JPH032231A - Leather like synthetic resin material - Google Patents

Abstract

PURPOSE:To obtain the title resin material having soft handle in matte state and properly having hygroscopic properties and moisture retaining properties and useful for bag, etc., by impregnating a specific organic solvent into a molding synthetic resin material containing geratin powder, swelling the impregnated resin material and washing the swollen material with water. CONSTITUTION:(B) An organic solvent in which a component A is insoluble, having good solubility with water and having molecular weight smaller than 80 or diluted aqueous solution of the organic solvent is impregnated into (A) molding synthetic resin to swell the component A and the component A is washed with water or dipped into water and geratin powder contained in the component A is pulled out to provide the aimed resin material. Furthermore, the component A is preferably molding synthetic resin coating film layer of molded article surface and synthetic resin coating film.

Description

Detailed Description of the Invention [Industrial Application Field] This invention relates to a leather-like molded synthetic resin material having a large number of holes on its surface, and various leather-like surfaces having a large number of holes on its coating surface. and a film having a large number of holes;
Regarding the provision and provision of various leather-like products having these films as a laminate layer, more specifically, molded synthetic resin materials are swollen using organic solvents under specific conditions or diluted aqueous solutions of these organic solvents. , relates to a synthetic resin material having leather-like properties that is provided by extracting gelatin powder contained in the molded synthetic resin material.

[Prior art] Synthetic resin molded products, synthetic resin films, or products with a resin coating layer or film layer on the surface all have a surface gloss unique to the resin, and inevitably have a sticky feeling when contacted. On the contrary, during cold and dry conditions such as winter, the contact resistance is low, and slippage generally occurs on the contact surface.

Therefore, the surface of these synthetic resin molded products, or the coating layer or coating layer that is coated on the film or surface,
It is formed by coating a solution of polyurethane resin in a water-miscible organic solvent, and the solvent is removed by immersing it in water.
Attempts have been made to coagulate polyurethane resins to form a leather-like surface as a wet microporous layer.

Films, synthetic leather fabrics, or various coatings or membranes made of a wet microporous layer of polyurethane resin provide a moderate dry feeling to the contact surface with little stickiness upon contact, and have a moderate moisture retention property. It felt moist to the touch and had good grip on handles, etc. Furthermore, due to the presence of the wet microporous layer, reflection of light rays was avoided and a soft, matte texture was brought to the surface of the product.

However, the porous pores formed by this method are
The diameters of the pores were extremely irregular, and the distribution of the pores also varied, making it impossible to provide uniform surface characteristics and a uniform texture to the surface of the molded product.

In particular, it is almost impossible to form fine pores with uniform diameters on the surface of molded products, film surfaces, coating parts, coating surfaces, etc. so that they have a uniform distribution density.
There was naturally a limit to the effectiveness of the leather-like properties of the porous layer formed by this method.

From this point of view, fine gelatin powder with a uniform particle size is mixed into a synthetic resin coating liquid, etc., and after forming a molded product surface, film, coating, coating, etc. with this coating liquid, etc. Attempts have been made to elute gelatin powder contained in these molded product surfaces, films, coatings, and barge films.

In order to elute the gelatin powder contained in the surface of a molded product, film, coating, coating, etc., the molded product, film, coating, coating, etc. must be immersed in water or washed. etc., and swell the gelatin powder contained in these molded products, films, coatings, coatings, etc. using cold water, hot water, or hot water to elute the gelatin powder from these molded products, etc., Fine pores were formed in the molded products, films, coatings, coatings, etc.

[Problems to be Solved by the Invention] However, conventional molded products, films, film laminate layers, coatings, coatings, etc. that have fine pores formed by swelling and dissolving gelatin powder with water cannot be used. However, the pores on the surface of these molded products are not perfect in shape, and a portion of the gelatin that has not been completely eluted remains in the pores.

This inconvenience was particularly noticeable when the gelatin powder contained in the molded products was eluted when the molded products were treated with low-temperature treated water for a short period of time.

1))> In elution of gelatin powder using filtered water, it is necessary to first swell the gelatin powder contained in the molded synthetic resin material with water and then dissolve it into the molded synthetic resin material.

However, some of the gelatin powder contained in molded synthetic resin materials is not necessarily exposed on the surface of these molded synthetic resin materials, and most of it is incorporated into the molded synthetic resin materials. It is said to be in a state of failure. From the viewpoint of the swelling, it is difficult to perform the swelling IfI treatment of the gelatin powder contained in these molded synthetic resin materials, and there are many difficulties in the elution treatment after swelling. In particular, water molecules do not penetrate into molded synthetic resin materials because of their molecular association, and the swelling of the gelatin powder contained in these molded synthetic resin materials is caused through the small gaps that reach the gelatin powder. I was waiting for the eggplant. As a result, elution of gelatin powder using water requires a relatively long processing time.

In addition, the gelatin powder contained in the molded synthetic resin material is swollen while still contained in the molded synthetic resin material,
Since it is eluted from the molded synthetic resin material in that state, the elution efficiency is poor, and the molded synthetic resin material must be subjected to treatments such as rolling, pressing, or ultrasonic cleaning. The extraction process from the molded synthetic resin material was complicated.

If a molded synthetic resin material is immersed in hot water to enhance the swelling and elution effects of gelatin powder contained in this molded synthetic resin material, this molded synthetic resin material or this molded synthetic resin material This has caused problems such as damage to the molded product itself, which has a coating film made of synthetic resin material, and deterioration in quality. In particular, when a molded synthetic resin material containing gelatin powder is washed in hot water for a long time with the intention of increasing the elution effect, the molded synthetic resin material that has been formed as a surface film layer, etc. There was an inconvenience that the parts were broken or separated.

Furthermore, since the gelatin powder contained in the molded synthetic resin material is removed only by swelling and elution, it is difficult to remove the gelatin powder, and the various treatments mentioned above must be performed separately. However, there was a problem in that the holes formed in the molded synthetic resin material were difficult to follow the shape of the gelatin powder contained therein, resulting in an incomplete flower shape.

In particular, when forming pores by swelling and eluting gelatin powder with water, if the gelatin powder contained in the molded synthetic resin material is fine, about 1 micron in size, it is difficult to elute the gelatin powder. There was an inconvenience that S remained in the material as it was. This inconvenience occurs particularly when the gelatin powder contained in the molded synthetic resin material is leached away from the surface layer, and the gelatin powder contained in the deep inner part of the molded synthetic resin material remained almost unchanged in the S state.

The residual gelatin powder contained in such molded synthetic resin materials, on the one hand, prevents the formation of uniform pores in the molded synthetic resin materials, and on the other hand, causes inconveniences such as discoloration of the molded synthetic resin materials. However, there were difficulties in quality control of molded synthetic resin materials.

In addition, since the pores formed in the molded synthetic resin material are not sufficient, it has difficulty in hygroscopicity and moisture retention, and it is difficult to provide an appropriate dry feeling and moist texture, and the texture is also insufficient.

In view of the disadvantages of conventional molded synthetic resin materials, the leather-like synthetic resin material according to the present invention can remove gelatin powder contained in molded synthetic resin materials in a short processing time, and can also be used in molded synthetic resin materials. It is possible to reliably extract the gelatin powder at a processing temperature that does not damage the gelatin powder, and to form holes in the molded synthetic resin material that retain the shape of the extracted gelatin powder. To provide a monovalent leather-like synthetic resin material with a soft texture, which ensures removal of gelatin powder contained in a molded synthetic resin material at a position distant from the surface, and has both hygroscopic and moisturizing properties. It is an object.

[Means for Solving the Problems] The leather-like synthetic resin material according to the present invention achieves the above object, and the invention of claim 1 provides a molded synthetic resin material containing gelatin powder. Impregnation with an organic solvent that does not dissolve this molded synthetic resin material, has good solubility in water, and has a molecular weight of less than 80, or impregnation with an aqueous solution obtained by diluting this organic solvent with water. The above-mentioned molded synthetic resin material is swollen, and the swollen molded synthetic resin material is washed with water or soaked in water to extract the gelatin powder contained in the molded synthetic resin material, resulting in a leather-like product. Next, as the synthetic resin material, the invention of claim 2 claims a leather-like synthetic resin material in which the molded synthetic resin material from which the gelatin powder has been extracted is used as a synthetic resin film layer formed on the surface of the molded product. The invention of claim 3 provides a leather-like synthetic resin material in which a similar molded synthetic resin material is made into a synthetic resin coating, and the invention in claim 4 provides a leather-like synthetic resin material in which a similar molded synthetic resin material is made into a synthetic resin film. Furthermore, in the invention of claim 5, a similar molded synthetic resin material is used as a laminate layer of a synthetic resin film to form a leather-like synthetic resin material.

[Function] An organic solvent with a molecular weight smaller than 80 that does not dissolve the molded synthetic resin material and has good solubility in water, or an aqueous solution obtained by diluting this organic solvent with water, easily penetrates into the molded synthetic resin material. , to swell this molded synthetic resin material without dissolving it.

Washing the molded synthetic resin material that has swollen and damaged in this way with water,
When immersed in water, the organic solvent contained in the molded synthetic resin material moves toward the treated water due to the concentration difference between the liquids, shrinks from the swollen state, and due to this contraction, the molded synthetic resin material It functions to extrude the gelatin powder, which is separated from the molded synthetic resin material, from the molded synthetic resin material.

Further, this gelatin powder passes through the fine pores of the molded synthetic resin material swollen by the organic solvent and is extruded out following the movement of the organic solvent toward the treated water.

In the case of water that has molecular associations, the molecular associations are broken by mixing it with the above-mentioned organic solvent, and it penetrates into the molded synthetic resin material and functions in the same way as the above-mentioned organic solvent.

[Example] An example of a typical leather-like synthetic resin material of the present invention will be described below with reference to the accompanying drawings.

1 is a base material, which may be a synthetic resin molded product, a metal molded product, or a wooden molded product.

FIG. 3 shows an example of a synthetic resin film that does not have the base material 1, and FIG. 4 shows an example in which the base material 1 is a flexible material such as woven, knitted fabric, non-woven fabric, synthetic leather sheet, resin sheet, etc. This is an example constructed from a certain material.

2 is made of a molded synthetic resin material and includes gelatin powder 3. If the molded synthetic resin material 2 is integrally formed on the surface of the base material 1, which is a molded product, as a polyurethane resin film layer, for example, it may be formed by coating the surface of various base materials 1 as a polyurethane resin film or the like. If so, various base materials 1
There are cases in which the surface is laminated with a polyurethane resin layer, etc., and cases in which it is formed as an extremely thin polyurethane resin film.

This molded synthetic resin material 2 made of polyurethane resin etc.
In order to extract the gelatin powder 3 contained in the molded synthetic resin material 2, it is necessary to remove the gelatin powder from several microns to 30 microns (hereinafter referred to as μm
is displayed. ) is preferably formed at the front and back.

Moreover, a molded synthetic resin material 2 made of this polyurethane resin etc.
is formed of a single layer, and "C" may also be formed of multiple layers.

In addition, when this molded synthetic resin material 2 is formed of polyurethane resin, polyester polyurethane, polyether polyurethane, polycaprolactone polyurethane 1,
It is preferable to use polycarbonate-based polyurethane, silicone-modified polyurethane, amino acid-modified polyurethane, polyamide-modified polyurethane, and the like.

This molded synthetic resin material 2 will be explained in more detail. This molded synthetic resin material 2 may be constructed as a resin molded product by, for example, forming a resin solution containing gelatin powder in a polyester-based polyurethane resin solution, and injecting or enlarging this into a mold.

In addition, after applying a polyurethane resin solution containing gelatin powder to the mold surface of the mold to form a thin coating film of 10 to 20 μm, polyethylene, polypropylene, polyacetal, polyamide, polyurethane, P ■C
, ABS, polyester resin is injected or press-fitted,
It may be constructed as a molded article having a thin molded synthetic resin material 2 containing gelatin powder on its surface. The method used in this case may be injection molding, transfer molding, rim molding, slush molding or injection molding.

Furthermore, using a polyester-based polyurethane solution containing gelatin powder, we can produce woven and knitted fabrics, non-woven fabrics, synthetic resin sheets,
A layer of several microns to 3
The skin layer of around 0 μm may be formed as a molded synthetic resin material 2 in some cases. In this case, the molded synthetic resin material 2 that will become the skin layer is formed by brush coating, dipping, etc., as well as roll coating using a doctor knife coater or other roll coating method. Furthermore, a top skin layer of polyurethane resin containing gelatin powder is laminated on the surface of the molded synthetic resin material 2 that will become the skin layer by means such as gravure coating, and the whole is made into the molded synthetic resin material 2. Sometimes.

Furthermore, a water-miscible organic solvent solution of polyurethane resin is applied to the surface of the base fabric, which is the base material 1, and this is immersed in water to remove the solvent in the solution and solidify the polyurethane. After forming a wet microporous layer of polyurethane resin on the surface of 1, a polyurethane resin coating containing gelatin powder is applied by the method described above, and a top skin layer containing gelatin powder is formed on the surface of this wet microporous layer. It may be configured as a synthetic resin material 2.

Next, a polyurethane resin solution containing gelatin powder is applied to the surface of the base material 1, which is various resin molded products, wooden molded products such as furniture, and metal molded products such as panels, and molded and synthesized as a surface coating layer. It may constitute the resin material 2. This surface coating layer is formed by applying a polyurethane resin i'g solution using a roll, a brush, etc., or by applying it using a spray gun, or by immersing the base material 1 in a polyurethane resin solution, etc. It's okay.

Furthermore, when the molded synthetic M4 resin material 2 is a resin film,
For example, a polyurethane resin solution containing gelatin powder is applied to the surface of a release paper by a method such as doctor knife coating to form a thin resin layer, and then this resin layer is separated from the release paper to form a molded synthetic resin material 2. Alternatively, the film-shaped molded synthetic resin material 2 may be formed by inflation molding using a synthetic resin material containing gelatin powder.

Further, the molded synthetic resin material 2 is configured as a laminate film in which the polyurethane resin layer formed on the release paper surface is transferred and adhered to the surface of the base material 1 such as woven or knitted fabric, non-woven fabric, synthetic resin sheet, synthetic leather, etc. . In this case, the laminate film may be integrally laminated onto the base material 1 using an adhesive, or may be fused to the surface of the base material 1 without using an adhesive.

3 is gelatin powder, and since it is included in the molded synthetic resin material 2 described above, the particle size is set within the thickness of the molded synthetic resin material 2. In this case, if the particle size of the gelatin powder 3 contained in the molded synthetic resin material 2 is fine and aligned within a certain range, the molded synthetic resin material 2 has pores with uniform and fine diameters. 4 is formed. Therefore, it is preferable for the gelatin powder 3 to be used to be as fine as possible with uniform particle sizes, and the gelatin powder to be used is
Those having a molecular weight of less than 16,000, particularly those having a molecular weight in the range of 1,000 to 8,000, were convenient for extracting the gelatin powder 3 from the molded synthetic resin material 2.

In addition, when grinding gelatin powder, it is best to grind gelatin powder while classifying it using a dry grinding method such as a jet mill in order to make the particle size uniform. It is preferable to use gelatin powder with a value of less than 16,000.

When gelatin powder with a small molecular weight was pulverized using a dry pulverization method such as a jet mill while classifying the amount of air,
Gelatin powder with a particle size of about 3 μm could be obtained in a relatively short time, and gelatin powder with a particle size of over 10 μm and under 1 μm could be almost eliminated. or,
The gelatin powder 3 obtained by this method could be easily and reliably extracted from the molded synthetic resin material 2.

The gelatin powder 3 is included in the molded synthetic resin material 2. The method and amount of gelatin powder 3 to be added to the molded synthetic resin material 2 are determined according to the characteristics of the molded synthetic resin material 2, the characteristics of the base material 1, and other factors.

In this case, in order to provide the molded synthetic resin material 2 with appropriate leather-like characteristics, the amount of gelatin powder 3 contained in the molded synthetic resin material 2 must be 30 parts by weight per 1001i parts of the solid content of the molded synthetic resin material 2. ~120 parts by weight is preferred, ideally 3 parts by weight of gelatin powder per 100 parts by weight of the solid content of the molded synthetic resin material.
is preferably 70 parts by weight.

In this section, the amount of gelatin powder 3 added when molding the molded synthetic resin material 2 with polyurethane resin will be explained.

The amount of gelatin powder 3 contained in the molded synthetic resin material 2 made of polyurethane resin is
When the gelatin powder 3 is extracted from the gelatin powder 3, the surface of the formed synthetic resin material 2 retains the gloss characteristic of resin molded products, and has a sticky feel when overhumidified. Moreover, since it gave a slippery feeling when drying, almost no leather-like characteristics were observed.

On the other hand, molded synthetic resin material 2 made of polyurethane resin mixed with 30 parts by weight of gelatin powder 3 to 100 parts by weight of the solid part of urethane resin has less gloss peculiar to resin molded products and is moist. The moisturizing property with a dry feel and the hygroscopic property with a dry feeling were enhanced, and this tendency was made even more remarkable by increasing the amount of gelatin powder 3 mixed in with respect to the solid content of the polyurethane resin.

However, if the blending amount of gelatin powder 3 is 120 parts by weight or more based on too many parts of the solid content of the polyurethane resin, the function of the polyurethane resin as a binder is lost, and the molded synthetic resin material 2 made of the polyurethane resin is formed. was found to be extremely brittle.

Therefore, 30 to 12,031 parts by weight, ideally 70 parts by weight, of gelatin powder 3 is blended with 100 parts by weight of the solid content of the polyurethane resin forming the molded synthetic resin material 2 to form a molded synthetic resin made of polyurethane resin. Preferably, the material 2 is formed.

Incidentally, when the molded synthetic resin material 2 is formed of a polyurethane resin and the gelatin powder 3 is blended therein, it is preferable that the polyurethane resin used here does not have unreacted isocyanate groups at its terminals.

In particular, when the amount of gelatin powder 3 blended into polyurethane resin having unreacted isocyanate groups is large, the isocyanate groups of the polyurethane resin react with the amine groups and carboxyl groups of gelatin powder 3, and the molded synthetic resin The polyurethane resin of the material 2 does not sufficiently function as a binder, and the surface properties such as abrasion resistance of the molded synthetic resin material 2 made of the polyurethane resin are impaired. Moreover, the gelatin powder 3 contained in the two-component polyurethane resin liquid having unreacted isocyanate groups reacts with the isocyanate groups contained in the polyurethane resin liquid and loses solubility in water. , and its use is not recommended.

The gelatin powder 3 contained in the molded synthetic resin material 2 made of polyurethane resin or the like having the above structure can be extracted more reliably by sanding the surface of the molded synthetic resin material 2. It is preferable that the surface of the molded synthetic resin material 2 is previously subjected to a surface treatment such as sanding, sandblasting, buffing, etc.

To extract the gelatin powder 3 contained in the molded synthetic resin material 2 consisting of a polyurethane resin film layer, etc., first,
The molded synthetic resin material 2 is impregnated with an organic solvent that has good solubility in water, has a small molecular weight, and does not dissolve the molded synthetic resin material 2, such as polyurethane resin, and swells the molded synthetic resin material 2. Let me do it. Alternatively, the molded synthetic resin material 2 may be impregnated with an aqueous solution prepared by diluting an organic solvent having a oxidizing property with wood, and the molded synthetic resin material 2 may be similarly swollen.

The molecular weight of this organic solvent is preferably less than 80,
Ideally, it is less than 60. In addition, when using an organic solvent with a low boiling point or an expensive organic solvent, it is preferable to dilute it with water. This eliminates the association of water molecules that do not penetrate into the resin material.
The water bodies are penetrated into the molded synthetic resin material 2.

The aqueous solution to be diluted with water may have a concentration of 25% or more, and in the case of acetone, it may have a concentration of 5% or more.

In addition, the organic solvent used here needs to be an organic solvent with a small molecular weight, and organic solvents with a large molecular weight will not penetrate into the molded synthetic resin material 2 such as polyurethane resin, and these molded synthetic resins It does not cause swelling of the material 2.

In addition, the organic solvent used in sawing must have good solubility in water, and if the organic solvent is not soluble in water or is difficult to dissolve in water, this material may be removed from the swollen molded synthetic resin material 2. This molded synthetic resin material 2 does not allow the solvent to migrate into the treated water.
It has no effect on the release of gelatin powder 3 contained in.

Furthermore, the organic solvent used here must not dissolve the molded synthetic resin material 2 containing the gelatin powder 3.

These points will be explained more specifically. Molded synthetic resin material 2
When is a polyurethane resin, even if it is a hydrophilic organic solvent, solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dioxane, and tetrahydrofuran will dissolve this molded synthetic resin material 2. , Not suitable for use here.

Furthermore, toluene does not dissolve the molded synthetic resin material 2 made of polyurethane resin, nor does it dissolve in water, so it is not suitable for use in this S.

Therefore, as organic solvents that do not dissolve the molded synthetic resin material 2 made of polyurethane resin and are easily soluble in water, methyl alcohol, ethyl alcohol, propyl alcohol,
Alcohols such as isopropyl alcohol, butyl alcohol, and pentyl alcohol, and acetone were prepared. In this organic solvent, the molecular weight of methyl alcohol is 32,
The molecular weight of ethyl alcohol is 46, the molecular weight of propyl alcohol and the molecular weight of isopropyl alcohol are 60, and both are small and suitable for penetrating into the molded synthetic resin material 2 made of polyurethane resin and swelling this molded synthetic resin material 2. Ta.

On the other hand, pentyl alcohol had a large molecular weight of 88, and did not sufficiently penetrate into the molded synthetic resin material 2, making it unfavorable for swelling the molded synthetic resin material 2 made of polyurethane resin.

In addition, the molecular weight of butyl alcohol is relatively large at 74,
Since the solubility in water was poor at 8%, it was necessary to consider the impregnation treatment time and other factors.

From this point of view, it is recommended to use methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, and acetone to swell the molded synthetic resin material 2 made of polyurethane resin and extract gelatin powder 3 from the swollen molded synthetic resin material 2. preferable. In addition, when the base material 1 or the molded synthetic resin material 2 is a styrene resin, acetone dissolves this styrene resin, so if the base material 1 or the molded synthetic resin material 2 is a styrene resin, acetone should not be used. is good.

In addition, when the molded synthetic resin material 2 is swollen using the organic solvent described above, there is a risk of vaporization or ignition during handling of the organic solvent used, problems with the disposal of the used organic solvent, and the cost of the organic solvent used is reduced by the extraction of gelatin. From the viewpoint of cost ratio, etc., it is preferable to use the above-mentioned organic solvent as an aqueous solution diluted with water. In this case, the diluted aqueous solution should have a concentration of 25% or more; Any diluted aqueous solution having a concentration of 5% or more may be used.

Synthetic resin material 2 molded with organic solvent or its diluted aqueous solution
To impregnate the molded synthetic resin material 2, the organic solvent or its diluted aqueous solution is applied to the molded synthetic resin material 2 by spraying, etc., or immersed in this liquid.The time required for this impregnation is is the time required for sufficient swelling by these organic solvents or diluted aqueous solutions thereof, and is set depending on the characteristics of the organic solvents or diluted aqueous solutions used, processing conditions, characteristics of the molded synthetic resin material 2, etc.

The molded synthetic resin material 2 swollen with the organic solvent or its diluted aqueous solution increases in volume by approximately 1.3 times when it is a polyurethane resin film, and the volume of the molded synthetic resin material 2 swelled with the organic solvent or its diluted aqueous solution increases by approximately 1.3 times. Gelatin powder 3 and molded synthetic resin material 2
The organic solvent or its diluted aqueous solution is impregnated into the gap 4.

(See B in FIG. 5) The molded synthetic resin material 2 thus treated with the organic solvent or its diluted aqueous solution is subjected to treatments such as immersion in water or washing with water. When this molded synthetic resin material 2 is subjected to water treatment, the organic solvent or diluted aqueous solution of the organic solvent contained in this molded synthetic resin material 2 rapidly migrates toward the treated water due to the concentration difference. Then, the swollen molded synthetic resin material 2 is contracted. (See C in Figure 5) The molded synthetic resin material 2 shrinks and the treated organic solvent or its diluted aqueous solution moves from the molded synthetic resin material 2 toward the treated water. Gelatin powder 3 contained in 2 is extracted to the treated water side to form holes 4.

Note that when this water treatment is performed by immersing the molded synthetic resin material 2 in water, the gelatin powder 3 contained in the molded synthetic resin material 2 is further shortened by the water pressure during this water treatment. The hole 4 is reliably extracted from the molded synthetic resin material 2 within a short period of time.

In addition, during this water treatment, by adding ultrasonic imaging to the molded synthetic resin material 2, or by subjecting the molded synthetic resin material 2 to a rolling treatment, or by performing a pressing treatment using a roll or the like, It is preferable to assist the extraction of the gelatin powder 3 contained in the molded synthetic resin material 2.

The molded synthetic resin material 2 from which the gelatin powder 3 has been extracted using water is thoroughly washed with water to remove the impregnated organic solvent, and the molded synthetic resin material 2 is free from any residual organic solvent. Dehydrate and dry.

The surface of the molded synthetic resin material 2 having a large number of holes 4 thus obtained is subjected to a sanding treatment, a puffing treatment, a sandblasting treatment, etc., and a top skin layer is formed by a gravure coating method or the like. Also, molding processing, graining processing,
Perform general surface treatments for synthetic leather such as coloring.

Example 1 A silicone-based mold release agent was sprayed onto the mold surface of a rim mold for a handle to a thickness of about 5 μm using a spray gun, and then a thin film to become the polyurethane resin skin layer 11i was formed on the mold surface.

This thin film was prepared by adding 2111 parts of gelatin powder to 1001 parts of a dry urethane resin solution with a solid content (non-volatile content) of 30% by weight.
Gelatin dispersion in dimethylformamide containing i parts 7
0! Prepare a mixture of i parts and add 10~2 parts of this mixture.
The film was sprayed onto the mold surface of the rim mold using a spray gun so that the film thickness was 0 μm.

In addition, the gelatin powder included in the thin film in this process is such that gelatin powder with a particle size of less than 8 μm and 1 μm or more accounts for 90.8% by weight of the total amount of gelatin powder, and in particular, gelatin powder with a particle size of 8 μm or more is The powder used was only 0.1% by weight of the total amount of gelatin powder.

In addition, in order to prepare gelatin powder with such a unique particle size distribution, gelatin powder is used which is obtained by pulverizing gelatin with a particularly low molecular weight of 1,000 to 3,000 using a jet mill while classifying the gelatin by air volume. there was.

Further, before blending this gelatin powder with dimethylformamide and stirring, the water content contained in this gelatin powder was adjusted to less than 7.5% by weight.

Mix 21 parts by weight of gelatin powder with 1 part by weight in dimethylformamide so that the gelatin mixture becomes 70 parts by weight.
Upon stirring, gelatin powder was dispersed in dimethylformamide in suspension.

70 parts by weight of a suspension of gelatin powder in dimethylformamide, 100 parts by weight of a dry urethane resin solution with a urethane resin solid content of 30% by weight, and 15 parts by weight of a pigment as necessary are mixed to form the above-mentioned 10 parts by weight. A thin film of ~20 μm was formed on the mold surface of the rim mold.

In this S, it is preferable that the water content of the gelatin powder mixed in suspension in dimethylformamide is less than 8% by air volume, and if gelatin powder with a high water content is used, the gelatin will weld together in the dimethylformamide. It was unsuitable for use because it mixed with the liquid and separated from the liquid.

In addition, when a suspension of gelatin powder is made using an organic solvent that does not dissolve in water, it is difficult to extract the mixed gelatin powder from the film on the surface of the molded product after molding, and dimethylformamide,
Dimethylacetamide, dioxane, N-methyl-2-
Preferably, pyrrolidone, tetrahydrofuran, etc. are used.

Next, the iron core was set in the rim mold and the mold was clamped, after which a molding resin was injected into the mold.

This injection molding resin is produced by injecting liquid A, which is a mixture of polyether, crosslinking agent, catalyst, and blowing agent, and liquid B, which is an isocyanate, into a mixing head using a pump.
The liquid was mixed by collision and then injected into a mold for use.

As a result, no unreacted isocyanate groups remained in the polyurethane resin injected into the mold, and no denaturation of the gelatin powder contained in the thin film coated on the mold surface was observed. .

The handle, whose surface was thus provided with a thin molded synthetic resin material containing gelatin powder, was immersed in a 50% aqueous methyl alcohol solution to sufficiently swell the molded synthetic resin material of the handle surface layer.

Next, this handle was immersed in water, and while applying ultrasonic vibrations, the handle surface was subjected to hand-kneading treatment to extrude the gelatin powder from the handle surface.

Furthermore, the handle was sprayed with washing water to remove the methyl alcohol that had swollen the handle surface, dehydrated, and then dried.

The handle molded in this way has countless fine pores of several microns in the shape of extracted gelatin powder on the surface, and there is almost no residual gelatin, and fine irregularities are formed on the surface of the molded product. Ta.

As a result, when I held the steering wheel, there was no sticky feeling at all and it felt dry. Furthermore, even in the dry winter season, the handle surface felt moist and had a suitable contact resistance.

In addition, the unevenness on the handle surface and the fine holes caused the light rays to interfere with each other, creating a soft matte state.

Furthermore, the surface film layer, which is a molded synthetic resin material, did not become brittle as the gelatin powder was extracted, and the surface properties such as abrasion resistance and tensile strength were approximately close to those of a pure polyurethane resin film.

Comparative Example 1 A handle was molded under the same conditions as in Example 1 except that the gelatin powder was extracted using hot water at 50°C.

When molding this handle, the elution of gelatin powder requires 40 to 9
A processing time of 0 minutes was required, which was significantly longer than the processing time (swelling-pressing and kneading processing) of the previous example.

Further, a portion of the gelatin powder contained in the molded synthetic resin material on the surface of the molded handle did not dissolve and remained. In particular, residual gelatin powder of less than 1 μm contained in the molded synthetic resin material was noticeable. Also, the gelatin powder contained inside the handle, not on the surface layer, remained almost intact.

Therefore, the handle of Example 1 was separately heated in hot water at 120° C. for 40 minutes. Many of the handles treated with this treatment had torn or distorted edges of the holes on the surface of the handle, and did not have a good feel to the touch.

Comparative Example 2 After the handle in Example 1 was immersed in a pentyl alcohol solution, a handle was molded under the same conditions except that the handle was immersed in water.

When molding this handle, the polyurethane resin film layer, which is a molded synthetic resin material on the surface of the handle, did not swell. Most of the gelatin powder remained, and no extraction effect was observed.

Comparative Example 3 A handle was molded under the same conditions as in Example 1 except that the handle was immersed in a toluene solution and then immersed in water.

In the handle obtained in this comparative example, gelatin powder in the polyurethane resin skin Ilj layer, which is a molded synthetic resin material, on the surface of the handle was not extracted at all and remained as it was.

Comparative Example 4 A handle was molded under the same conditions as in Example 1 except that the handle was immersed in a dioxane solution and then treated by being immersed in water.

In the handle obtained in this comparative example, the polyurethane resin film layer, which is a molded synthetic resin material, on the surface of the handle was in a broken state, and the handle had a particularly rough and brittle surface.

Comparative Example 5 A handle was molded under the same conditions as in Example 1 except that the amount of gelatin powder was 6 parts by weight.

This molded handle is made of only polyurethane resin without using gelatin powder, and has the surface properties of a molded synthetic resin material such as a surface film layer and abrasion resistance between the grooves. A sticky feeling was produced. In addition, the grip was loose in the dry conditions of winter, causing the grip to slip when operating the handle.

Also, the strong reflection of light made it difficult to operate the steering wheel.

Example 2 A handle was molded under the same conditions as in Example 1 except that the blended amount of gelatin powder was 9 parts by weight.

This molded handle felt a little sticky when I touched it, but it had a moist feel, had a good grip, and didn't bother me too much with the reflection of light. especially,
The mechanical properties of the film layer, which is a molded synthetic resin material, on the surface of this handle were good.

Example 3 A handle was molded under the same conditions as in Example 1 except that the blended amount of gelatin powder was 36 parts by weight.

This molded handle feels close to leather when you touch it.
It had a dry feeling with no stickiness at all, and the grip was particularly good. The texture was also soft, similar to that of leather, but the surface of the molded synthetic resin material was noticeably rough, and it was observed that part of the surface would peel off slightly when the surface was rubbed strongly.

Comparative Example 6 A handle was molded under the same conditions as in Example 1 except that the blended amount of gelatin powder was 43 parts by weight.

This molded handle had a rough surface, and the film layer of the molded synthetic resin material was not sufficiently formed, making it unsuitable for use.

Example 4 A polyurethane resin solution containing 70 parts by weight of gelatin powder per 100 parts by weight of solid content (nonvolatile content) of polyurethane resin was poured into a mold to obtain a molded panel.

Next, a 30% concentration ethyl alcohol aqueous solution was sprayed onto the panel to impregnate the panel with the ethyl alcohol aqueous solution.

In this state, the panel was immersed in warm water at 50° C., and the surface was pressed and rubbed by hand to obtain a panel.

In this obtained panel, the gelatin powder contained in the layer near the panel surface was almost completely extracted, and fine pores from which the gelatin powder was extracted were formed on the panel surface.

Example 5 100 parts by weight of a dry polyurethane resin solution having a solid content (nonvolatile content) of 30% by weight and 70 parts by weight of a gelatin dispersion in DMF-ME containing 20 parts by weight of gelatin powder were mixed, A molded synthetic resin material was sprayed on the surface of the metal panel to a film thickness of 15 μm, and after drying, the metal panel was
After being immersed in a 0% concentration methyl alcohol aqueous solution, it was further washed in water to which ultrasonic vibrations were applied for 20 minutes.

The metal panel obtained by sawing has a leather-like film on the surface of the metal panel due to the gelatin powder contained in the molded synthetic resin material on the surface being extracted, which eliminates the coldness upon contact and makes it easier to touch. The sticky feeling of time was gone. In addition, there was no slippery feeling peculiar to metal panels, and the surface felt moist to the touch. Furthermore, there was less sweating and dew condensation on the surface of the metal panel.

Example 6 The coating film was formed on the armrest of a wooden chair, and the other conditions were the same as in Example 5 except that the film thickness of the molded synthetic resin film was 25 μm. I created a hook.

The armrests obtained in this process were said to have a soft matte texture, unlike wooden armrests, and were less sticky than wooden armrests. Also, the moist feel of the touch upon contact was superior to that of wooden armrests. It has also been found that the method prevents the wooden armrest from getting wet more than necessary and also provides a suitable level of humidity to the wooden portion of the armrest.

Example 7 1 containing 50% by weight of gelatin powder on the surface of release paper
A solution was applied to 20% DMF-ME of a polyester polyurethane resin with a 00% modulus of 60 kg/cm' using a knife coater so that the dry thickness was 30 μm, and after drying, the release paper was coated with polyurethane resin. The film surface was coated with butyl alcohol and impregnated to swell the polyurethane resin coating, which is a molded synthetic resin material.6 Next, the release paper with the polyurethane resin coating was immersed in water, and while being squeezed between rolls, After extracting the gelatin powder contained in this polyurethane resin coating, it was dehydrated and dried, and the polyurethane resin coating, which is a molded synthetic resin material, was peeled off from the release paper to obtain a porous film. .

In the 30 μm thick film obtained by this process, holes were formed as they were after the gelatin powder was extracted, and almost no residual gelatin powder was observed.

Example 8 A polyester polyurethane resin with a 100% modulus of 20 J/cm was applied to the roughly brushed surface of a polyester woven fabric.
After applying a 2% DMF solution to a basis weight of 700 g/m2, it was desolvated and solidified in 20 tons of water.
This is dehydrated and then dried with hot air at 120° C. to form a polyester woven fabric having a wet microporous layer of 0.6 μm.

In addition, on the surface of the release paper, a solution of 20% DMF-ME of a polyester polyurethane resin with a 100% modulus of 60 kg/cm2 containing 50% by weight of gelatin powder was applied so that the dry thickness was 30 μm. and dry at 90°C for 2 minutes.

Next, the wet microporous layer on the polyester woven fabric surface is heated while being superimposed on the polyurethane resin layer on the release paper surface, laminated at 130° C., and the release paper is peeled off.

Furthermore, a 50% aqueous methyl alcohol solution was applied to the polyurethane resin layer, which is a molded synthetic resin material laminated on the polyester woven fabric, to swell the polyurethane resin layer, and then the cloth was heated at a speed of 250 m/min and a pressure of 1. .5kg
A leather-like synthetic resin material was obtained by rubbing in water at 25° C. for 10 minutes under the condition of “/cm”.

There was no residual gelatin powder in the polyurethane resin laminate layer of the resulting leather-like synthetic resin material, and fine pores were formed after the mixed gelatin powder was extracted.

[Effect] In the leather-like synthetic resin material according to the present invention, the molded synthetic resin material is prepared by using an organic solvent such as methyl alcohol that has a small molecular weight and good solubility in water, or a diluted aqueous solution of this organic solvent. The gelatin powder contained in the molded synthetic resin material was extracted without unraveling the molded synthetic resin material in the inflated state.The following features also apply to the leather-like synthetic resin material. is being applied.

First, it is possible to extract the gelatin powder contained in the molded synthetic resin material in a short period of time ranging from several minutes to several tens of minutes, making it possible to efficiently mold the leather-like synthetic resin material. can.

In addition, gelatin powder contained in this molded synthetic resin material can be reliably and smoothly extracted by simply immersing it in treated water at a relatively low temperature. is particularly easy.

Furthermore, when extracting gelatin powder, there is no need to rub and wash the molded synthetic resin material in hot water for a long time, and there is no wear and tear on the molded synthetic resin material or deterioration of quality. Will not deform or break.

Furthermore, since the gelatin powder contained in the molded synthetic resin material is not dissolved but removed by the extraction method, after the gelatin powder is extracted, a clean inner periphery is created. It has the feature that the pores having surfaces are formed in a continuous or discontinuous state.

Next, the gelatin powder contained in the molded synthetic resin material is
Particles with a particle size of less than 1 μm are reliably extracted, and gelatin powder contained relatively inside is also extracted, and fine, clear pores that are continuous or not are formed. It has the feature of being formed.

From this point of view, it is an object of the present invention to provide a leather-like synthetic resin material that has a soft texture with a matte appearance and also has a contact surface that has both appropriate hygroscopicity and moisture retention. is possible.

Therefore, the leather-like synthetic resin material according to the present invention can be applied to all products that are around us every day, such as various synthetic leather fabrics, films, bags, cases for small items, etc.
As personal items such as buckles, furniture such as chairs, building materials such as flooring, grips for operating various devices, keyboards, automobile interior parts such as steering wheels, horn pads, shift knobs, armrests, console boxes, etc. used.

[Brief explanation of drawings]

Fig. 1 is an enlarged sectional view of the main part of the leather-like synthetic resin material according to the present invention before removing gelatin powder, Fig. 2 is an enlarged sectional view of the main part with gelatin powder removed, and Fig. 3 FIG. 4 is an enlarged cross-sectional view of the main part of an example in which the leather-like synthetic resin material is a film, FIG. Figures A to D are enlarged sectional views of main parts showing the state in which gelatin powder is extracted. 1... Base material, 2... Molded synthetic resin material, 3... Gelatin powder, 4... Hole, 4°... Gap.

Claims (1)

[Claims] 1. The molded synthetic resin material containing gelatin powder is insoluble, has good solubility in water, and has a molecular weight of 80.
After the molded synthetic resin material is impregnated with a smaller organic solvent or a diluted aqueous solution of the organic solvent and swelled, the molded synthetic resin material is washed with water or immersed in water to remove the gelatin contained in the molded synthetic resin material. A leather-like synthetic resin material made by extracting powder. 2. The leather-like synthetic resin material according to claim 1, wherein the molded synthetic resin material containing gelatin powder is a molded synthetic resin film layer on the surface of the molded product. 3. The leather-like synthetic resin material according to claim 1, wherein the molded synthetic resin material containing gelatin powder is a synthetic resin coating. 4. The leather-like synthetic resin material according to claim 1, wherein the molded synthetic resin material containing gelatin powder is a synthetic resin film. 5. The leather-like synthetic resin material according to claim 1, wherein the molded synthetic resin material containing gelatin powder is a synthetic resin film laminate layer.