound by spinning and drawing, ultra-fine wet-spun yarn with a binder, multi-component fibers that become ultra-fine fibers or fibrils by mechanically vigorous kneading, and fibers that exhibit similar characteristics. .

A fiber entangled sheet is made using such fibers.

The most typical sheet is obtained by needle-punching a single-layer or laminated web using a cross wrapper, random webper, or the like.

In some cases, to improve physical properties, a woven or knitted fabric is inserted between the layers of the web (or paper web) and needle punched or water punched.

This is sometimes called twenty-one dollar woven fabric, felt, or non-woven fabric.

This yields an entangled sheet of fiber bundles; however, when polymeric mutually arranged fibers are used, it is necessary to remove the sea component.

This results in an extremely flexible fiber entanglement.

However, if the overall fiber density is low, it may be too flexible for handling in post-processing.

In that case, polyvinyl alcohol, partially saponified products, carboxymethylcellulose, methylcellulose, sodium polyacrylate, polyacrylamide, starch,
It is preferable to previously apply a form fixing agent that dissolves in water or hot water to the fiber entangled body, and such a method has already been provided by the present inventors.

This is removed when there is no longer a need for form fixation.

When the sea component of the polymeric mutual array fiber is polystyrene and its copolymer, one or more solvents selected from the group of solvents thereof, such as trichlorethylene, perchlorethylene, toluene, xylene, benzene, etc. A combination of is used as a remover.

A hardened polyorganosilicon compound or composition is applied to the ultrafine fiber entangled sheet 1 thus obtained,
It is cured as a polymeric organosilicon compound.

A typical example of forming a cured polymeric organic compound is a combination of a polyorganosiloxane and the chemicals necessary for curing (also sometimes called vulcanization in the case of rubber, but also inclusive).

For example, (a) a polydiorganosiloxane having a hydroxyl group bonded to a terminal silicon atom and having a molecular weight of at least 750, wherein at least 5 of its organic substituents
Polydiorganosiloxane (b) has the general formula (wherein G is a hydrogen atom, monovalent is a hydrocarbon group or a monovalent halogenated hydrocarbon group, and J has 1 to 1 carbon atoms.
4 alkoxy or alkoxyalkoxy groups,
And X is O or 1.

) of silane and/or its hydrolyzate and the combined additive ((
c) General formula G'Siσ'T2 (where σ contains at least one amine group and is bonded to the silicon atom via a silicon-carbon bond, from carbon, hydrogen, nitrogen and optionally oxygen) G" is an alkyl group or an aryl group, and T is an alkoxy or alkoxyalkoxy group having 1 to 14 carbon atoms, respectively.

This is a composition in which the dialkoxyaminosilane and/or its partial hydrolyzate of () and (d) zinc octylate and/or zirconium octylate are mixed.

An example of the substituent G' in the dialkoxyaminosilane of the general formula G'SiG//T2 in (c) is -(CH2)3NH2 -(CH2)3NH(CH2)2NH2 -CH2.CH-CH3CH2NH(CH2)2NH2
-(CH2)3NH(CH2)2NHCH2CH2C0
Examples of the substituent G" are methyl, ethyl, probyl, phenyl, etc., and examples of the substituent T are methoxy, ethoxy, propoxy, hexoxy, methoxyethoxy, etc.

The most preferred example of each substituent in component (e) is a zirkoxyaminosilane in which G' is a --(CH2)3NH(CH2)2NH2 group, G is a methyl group, and T is a methoxy or methoxy group.

It is known that such silicon is cured by the following reaction.

The chemical formula of only the main reaction part is as follows.

The main skeleton of dealcohol condensation and dehydration condensation is polysiloxane, and polydimethylsiloxane is the most typical, but in addition, polysiloxanes with phenyl groups, hydrogen, or vinyl groups as cross-linking reactivity may also be used. Are known.

The terminal terminal is generally 10H, which reacts with itself or with various silane compounds.

A catalyst is also used in the reaction.

In addition to the aminosilane specified in the present invention, other silane compounds may also be used at the same time.

The molecular weight of the main skeleton is 10,000 to several hundreds of thousands, which is most commonly used.

Silicon oxides such as fumed silica are most often used to improve the physical properties of cured products.

Other materials include titanium oxide, carbon black, calcium carbonate, diatomaceous earth, quartz powder, asbestos, zinc oxide, and zirconium silicate.

These are preferably treated with linear and cyclic silanes, silanols, siloxanes, and silazane.

Needless to say, various additives such as coloring pigments and extractants for making pores are used in the scales.

You can learn more about these in the many patents of the Dow Corning Company in the US, as well as various technical materials for sale by Toray Silicon, Toshiba Silicon, Shin-Etsu Chemical, and others.

In the present invention, an organosilicon compound or composition is first applied to a fiber entangled sheet, that is, it is impregnated or applied in a soaking manner.

Since silicon often has a viscosity that makes it easy to apply when it is in an unreacted state, it can be applied directly (impregnation or coating), but it is preferably applied in the form of a solution or emulsion (dispersion).

This is because it is not only easy to apply, but also excellent in terms of uniformity, controllability of the amount applied, workability, etc.

Naturally, the solvent and dispersion medium are later removed by drying or the like.

Next, a reaction is carried out in the applied state.

The reaction is generally carried out by heat treatment to accelerate the curing reaction, and aging processing (leaving it naturally in the air to encourage the growth reaction) to proceed with slow curing.

Aging and curing is usually carried out for 48 hours or more, but most preferably from 120 hours to 240 hours.

If the curing reaction is to proceed by simply leaving the sheet in the air without heat treatment, this can be achieved by leaving the sheet in the air for a sufficient period of time to ripen.

Although acceleration of the curing reaction by heat treatment is advantageous from an industrial point of view, it does not necessarily bring good results from the point of view of products.

Sometimes it is better to leave it in the air for a long time and let it harden naturally.

This means that there is a close relationship between the hardening state of the silicone and the quality of each product at the time of applying the next polymeric elastic body, and the smaller the change in the degree of hardening, the longer the period during which the elastic body is applied under optimal processing conditions. This is because it can be used for a long time, making process control easier and quality stable.

In addition to stabilizing the quality, silicone cured over a long period of time also provides good quality that is less likely to crack.

In such cases, it is important to allow natural curing (rubberization), even if this may reduce the industrial value in some respects.

The reason why the present inventors chose a catalyst with relatively low activity as a silicon curing catalyst was to proceed with the curing reaction slowly as described above and aim to improve the quality of the product, as well as to improve the ease of process control. This is the result of consideration of quality stabilization, etc.

Incidentally, the present invention naturally includes a technique for coloring silicon in advance.

Needless to say, it also includes various additives for other purposes.

In this way, the silicone hardens and solidifies and adheres mainly between the fiber bundles and around them.

Due to the interfacial tension and the shape fixing agent, which will be explained in detail later, it tends to adhere in and around the fiber bundles and at the intersections of the fiber bundles.

A variety of polymeric elastomers such as polyurethane are then applied.

The polymeric elastomer is preferably applied in a solution or emulsion state.

After coagulation and solidification, if a form fixing agent is used, it can be removed by washing.

When a solvent is used during the application of the polymeric elastomer, it is preferred that most or substantially all of the solvent used be removed in parallel with the removal of the form-fixing agent.

Polymer elastomers include ether polyurethane, ester polyurethane, natural rubber, chloroprene rubber, and SBR.
All kinds of so-called rubbers such as 1NBR, acrylic comb-like materials, and fluorine-based rubber materials can be used.

In particular, those that can withstand the dyeing temperature are preferred.

In general, there are two methods for coloring sheet-like materials: a dope dyeing method and a dyeing method, and in the latter, consideration is given to hardened silicone and polymeric elastomer to make them suitable for dyeing.

An example of a preferred combination in such a case is when polyester is used as the fiber, partially saponified polyvinyl alcohol is used as the shape fixing agent, silicone rubber is used as the cured silicone, and polyurethane is used as the polymeric elastomer.

The dried sheet from which the solvent, shape fixing agent, etc. have been removed may, if necessary, be left in the air again to promote the aging and hardening reaction of the silicone.

This processing is for optimizing the subsequent fluffing process by buffing.

The finished sheet is then buffed.

In some cases, it is sliced and buffed.

This makes it fluffy.

Sometimes it is puffed after the necessary processing is performed before puffing.

If the fluffed greige is not dyed, it is usually dyed next.

If the material is polyester, it can be dyed with disperse dyes, and if it has been modified to basic town dyeing, it can be dyed with basic dyes.

Nylon such as nylon 6 and 66 can be dyed with acid dyes in a broad sense.

Furthermore, in dyeing (other than original dyeing), it is important that the remaining silicone (silicon used for binding, etc.) does not fall off as much as possible; if it falls off, it will be difficult to achieve the purpose of the present invention.

In this respect, a silicon composition in which the main silane compound is a combination of an aminosilane consisting of only two alkoxy functional groups directly bonded to a silicon atom and zinc octylate and/or zirconium octylate is different from other combination silicon compositions. In comparison, cured silicone hardly cracks or falls off during dyeing, and silicone also has good durability against rubbing during product use.

After the polyester fibers have been dyed, it is preferable to perform reduction cleaning using a surfactant, hydrosulfite, caustic soda, etc., and it goes without saying that known finishing agents suitable for fabrics are commonly used.

Although there are cases where no finishing agent is used, it is preferable to use it to further improve the sliminess, gloss, touch, flexibility, etc.

Next, as explained so far, the changes in the structure of the composite sheet during the manufacturing process of the present invention will be explained in the seventh section.
It will be explained in more detail according to figure a=f.

Further, FIG. 7 shows a model of a preferred embodiment of the present invention.

a shows a cross section of the sea-island type multicomponent fiber constituting the entangled sheet, 6 shows the island component, and 7 shows the sea component.

At the time when the entangled sheet was constructed, 7 had not yet been removed.

b is a model diagram when a shape fixing agent (which is also one component of the composite described later) is applied, and 9 indicates the shape fixing agent.

In this case, polyvinyl alcohol is used as a shape fixing agent.

The shape fixing agent surrounds and covers the outside of the multicomponent fiber.

9 also plays a role in significantly filling the spaces created between the multicomponent fibers.

This will play an important role in the subsequent distribution of silicon adhesion.

In state b, the sheet can be said to be a three-component composite sheet.

C is a model diagram showing the state when the sea component 7 is removed.

This produces ultrafine fibers with island components, but since they are covered with a shape-fixing agent, C can also be viewed as a new hollow multicomponent fiber.

Therefore, in this state, the ultrafine fibers are exposed on the surface of the sheet, making it a fairly hard and stiff plate-like sheet (the ultrafine fibers are hardly visible from the outside because they are composed of other composite components, i.e., shape fixing agents). , its correct color, luster,
(Of course I don't know the texture, etc.)

d is a model diagram showing the state when impregnated with silicon.

10 indicates silicon. Silicone is applied even to the microscopic fibers in the hollow.

The spaces between the fibers (multi-component fibers) have already been filled to some extent with the shape fixing agent, so the silicone is concentrated in the hollow portions covered with the shape fixing agent (remains where the sea component has escaped).
As a result, the ultrafine fibers of the island component are better bound as a bundle.

It goes without saying that silicone also adheres to some extent on the shape fixing agent.

e is a model diagram showing the state when polyurethane is further applied.

11 indicates polyurethane. It can be seen that the structure is significantly different from conventional artificial leather manufactured without going through the process d.

f is a model diagram showing the state when the form fixing agent is removed.

A space 12 is created between the internal silicone and polyurethane, thus making the sheet flexible.

In this way, the structure of the composite sheet changes for other examples of ultrafine fiber-generating fibers.A model diagram of an example in which no shape fixing agent is used is shown in Figure 9a.
c and as shown in Figures 11a-c.

FIG. 9a and FIG. 11a respectively show a cross section and a three-dimensional view of different types of split type ultrafine fibers, 13 is a split fiber component A, and 14 is a split fiber component B.

15 indicates a hollow part. b is a model diagram when silicon is applied, and 10 indicates silicon.

In addition to what is shown in the diagram, silicone is also applied by penetrating into the spaces between the ultrafine fibers that have been partially or totally fibrillated due to hot water shrinkage or physical action during the process, and is applied to the entire structure. As a result, the shape of the ultrafine fiber bundle is maintained by silicone.

C is a model diagram when polyurethane is applied, and 11 indicates polyurethane.

Since no shape fixing agent is used in this example, the polyurethane is applied relatively close to the ultrafine fiber bundle.

When a shape fixing agent is applied and silicone is processed, the silicone is strongly pushed and penetrates into the space between the ultrafine fibers created by fibrillation as described above, and therefore the cohesiveness of the ultrafine fibers due to silicone is The trend is to further increase,
The composite sheet after polyurethane application also becomes more flexible.

After that, it is puffed, sliced and dyed if necessary.

In addition to removing polyurethane from the pilsed area, the puff
The silicone is ground and falls from the tip of the nape, and at the tip of the nape, the ultrafine fibers are untied by the silicone.

An example of the raised state of a new material resembling a high quality woolen fabric produced by such a method is the one sketched in Figure 1.

This raised material is thicker and different from the material made for conventional suede.

In this example, the raised fibers are bundled together with hardened silicone or something containing a large amount of silicone (the number of bundled ultrafine fibers is n=1, 2, or 3, etc.)
・).

FIG. 3 is a partially enlarged view of FIG. 1, and is used to more clearly explain the raised state of the composite sheet of the present invention.

In order to further facilitate understanding, FIG. 8 shows a photograph (magnification: 87 times) of a cross section of the composite sheet of the present invention taken with a scanning electron microscope.

As is clear from FIGS. 1, 3 to 8, the number of strands decreases midway due to puffing, and some tend to become tapered.

In FIGS. 1 and 3, 1 indicates the tip of the ultrafine fibers, 2 indicates a portion where the ultrafine fibers are bundled but the number of fibers is reduced, and 3 indicates a portion where the ultrafine fibers are bundled.

FIG. 10 and FIG. 12 are enlarged model diagrams showing the raised state of split-type ultrafine fibers.

FIG. 10 corresponds to the split type microfiber shown in FIG. 9, and FIG. 12 corresponds to the split type ultrafine fiber shown in FIG. 11.

The 130-split ultrafine fiber A and the 140-split ultrafine fiber B are shown separated at the tip of the napped nape, and the root portion is bound by silicone 10.

11 is polyurethane. On the other hand, as a comparison for reference, an example is shown in which only polyurethane is used without using a silicon compound.

In this case, it will have a suede-like appearance, and its raised state will be as shown in FIG. 2, for example.

Like the part 4 near the tip of the nape, the root part 5 is also thin (this usually has a suede effect, so the nape often looks like it has fallen down).

As described above, the seal of the present invention has a thick tip that is tied together at the base of the raised hair, and a thin tip that is fine to the touch, either tapered or branched.

The bundles are mainly made up of fiber bundles, but in some cases, they also include thicker bundles that are made up of bundles generated during needle punching.

The roots are thick, resulting in standing hair with a waist.

For this reason, compared to the case where it is not tied, that is, the suede-like one, the nape has changed to a reversible way of falling down, that is, it is extremely difficult to show the suede effect.

This is thought to be the reason why it has a woolen texture.

The tapering of the tip is thought to be due to the fact that bundles of fibers are originally thin, and the tips are scraped off by the puff or the bundles are untied by splitting.

On the other hand, the elastic polymer such as polyurethane applied later will naturally be located around the fibers, since the rubbery silicone or cured silicone has already occupied the area around the fibers.

It appears that the adhesion to the rubbery silicone or cured silicone was poor, and that the polymeric elastomer in that area peeled off first during puffing.

From this point of view, it can be said that the following conditions are preferable.

First, A: the relationship between fibers and cured silicone B: the relationship between cured silicone and other polymeric elastomers. A higher one is preferable, and from the viewpoint of texture and touch, it is preferable that B is the opposite.

Weight is the balance between A and B, and if A is high enough, the higher B is, the less shedding will occur.

Therefore, in order to increase the adhesion affinity of A, it is preferable that the fiber bundle is pre-primed with a silane coupling agent.

In addition, to make the cured silicone more compatible with the fibers,
During spinning, a silane compound or the like may be added.

Examples of silane coupling agents for polyester include and so on.

For example, the above f is used as the polyamide, and these are used alone or in combination with a reaction accelerator.

Regarding B, it is better not to have strong adhesiveness in relation to the texture and the touch of the nap.

However, in terms of preventing hair loss, it should not be too low.

Originally, cured silicone and other polymeric elastomers such as polyurethane have poor adhesion, so much consideration is not required.

When the importance is placed on resistance to shedding of hair at the expense of texture, it is preferable to increase the bond between silicone and polyurethane.

In that case, it is necessary to sufficiently increase the bond between the fiber and silicon.

In order to prevent the hair from falling out of the dyed product, for example, remove the hair that easily falls off by rubbing it with a textured rubber, fibrous or metal brush roll, or use a self-crosslinking acrylic emulsion or It is preferable to treat with a silicone rubber (resin) forming liquid or emulsion.

Excessive shedding prevention treatment impairs the feel, touch, etc. of the sheet, so it is desirable to control the degree of treatment (for example, treatment density, degree of abrasion) depending on the purpose.

The relationship between the fiber bundle and the two types of polymer compounds, which is the key point of the above structure, can be illustrated in an easy-to-understand model as shown in FIG. 6, for example.

That is, 6 is ultrafine fiber, 10 is hardened silicone, and 11 is polyurethane (example).

11 surrounds 10 either partially or completely (in this figure, entirely).

Therefore, something like this model is formed for the entire entangled body or a considerable part, and also for the standing part.

The part where the hair is raised by puffing has raised hairs consisting of numbers 6 and 10, and number 11 comes off when the puff is applied.

6 and 10 are retained at the base, but 10 is peeled off at the tip, or 6 and 10 are partially chipped off at the same time and become thinner, or separated, resulting in a state of tapering or dispersion. .

When this condition can be achieved, the fabric will have the appearance of a high-quality woolen fabric (if this condition cannot be achieved, the result will be a suede effect, etc.).

The amount of silicone and polymeric elastic material to be added to the entangled sheet is such that the total amount of both is 1 for 100 parts by weight of the entangled sheet.
About 5 to 80 parts by weight is preferable.

Further, the ratio of silicon to the polymeric elastic body is 0.5 to 50% by weight, especially 20 to 50% by weight of silicon based on 100% of the polymeric elastic body.
About 40% by weight is preferable.

This product includes clothing such as coats and blazers, furniture, wall coverings,
Effectively used for decorations, etc.

Next, the effectiveness of the present invention will be shown in Examples, but the effectiveness of the present invention is not limited by these in any way, but rather brings about the following development and development.

Example 1 A seabird type fiber with a sea component of polystyrene and an island component of polyethylene terephthalate, sea-island ratio 50/50, number of islands 16,
Thickness of sea-island fiber 3. Using raw cotton with a crimp count of 13 threads/inch and a fiber length of 51, a web was formed with a cross wrapper and needle punched at 3000 threads/cd to give a basis weight of 5201/m' and an apparent density of 0. 1 9 5g/
The entangled nonwoven fabric of d was obtained.

Next, this nonwoven fabric is shrunk with hot water and dried, with a saponification degree of approximately 85.
% polyvinyl alcohol solution was applied to the sea-island fibers in an amount of about 35 parts in terms of solid content.

After removing the sea component using trichlorethylene, (a) the terminal is -OH and the molecular weight is approximately 42,000 (at 25°C).
, about 60 parts by weight 14,000 C. Polydimethylsiloxane (S) has -OH terminals and a molecular weight of approximately 180,000 (
25°C, about 35 parts by weight of polydimethylsiloxane (3 million C, S) → CH3Si(OCH3)30
Partial condensate 5 parts by weight (-1:)'N
H2(CH2)2'NH(CH2)3S
i (OCH3) 2 1 0 parts by weight l CH3 (;"I") (C8H,502)2Zn
A 5% silicon composition solution prepared with 1 part by weight of trichlorethylene was applied to the sheet to impregnate it to about 250% by wet weight.

After most of the trichlorethylene was scattered at about 100°C, it was heat-treated at 130°C for 3 minutes.

Furthermore, this processed sheet was placed in the air (approximately 25℃ x 60℃) for 5 days.
% RH) to age, and the curing reaction of unreacted silicon proceeded slowly.

Next, the sheet is impregnated with a dimethylformamide solution of polyurethane so that the amount of polyurethane applied is approximately 50% of the island component in terms of solid content, and through the steps of coagulation, removal of polyvinyl alcohol, and removal of solvent, the thickness of the sheet is reduced. Slice it into two equal pieces.

Finally, the non-sliced surface was mainly puffed to form a raised sheet, and then pressure dyed with a disperse dye at 125°C.

The obtained product had the appearance of a high-quality woolen fabric, a supple texture, and a moderate gloss with a luxurious feel, and was good with very little change in the nap quality even when rubbed.

? On the other hand, in the silicon composition liquid, NH2(CH2)2NH(CH2)3Si(OCH3) where (d) is likely to become three-dimensional
3. In addition, a comparative product (comparative example) was prepared by changing (e) to (C4H9)2Sn(0C1H23)2 with high catalytic activity and selecting the optimum silicon curing conditions, and using the same processing conditions as in the example. In case 1), the raised quality after dyeing was good, but when rubbed, the bundle of ultrafine fibers bound by silicone was easily broken, and the raised quality changed, so that the purpose of the present invention could not be achieved.

Examples 2 to 7, Comparative Examples 2 to 34 All of the silicone composition of Example 1 was the same as Example 1, except that the aminosilane of Example 1, the silicon curing catalyst of (e), and the aging and curing time of silicone were changed according to the table. A sheet was prepared in the same manner.

Various properties are shown in Table 1.

(10) As is clear from the results in Table 1, aminosilanes with only two alkoxy groups directly bonded to silicon atoms and silicon curing catalysts with relatively low catalytic activity (zinc octylate and/or octylate Products processed with a silicone composition containing a combination of zirconium chloride (zirconium acid) and with a sufficiently long aging and hardening time of the silicone composition before adding a polymeric elastomer other than silicone have a good appearance and texture. A nappy sheet with a woolen fabric appearance was obtained, and even when the napping surface was forcibly rubbed, there was very little change in quality and the product was good.

On the contrary, in Comparative Examples 2 to 34, desired products were not obtained.

In particular, combinations of silicon catalysts other than zinc octylate and zirconium octylate and dialkoxyaminosilanes,
It should be noted that the combination of alkoxyamine silanes other than dialkoxyaminosilane and zinc octylate or zirconium octylate had relatively good nap quality after dyeing, but the durability of the nap quality due to abrasion was not good. Should.

This can be said to prove the synergistic effect of the combination of dianolecoxyaminosilane and zinc octylate or zirconium octylate.

It can also be understood that the longer the curing time is, the better the durability of the cured silicone and the quality of the products will be.

[Brief explanation of drawings]

FIG. 1 is a side view of a model of the raised portion of the wool-like composite seal l according to the present invention, FIG. 2 is a side view of a model of the raised portion of conventional artificial suede, and FIG. 3 is the same as that of FIG. This is an example of a partially enlarged view. FIG. 4 is a model perspective view of a sea-island type multicomponent fiber preferably used in the present invention, and FIG. 5 is an example of a cross-sectional view of the fiber (b
FIG. 6 is a model diagram showing the positional relationship between the ultrafine fiber bundle, silicone, and polymer elastic body in the composite sheet according to the present invention. FIG. 7 is a diagram showing a model of how the structure of a composite sheet changes according to the manufacturing process of the present invention. FIG. 8 is an example of a scanning electron micrograph of a cross section of a composite sheet in one embodiment of the present invention, and FIG. 9 is an example of a composite sheet of one split type microfiber according to the manufacturing process of the present invention. Figure 10 is an enlarged model diagram of the raised part of the wool-like composite seal l corresponding to the split-type ultrafine fiber in Figure 9, and Figure 11 is a model showing how the structure changes. Figure 12 is a model showing how the structure of a composite sheet changes according to the manufacturing process of the present invention for other examples of splittable ultrafine fibers, and FIG. 12 is a woolen fabric corresponding to the splittable ultrafine fibers shown in FIG. FIG. 3 is an enlarged model diagram of the raised portion of the composite sheet.

Claims (1)

[Claims] 1 At least a part of the raised hair is bound with a hardened polymeric organosilicon compound, and the majority of the tips of the bundled raised hair are in the form of ultrafine fibers of 07 denier or less, and/or are formed from the bundled part. A woolen-like composite consisting of an aggregate of fine single fibers of 0.7 denier or less.
- When producing the above material, 1.
(1) Formation of a curable organosilicon compound in which the main organosilane compound is dialkoxyaminosilane and the curing catalyst is zinc octylate and/or zirconium octylate, (2) Formation of a polymeric elastomer other than the silicone compound. A method for producing a woolen fabric-like composite sheet, comprising the steps of applying and buffing.