JP2673881B2 - Resin film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin film formed by using crushed gelatin powder.

[0002]

2. Description of the Related Art Gelatin is a kind of derived protein which is insoluble in organic solvents, has a characteristic that it swells in cold water and dissolves in warm water to become a highly viscous sol, and at a concentration of 2 to 3% or more, it is a greenhouse. It is used as a modifier for synthetic rubber because of its property of forming an elastic gel.

In addition, it has been attempted to mix a resin film with a resin film in order to produce a film having good stretchability by utilizing the same characteristics and to produce a film having a moisture absorbing / releasing function and having good water and air resistance. ing.

As a result of many experiments, it has been clarified that the gelatin contained in these synthetic rubbers or resins brings a unique effect to the synthetic rubber or resin film as the particle size becomes finer. There is.

In particular, in order to provide a resin film with elasticity, moisture absorption / release properties and water repellency by thinning the resin film, the particle size of gelatin powder contained in the resin film must be reduced. It was necessary to align in the range.

Therefore, gelatin that has been powdered or granulated has been pulverized with a dry ball mill or the like, and classified before use.

[0007]

However, in the conventional method of pulverizing with a ball mill, it is difficult to re-pulverize gelatin, and a pulverized gelatin powder having a uniform quality and a uniform fine particle size is obtained. I couldn't produce it.

Further, such a characteristic of gelatin is impaired, or a resin film produced by using crushed gelatin powder mixed with gelatin powder having a relatively large particle diameter has a peculiar smoothness and touch feeling. Is not brought
Unique moisture absorption and desorption function due to gelatin mixed in this film,
It had the drawback that it did not provide the stretch function and water repellency function.

In particular, in the crushing by the simple method of crushing and grinding by the dry ball mill which is the conventional method, in this crushing,
A large amount of heat was generated due to the grinding, and various inconveniences were caused by this heat generation.

First, the heat generated during the pulverization by the ball mill may sometimes cause the gelatin being pulverized to be partially in a viscoelastic gel state, and it often happens that the gelatin cannot be efficiently pulverized into fine powder. Alternatively, powdery or granular gelatin is fused together to form a viscoelastic block. In particular, such inconveniences occurred remarkably, for example, when the water content of the gelatin to be pulverized was high, or when the gelatin was pulverized under humid conditions.

Next, when water is rapidly removed from the gelatin being crushed by the heat generated during the crushing by the ball mill, the hydrophilicity of the crushed gelatin powder is impaired, and the swelling by the water or the elution function to hot water is lost. In particular, the crushed gelatin powder based on crushing under the condition that the water content in the crushed gelatin is less than 2% by weight has such viscoelasticity and adhesion as to the gelatin powder, including its hydrophilicity. It has a drawback that various properties such as elasticity and stretchability are impaired.

From this point of view, in order to pulverize powder or granular gelatin by the pulverization method using a dry ball mill, the heat generated by friction during pulverization is accumulated as much as possible, or the friction heat is excessively generated. I needed to crush it slowly, taking a long time to avoid it. For this reason,
The crushing efficiency of gelatin was poor, and the particle size of the crushed gelatin powder to be finished had to be stopped within a relatively large range, and a finer gelatin powder could not be obtained.

Therefore, powder or granular gelatin is mixed and mixed with a liquid polymer or a resin solution diluted with various solvents, and the powder or granular gelatin mixed with the liquid polymer or resin solution is charged into a wet pulverizer. And then crushed.

The wet pulverization method has the drawbacks that the flow resistance of the liquid polymer or resin solution is large, stirring and pulverization are not performed smoothly, and the mixed gelatin is not uniformly dispersed in the polymer. Was. In particular, when the stirring of this kind of liquid polymer or resin solution is continued, the viscosity of these polymer or resin solutions tends to increase with time, and it may be difficult to perform a smooth pulverization treatment by a wet pulverizer. In many cases, when the pulverization temperature in the pulverizer was increased with the stirring of the pulverizer, such inconvenience on pulverization tended to occur more remarkably.

When gelatin is crushed by a dry ball mill, the device itself is provided with a cooling or exhaust device for removing the heat generated by the friction or impact, or a device for keeping the water content of gelatin constant. However, the crusher itself has the drawback of being large-scale.

Further, when powdered or granular gelatin is crushed by such a dry ball mill, the particle size of the gelatin powder produced varies depending on various conditions such as temperature and humidity in the crusher or agitation speed of the ball, resulting in a long particle size. Even if the powder is pulverized for a long time, the gelatin powder having a large particle size remains in the gelatin powder having a fine particle size.

In particular, when powder or granular gelatin is pulverized by such a dry ball mill, the particle size is 1.0 micron (in the case of elongated particles, the measurement is made on the short side.
Display as m. ) To about 50 μm, a gelatin powder having an extremely fine particle size is produced, but a considerable amount of gelatin powder having a relatively large particle size remains, which is caused by a ball mill for a long time. The same was true when crushing was continued.

As a result, when these gelatin powders are contained in a resin material such as a polyurethane resin solution to form a sheet or film, a part of the mixed gelatin protrudes from the surface of the sheet or film, and this causes In addition to giving a rough feeling to the surface, edge breakage easily occurs between the peripheral portion of the large gelatin particle and the sheet or film, and the large particle diameter of the gelatin particle falls off from the sheet or film, or from the portion. However, there was a problem that the surface of the film was cracked.

[0019] In particular, the inconvenience associated with the irregularity of the particle size of the gelatin powder in the above description is that the thickness of the film to be formed is reduced to 0.
This was noticeable when the thickness was extremely thin, such as from 02 to 0.006 mm.

In a method of pulverizing gelatin powder by a dry ball mill and a method of using the pulverized gelatin powder, granulated or powdered gelatin is pulverized at a water content of about 10 to 15% by weight, and the pulverized gelatin is pulverized. It is mixed with various resin materials in the same state. However, when such gelatin powder is mixed with a resin material, the finer the gelatin powder to be mixed, the more it tends not to be smoothly dispersed in the resin material. In the case of a certain solution or the like, it has a drawback that it is not uniformly dispersed in the resin solution.

In view of the inconveniences in the conventional examples, the present invention eliminates the adverse effect on the crushed gelatin caused by the heat generated by the friction generated during the crushing of the powder or granular gelatin powder, and also provides a uniform grain in a short time. It enables the pulverization and molding of fine gelatin powder with a diameter, and does not impair the quality peculiar to gelatin, and forms a gelatin powder with a uniform particle size using a jet mill. The purpose of the present invention is to provide a resin film in which gelatin powder is uniformly mixed by preparing it in a suspension form.

[0022]

Means for Solving the Problems The resin film using the crushed gelatin powder according to the present invention achieves the above-mentioned object, and gelatin crushed using a jet mill belongs to a finer range than 6 μm. Powder is contained in a resin film, and crushed gelatin powder is mixed in a solvent and mixed with the mixed solvent into a resin material to obtain a film mainly having a thickness of 0.02 to 0.006 mm. .

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION A resin film according to a typical embodiment of the present invention will be described below. Usually, solid gelatin that is prepared as a white powder or transparent flakes that is tasteless and odorless (herein, gelatin is mainly industrial gelatin, but various properties and concentrations of gelatin may be used, including glue. Is basically put in a jet mill in a state of air-dry water content (water content in the state of being left in the air = equilibrium water content) and pulverized. The pulverization by the jet mill is continued until the particles of the pulverized gelatin powder are in a range smaller than 6 μm in a state where the gelatin is not contacted and ground by the jet air.

In order to make the particle size of the gelatin powder crushed by this jet mill uniform and to crush the crushed gelatin to the target particle size in a short time, the jet air used in the jet mill is The gelatin powder is jetted into the crusher as about 15 ° C., and the gelatin powder to be put into this jet mill is classified.
Fine gelatin powder belonging to a range smaller than μm is preferably classified by a sieve or an air classifier so as to be 90% by weight or more of the total amount of the gelatin powder.

The pulverization by the jet mill is continued until the grain size of the introduced grain or powdery gelatin becomes finer than 6 μm. Therefore, the grinding conditions such as the grinding time by the jet mill are as follows: the capacity of the jet mill, the air pressure and the air input amount used in the jet mill, the type and input amount of the gelatin to be input to the jet mill, and the jet mill. Although it may be changed as needed depending on various conditions such as the grinding temperature, it is necessary to grind the gelatin within the range where the temperature of the jet air during the grinding is not increased as much as possible so as not to deteriorate the quality of the ground gelatin.

Further, in order to make the crushing by the above-mentioned crusher more effective, the crushed gelatin is pre-crushed and the particle size thereof is determined by air classification by true specific gravity or sieve classification by bulk. They are prepared and usually prepared by crushing with a dry crusher such as a turbo mill.

Further, the air used for crushing in this jet mill is dehumidified by cooling to about -15 ° C., and the temperature rise due to impact crushing occurring in the jet mill is suppressed as much as possible.

The average particle size of gelatin put into this jet mill is 100 μm, and jet air jetted into the jet mill is 6 kg / cm ^{2 to} 8 kg / cm ^2.
Moreover, when the air was cooled to -15 ° C and used, the hydrophilicity of the crushed gelatin was not impaired, and a gelatin powder having a particle size finer than 6 µm was obtained in a very short time compared with crushing by a dry ball mill. We were able to.

Since the gelatin is crushed with the air of the jet mill in this way, the gelatin being crushed is less likely to melt, swell, or harden due to the heat generated during crushing. It has the feature that the moisture absorption and desorption phenomenon of gelatin inside is small. As a result, in the process of grinding the gelatin, the water content of the gelatin is not increased, and the gelatin does not fuse with each other or become soft and unsuitable for grinding or impact grinding.
Further, the quality does not deteriorate until the water content of the gelatin is reduced in the process of grinding the gelatin and the hydrophilicity is impaired. The gelatin powder crushed in this way is mixed with a solvent and used for molding a plastic film.

Example 1 Gelatin was pulverized with a turbo mill in the air-dry water content state and classified to have an average particle size of 34 μm. The water content of this gelatin powder was 12% by weight, but in actual grinding of gelatin powder, it was possible to use gelatin powder having a water content in the range of 5 to 15% by weight. 8 kg of crushed air of a jet of gelatin having an average particle diameter of 34 μm
/ Cm ² and a classification rotor at 7,000 rpm for 60 minutes, and gelatin powder having a particle size of less than 6 μm was produced while sequentially performing classification correction. The particle size distribution of the gelatin pulverized by this jet mill is as follows. The pulverized gelatin powder was classified by an air volume classifier based on the true specific gravity to obtain a gelatin powder having a range smaller than 6 μm. 10.00 μm or more to 0.0 wt% 9.00 〃 to less than 10.00 μm 39.4 〃 8.00 〃 to 9.00 〃 36.0 〃 7.00 〃 to 8.00 〃 0.0 〃 6 0.00 〃 to 7.00 〃 10.6 〃 5.00 〃 to 6.00 〃 7.0 〃 4.00 〃 to 5.00 〃 2.4 〃 3.00 〃 to 4.00 〃 3.0 〃 2.00 〃 to 3.00 〃 1.0 〃 1.00 〃 to 2.00 〃 0.5 〃 0.09 〃 to 1.00 〃 0.1 〃

Example 2 Gelatin powder pulverized by the above-mentioned turbo mill and classified by the particle size of 100 μm was put into a jet mill to obtain 6 kg / c.
Milling air of m ² was cooled to −15 ° C. and sprayed into a jet mill to mill gelatin powder. Grinding with this jet mill was continued for 70 minutes while classifying with a classifying rotor of 7,000 rpm, most of which was 6 μm.
It was considered to be a finer range of gelatin powder. 8.0 μm or more to less than 9.0 μm 21.0% by weight 7.0 〃 to 8.0 〃 18.0 〃 6.0 〃 to 7.0 〃 15.0 〃 5.0 〃 to 6.0 〃 19 0.0 〃 4.0 〃 to 5.0 〃 12.0 〃 3.0 〃 to 4.0 〃 10.0 〃 2.0 〃 to 3.0 〃 3.0 〃 1.0 〃 to 2.0 〃 1.7 〃 0.09 〃 to 1.0 〃 0.3 〃

In this embodiment, the reduction of the water content in the crushed gelatin powder can be avoided more than in the above-mentioned Example 1, and the quality of the crushed gelatin powder is not deteriorated by the heat generated during the crushing. It was Therefore, the gelatin powder pulverized by the method of Example 2 has the same hydrophilicity as that of the gelatin material before the pulverization treatment, and has the property of causing swelling due to moisture absorption, appropriate sol and gelation. Had.

The gelatin powder pulverized by the above method has the following features in the pulverization process and the produced gelatin powder. First, the granular or powdered gelatin put into the jet mill is crushed in a state of being wrapped in the air of the jet mill, so that the gelatin does not fuse with each other and the surface of the ball or the crusher is not crushed. No fusion. In particular, heat generated by grinding or impact of the ball is not dispersed and directly transmitted to the gelatin by the air of the jet mill, and there is no risk of deterioration of the gelatin or fusion of the gelatin due to the heat. In addition, when the gelatin is pulverized while being covered with low-temperature jet air, in the pulverization process of the gelatin, the gelatin becomes wet and swells or becomes sol-like, or water evaporates and heats in the pulverization process. No accompanying gelling phenomenon occurs. Therefore, the gelatin milled by this jet mill does not impair the swelling function specific to gelatin or the characteristics such as hydrophilicity and specific viscoelasticity. Also, it is possible to reliably and easily produce a fine gelatin powder having a uniform particle size without making it difficult to pulverize due to the dampness of gelatin and the increase in viscosity with heating during the pulverization process of gelatin. Can be.

Further, the gelatin powder obtained by pulverizing and classifying has a particle size smaller than 6 μm in the case of the above pulverizing method, and is fused or entangled with each other. When the pulverized gelatin powder is mixed in a solvent, it is uniformly dispersed in the solvent, and the gelatin powder is generally dispersed like a suspension.

The gelatin thus pulverized using a jet mill is mixed and mixed with a solvent. Each of the gelatin powders mixed and mixed in these solvents floats in the solvent in an independent state and is shielded from the outside air. This facilitates the management of the pulverized gelatin powder, and the pulverized gelatin powder does not become wet, harden, or fuse with each other.

The gelatin powder crushed in this way is
The mixture is mixed with the gelatin powder and mixed with the resin for molding. The method of this compounding and the amount of the compounding are appropriately determined according to the characteristics of the resin film to be molded.

The solvent used above is typically an organic solvent, and a solvent suitable for a resin material such as a resin solution containing crushed gelatin is used. And this solvent requires that the gelatin be insoluble, typically dimethylformamide, toluene,
Methyl ethyl ketone and the like are used other methanol, isopropyl alcohol, n-butanol, benzyl alcohol, ethyl acetate, butyl acetate, acetone, methyl isobutyl ketone, cyclohexane, tetrahydrofuran,
Dioxane, xylol, 2-nitropropane, ethane dichloride, trichlorethylene, perchlorethylene, methyl cellosolve, ethyl cellosolve and the like are used.

Since such a solvent is insoluble in gelatin, even if gelatin is mixed into this solvent, the gelatin does not swell or melt, and the water content in the gelatin is absorbed by the solvent. The gelatin does not harden. In addition, during storage of gelatin, it has a feature that gelatin put in this solvent is stored in the same state as when it is mixed in this solvent.

The solvent-blended resin having the gelatin powder is a resin suitable for the film to be produced,
It is made into a solution by the solvent. That is, usually, the above-mentioned gelatin powder is pulverized using a solvent suitable for the resin material of the resin film to be formed.

Therefore, various resin films can be formed by selecting the solvent and the resin material used for mixing and mixing the gelatin powder.

The resin mixed with the solvent containing the gelatin powder may be in the form of paste, powder or liquid, and the paste or viscosity may be adjusted by adjusting the amount of the solvent. It is in the form of a high solution or a dilute solution having low viscosity.

Thus, a film is produced using the resin mixed with the solvent. As a method for producing this film, an appropriate method such as inflation molding is used,
After coating the surface of the release paper, there is a method in which the release paper is peeled off to form a film.

The film produced in this way is
Since the particle size of gelatin powder contained in these materials belongs to a finer range than 6 μm, even if the film thickness is in the range of 0.02 to 0.002 mm, The mixed gelatin powder did not stand up or stick out, and the film was smooth and had a good feel to the touch.

Further, by eluting part of the gelatin powder contained in the resin molded product of the film produced as described above, a large number of pores finer than several microns are provided on the surface of this film. be able to.

By providing pores finer than 2 to 3 μm on the surface of the film, the film is provided with air permeability, and in particular, the air permeability of the film is about 0.0004 μm. It has the feature that it allows water vapor of a certain particle size to pass through but does not allow water droplets to pass through. For this reason, the film can be provided with water resistance and moisture permeability.

Therefore, 0.02-0.00 containing the above-mentioned gelatin powder on the surface of various fabrics, leathers, wood products, etc.
When the gelatin powder in the film is eluted by laminating a film having a thickness of 2 mm, water resistance and moisture permeability specific to these fabrics, leathers, wood products and the like are brought. By the way, the diameter of a normal raindrop is 2000μ.
m, even in fine rain, 100 μm,
It does not pass through the fine holes provided in this film. Also, raindrops attached to the film surface do not seep through the fine holes because of the surface tension.

Example 3 A polyurethane resin film was prepared by using the solvent containing the gelatin powder, and this film was transferred onto the surface of the woven or knitted fabric. Gelatin powder finer than 6 μm 10 parts by weight Toluene 70 parts by weight Polyurethane resin solid content 30 parts by weight This resin solution was applied on the surface of a release paper by a doctor knife coating method to a thickness of 0.008 mm and dried. After that, it was peeled off from the release paper to form a film having a thickness of 0.008 mm.

Further, without peeling off this film, 1.
The release paper was peeled off while adhering to the surface of the non-woven fabric having a thickness of 5 mm to form a film skin layer on the surface of the non-woven fabric. Then, this nonwoven fabric was immersed in warm water at 60 ° C. and washed with hot water for 15 minutes. As a result, gelatin powder contained in the film disappeared by 35% by weight of the total amount.

A film was prepared by increasing the amount of the gelatin powder mixed by 5 parts by weight between 3 parts by weight and 30 parts by weight. Although the gloss of the film surface was good and it had a sufficient waist strength, it had a sticky feeling at the time of contact. On the other hand, the film surface containing 35 parts by weight of gelatin powder has a contact resistance peculiar to gelatin and a good feeling to the skin, but when a strong force acts on the film surface, wrinkles are generated on the film surface. In the product in which the film of (1) was laminated, the surface of the base material was partially exposed when the surface was twisted. Therefore, the optimal amount of the gelatin powder is 3 to 30 parts by weight. However, the amount of the gelatin powder can be further changed depending on the type of the resin for forming the film, the amount of the solvent used, the molding conditions, and the like.

In the elution of the gelatin powder by washing with hot water as described above, the higher the temperature of the hot water used, the more the gelatin powder contained can be eluted in a shorter time, but the film or laminate film is damaged. Or, there is a disadvantage that the base material is damaged. From this fact, comprehensively taking into consideration the type of material to be laminated on the film, material characteristics and material characteristics of the film itself, the amount of gelatin powder contained in the film, the amount of gelatin powder eluted from the film, etc. , The gelatin powder contained in this film is eluted. In the polyurethane resin film of the above example, it is ideal to elute the contained gelatin powder with warm water or hot water of 60 to 150 ° C, and the elution amount of the contained gelatin powder is small with warm water of 60 ° C or less, It took a long time.

Example 4 Toluene 70 parts by weight Gelatin powder finer than 6 μm 10 parts by weight Polyvinyl chloride resin 30 parts by weight The vinyl chloride film produced in this Example 4 has increased flexibility and is more stretchable than a conventional vinyl chloride film. Significantly increased and provided a moisture absorption function.

Example 5 Toluene 70 parts by weight Gelatin powder finer than 6 μm 10 parts by weight Acrylic resin 30 parts by weight The film produced by the compounding ratio of Example 5 has excellent weather resistance and good abrasion resistance. It had the feature that it did not have a sticky feel when contacted, and the gloss of the film surface was also good.

Example 6 Toluene 70 parts by weight Gelatin powder finer than 6 μm 10 parts by weight Polyvinyl chloride resin 15 parts by weight Acrylic resin 15 parts by weight The film produced by the mixing ratio of this Example 6 was prepared as in Example 5 above.
Although the abrasion resistance tended to be inferior to that of the film No. 1, the feel was good and the adhesiveness at the time of lamination was good.

Example 7 A film having a thickness of 0.006 mm obtained by coating a release liquid with a mixed solution obtained by blending 100 parts by weight of a urethane resin with a solvent containing 30 parts by weight of gelatin powder and drying it. Was transferred to a textile substrate and laminated. The surface of the woven fabric thus produced had no stickiness and was excellent in feel.

Example 8 A one-pack type urethane resin containing gelatin powder (mixed solution of non-volatile content of 30% by weight using gelatin powder-containing methyl ethyl ketone as a solvent) was coated on release paper with comma roll and dried.
Further, on this coating layer, a two-pack type urenta resin containing gelatin powder (a mixed solution of non-volatile content of 50% by weight using gelatin powder-containing methyl ethyl ketone as a solvent) was applied,
After drying, a laminated film was formed, and the laminated film was peeled off from the release paper and laminated and bonded to the surface of the nonwoven fabric.
The surface of the non-woven fabric having the laminated film was free of stickiness and had the same adhesive strength as the laminating adhesive containing no gelatin powder.

[0056]

In the present invention, the gelatin powder is pulverized in the state of being separated by the air of the jet mill, so that the gelatin powders do not directly touch each other and are fused to each other.

Further, when the gelatin powder is crushed, heat is not generated due to impact crushing, and there is no problem of fusion between gelatin powders or quality deterioration due to heat change.

Furthermore, since the gelatin powder is crushed in the state of being wrapped in the air of the jet mill, the gelatin powder does not extremely dry or swell in the crushing process. From this, there is little inhibition of hydrophilicity due to drying of the gelatin powder, and there is little inconvenience that the gelatin powder becomes viscous with swelling and the pulverization is inhibited. From these facts, it was possible to reliably and efficiently produce a gelatin powder having a particle size in a range smaller than 6 μm.

Furthermore, since the finely pulverized gelatin is dispersed in a solvent in a suspended state, the film can be smoothly and easily blended with the molding resin, and the film is mixed in the resin mixture. It has the feature that gelatin powder is uniformly dispersed.

Therefore, when a film is formed using a resin mixture containing gelatin powder belonging to a finer range than 6 μm, the film, etc., in a state where the gelatin powder is uniformly dispersed in the film, etc. Is formed. From this fact, this film and the like have a characteristic that moisture absorption and desorption characteristic of gelatin, an appropriate contact resistance, and stretchability are provided, and electrostatic charging is prevented.

Further, since the grain size of gelatin powder contained in these films is finer than 6 μm, it was made possible to form these films thin. In particular, a film having a thickness of 0.006 mm was produced, and the gelatin powder mixed in did not rise or stick out from the surface of the formed film, and the surface had a good touch and a smooth surface.

Further, since the gelatin powder is uniformly exposed on the surface of the formed film, hygroscopicity is effectively provided on the surface of the film, and a good feeling of touch is provided.

Furthermore, when the mixed gelatin powder is eluted from the surface of the film to be formed, countless fine holes of several microns are formed on the surface of this film, which is peculiar to the surface of the film to be formed. It has the feature of providing moisture absorption and desorption function, especially water-moisture resistance function.

When the surface of the film formed above is subjected to sanding treatment, the gelatin powder contained in the film further promotes the moisture absorption function, the water vapor permeation resistance function, and the good touch feeling. .

The film using the gelatin powder according to the present invention is used as a synthetic leather material for various furnitures, personal belongings such as bags, interior materials for automobiles, etc. because of its characteristic content above. It is used as a surface material for various electronic devices and keyboards for these operators.

Further, the film containing the above gelatin powder can be produced or used by the same method or method as the molding method of the usual film containing no gelatin powder. From this, the film using the ground gelatin powder according to the present invention can be used as a means such as surface makeup for all commodities in daily life.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location (C08L 101/00 89:00)

Claims (1)

(57) [Claims] 1. Gelatin in the form of powder or granules is crushed by a jet mill and classified to obtain gelatin powder having a particle size smaller than 6 microns, and the gelatin powder is a solvent such as dimethylformamide and toluene. A resin film which is mixed and blended with the above to form a part of the resin film composition.